Selection of lubricant components to reduce engine sludge

Abstract

The present invention provides a method for lubricating a combustion engine that is suitable for improving at least one of the following: deposits, sludge, oxidation, and wear. [Solution] A method for lubricating a combustion engine comprises lubricating the combustion engine with a lubricating oil composition, wherein the lubricating oil composition comprises a base oil having a lubricating viscosity having more than about 90 weight percent saturated material, less than about 0.03 weight percent sulfur, and more than about 50 weight percent hydrogenated mineral oil having a viscosity index of less than or equal to about 120; a detergent system having less than about 5 weight percent metal from a non-sulfonate detergent and (ii) a total base number (TBN) of a specific value, giving about 60 to about 85 percent of the total lubricating oil composition TBN; an anti-wear system comprising one or more zinc dihydrocarbyl dithiophosphate compounds; and an antioxidant system comprising one or more phenolic antioxidant compounds, one or more amine antioxidant compounds, or a combination thereof.

Description

[Technical Field]

[0001] This disclosure relates to an additive package for lubricating compositions, and more particularly to the selection of components for an additive package to achieve improved performance in passenger car motor oil lubricating compositions. [Background technology]

[0002] Lubricants intended for use as motor oil in gasoline or diesel vehicle engines (commonly also referred to as engine oil, crankcase oil, lubricating composition, or lubricating oil composition) generally contain a base oil or a blend of a base oil and one or more additives with a lubricating viscosity that meets certain performance requirements for the intended application. Modern automotive industry standards impose increasingly stringent requirements in terms of the composition and / or performance of such oils, which often leaves little room for flexibility in lubricant formulations. As lubricant manufacturers strive to meet various automotive industry standards, the challenge is to achieve all required performance and industry standards simultaneously in a cost-effective manner.

[0003] The American Petroleum Institute (API) classifies base oils for lubricants into five groups. API Groups I, II, and III define mineral oils classified by saturation, sulfur content, and viscosity index. API Group IV concerns polyalphaolefin base oils, and API Group V includes all other base oils. In the context of mineral oils, the performance that mineral oils provide to lubricants improves from Group I to Group III, with API Group III mineral oils being the most preferred in terms of performance quality, while Group I and Group II mineral oils tend to offer one or more performance degradations under modern automotive industry standards. Therefore, to meet the stringent requirements of today's industrial and automotive standards, the use of larger amounts of API Group III mineral oil when formulating lubricants has become a trend in the automotive lubricant industry.

[0004] A recent area of ​​focus in the automotive industry is the evaluation of the role of lubricants in sludge formation in the cylinder heads, reservoirs, valve covers, and / or timing covers of engines during prolonged operation. Newer and more rigorous engine tests, such as the M271 EVO combustion engine test (CEC L-107-19), require that lubricants not only minimize sludge formation but also properly suspend the sludge in the solution, minimizing increases in fluid viscosity and, simultaneously, the associated increases in oil pressure. The M271 EVO combustion engine test is a demanding test to achieve pass performance, and in many cases, OEMs require performance higher than pass performance; therefore, API Group III mineral oils are the key base oils for achieving performance in this test. [Overview of the project]

[0005] This disclosure relates to passenger car motor oil lubrication compositions and methods for lubricating combustion engines, which are suitable for improving at least one of deposits, sludge, oxidation, and wear. In one approach or embodiment, the passenger car motor oil lubrication composition and the method of using the composition comprises a blend of base oils of lubrication viscosity comprising a majority of API Group II base oils. In one embodiment, a method for lubricating a combustion engine to pass the M271 EVO combustion engine test of CEC L-107-19 (as defined herein) comprises: lubricating the combustion engine with a lubricating oil composition, the lubricating oil composition comprising a base oil of lubrication viscosity having more than about 90 wt percent saturated, less than about 0.03 wt percent sulfur, and more than about 50 wt percent hydrotreated mineral oil having a viscosity index of less than about 120 (ASTM D2270), and (i) less than about 5 wt percent metal from non-sulfonate detergents, and (ii) its total base number (total base) less than about 10 mg KOH / gram as measured according to ASTM D2896 The lubricating oil composition comprises a detergent system having a number (TBN) and giving about 60 to about 85 percent of the total lubricating oil composition TBN; an anti-wear system containing one or more zinc dihydrocarbyl dithiophosphate compounds having alkyl groups derived from primary alcohols, secondary alcohols, or combinations thereof and providing about 200 to about 1000 ppm of phosphorus; and an antioxidant system containing one or more phenolic antioxidant compounds, one or more amine antioxidant compounds, or combinations thereof, wherein the lubricating oil composition is CEC To achieve a high passing average engine sludge grade of 9.0+ / -0.3 merit or higher under L-107-19, the following must be included: (a) the detergent system must consist of a majority of one or more overbasic sulfonate detergents (preferably overbasic magnesium sulfonate detergents); (b) the anti-wear system must consist of a majority of zinc dihydrocarbyl dithiophosphate compounds having an average of 8 or more carbon atoms per phosphorus atom; and / or (c) the antioxidant system must consist of a majority of phenolic antioxidant compounds.

[0006] In further embodiments, the methods described in the preceding paragraph may include one or more other steps, features, or embodiments in any combination. These other steps, features, or embodiments are as follows: the lubricating oil composition (a) having a majority of one or more overbasic sulfonate detergents, preferably overbasic magnesium sulfonate detergents, and in some approaches further comprising a magnesium-to-calcium weight ratio of about 600:1 or higher, according to ASTM The lubricating oil composition further comprises a detergent system that provides about 70 to about 85 percent of the total TBN of the lubricating oil composition as measured according to D2896, and / or the lubricating oil composition further comprises a majority of phosphorus from a dihydrocarbyl dithiophosphate zinc compound of an anti-wear system provided by one or more dihydrocarbyl dithiophosphate zinc compounds having an average of 6 or fewer carbon atoms per phosphorus atom, and / or the lubricating oil composition further comprises one or more phenolic antioxidant compounds and one or more amine antioxidants in an antioxidant system, with a weight ratio of about 4:1 to about 6:1 of oxygen in ppm from the phenolic compounds to nitrogen in ppm from the amine compounds (e.g., O / N ratio) (b) The lubricating oil composition contains a majority of phosphorus from a dihydrocarbyl dithiophosphate zinc compound of the anti-wear system, provided by a dihydrocarbyl dithiophosphate zinc compound having an average of 8 or more carbon atoms per phosphorus atom, and / or about 90 to about 100 weight percent of the phosphorus from a dihydrocarbyl dithiophosphate zinc compound of the anti-wear system is provided by a dihydrocarbyl dithiophosphate zinc compound having an average of 8 or more carbon atoms per phosphorus atom, and / or the lubricating oil composition further contains both calcium and magnesium provided by a detergent system, in a calcium to magnesium ratio of about 0.8 to about 1.(c) The lubricating oil composition has a weight ratio of 5, and / or further comprises one or more phenolic antioxidant compounds and one or more amine-based antioxidant compounds in the antioxidant system, and has a weight ratio of approximately 4:1 to approximately 6:1 of ppm oxygen to ppm nitrogen provided by one or more phenolic antioxidant compounds (e.g., O / N weight ratio), and / or the lubricating oil composition has (c) a majority of phenolic antioxidant compounds, and further has a weight ratio of more than approximately 100:1 (O / N) of ppm oxygen to ppm nitrogen from amine-based antioxidant compounds The lubricating oil composition further contains both calcium and magnesium provided by a detergent system, having a weight ratio of at least about 0.8:1 to about 1.5:1 of detergent calcium to detergent magnesium, and / or the lubricating oil composition further contains a majority of phosphorus from a dihydrocarbyl dithiophosphate zinc compound of an anti-wear system, provided by a dihydrocarbyl dithiophosphate zinc compound having an average of 6 or fewer carbon atoms per phosphorus atom, and / or the base oil of the lubricating viscosity contains more than about 90 weight percent saturated, less than about 0.03 weight percent sulfur, and a viscosity index (ASTM) of about 120 or less. The lubricating oil composition is approximately 75 to approximately 90 weight percent hydrogenated mineral oil having D2270, and / or the detergent system TBN is less than approximately 5 to approximately 10 mg KOH / gram, and / or the TBN of the lubricating oil composition is approximately 7 to approximately 12 mg KOH / gram as measured according to ASTM D2896, and / or the detergent system is substantially free of phenate detergents, and / or the detergent system essentially consists of sulfonate detergents providing calcium, magnesium, or a combination thereof, and / or the antioxidant system is substantially free of mono-alkylphenolamine antioxidants, and / or the lubricating oil composition is approximately 1.The lubricating oil composition contains one or more dispersant olefin copolymer viscosity index improvers in an amount of 3% by weight or less, and / or substantially no dispersant olefin copolymer viscosity index improvers, and / or has at least about 1000 ppm of total nitrogen, and / or contains one or more nitrogen-containing dispersant additives that provide about 600 ppm or more of dispersant nitrogen to the lubricating oil composition, and / or contains less than about 200 ppm of molybdenum, and / or contains less than about 150 ppm of boron, and / or substantially does not contain API Group III base oil, or one or more of these conditions.

[0007] In further embodiments, the disclosure includes lubricating compositions comprising any embodiment described in this summary.

[0008] In further embodiments, the disclosure includes the use of any embodiment of the method described herein and / or any embodiment of the lubricating composition to achieve a high pass average engine sludge grade of 9.0+ / -0.3 merit or higher under CEC L-107-19. [Modes for carrying out the invention]

[0009] This disclosure relates to passenger car motor oil and a method for lubricating a combustion engine using passenger car motor oil to achieve passing performance, and in some cases high passing performance, in the M271 EVO combustion engine test of CEC L-107-19, particularly a method for achieving passing (and preferably high) performance in this combustion engine test when the passenger car motor oil contains an increased amount of less desirable API Group II base oil. Surprisingly, it has been found that the performance degradation when using less desirable API Group II base oil can be overcome by carefully controlling selected components of the lubricant additive system and using them in combination with an increased amount of less desirable API Group II base oil.

[0010] In particular, the methods and passenger car motor oil lubrication compositions herein contain at least about 50 weight percent (preferably about 60 weight percent, about 70 weight percent, about 80 weight percent, or about 85 weight percent) of a base oil or blend of base oils of lubricating viscosity, including a base oil derived from hydrotreated mineral oil (e.g., a majority of API Group II base oils) containing more than 90 weight percent saturated material, less than 0.03 weight percent sulfur, and a viscosity index of 120 or less (ASTM D2270), and still achieve pass (and preferably high) performance as defined herein in the M271 EVO combustion engine test of CEC L-107-19 (i.e., average engine sludge rating (AES) or 9.0+ / -0.3 merit or better).

[0011] Surprisingly, it has been found that when a passenger car motor oil lubrication composition contains selected additive components that achieve a performance synergy, it is possible to overcome any performance degradation from this lower quality base oil in the M271 combustion engine test, even when using a higher level of less desirable API Group II base oil. Such selected additive components include (1)(i) detergent systems having less than about 5 weight percent, preferably less than 2 weight percent, more preferably less than 1 weight percent of metal from non-sulfonate detergents (e.g., non-sulfonate detergents include metal-containing phenates, salicylates, calixyrates, and / or other non-sulfonate detergents), most preferably a functional amount of metal from non-sulfonate detergents, and (1)(ii) detergent systems having a total base number (TBN) of less than 10 mg KOH / gram, and giving about 60 to about 85 percent of the total lubricating oil composition TBN as measured according to ASTM D2896, and (2) when used in combination with a detergent system, CEC The additive system comprises at least one of the following: (2)(a) a detergent system comprising a majority of one or more overbasic sulfonate detergents (preferably overbasic magnesium sulfonate detergents); (2)(b) an anti-wear system comprising a majority of zinc dihydrocarbyl dithiophosphate compounds having an average of 8 or more carbon atoms per phosphorus atom; and / or (2)(c) an antioxidant system comprising a majority of phenolic antioxidant compounds. A method of lubricating a combustion engine using such a passenger car motor oil lubricant composition containing a large amount of API group II base oil surprisingly exhibits an average engine sludge (AES) grade of at least about 9.0 merit (+ / -0.3 merit) under CEC L-107-19.

[0012] Base oil or base oil blend: As discussed in the background technology, API Group II base oils are less desirable when formulated for passenger car motor oils due to numerous performance degradations when required for industrial testing. API Group II base oils are generally less pure and refined than preferred API Group III base oils. For example, API Group II base oils typically contain more than 90% by weight saturated material, less than 0.03% by weight sulfur, and hydrotreated mineral oil with a viscosity index of 120 or less (ASTM D2270). From the perspective of mineral oil base oils, this is less refined than the more preferred API Group III base oils, which have a higher viscosity index, are more heavily hydrocracked, and are generally more refined than Group II base oils. In some embodiments, the base oils or base oil blends herein may not substantially contain API Group III base oils, and in such context may contain less than about 10 weight percent, less than about 5 weight percent, less than about 2 weight percent, less than about 1 weight percent, less than about 0.5 weight percent, or less than about 0.1 weight percent of API Group III base oils, or may not contain any functional amount of API Group III base oils at all. The base oils are generally listed in Table 1 below.

[0013] [Table 1]

[0014] In one approach or embodiment, the methods and lubricating oil compositions herein include a base oil or blend of base oils of lubricating viscosity, comprising a majority or at least about 50% by weight (preferably about 60% by weight or more, about 70% by weight or more, about 80% by weight or more, or about 85% by weight or more) of a base oil derived from an API Group II base oil or a base oil having more than 90% by weight of saturated material, less than 0.03% by weight of sulfur, and a viscosity index of 120 or less (ASTM D2270). In other approaches or embodiments, the methods and lubricating oil compositions herein include a base oil blend in which the base oil or at least about 50 weight percent is an API Group II base oil, or in other embodiments, the composition includes about 50 to about 100 weight percent (about 75 to about 90 weight percent, about 80 to about 90 weight percent, or about 85 to about 90 weight percent) of a base oil derived from an API Group II base oil or a hydrotreated mineral oil having more than 90 weight percent saturated, less than 0.03 weight percent sulfur, and a viscosity index of 120 or less (ASTM D2270). The remainder of the base oil in any blend herein is one of API Group I or III mineral base oils, API Group IV base oils, API Group V base oils, or any mixture thereof. In some embodiments, the base oil or base oil blend described herein may have a KV100 of about 2 to about 20 cSt, in other approaches about 5 to about 15 cSt, about 8 to about 15 cSt, and in yet another approach about 10 to about 15 cSt.

[0015] As will be understood by those skilled in the art, mineral oils may include oils obtained by drilling or from plants and animals, or any mixture thereof. For example, such oils may include, but are not limited to, castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricants, such as liquid petroleum, and paraffinic, naphthenic, or mixed paraffin-naphthenic type solvent-treated or acid-treated mineral lubricants. Such oils may be partially or completely hydrogenated if desired. Oils derived from coal or shale may also be useful.

[0016] Useful synthetic lubricants include hydrocarbon oils, for example, polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylene, polypropylene, propylene isobutylene copolymer); trimers or oligomers of poly(1-hexene), poly(1-octene), and 1-decene, for example, poly(1-decene) (such materials are often referred to as α-olefins), and mixtures thereof; alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers, and alkylated diphenyl sulfides, as well as their derivatives, analogs, and homologs, or mixtures thereof. Polyalphaolefins are typically hydrogenated materials.

[0017] Other synthetic lubricants include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl esters of decanephosphonic acid), or polymeric tetrahydrofurans. Synthetic oils may be produced by the Fischer-Tropsch reaction and are typically hydrogenated isomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil may be prepared by the Fischer-Tropsch gas-liquid synthesis procedure and other gas-liquid oils.

[0018] The amount of oil with lubricating viscosity present may be the difference remaining after subtracting the total amount of performance additives, including viscosity index improvers and / or pour point depressants and / or other top-treatment additives, from 100% by weight. For example, the amount of oil with lubricating viscosity that may be present in the final fluid may be the main amount, e.g., more than about 50% by weight, more than about 60% by weight, more than about 70% by weight, more than about 80% by weight, more than about 85% by weight, or more than about 90% by weight.

[0019] Generally, as used herein, the terms "oil composition", "lubricating composition", "lubricating oil composition", "lubricating oil", "lubricant composition", "lubricant", and "lubricant material" are synonymous and are considered to be fully interchangeable terms, and refer to a passenger vehicle motor oil lubricant product that includes a minor amount of an additive system and / or, preferably, any other optional components that are possible for one or more industry or OEM specification standards, in addition to a major amount of a base oil component having the blend amounts described above.

[0020] Detergent system The lubricating oil compositions herein include a detergent system that contains little or no metal provided from a non-sulfonate detergent (e.g., little or no metal from a metal-containing phenate detergent, salicylate detergent, calixylate detergent, and other non-sulfonate detergents), and otherwise a selected detergent composition that provides a specific contribution to the total base number (TBN) of the entire lubricating oil composition. In one embodiment, for example, the methods and lubricating oil compositions herein can have (i) less than about 5 weight percent metal from a non-sulfonate detergent (preferably less than about 2 weight percent metal from a non-sulfonate detergent, more preferably less than 1 weight percent metal from a non-sulfonate detergent, and most preferably may have no metal provided from a non-sulfonate detergent), and (ii) a detergent total base number (TBN) of less than about 10 mg KOH / gram, which, when measured according to ASTM D2896, provides from about 60 to about 85 percent of the total lubricating oil composition TBN.

[0021] In one approach or embodiment, the detergent system of the present specification preferably includes one or more detergent additives, more preferably a sulfonate-based calcium-providing detergent, which is a calcium-containing detergent additive. In another embodiment, the one or more detergent additives may also include a magnesium-containing detergent additive, more preferably a sulfonate-based magnesium detergent additive. In still other embodiments, the detergent system may be a blend of a calcium detergent and a magnesium detergent, preferably a blend of a sulfonate-based calcium detergent and a magnesium detergent. These selected detergent additives provide a total base number (TBN) of at least about 4 mg KOH / g, at least about 5 mg KOH / g, at least about 6 mg KOH / g, or at least about 7 mg KOH / g to the lubricant when measured according to ASTM D2896. In other approaches or embodiments, the detergent additives of the present specification provide a detergent TBN of about 10 mg KOH / g or less (e.g., about 4 to about 10 mg KOH / g, about 5 to about 10 mg KOH / g, about 6 to about 10 mg KOH / g, or about 7 to about 10 mg KOH / g) to the lubricant. Such detergent additives provide about 60 to about 85 percent (in other approaches, about 65 to about 85 percent, about 70 to about 85 percent, or about 75 to about 85 percent) of the total lubricating oil composition TBN when measured according to ASTM D2896. That is, the total lubricating oil composition of the present specification may have a final fluid TBN of about 7 to about 12 mg KOH / gram when measured according to ASTM D2896, and the detergent system of the present specification may provide about 60 to about 85 percent (in other approaches, about 65 to about 85 percent, about 70 to about 85 percent, or about 75 to about 85 percent) of the total fluid TBN.

[0022] Suitable detergents and methods for preparing them are described in more detail in numerous patent publications, including U.S. Patent No. 7,732,390 and the references cited herein, which are incorporated herein by reference. The passenger car motor oil lubrication compositions herein may contain about 0.1 to about 5 weight percent of individual and / or total detergent additives, in other approaches about 0.15 to about 3 weight percent, and in yet other approaches about 0.15 to 2.6 weight percent of individual and / or total detergent additives, insofar as the detergent additives satisfy the calcium levels, magnesium levels, and / or TBN levels described herein.

[0023] In general, suitable detergents in the lubricants of this specification (meeting the requirements described herein for metals, detergent type, calcium, magnesium, and / or TBN) may include linear or branched alkali or alkaline earth metal salts, such as calcium, sodium, or magnesium, of petroleum sulfonic acid, and long-chain mono- or di-alkylarylsulfonic acid having an aryl group of benzyl, tolyl, and xylyl, and / or various phenates or derivatives of phenates. Examples of suitable cleaning agents include the required amount of sulfonate soap mentioned above, as well as the following low-basic / neutral and over-basic variations of cleaning agents: calcium carbonate, calcium sulfur-containing phenate, calcium sulfonate, calcium calixalate, calcium salixalate, calcium salicylate, calcium carboxylic acid, calcium phosphate, calcium mono- and / or di-thiophosphate, calcium alkylphenol, calcium sulfur-bonded alkylphenol compounds, calcium methylene crosslinked phenol, magnesium carbonate, magnesium sulfur-containing phenate, magnesium sulfonate, magnesium calixalate, magnesium salixalate, magnesium salicylate, magnesium carboxylic acid, magnesium phosphate, magnesium mono- and / or di-thiophosphate, magnesium alkylphenol, magnesium sulfur-bonded alkylphenol compounds, magnesium methylene crosslinked phenol, sodium carbonate, sodium sulfur-containing phenate, sodium sulfonate, sodium calixalate, sodium salixalate, sodium salicylate, sodium carboxylic acid, sodium phosphate, sodium mono- and / or di-thiophosphate, sodium alkylphenol, sodium sulfur-bonded alkylphenol compounds, or sodium methylene crosslinked phenol.

[0024] The detergents described herein may be overbasic, and as understood, overbasic detergent additives are well known in the art, and may be alkali metal or alkaline earth metal overbasic detergent additives. Such detergent additives may be prepared by reacting a metal oxide or metal hydroxide with a base and carbon dioxide gas. The base is typically an acid, such as an aliphatic-substituted sulfonic acid, aliphatic-substituted carboxylic acid, or aliphatic-substituted phenol. The term “overbasic” refers to metal salts in which the amount of metal present exceeds the stoichiometric amount, such as metal salts of sulfonates, carboxylates, salicylates, and / or phenates. Such salts may have a conversion level greater than 100% (i.e., such salts may contain more than 100% of the theoretical amount of metal required to convert an acid to its “standard” salt, “neutral” salt). The term "metal ratio," often abbreviated as MR (metal ratio), is used to indicate the ratio of the total chemical equivalents of metal in an overbasic salt to the chemical equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. For standard or neutral salts, MR is 1, and for overbasic salts, MR is greater than 1. These are generally referred to as overbasic, highly basic, or ultrabasic salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.

[0025] As used herein, the term "TBN" is used to express the total base number in mg KOH / g, measured by the method of ASTM D2896. The cleaning agents herein may be neutral or overbasic. For example, the low-basic or neutral cleaning agents herein may have a total base number (TBN) of less than about 250 mg KOH / gram (e.g., about 0 to less than about 250). The overbasic cleaning agents herein may have a total base number (TBN) of about 250 mg KOH / gram or more, or about 300 mg KOH / gram or more, or about 350 mg KOH / gram or more, or about 375 mg KOH / gram or more, or about 400 mg KOH / gram or more. The overbasic cleaning agent may have a metal-to-base ratio of 1.1:1 or less, or 2:1 or less, or 4:1 or less, or 5:1 or less, or 7:1 or less, or 10:1 or less, or 12:1 or less, or 15:1 or less, or 20:1 or less.

[0026] Examples of suitable overbasic detergents (that satisfy the requirements described herein for non-sulfonic metal contributions, calcium, magnesium, and / or TBN) include overbasic calcium phenate, overbasic calcium sulfur-containing phenate, overbasic calcium sulfonate, overbasic calcium calixalate, overbasic calcium salixalate, overbasic calcium salicylate, overbasic calcium carboxylic acid, overbasic calcium phosphate, overbasic calcium mono- and / or di-thiophosphate, overbasic calcium alkylphenol, overbasic calcium sulfur-bonded alkylphenol compounds, and overbasic Examples of such cleaning agents include, but are not limited to, calcium methylene crosslinked phenols, overbasic magnesium phenates, overbasic magnesium sulfur-containing phenates, overbasic magnesium sulfonates, overbasic magnesium calixalates, overbasic magnesium salixalates, overbasic magnesium salicylates, overbasic magnesium carboxylic acids, overbasic magnesium phosphates, overbasic magnesium mono- and / or di-thiophosphates, overbasic magnesium alkylphenols, overbasic magnesium sulfur-bonded alkylphenol compounds, or overbasic magnesium methylene crosslinked phenols. Preferably, the cleaning agent is magnesium sulfonate and / or calcium sulfonate, and is substantially free of non-sulfonate cleaning agents as described above (for example, preferably substantially free of phenate cleaning agents). More preferably, the cleaning agent herein is overbasic magnesium sulfonate and / or overbasic calcium sulfonate cleaning agents, as described in various embodiments.

[0027] In other embodiments, the TBN of the cleaning agents herein may reflect undiluted or undiluted versions of the cleaning agent components. For example, the fluids herein may include overbasic calcium sulfonate and / or calcium sulfonate as undiluted additives having a TBN of about 300 to about 450, and in other approaches, about 380 to about 420.

[0028] In one embodiment, the detergent system of this specification provides primarily magnesium metal (and preferably substantially all or all magnesium metal). In such embodiments, the detergent system of this specification is primarily magnesium sulfonate (e.g., more than 80 wt percent magnesium sulfonate, more than 90 wt percent magnesium sulfonate, more than 95 wt percent magnesium sulfonate, more than 98 wt percent magnesium sulfonate, or in some approaches, 100 wt percent magnesium sulfonate (or any range in between)). In yet another embodiment, the detergent system mainly containing magnesium metal may also have an optional weight ratio of magnesium detergent to calcium detergent of about 600:1 or more (and in other approaches, 620:1 or more, 650:1 or more, or about 600:1 to about 1000:1). In embodiments, such detergent systems of this specification may also provide about 70 to about 85 wt percent of the total lubricating oil composition TBN, as measured according to ASTM D2896. Furthermore, as will be discussed further below, in other embodiments, such cleaning systems according to this specification may be combined with (1) an additive system substantially free of dispersant olefin copolymer viscosity index improvers to achieve M271 EVO performance, (2) an anti-wear system having a dihydrocarbyl dithiophosphate metal compound derived from a secondary alcohol and having an average of 6 or fewer carbon atoms per phosphorus (and in some embodiments, 200 to 800 ppm of phosphorus from such anti-wear compounds), and / or (3) a mixed antioxidant system providing an antioxidant oxygen to antioxidant nitrogen weight ratio (e.g., O / N weight ratio) of 4:1 to 10:1. As used herein, substantially free (in any embodiment of this disclosure unless otherwise stated) means a composition having less than 1 weight percent, less than about 0.5 weight percent, less than about 0.2 weight percent, less than about 0.1 weight percent of the additives described herein, or no additives described in functional amounts.

[0029] In a further approach, the cleaning agent system provides both calcium metal and magnesium metal (preferably calcium sulfonate cleaning agent and magnesium sulfonate cleaning agent), having a selected ratio of cleaning agent calcium to cleaning agent magnesium of about 0.8:1 to about 1.5:1 (in other approaches, about 0.8:1 to about 1.2:1 or about 0.8:1 to about 1.0:1). As will be discussed further below, such a cleaning agent system may, in yet another embodiment, be combined with (1) a selected anti-wear system and / or (2) a selected antioxidant system to achieve M271 EVO performance. For example, such a cleaning agent system may be combined with an additive system comprising a metal-containing anti-wear system derived from a primary alcohol and provided from a zinc dihydrocarbyl dithiophosphate compound having an average of 8 or more carbon atoms per phosphorus, while the additive system may substantially not contain dispersant olefin copolymer viscosity index improvers. In further embodiments, such a cleaning agent system of this embodiment may also be combined with an additive system comprising one or more antioxidant additives, the majority of which are phenolic antioxidant additives (and preferably substantially all phenolic antioxidant additives), wherein in some embodiments the weight ratio of oxygen in ppm to nitrogen in ppm from the phenolic antioxidant compound (i.e., the weight ratio of O / N) is greater than 100:1 (greater than 150:1, greater than 175:1, greater than 200:1), and in yet other embodiments the additive system may also substantially omit the dispersant olefin copolymer viscosity index improver.

[0030] Selective viscosity index improvers In some embodiments, the methods and lubricating oil compositions of this specification may also include an additive system comprising one or more optional viscosity index improvers coupled with the above-described detergent system, where the optional viscosity index improvers are preferably dispersant olefin copolymer viscosity index improvers (in this context, the lubricating oil composition may contain up to about 1.5 weight percent or up to about 1.3 weight percent of the viscosity index improver). In other embodiments, as described above, the lubricating oil compositions of this specification are substantially free of dispersant olefin copolymer viscosity index improvers (in this context, substantially free of dispersant olefin copolymer viscosity index improvers means that the dispersant olefin copolymer viscosity index improver is less than about 1.0 weight percent, about 0.5 weight percent or less, about 0.2 weight percent or less, about 0.1 weight percent or less, or not a functional amount). If included, suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, styrene-isoprene polymers, styrene / maleate copolymers, styrene-butadiene copolymers, styrene-isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrated alkenylaryl conjugated diene copolymers, or mixtures thereof.

[0031] One approach is to use a suitable dispersant olefin copolymer viscosity index improver, which is (1) an acylated copolymer with ethylene and one or more C3-C3 copolymers. 20 The present invention may include a highly grafted polyfunctional olefin copolymer, which is a reaction product of (2) a polyamine compound, comprising an acylated olefin copolymer, which includes a copolymer, multiple copolymers, or terpolymer of an alpha-olefin and an ethylenically unsaturated carboxylic acid reaction product of an ethylenically unsaturated carboxylic acid reaction product grafted to a level of 0.3 to 0.75 carboxyl groups per thousand-something average molecular weight unit (Mn), and (2) a polyamine compound. Suitable dispersants and olefin copolymer viscosity index improvers are described in U.S. Patent No. 6,107,257, which is incorporated herein by reference.

[0032] In one approach or embodiment, the polyamine compound of the dispersant olefin copolymer viscosity index improver is preferably an N-arylphenylenediamine represented by formula I.

[0033] [ka] In the formula, R1 is a branched or linear radical having 4 to 24 carbon atoms, which may be hydrogen, -NH-aryl, -NH-arylalkyl, -NH-alkyl, or alkyl, alkenyl, alkoxyl, aralkyl, alkaryl, hydroxyalkyl, or aminoalkyl, and R2 is -NH2, -CH2-(CH2) n The molecule is -NH2 or -CH2-aryl-NH2, where n is an integer from 1 to 10, and R3 is hydrogen, alkyl, alkenyl, alkoxyl, aralkyl, or alkaryl, and any part thereof may have 4 to 24 carbon atoms.

[0034] In some embodiments, the olefin copolymer substate consists of about 15 to about 80 mole percent ethylene and about 85 to about 20 mole percent of one or more C3-C3 molecules. 23 It may contain alpha-olefins, and the preferred molar ratio is about 35 to about 75 mole percent of ethylene and about 65 to about 25 mole percent of one or more C3-C3 olefins. 20 It is an alpha-olefin, and a more preferred molar ratio is about 50 to about 70 mole percent of ethylene and about 50 to about 30 mole percent of one or more C3-C3 olefins. 20 It is an alpha-olefin, and the most preferred molar ratio is about 55 to about 65 mole percent of ethylene and about 45 to about 35 mole percent of one or more C3-C3 olefins. 20 It is an alpha-olefin. The polymer substrate, i.e., ethylene copolymer or terpolymer, is an oil-soluble, linear or branched polymer or copolymer, having a number-average molecular weight of about 20,000 to about 150,000 as defined by gel permeation chromatography, with a preferred number-average molecular weight range of about 30,000 to about 110,000.

[0035] Next, an ethylenically unsaturated carboxylic acid material is grafted onto the polymer backbone to form an acylated ethylene copolymer. Suitable carboxylic acid reactants for grafting onto these ethylene copolymers contain at least one ethylene bond and at least one, preferably two carboxylic acid groups or their anhydride groups, or polar groups that can be converted to the carboxyl groups by oxidation or hydrolysis. Preferably, the carboxylic acid reactant is selected from the group consisting of acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid reactants. More preferably, the carboxylic acid reactant is selected from the group consisting of maleic acid, fumaric acid, maleic anhydride, or a mixture of two or more of these. Due to their commercial availability and ease of reaction, maleic anhydride or its derivatives are generally the most preferred. In the case of unsaturated ethylene copolymers or terpolymers, itaconic acid or its anhydride is preferred due to its reduced tendency to form crosslinked structures during the free radical grafting treatment.

[0036] Ethylene-unsaturated carboxylic acid substances can typically provide one or two carboxyl groups per mole of reactant to the grafted polymer. For example, maleic anhydride can provide two carboxyl groups per molecule to the grafted polymer. The carboxyl reactant is grafted onto a given polymer backbone in an amount that provides 0.3 to 0.75 carboxyl groups per 1000 number-average molecular weight units of the polymer backbone, preferably 0.3 to 0.5 carboxyl groups per 1000 number-average molecular weight units. For example, a copolymer substrate with 20,000 Mn is grafted with 6 to 15 carboxyl groups per polymer chain or 3 to 7.5 moles of maleic anhydride per mole of polymer. A copolymer with 100,000 Mn is grafted with 30 to 75 carboxyl groups per polymer chain or 15 to 37.5 moles of maleic anhydride per polymer chain.

[0037] In embodiments comprising a dispersant olefin copolymer viscosity index improver, the lubricating oil composition herein may contain up to about 1.5 weight percent, up to about 1.3 weight percent, up to about 1.25 weight percent, or up to about 1 weight percent of the dispersant olefin copolymer viscosity index improver. In other embodiments, if included, the lubricating oil composition herein may contain about 0.8 weight percent to about 1.5 weight percent, about 0.8 to about 1.3 weight percent, or about 0.9 to about 1.2 weight percent (or any other range within such endpoints) of the dispersant olefin copolymer viscosity index improver. As described above, such amounts of dispersant olefin copolymer viscosity index improver may, in some embodiments, be coupled or combined with selected characteristics of a detergent system (e.g., a detergent system that provides both calcium and magnesium metals, with a detergent calcium to detergent magnesium ratio of at least 2:1) to achieve M271 EVO performance.

[0038] Dihydrocarbyl dithiophosphate compounds The methods and lubricating compositions described herein may also, in some embodiments, include an anti-wear system of one or more metal dihydrocarbyl dithiophosphate compounds, such as but not limited to zinc dihydrocarbyl dithiophosphate (ZDDP). When used, one or more metal dihydrocarbyl dithiophosphate compounds may provide up to about 1,000 ppm of phosphorus to the lubricant, up to about 900 ppm of phosphorus, or up to about 800 ppm of phosphorus to the lubricating oil composition, or at least about 200 ppm of phosphorus, at least about 400 ppm of phosphorus, at least about 600 ppm of phosphorus, or about 700 ppm of phosphorus. When used in the lubricants described herein, the hydrocarbyl groups of one or more metal dihydrocarbyl dithiophosphate compounds may be derived from primary alcohols, secondary alcohols, or mixtures of secondary and primary alcohols, as described further herein.

[0039] In one approach, the metal dihydrocarbyl dithiophosphate compounds described herein may be derived from primary alcohols, and the average number of carbon atoms in the hydrocarbyl group of the metal dihydrocarbyl dithiophosphate compound may be an average of 8 or more carbon atoms per phosphorus (e.g., an average of 8 to 16, 8 to 12, or 8 to 10 carbon atoms per phosphorus). In this approach, the metal dihydrocarbyl dithiophosphate compounds may provide about 1,000 ppm of phosphorus to a lubricant, up to about 900 ppm of phosphorus, or up to about 800 ppm of phosphorus to a lubricating oil composition, or at least about 200 ppm of phosphorus, at least about 400 ppm of phosphorus, at least about 600 ppm of phosphorus, or about 700 ppm of phosphorus. In this embodiment, such dihydrocarbyl dithiophosphate metal compounds can provide substantially all or all anti-wear phosphorus (e.g., about 80% or more by weight anti-wear phosphorus, about 90% or more by weight anti-wear phosphorus, about 95% or more by weight anti-wear phosphorus, about 98% or more by weight anti-wear phosphorus, about 99% or more by weight anti-wear phosphorus, or about 100% by weight anti-wear phosphorus). In embodiments of the methods and lubricating compositions comprising the mixed calcium and magnesium detergents and mixed amine-based and phenol-based antioxidants described herein, such ZDDP may be particularly preferred.

[0040] Alternatively, the metal dihydrocarbyl dithiophosphate compounds described herein may be derived from secondary alcohols, and the average number of carbon atoms in the hydrocarbyl group may be six or fewer carbon atoms per phosphorus (e.g., two to six, three to six, or four to six carbon atoms per phosphorus). In this alternative approach, such metal dihydrocarbyl dithiophosphate compounds may provide about 1,000 ppm of phosphorus to a lubricant, up to about 900 ppm of phosphorus, or up to about 800 ppm of phosphorus to a lubricating oil composition, or at least about 200 ppm of phosphorus, at least about 400 ppm of phosphorus, at least about 600 ppm of phosphorus, or about 700 ppm of phosphorus. In this embodiment, such dihydrocarbyl dithiophosphate metal compounds can provide substantially all or all anti-wear phosphorus (e.g., about 80% or more by weight anti-wear phosphorus, about 90% or more by weight anti-wear phosphorus, about 95% or more by weight anti-wear phosphorus, about 98% or more by weight anti-wear phosphorus, about 99% or more by weight anti-wear phosphorus, or about 100% by weight anti-wear phosphorus). In embodiments of methods and lubricating compositions comprising a mixed calcium and magnesium detergent combined with an antioxidant system comprising only the phenolic antioxidants described herein, this alternative ZDDP may be particularly preferred, or such ZDDP may also be preferred in embodiments of methods and compositions herein comprising a magnesium-only detergent system.

[0041] In various embodiments, a suitable metal dihydrocarbyl dithiophosphate compound may contain 5 to about 10 weight percent of metal (such as about 6 to about 9 weight percent of a metal like zinc), about 8 to about 18 weight percent of sulfur (such as about 12 to about 18 weight percent of sulfur, or about 8 to about 15 weight percent of sulfur), and about 4 to 20 weight percent of phosphorus (such as about 4 to about 15 weight percent of phosphorus, or about 4 to about 9 weight percent of phosphorus). A suitable metal dihydrocarbyl dithiophosphate compound may include a metal dihydrocarbyl dithiophosphate salt, the metal of which may be an alkali metal, an alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, zirconium, zinc, or a combination thereof. Preferably, the metal is zinc.

[0042] When used in passenger car motor oil as herein, the alkyl groups on the metal dihydrocarbyl dithiophosphate compound may be derived from primary alcohols, secondary alcohols, phenols, or mixtures thereof, depending on the embodiments described herein and as necessary. For example, the hydrocarbyl group may be derived from 2-ethylhexanol, methyl isobutyl carbinol (MIBC), isobutanol, and isopropanol, etc. One approach is that about 60 mole percent or more of alkyl groups may be derived from primary alcohols (e.g., but not limited to 2-ethylhexanol and / or isobutyl alcohol), and about 40 mole percent or less of alkyl groups may be derived from secondary alcohols (e.g., but not limited to isopropyl alcohol, methyl isobutyl carbinol, etc., and / or combinations thereof). Another approach is that all alkyl groups on the metal dihydrocarbyl dithiophosphate compound may be derived from primary alcohols such as 2-ethylhexanol or others described herein. In other approaches, all alkyl groups on the metal dihydrocarbyl dithiophosphate compound may be derived from secondary alcohols, such as isopropyl alcohol or methyl isobutylcarbinol, but are not limited to these.

[0043] Generally, metal dihydrocarbyl dithiophosphate compounds for passenger car motor oil that satisfy the above limitations can be derived from alcohols selected from, but are not limited to, 2-ethylhexanol, propanol, methylpentanol, methylheptanol, heptanol, octanol, nonanol, decanol, dodecanol, and / or their isovariants. Examples of suitable metal dihydrocarbyl dithiophosphate compounds include O,O-di(C 3~14 Examples include, but are not limited to, zinc (alkyl)dithiophosphate, zinc bis(2-ethylhexyl)dithiophosphate, zinc bis(2-ethylhexyl)dithiophosphate, zinc bis(2-methylpropyl)dithiophosphate, zinc bis(2-methylbutyl)-O-(2-methylpropyl)dithiophosphate, zinc bis(2-methylbutyl)-O-(2-methylpropyl)dithiophosphate, and zinc bis(2-methylpropyl)-O-(2-methylpropyl)dithiophosphate, or combinations thereof.

[0044] In the approach or embodiment, the metal dihydrocarbyl dithiophosphate compound suitable for passenger car motor oil according to this specification may have the structure of formula II.

[0045] [ka] In the formula, each R in formula I independently contains 3 to 18 carbon atoms, or 3 to 12 carbon atoms, or about 3 to 10 carbon atoms, in one embodiment (and preferably derived from a primary alcohol), each phosphorus atom has an average of at least 8 total carbon atoms (e.g., an average of 8 to 16 carbon atoms), and in another embodiment (and preferably derived from a secondary alcohol), each phosphorus atom has an average of 6 or fewer carbon atoms per phosphorus atom (e.g., an average of 2 to 6 carbon atoms). Again, mixtures of such compounds may also be used. For example, each R independently may be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, ethylhexyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl, and such groups. The number of carbon atoms in each R group in the above formula will generally be 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more. In one embodiment, each phosphorus atom may have an R group having an average of 3 to 6 carbon atoms per phosphorus atom (derived from isopropyl and methylpentyl groups), and in another embodiment, each phosphorus atom may have an R group having an average of 8 or more carbon atoms per phosphorus atom (e.g., an average of 10 to 16 carbon atoms) (derived from ethylhexyl or isobutyl groups). Mixtures of such compounds may also be used. Preferably, each R may be a linear or branched C8 or 2-ethylhexyl group, a C3 or isopropyl group, a C4 or isobutyl group, and / or a C8 or methylpentyl group. In formula I, A is a metal, such as aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, zirconium, zinc, or a combination thereof, preferably A is zinc. When the dihydrocarbyl dithiophosphate metal compound has the structure shown in formula I, and A is zinc, the compound may have about 4 to about 9 weight percent phosphorus, about 6 to about 9 weight percent zinc, and a zinc-to-phosphorus ratio of about 1.0 to about 1.5.

[0046] In some approaches or embodiments, it is understood in the art that a more precise representation of the sulfur-zinc coordination sequence can be expressed by the symmetric sequence shown below, and that the chemical structure of formula II, which may be used herein, is interchangeable with that of formula I shown above. It is also understood that the structures shown in formulas I and II may exist as monomers, dimers, trimers, or oligomers (e.g., tetramers).

[0047] [ka]

[0048] Dihydrocarbyl dithiophosphate metal salts can be prepared according to known techniques, usually by first reacting one or more alcohols or phenols with P2S5 to form dihydrocarbyl dithiophosphoric acid (DDPA), and then neutralizing the formed DDPA with a metal compound such as zinc oxide. For example, DDPA can be produced by reacting a mixture of alcohols containing a suitable amount of primary alcohol (and, if necessary, a suitable blend of primary and secondary alcohols) with P2S5. In this case, DDPA contains alkyl groups derived mainly from primary alcohols, or from both primary and secondary alcohols, as necessary to satisfy the required primary alcohol content in the final product. Alternatively, multiple DDPAs can be prepared, with the alkyl group on one DDPA being entirely derived from a secondary alcohol and the alkyl group on another DDPA being entirely derived from a primary alcohol. The DDPAs are then blended together to form a mixture of DDPAs having alkyl groups that satisfy the above primary alcohol content.

[0049] As described above, passenger car motor oil may contain a blend of dihydrocarbyl dithiophosphate metal compounds derived from primary and / or secondary alcohols. In one approach, the final lubricant herein may contain any of the described dihydrocarbyl dithiophosphate metal compounds individually or in a blend thereof in an amount of about 1 to about 5 weight percent.

[0050] Antioxidant type The methods and lubricating compositions described herein may also, in some embodiments, include an additive system having a selected antioxidant compound (or a blend thereof), which comprises one or more phenolic antioxidant compounds, one or more amine-based antioxidant compounds, or a combination thereof. In some embodiments, for example, the methods and lubricating compositions herein include both one or more phenolic antioxidant compounds and one or more amineic antioxidant compounds, and in some embodiments also have a selected weight ratio (e.g., O / N weight ratio) of about 300:1 or less of oxygen in ppm from one or more phenolic antioxidant compounds to nitrogen in ppm from one or more amineic antioxidant compounds, and in other approaches or embodiments, the weight ratio (e.g., O / N weight ratio) of oxygen in ppm from one or more phenolic antioxidant compounds to nitrogen in ppm from one or more amineic antioxidant compounds is about 300:1 to about 4:1, or about 300:1 to about 100:1, or about 200:1 to about 300:1, or about 4:1 to about 50:1, or about 4:1 to about 20:1, or preferably about 4:1 to about 10:1.

[0051] In one approach or embodiment, amine antioxidants may include, but are not limited to, antioxidants selected from aromatic amines, alkylated diphenylamines, phenyl-α-naphthylamines, alkylated phenyl-α-naphthylamines, hindered non-aromatic amines, or combinations thereof. The total amount of amine antioxidants in the methods and lubricating compositions herein is such that it delivers up to about 200 ppm of antioxidant nitrogen, about 100 ppm to about 200 ppm in some approaches, about 125 ppm to about 190 ppm in other approaches, or even more advanced approaches that deliver up to about 150 ppm to about 180 ppm of antioxidant nitrogen. In other approaches, the methods and lubricating compositions herein may contain up to about 1 weight percent of amine antioxidants, or about 0.5 to about 1 weight percent of amine antioxidants.

[0052] In some approaches, the amine antioxidant may be one or more aromatic amine antioxidants, and may include, but is not limited to, diarylamines having the following formula:

[0053] [ka] In the formula, R' and R'' each independently represent a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. When substituted, preferred substituents for the aryl groups R' and R'' include aliphatic hydrocarbon groups such as alkyls having 1 to 30 carbon atoms, hydroxyl groups, halogen radicals, carboxylic acid or ester groups, or nitro groups. The aryl groups may be substituted or unsubstituted phenyl or naphthyl groups, particularly one or both aryl groups being substituted with at least one alkyl group having 4 to 30 carbon atoms, preferably 4 to 18 carbon atoms, most preferably 4 to 9 carbon atoms. In the approach, one or both aryl groups may be substituted with mono-alkylated diphenylamines, di-alkylated diphenylamines, C9 alkylated diphenylamines, or mixtures of mono- and di-alkylated diphenylamines.

[0054] Examples of diarylamine antioxidants that may be used include, but are not limited to, diphenylamine; various alkylated diphenylamines, 3-hydroxydiphenylamine, N-phenyl-1,2-phenylenediamine, N-phenyl-1,4-phenylenediamine, monobutyldiphenylamine, dibutyldiphenylamine, monooctyldiphenylamine, dioctyldiphenylamine, monononyldiphenylamine, dinonyldiphenylamine, monotetradecyldiphenylamine, ditetradecyldiphenylamine, phenyl-alpha-naphthylamine, monooctylphenyl-alpha-naphthylamine, phenyl-beta-naphthylamine, monoheptyldiphenylamine, diheptyldiphenylamine, p-oriented styrene-diphenylamine, mixed butyloctyldiphenylamine, and mixed octylstyryldiphenylamine.

[0055] Suitable phenolic or hindered phenolic antioxidants may contain secondary butyl groups and / or tertiary butyl groups as sterically hindering groups. The phenolic group may be further substituted with a hydrocarbyl group and / or a crosslinking group bonded to a second aromatic group. Examples of suitable phenolic or hindered phenolic antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester and may include, for example, Irganox® L-135 available from BASF, or an addition product derived from 2,6-di-tert-butylphenol and alkyl acrylate, wherein the alkyl group may contain about 1 to about 18, or about 2 to about 12, or about 2 to about 8, or about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant may be an ester and may include Ethanox® 4716 available from Albemarle Corporation. In embodiments, the phenolic antioxidant of the methods and compositions herein gives up to about 800 ppm of phenolic antioxidant oxygen, in other approaches about 500 to about 800 ppm of phenolic antioxidant oxygen, or about 600 to about 800 ppm of phenolic antioxidant oxygen. In some embodiments, the methods and lubricating compositions herein may also contain about 0.5 to about 1.5 weight percent of a phenolic or hindered phenolic antioxidant, and in other embodiments, about 0.6 to about 1.2 weight percent of a phenolic or hindered phenolic antioxidant. In one embodiment, the antioxidant system contains only a phenolic antioxidant.

[0056] As described above, if the method and lubricating composition include both one or more amine antioxidants and one or more phenolic or hindered phenolic antioxidants, in such embodiments the method and composition also have a weight ratio (e.g., O / N ratio) of about 300:1 or less of oxygen in ppm from one or more phenolic antioxidant compounds to nitrogen in ppm from one or more amine antioxidant compounds, and in other approaches or embodiments the weight ratio (O / N) of oxygen in ppm from one or more phenolic antioxidant compounds to nitrogen in ppm from one or more amine antioxidant compounds is about 300:1 to about 4:1, or about 300:1 to about 100:1, or about 200:1 to about 300:1, or about 4:1 to about 50:1, or about 4:1 to about 20:1, or about 4:1 to about 10:1. In other approaches, the methods and compositions described herein may contain substantially all phenolic antioxidant compounds (e.g., at least about 700 ppm of antioxidant oxygen (about 900 to about 1500 ppm of antioxidant oxygen, or about 1000 to about 1500 ppm of antioxidant oxygen)) and little to no antioxidant nitrogen (e.g., less than 10 ppm of antioxidant nitrogen, less than 5 ppm of antioxidant nitrogen, less than 2 ppm of antioxidant nitrogen, or antioxidant nitrogen in non-functional amounts).

[0057] Lubrication of combustion engines to achieve low engine sludge This disclosure relates to various methods for lubricating a combustion engine to pass (or achieve high pass performance) the M271 EVO combustion engine test of CEC L-107-19 when a majority of less desirable API Group II base oils are used (pass is defined herein as high pass performance having an average engine sludge (AES) rating of 9.0+ / -0.3 merit). As shown by the following examples, the method involves lubricating a combustion engine with a lubricating viscosity base oil (e.g., a majority of less desirable API Group II base oils) having more than 90 wt percent saturated, less than 0.03 wt percent sulfur, and more than 50 wt percent hydrotreated mineral oil with a viscosity index of 120 or less (ASTM D2270), in combination with additive components selected to overcome the performance degradation of lower quality API Group II base oils.

[0058] In one embodiment, the selected additive components include (i) little to no non-sulfonate detergents, or preferably less than 5 weight percent of metals from the non-sulfonate detergents, and (ii) a detergent system having a total base number (TBN) of less than 10 mg KOH / gram, which, as measured according to ASTM D2896, gives about 60 to about 85 percent of the total lubricating oil composition TBN. However, in some cases, the detergent system itself may not be able to achieve a high average engine sludge (e.g., M271 merit of 9.0+ / -0.3 or higher) when using a large amount of less desirable API group II base oil, and therefore other specifically selected components are combined with the detergent system to achieve performance.

[0059] Accordingly, in other embodiments, the additive systems of this specification also include one or more specifically selected other components, which have been found to have a synergistic effect with the detergent system, comprising an API Group II base oil and containing little to no phenate detergents, achieving a high average engine sludge grade of 9.0+ / -0.3 merit or higher according to CEC L-107-19. Such components of the additive system are described more specifically above, and in various embodiments, include at least one of the following: (a) an anti-wear system comprising one or more zinc dihydrocarbyl dithiophosphate compounds having alkyl groups derived from primary alcohols, secondary alcohols, or combinations thereof, and providing about 200 to about 1000 ppm of phosphorus; (b) an antioxidant system comprising one or more phenolic antioxidant compounds, one or more amineic antioxidant compounds, or combinations thereof; and (c) a detergent system comprising a majority of one or more magnesium per basic sulfonate detergents, (d) an anti-wear system comprising a majority of zinc dihydrocarbyl dithiophosphate compounds having an average of 8 or more carbon atoms per phosphorus atom, and / or (e) an antioxidant system comprising a majority of phenolic antioxidant compounds. In some embodiments, the additive system may also include a selected amount of one or more of the above-mentioned dispersant olefin copolymer viscosity index improvers. As shown in the examples, selecting the correct detergent system and additive system components overcomes any performance degradation in the M271 EVO combustion engine test, where it was previously thought necessary to include phenate detergents and large amounts of API Group III base oils to achieve low engine sludge (e.g., high merit) in this test, by using a majority of API Group II base oils and using little to no phenate detergents.

[0060] Optional components: The methods and lubricating oil compositions described herein may also include several optional components, combined with the detergent and other additive components discussed above, as necessary to meet performance criteria. These optional components are described in the following paragraphs. In some embodiments, the methods and lubricating oil compositions described herein may contain at least about 1000 ppm of total nitrogen, including at least about 600 ppm of dispersant nitrogen. In other embodiments, the methods and lubricating oil compositions described herein may also include additives that provide molybdenum but less than about 200 ppm of molybdenum (in other approaches, about 150 ppm or less, about 100 ppm or less, about 80 ppm or less, or about 50 ppm or less), and further additives that provide boron but less than about 150 ppm of boron.

[0061] Dispersants: Methods and lubricating oil compositions may optionally include one or more other dispersants or mixtures thereof. Dispersants are often known as ashless dispersants because they do not contain metals that form ash before being mixed into the lubricating oil composition and do not impart ash when added to the lubricant. Ashless dispersants are characterized by polar groups being bonded to hydrocarbon chains with relatively high molecular weights. Typical ashless dispersants include N-substituted long-chain alkenyl succinimides. An example of an N-substituted long-chain alkenyl succinimide is polyisobutylene succinimide, in which the number-average molecular weight of the polyisobutylene substituent is in the range of about 350 to about 50,000, or about 5,000, or about 3,000, when measured by GPC. Succinimide dispersants and their preparations are disclosed, for example, in U.S. Patent No. 7,897,696 or No. 4,234,435. Alkenyl substituents can be prepared from polymerizable monomers containing about 2 to about 16 carbon atoms, or about 2 to about 8 carbon atoms, or about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines (typically poly(ethyleneamine)). In embodiments, the dispersant may provide about 600 to about 1000 ppm of dispersant nitrogen.

[0062] Preferred amines are selected from polyamines and hydroxylamines. Examples of polyamines that can be used include, but are not limited to, higher homologues such as diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and pentaethylamine hexamine (PEHA).

[0063] A suitable heavy polyamine is a polyalkylene-polyamine mixture containing small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine), but mainly containing six or more nitrogen atoms, two or more primary amines per molecule, and oligomers having a broader branching range than conventional polyamine mixtures. The heavy polyamine preferably contains polyamine oligomers containing seven or more nitrogen atoms per molecule and two or more primary amines per molecule. The heavy polyamine contains more than 28% by weight (e.g., more than 32% by weight) of total nitrogen and 120 to 160 grams of primary amine groups per equivalent weight.

[0064] In some approaches, preferred polyamines are commonly known as PAMs and contain a mixture of ethyleneamines, with TEPA and pentaethylenehexamine (PEHA) being the main components of the polyamine, usually less than 80%.

[0065] Typically, PAMs contain 8.7–8.9 milliequivalents of primary amine per gram (115–112 gram equivalents per primary amine equivalent) and a total nitrogen content of approximately 33–34% by weight. Heavier cuts of PAM oligomers, which are substantially TEPA-free and contain very small amounts of PEHA, but mainly contain oligomers with more than six nitrogen atoms and broader branching, can produce dispersants with improved dispersibility.

[0066] In embodiments, the disclosure further includes at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight in the range of about 350 to about 50,000, or about 5,000, or about 3,000, as determined by GPC. Polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0067] In some embodiments, polyisobutylene, if present, may have a terminal double bond content of more than 50 mol%, more than 60 mol%, more than 70 mol%, more than 80 mol%, or more than 90 mol%. Such PIBs are also referred to as highly reactive PIBs ("HR-PIBs"). HR-PIBs having a number-average molecular weight in the range of about 800 to about 5000 as determined by GPC are suitable for use in the embodiments of this disclosure. Conventional PIBs typically have a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0068] HR-PIB having a number-average molecular weight in the range of approximately 900 to 3000, as determined by GPC, may be preferred. Such HR-PIBs are commercially available or can be synthesized by polymerization of isobutene in the presence of a non-chlorinating catalyst such as boron trifluoride, as described in U.S. Patent No. 4,152,499 by Boerzel et al. and U.S. Patent No. 5,739,355 by Gateau et al. When HR-PIB is used in the above-mentioned thermal ene reaction, it may result in a higher conversion rate and less precipitate formation during the reaction due to increased reactivity. A preferred method is described in U.S. Patent No. 7,897,696.

[0069] In one embodiment, the disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride, “PIBSA”. PIBSA may have an average succinic acid moiety of about 1.0 to about 2.0 per polymer.

[0070] The percentage of active ingredients in alkenyl or alkyl succinic anhydride can be determined using chromatographic techniques. This method is described in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0071] The conversion percentage of polyolefins is calculated from the active ingredient percentage using the formulas in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0072] Unless otherwise stated, all percentages are weight percentages, and all molecular weights are number-average molecular weights determined by gel permeation chromatography (GPC) using commercially available polystyrene standards (with a number-average molecular weight of 180 to approximately 18,000 as a calibration standard).

[0073] In one embodiment, the dispersant may be derived from polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant may be derived from olefin maleic anhydride copolymer. As an example, the dispersant may be described as poly-PIBSA. In an embodiment, the dispersant may be derived from an anhydride grafted onto an ethylene-propylene copolymer.

[0074] A suitable class of nitrogen-containing dispersants can be derived from olefin copolymers (OCPs), more specifically from ethylene-propylene dispersants that can be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that can be reacted with functionalized OCPs is described and / or commercially available in U.S. Patents No. 7,485,603, 7,786,057, 7,253,231, 6,107,257, and 5,075,383.

[0075] One class of suitable dispersants may also be Mannich bases. Mannich bases are materials formed by the condensation of higher molecular weight alkyl-substituted phenols, polyalkylene polyamines, and aldehydes such as formaldehyde. Mannich bases are described in detail by U.S. Patent No. 3,634,515.

[0076] A suitable class of dispersants may also be high molecular weight esters or semi-esteramides. Suitable dispersants may also be post-treated by conventional methods with any of a variety of agents. These include boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydride, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds. U.S. Patents 7,645,726, 7,214,649, and 8,048,831 are incorporated herein by reference in their entirety.

[0077] In addition to the post-treatment of carbonates and boric acid, each compound may be post-treated or further post-treated by a variety of post-treatments designed to improve or impart different properties. Such post-treatments include those summarized in columns 27-29 of U.S. Patent No. 5,241,003, which is incorporated herein by reference. Such treatments include treatment by: inorganic phosphoric acid or anhydride (e.g., U.S. Patents No. 3,403,102 and No. 4,648,980), organophosphorus compounds (e.g., U.S. Patent No. 3,502,677), phosphorus pentasulfide, boron compounds as already described above (e.g., U.S. Patents No. 3,178,663 and No. 4,652,387), carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Patents No. 3,708,522 and No. 4,9 (Patent No. 48,386), epoxides, polyepoxyates, or thioepoxides (e.g., U.S. Patents No. 3,859,318 and 5,026,495), aldehydes or ketones (e.g., U.S. Patent No. 3,458,530), carbon disulfide (e.g., U.S. Patent No. 3,256,185), glycidol (e.g., U.S. Patent No. 4,617,137), urea, thiourea, or guanidine (e.g., U.S. Patents No. 3,312,619 and 3,865,813, and British Patent No. 1,065) ,595), organic sulfonic acids (e.g., U.S. Patent No. 3,189,544 and UK Patent No. 2,140,811), alkenyl cyanides (e.g., U.S. Patents No. 3,278,550 and No. 3,366,569), diketenes (e.g., U.S. Patent No. 3,546,243), diisocyanates (e.g., U.S. Patent No. 3,573,205), alkansultones (e.g., U.S. Patent No. 3,749,695), 1,3-dicarbonyl compounds (e.g., U.S. Patent No. 4,579,675) U.S. Patent No. 4,617,138, 4,645,515, 4,668,246, 4,963,275, and 4,971,711), cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Patent No. 4,612,132, 4,647,(Patents No. 390, No. 4,648,886, No. 4,670,170), nitrogen-containing carboxylic acids (e.g., U.S. Patent No. 4,971,598 and UK Patent No. 2,140,811), hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Patent No. 4,614,522), lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Patents No. 4,614,603 and No. 4,666,460), cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Patent Nos. 4,612,132, 4,647,390, 4,646,860, and 4,670,170), nitrogen-containing carboxylic acids (e.g., U.S. Patent No. 4,971,598 and UK Patent No. 2,440,811), hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Patent No. 4,614,522), lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Patents No. 4,614,603 and 4,666,460), cyclic carbamates, cyclic thiocarbamates, or cyclic dithiocarbamates (e.g., U.S. Patent Nos. 4,663,062 and 4,666,459), hydroxyaliphatic carboxylic acids (e.g., U.S. Patents Nos. 4,482,464, 4,521,318 and 4,713,189), oxidizing agents (e.g., U.S. Patent No. 4,379,064), combinations of phosphorus pentasulfide and polyalkylene polyamines (e.g., U.S. Patent No. 3,185,647), combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (e.g., U.S. Patents Nos. 3,390,086 and 3,470,098), hydrazine and disulfide Combinations of carbon (e.g., U.S. Patent No. 3,519,564), combinations of aldehydes and phenols (e.g., U.S. Patents No. 3,649,229, 5,030,249, and 5,039,307), combinations of aldehydes and O-diesters of dithiophosphate (e.g., U.S. Patent No. 3,865,740), combinations of hydroxyaliphatic carboxylic acids and boric acid (e.g., U.S. Patent No. 4,554,086), combinations of hydroxyaliphatic carboxylic acids followed by formaldehyde and phenol (e.g., U.S. Patent No. 4,636,(e.g., U.S. Patent No. 322), combinations of hydroxyaliphatic carboxylic acids and subsequent aliphatic dicarboxylic acids (e.g., U.S. Patent No. 4,663,064), combinations of formaldehyde and phenol and subsequent glycolic acid (e.g., U.S. Patent No. 4,699,724), combinations of hydroxyaliphatic carboxylic acids or oxalic acid and subsequent diisocyanates (e.g., U.S. Patent No. 4,713,191), combinations of inorganic acids or anhydrides of phosphorus or their partial or whole sulfur analogs and boron compounds (e.g., U.S. Patent No. 4,857,21 (4) Combinations of organic diacids, followed by unsaturated fatty acids, followed by nitroso aromatic amines, optionally followed by boron compounds, and subsequently glycolating agents (e.g., U.S. Patent No. 4,973,412), combinations of aldehydes and triazoles (e.g., U.S. Patent No. 4,963,278), combinations of aldehydes and triazoles, followed by boron compounds (e.g., U.S. Patent No. 4,981,492), and combinations of cyclic lactones and boron compounds (e.g., U.S. Patents No. 4,963,275 and 4,971,711). In this specification, the patents mentioned above are incorporated herein in their entirety.

[0078] A suitable dispersant may have a TBN of approximately 5 to 30 TBN when measured in a dispersant sample containing approximately 50% diluted oil, and may be a dispersant of approximately 10 to 65 mg KOH / g on an oil-free basis. TBN is measured by the method of ASTM D2896.

[0079] In further embodiments, the optional dispersion additive may be a hydrocarbyl-substituted succinamide or succinimide dispersant. In some approaches, the hydrocarbyl-substituted succinamide or succinimide dispersant may be derived from a hydrocarbyl-substituted acylating agent reacted with a polyalkylene polyamine, where the hydrocarbyl substituent of the succinamide or succinimide dispersant is a linear or branched hydrocarbyl group having a number average molecular weight of about 250 to about 5,000 when measured by GPC using polystyrene as the calibration standard.

[0080] In some approaches, the polyalkylene polyamine used to form the dispersant has the following formula:

[0081] [ka] In the formula, each R and R' is independently a divalent C1-C6 alkylene linker, each R1 and R2 independently forms a 5-membered or 6-membered ring by being fused with one or more aromatic or non-aromatic rings, either with hydrogen, a C1-C6 alkyl group, or the nitrogen atom to which they are bonded, and n is an integer from 0 to 8. Another approach is to select polyalkylene polyamines from the group consisting of mixtures of polyethylene polyamines having an average of 5-7 nitrogen atoms, triethylenetetramine, tetraethylenepentamine, and combinations thereof.

[0082] If present, the dispersant may be used in an amount sufficient to provide up to about 20% by weight, based on the final weight of the lubricating oil composition. Other amounts of dispersant that may be used may be about 0.1% to about 15% by weight, or about 0.1% to about 10% by weight, about 0.1% to about 8% by weight, or about 1% to about 10% by weight, or about 1% to about 8% by weight, or about 1% to about 6% by weight, based on the final weight of the lubricating oil composition. In some embodiments, the lubricating oil composition utilizes a mixed dispersant system. A single type or a mixture of two or more types of dispersants in any desired ratio may be used.

[0083] Other Antioxidants: The lubricating oil compositions herein may also optionally contain one or more additional antioxidants. Known antioxidant compounds include, for example, phenates, phenate sulfides, sulfurized olefins, phosphosulfur terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, di-nonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine), phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, polymeric antioxidants, or mixtures thereof. Antioxidant compounds may be used alone or in combination.

[0084] Suitable olefins that can be sulfurized to form sulfurized olefins include propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof, as well as their dimers, trimers, and tetramers, are particularly useful olefins. Alternatively, the olefins may be Diels-Alder adducts of dienes such as 1,3-butadiene and unsaturated esters such as butyl acrylate.

[0085] Another class of sulfurized olefins includes sulfurized fatty acids and their esters. Fatty acids are often obtained from vegetable or animal oils and typically contain about 4 to about 22 carbon atoms. Suitable examples of fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof. Often, fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or mixtures thereof. Fatty acids and / or esters can be mixed with olefins such as α-olefins.

[0086] In another alternative embodiment, the antioxidant composition also contains a molybdenum-containing antioxidant in addition to the phenolic and / or amine-based antioxidants discussed above. When a combination of these three antioxidants is used, the treatment rate ratio of the phenolic, amine- and molybdenum-containing components is preferably (0-3):(0-3):(0-3).

[0087] One or more antioxidants may be present in the lubricating oil composition in an amount ranging from about 0% to about 20% by weight, or from about 0.1% to about 10% by weight, or from about 1% to about 5% by weight.

[0088] Anti-wear agents: The methods and lubricating oil compositions described herein may also optionally contain one or more other anti-wear agents. Examples of suitable additional anti-wear agents include, but are not limited to, metal thiophosphates; metal dialkyldithiophosphates; phosphate esters or salts thereof; phosphate esters; phosphites; phosphorus-containing carboxylic acid esters, ethers, or amides; sulfurized olefins; thiocarbamate-containing compounds such as thiocarbamate esters, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfide; and mixtures thereof. A suitable anti-wear agent may be molybdenum dithiocarbamate. Phosphorus-containing anti-wear agents are fully described in European Patent No. 612839. The metal in the dialkyldithiophosphate salt may be alkali metals, alkaline earth metals, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful anti-wear agent may be zinc dialkyldithiophosphate.

[0089] Further examples of suitable abrasion resistant agents include titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, phosphates (e.g., dibutylphosphite), phosphonates, thiocarbamate-containing compounds such as thiocarbamate esters, thiocarbamate amides, thiocarbamate ethers, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides. Tartarates or tartrimides may contain alkyl ester groups, and the total number of carbon atoms on the alkyl group may be at least 8. In one embodiment, the abrasion resistant agent may include citrates.

[0090] The anti-wear agent may be present in the range of about 0% to about 15% by weight, or about 0.01% to about 10% by weight, or about 0.05% to about 5% by weight, or about 0.1% to about 3% by weight of the lubricating oil composition.

[0091] Boron-containing compounds: The methods and lubricating oil compositions of this specification may optionally contain one or more boron-containing compounds. Examples of boron-containing compounds include borate esters, borate fatty amines, borate epoxides, borate detergents, and borate dispersants such as succinimide borate dispersants, as disclosed in U.S. Patent No. 5,883,057. If present, the boron-containing compound may be used in an amount sufficient to provide up to about 8% by weight, about 0.01% to about 7% by weight, about 0.05% to about 5% by weight, or about 0.1% to about 3% by weight of the lubricating oil composition.

[0092] Extreme pressure agents: The methods and lubricating oil compositions of this specification may also optionally contain one or more extreme pressure agents. Oil-soluble extreme pressure (EP) agents include sulfur and chlorosulfur-containing EP agents, chlorinated hydrocarbon EP agents, and phosphorus EP agents. Examples of such EP agents include chlorinated waxes; organic sulfides and polysulfides such as dibenzyl disulfide, bis(chlorobenzyl) disulfide, dibutyltetrasulfide, methyl sulfide esters of oleic acid, alkylphenol sulfides, dipentene sulfides, terpenes sulfides, and Diels-Alder sulfide adducts; phosphorus sulfide hydrocarbons such as reaction products of phosphorus sulfide with terpentine or methyl oleate; phosphate esters such as dihydrocarbyl and trihydrocarbyl phosphite, e.g., dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, and pentylphenyl phosphite; dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene-substituted phenyl phosphite; metal thiocarbamates such as zinc dioctyl dithiocarbamate and barium heptylphenol dioate; amine salts of alkyl and dialkyl phosphates, e.g., amine salts of reaction products of dialkyldithiophosphate and propylene oxide; and mixtures thereof.

[0093] Friction modifiers: The methods and lubricating oil compositions of this specification may also optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing and metal-free friction modifiers, and may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated etheramines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerol esters, sulfurized fatty compounds and olefins, sunflower oil, other naturally occurring vegetable or animal oils, dicarboxylic acid esters, esters or partial esters of polyols with one or more aliphatic or aromatic carboxylic acids, and the like.

[0094] Suitable friction modifiers may contain hydrocarbyl groups selected from linear, branched, or aromatic hydrocarbyl groups, or mixtures thereof, and may be saturated or unsaturated. Hydrocarbyl groups may consist of carbon and a heteroatom such as hydrogen or sulfur or oxygen. Hydrocarbyl groups may range from about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long-chain fatty acid ester. In other embodiments, the long-chain fatty acid ester may be a mono-ester, di-ester, or (tri)glyceride. Friction modifiers may be long-chain fatty amides, long-chain fatty esters, long-chain fatty epoxide derivatives, or long-chain imidazolines.

[0095] Other suitable friction modifiers may include organic, ashless (metal-free), and nitrogen-free organic friction modifiers. Such friction modifiers may contain esters formed by reacting a carboxylic acid and an anhydride with an alkanol, and may generally contain polar end groups (e.g., carboxyl or hydroxyl) covalently bonded to a lipophilic hydrocarbon chain. An example of an organic ashless nitrogen-free friction modifier is commonly known as glycerol monooleate (GMO), which may contain mono-, di-, and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Patent No. 6,723,685, which is incorporated herein by reference in whole.

[0096] Amine-based friction modifiers may include amines or polyamines. Such compounds may have hydrocarbyl groups that are linear, saturated, unsaturated, or mixtures thereof, and may contain about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated etheramines. Such compounds may have hydrocarbyl groups that are linear, saturated, unsaturated, or mixtures thereof. These may contain about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated etheramines.

[0097] Amines and amides may be used on their own or as adducts or reaction products with boron compounds such as boron oxide, boron halides, metaborates, boric acid, or mono-, di-, or tri-alkylborates. Other suitable friction modifiers are described in U.S. Patent No. 6,300,291, which is incorporated herein by reference in whole.

[0098] The friction modifier may be optionally present in a range such as approximately 0% to 10% by weight, approximately 0.01% to 8% by weight, or approximately 0.1% to 4% by weight.

[0099] Molybdenum-containing components: The methods and lubricating oil compositions of this specification may also optionally contain one or more molybdenum-containing compounds. Oil-soluble molybdenum compounds may have the functional properties of anti-wear agents, antioxidants, friction modifiers, or mixtures thereof. Examples of oil-soluble molybdenum compounds include molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum dithiophosphinate, amine salts of molybdenum compounds, molybdenum xanthate, molybdenum thioxanthate, molybdenum sulfide, molybdenum carboxylate, molybdenum alkoxide, trinuclear organic molybdenum compounds, and / or mixtures thereof. Examples of molybdenum sulfide include molybdenum disulfide. Molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound may be a molybdenum dithiocarbamate.

[0100] Suitable examples of molybdenum compounds that can be used include Molyvan® 822, Molyvan® A, Molyvan® 2000, Molyvan® 855, Molyvan® 1055, and Molyvan® 3000 manufactured by R.T. Vanderbilt Co., Ltd., and commercially available materials sold under trade names such as Adeka Sakura-Lube® S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 available from Adeka Corporation, and mixtures thereof. Suitable molybdenum components are described in U.S. Patent No. 5,650,381, U.S. Reissue Patent No. 37,363 (E1), U.S. Reissue Patent No. 38,929 (E1), and U.S. Reissue Patent No. 40,595 (E1), the entireties of which are incorporated herein by reference.

[0101] Additionally, the molybdenum compound can be an acidic molybdenum compound. Those included are molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, for example, sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide or similar acidic molybdenum compounds. Alternatively, the composition can provide molybdenum by a molybdenum / sulfur complex of a basic nitrogen compound, as described, for example, in U.S. Patent Nos. 4,263,152, 4,285,822, 4,283,295, 4,272,387, 4,265,773, 4,261,843, 4,259,195, and 4,259,194, and International Publication No. 94 / 068,97, the aforementioned patent documents being incorporated herein by reference in their entireties.

[0102] Another class of suitable organomolybdenum compounds are trinuclear molybdenum compounds, for example, of the formula Mo3S k L n Q zThe compounds and mixtures thereof are, in the formula, S represents sulfur, L represents an independently selected 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 varies from 4 to 7, Q is selected from the group of neutral electron-donating compounds, e.g., water, amines, alcohols, phosphines, and ethers, and z is in the range of 0 to 5, including non-stoichiometric values. In all ligand organic groups, there may be at least 21 total carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms. Additional preferred molybdenum compounds are described in U.S. Patent No. 6,723,685, which is incorporated herein by reference in whole.

[0103] Oil-soluble molybdenum compounds may be present in amounts sufficient to provide molybdenum in concentrations of approximately 0.5 ppm to 2000 ppm, 1 ppm to 700 ppm, 1 ppm to 550 ppm, 5 ppm to 300 ppm, or 20 ppm to 250 ppm.

[0104] Transition metal-containing compounds: In another embodiment, the oil-soluble compound may be a transition metal-containing compound or a metalloid. Examples of transition metals include, but are not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, and tungsten. Examples of preferred metalloids include, but are not limited to, boron, silicon, antimony, and tellurium.

[0105] In embodiments, oil-soluble transition metal-containing compounds may function as a wear inhibitor, friction modifier, antioxidant, deposit control additive, or two or more of these functions. In embodiments, oil-soluble transition metal-containing compounds may be oil-soluble titanium compounds such as titanium(IV) alkoxides. Titanium-containing compounds that may be used in or for the preparation of oil-soluble materials in the art of this disclosure include, but are not limited to, various Ti(IV) compounds such as titanium(IV) oxide; titanium(IV) sulfide; titanium(IV) nitrate; titanium(IV) alkoxides, e.g., titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide; and other titanium compounds or complexes, e.g., titanium phenate; titanium carboxylates, e.g., titanium(IV) 2-ethyl-1,3-hexanedioate or titanium citrate or titanium oleate; and titanium(IV) (triethanolamine) isopropoxide. Other forms of titanium included in the disclosed technology include titanium phosphates such as titanium dithiophosphates (e.g., dialkyldithiophosphates) and titanium sulfonates (e.g., alkylbenzene sulfonates), or reaction products of titanium compounds that form salts, such as oil-soluble salts, with various acidic materials. Therefore, titanium compounds can be derived, in particular, from organic acids, alcohols, and glycols. Ti compounds may also exist in dimer or oligomeric forms containing a Ti-O-Ti structure. Such titanium materials are commercially available or readily prepared by appropriate synthetic techniques evident to those skilled in the art. Depending on the specific compound, they may exist as solids or liquids at room temperature. They may also be provided in solution form in a suitable inert solvent.

[0106] In one embodiment, titanium can be supplied as a Ti-modified dispersant, such as a succinimide dispersant. Such a material may be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as alkenyl-(or alkyl) succinic anhydride. The resulting titanate-succinate intermediate may be used directly or reacted with any of several materials, such as (a) a polyamine-based succinimide / amide dispersant having a free, condensable -NH functional group; (b) a component of a polyamine-based succinimide / amide dispersant, i.e., alkenyl-(or alkyl) succinic anhydride and a polyamine; or (c) a hydroxy-containing polyester dispersant prepared by the reaction of substituted succinic anhydride with a polyol, amino alcohol, polyamine, or a mixture thereof. Alternatively, the titanate-succinate intermediate may be reacted with other agents such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product may be used directly to impart Ti to the lubricant or further reacted with a succinic acid dispersant as described above. As an example, to provide a titanium-modified dispersant or intermediate, 1 part (mol) of tetraisopropyl titanate may be reacted with about 2 parts (mol) of polyisobutene-substituted succinic anhydride at 140-150°C for 5-6 hours. The resulting material (30 g) may be further reacted at 150°C for 1.5 hours with a succinimide dispersant from a mixture of polyisobutene-substituted succinic anhydride and polyethylene polyamine (127 g + diluent oil) to produce a titanium-modified succinimide dispersant.

[0107] Another titanium-containing compound is titanium alkoxide and C6-C6 25 It may be a reaction product with a carboxylic acid. The reaction product is given by the following formula:

[0108] [ka] It can be represented by, In the formula, n is an integer selected from 2, 3, and 4, and R is a hydrocarbyl group containing approximately 5 to approximately 24 carbon atoms, or the following formula:

[0109] [ka] It can be represented by, In the formula, m+n=4, n is in the range of 1 to 3, R4 is an alkyl moiety having 1 to 8 carbon atoms, R1 is selected from a hydrocarbyl group containing approximately 6 to 25 carbon atoms, and R2 and R3 are the same or different, selected from a hydrocarbyl group containing 1 to 6 carbon atoms, or the titanium compound is given by the following formula:

[0110] [ka] It can be represented by, In the formula, x is in the range of 0 to 3, R1 is selected from hydrocarbyl groups containing approximately 6 to 25 carbon atoms, R2 and R3 are the same or different and selected from hydrocarbyl groups containing approximately 1 to 6 carbon atoms, and R4 is H, C6 to C 25 Selected from the group consisting of any of the carboxylic acid moieties.

[0111] Suitable carboxylic acids include, but are not limited to, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, and neodecanoic acid.

[0112] In the embodiment, the oil-soluble titanium compound may be present in the lubricating oil composition in amounts to provide about 0 to about 3000 ppm by weight of titanium, or 25 to about 1500 ppm by weight of titanium, or about 35 ppm to 500 ppm by weight of titanium, or about 50 ppm to about 300 ppm by weight of titanium.

[0113] Viscosity Index Modifiers: The lubricating oil compositions of this specification may also optionally contain one or more viscosity index modifiers. Suitable viscosity index modifiers include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, styrene-isoprene polymers, styrene / maleate copolymers, styrene-butadiene copolymers, styrene-isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrated alkenylaryl conjugated diene copolymers, or mixtures thereof. Viscosity index modifiers may include star polymers, but a preferred example is described in U.S. Patent Application Publication No. 20120101017(A1).

[0114] The lubricating oil compositions described herein may optionally contain, in addition to or instead of viscosity index improvers, one or more dispersant viscosity index improvers. Suitable viscosity index improvers include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with reaction products of acyling agents (e.g., maleic anhydride) and amines, amine-functionalized polymethacrylates, or esterified maleic anhydride-styrene copolymers reacted with amines.

[0115] Viscosity index improvers and / or dispersants: The total amount of viscosity index improvers may be about 0% to about 20% by weight, about 0.1% to about 15% by weight, about 0.1% to about 12% by weight, or about 0.5% to about 10% by weight of the lubricating oil composition.

[0116] Other optional additives: Other additives may be selected to perform one or more functions required of the lubricating fluid. Furthermore, one or more of the additives mentioned may be polyfunctional and may provide functions in addition to or other than those specified herein. Lubricating oil compositions according to this disclosure may optionally include other performance additives. Other performance additives may be in addition to the additives specified herein and / or may include one or more of the following: metal deactivators, viscosity index improvers, detergents, ashless TBN boosters, friction modifiers, anti-wear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, emulsifiers, pour point depressants, seal swelling agents, and mixtures thereof. Typically, a complete lubricating oil will contain one or more of these performance additives.

[0117] Suitable metal deactivators include derivatives of benzotriazole (typically toltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzothiazole; foam inhibitors comprising copolymers of ethyl acrylate, 2-ethylhexyl acrylate, and optionally vinyl acetate; demulsifiers comprising trialkyl phosphates, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers; and pour point depressants comprising esters of maleate-styrene anhydride, polymethacrylate, polyacrylate, or polyacrylamide.

[0118] Suitable foam inhibitors include silicon-based compounds such as siloxanes.

[0119] Suitable pour point depressants may include polymethyl methacrylate or mixtures thereof. The pour point depressant may be present in an amount sufficient to provide about 0% to about 1% by weight, about 0.01% to about 0.5% by weight, or about 0.02% to about 0.04% by weight, based on the final weight of the lubricating oil composition.

[0120] Suitable rust inhibitors may be a single compound or a mixture of compounds having properties that inhibit corrosion of iron metal surfaces. Non-limiting examples of useful rust inhibitors as used herein include oil-soluble high molecular weight organic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid, as well as oil-soluble polycarboxylic acids including dimeric and trimeric acids such as those derived from tall oil fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long-chain alpha- and omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000, and alkenyl succinates containing about 10 or more carbon atoms in the alkenyl group, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Another useful type of acidic corrosion inhibitor is a semi-ester of alkenyl succinic acid having about 8 to about 24 carbon atoms in the alkenyl group with an alcohol such as polyglycol. The corresponding semiamides of such alkenyl succinic acids are also useful. Useful rust inhibitors are high molecular weight organic acids.

[0121] If present, the rust inhibitor can be used in an amount sufficient to provide about 0% to about 5% by weight, about 0.01% to about 3% by weight, and about 0.1% to about 2% by weight, based on the final weight of the lubricating oil composition.

[0122] Generally speaking, preferred lubricants containing cleaning metals as used herein may contain additive components within the range listed in the table below.

[0123] [Table 2]

[0124] The percentages of each component listed above represent the weight percentage of each component based on the weight of the final lubricating oil composition. The remainder of the lubricating oil composition consists of one or more base oils. The additives used in formulating the compositions described herein may be blended with the base oils individually or in various partial combinations. However, it may be preferable to blend all the components simultaneously using an additive concentrate (i.e., the additive plus a diluent such as a hydrocarbon solvent). A complete lubricant conventionally contains an additive package, referred herein as a dispersant / inhibitor package or DI package, which provides the properties required in the formulation.

[0125] definition For the purposes of this disclosure, chemical elements are identified according to the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75th Ed. In addition, the general principles of organic chemistry are described in "Organic Chemistry," Thomas Sorrell, University Science Books, Sausolito: 1999, and "March's Advanced Organic Chemistry," 5th Ed., Ed.: Smith, MB and March, J., John Wiley & Sons, New York: 2001, the entire contents of which are incorporated herein by reference.

[0126] As described herein, compounds may be optionally substituted with one or more substituents, as generally illustrated above or as illustrated by specific classes, subclasses, and species of the Disclosure.

[0127] Unless otherwise made clear from the context, the terms “majority” or “major amount” shall be understood to mean an amount of 50 weight percent or more, more than about 60 weight percent, more than about 70 weight percent, or, for example, 50 to about 98 weight percent, about 60 to about 98 weight percent, about 70 to about 98 weight percent, or about 80 to about 98 weight percent, or about 50 to about 90 weight percent (or any other range between such endpoints) of the total weight of the composition. Also, as used herein, the term “small amount” shall be understood to mean an amount of less than 50 weight percent of the total weight of the composition.

[0128] As used herein, the terms "hydrocarbyl group" or "hydrocarbyl" are used in their ordinary sense as is well known to those skilled in the art. Specifically, it refers to a group having carbon atoms directly bonded to the rest of the molecule and having primarily hydrocarbon properties. Examples of hydrocarbyl groups include (1) hydrocarbon substituents, i.e., aliphatic (e.g., alkyl or alkenyl) substituents, alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic substitutions, aliphatic substitutions, and alicyclic-substituted aromatic substituents, as well as cyclic substituents where the ring is completed via another part of the molecule (e.g., two substituents together form an alicyclic radical); (2) substituted hydrocarbon substituents, i.e., substituents containing non-hydrocarbon groups that do not primarily alter the hydrocarbon substituent in the context of this disclosure (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, amino, alkylamino, and sulfoxy); and (3) heterosubstituted substituents, i.e., substituents that primarily possess hydrocarbon properties in the context of this disclosure, while containing non-carbon elements in the ring or chain, or otherwise composed of carbon atoms. Heteroatoms include sulfur, oxygen, and nitrogen, and include substituents such as pyridyl, furyl, thienyl, and imidazolyl. Generally, there are two or fewer non-hydrocarbon substituents for every 10 carbon atoms in the hydrocarbyl group, or in further examples, just one, and in some embodiments, there may be no non-hydrocarbon substituents in the hydrocarbyl group.

[0129] As used herein, the term “aliphatic” encompasses the terms alkyl, alkenyl, and alkynyl, each of which is optionally substituted as described below.

[0130] As used herein, the “alkyl” group refers to a saturated aliphatic hydrocarbon group containing 1 to 12 carbon atoms (e.g., 1 to 8, 1 to 6, or 1 to 4). Alkyl groups may be linear or branched. Examples of alkyl groups, but not limited to, include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-heptyl, or 2-ethylhexyl. Alkyl groups include halo, phospho, alicyclic [e.g., cycloalkyl or cycloalkenyl], heteroalicyclic [e.g., heterocycloalkyl or heterocycloalkenyl], aryl, heteroaryl, alkoxy, alloyl, heteroaloyl, acyl [e.g., (aliphatic) carbonyl, (alicyclic) carbonyl, or (heteroalicyclic) carbonyl], nitro, cyano, and amide [e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylaminoalkylaminocarbonyl] It may be substituted (i.e., optionally substituted) with one or more substituents such as cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl, or heteroarylaminocarbonyl, amino, [e.g., aliphatic amino, alicyclic amino, or heteroalicyclic amino], sulfonyl [e.g., aliphatic-SO2-], sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamide, oxo, carboxy, carbamoyl, alicyclic oxy, heterocycloaliphatic oxy, aryl oxy, heteroaryl oxy, aralkyl oxy, heteroarylalkoxy, alkoxycarbonyl, alkylcarbonyl oxy, or hydroxy.Some examples of substituted alkyls, though not limited to them, include carboxyalkyls (e.g., HOOC-alkyls, alkoxycarbonylalkyls, and alkylcarbonyloxyalkyls), cyanoalkyls, hydroxyalkyls, alkoxyalkyls, acylalkyls, aralkyls, (alkoxyaryl)alkyls, (sulfonylamino)alkyls (e.g., (alkyl-SO2-amino)alkyls), aminoalkyls, amidealkyls, (alicyclic)alkyls, or haloalkyls.

[0131] As used herein, the “alkenyl” group refers to an aliphatic carbon group containing 2 to 8 (e.g., 2 to 12, 2 to 6, or 2 to 4) carbon atoms and at least one double bond. Like alkyl groups, alkenyl groups can be linear or branched. Examples of alkenyl groups, but not limited to, include allyl, isoprenyl, 2-butenyl, and 2-hexenyl. The alkenyl group may have one or more substituents, e.g., halo, phospho, alicyclic [e.g., cycloalkyl or cycloalkenyl], heteroalicyclic [e.g., heterocycloalkyl or heterocycloalkenyl], aryl, heteroaryl, alkoxy, aroyl, heteroaloyl, acyl [e.g., (aliphatic) carbonyl, (alicyclic) carbonyl, or (heteroalicyclic) carbonyl], nitro, cyano, amide [e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylaminoalkylaminocarbon These can be optionally substituted with [nyl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl, or heteroarylaminocarbonyl], amino [e.g., aliphatic amino, alicyclic amino, heteroalicyclic amino, or aliphatic sulfonylamino], sulfonyl [e.g., alkyl-SO2-, alicyclic-SO2-, or aryl-SO2-], sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamide, oxo, carboxy, carbamoyl, alicyclic oxy, heteroalicyclic oxy, aryl oxy, heteroaryl oxy, aralkyl oxy, heteroaralkoxy, alkoxycarbonyl, alkylcarbonyl oxy, or hydroxy. Some examples of substituted alkenyls, though not limited to them, include cyanoalkenyls, alkoxyalkenyls, acylalkenyls, hydroxyalkenyls, aralkenyls, (alkoxyaryl)alkenyls, (sulfonylamino)alkenyls (e.g., (alkyl-SO2-amino)alkenyls), aminoalkenyls, amidealkenyls, (alicyclic)alkenyls, or haloalkenyls.

[0132] As used herein, the “alkynyl” group refers to an aliphatic carbon group containing 2 to 8 carbon atoms (e.g., 2 to 12, 2 to 6, or 2 to 4) and having at least one triple bond. The alkynyl group may be linear or branched. Examples of alkynyl groups include, but are not limited to, propargyl and butynyl. The alkynyl group is a substituent of one or more types, such as aroyl, heteroaloyl, alkoxy, cycloalkyloxy, heterocycloalkyloxy, aryloxy, heteroaryloxy, aralkyloxy, nitro, carboxy, cyano, halo, hydroxy, sulfo, mercapto, sulfanyl [e.g., aliphatic sulfanyl or alicyclic sulfanyl], sulfinyl [e.g., aliphatic sulfinyl or alicyclic finyl], sulfonyl [e.g., aliphatic-SO2-, aliphatic-amino-SO2-, or alicyclic-SO2-], amide [e.g., aminocarbonyl, alkylaminocarbonyl, alkylcarbonylamino, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, cycloalkylcarbonylamino, aryl] The aminocarbonyl, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (cycloalkylalkyl)carbonylamino, heteroaralkylcarbonylamino, heteroarylcarbonylamino, or heteroarylaminocarbonyl], urea, thiourea, sulfamoyl, sulfamide, alkoxycarbonyl, alkylcarbonyloxy, alicyclic, heteroalicyclic, aryl, heteroaryl, acyl [e.g., (alicyclic)carbonyl or (heteroalicyclic)carbonyl], amino [e.g., aliphatic amino], sulfoxy, oxo, carboxy, carbamoyl, (alicyclic)oxy, (heteroalicyclic)oxy, or (heteroaryl)alkoxy can be optionally substituted.

[0133] As used herein, the "amino" group means -NR X R Y It refers to, and in the formula, R X and R YEach of these is independently hydrogen, alkyl, cycloalkyl, (cycloalkyl)alkyl, aryl, aralkyl, heterocycloalkyl, (heterocycloalkyl)alkyl, heteroaryl, carboxy, sulfanyl, sulfinyl, sulfonyl, (alkyl)carbonyl, (cycloalkyl)carbonyl, ((cycloalkyl)alkyl)carbonyl, arylcarbonyl, (aralkyl)carbonyl, (heterocycloalkyl)carbonyl, ((heterocycloalkyl)alkyl)carbonyl, (heteroaryl)carbonyl, or (heteroaralkyl)carbonyl, each of which is defined herein and optionally substituted. Examples of amino groups include alkylamino, dialkylamino, or arylamino. If the term "amino" is not a terminal group (e.g., alkylcarbonylamino), it is -NR X It is represented by -. X This has the same meaning as defined above.

[0134] As used herein, the “cycloalkyl” group refers to a saturated carbocyclic, monocyclic, or bicyclic (fused or crosslinked) ring of 3 to 10 (e.g., 5 to 10) carbon atoms. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, Cuville, octahydroindenyl, decahydronaphthyl, bicyclo[3.2.1]octyl, bicyclo[2.2.2]octyl, bicyclo[3.3.1]nonyl, bicyclo[3.3.2.]decyl, bicyclo[2.2.2]octyl, adamantyl, or ((aminocarbonyl)cycloalkyl)cycloalkyl.

[0135] As used herein, the "heterocycloalkyl" group refers to a 3- to 10-membered monocyclic or bicyclic (fused or bridged) saturated ring structure (e.g., a 5- to 10-membered monocyclic or bicyclic), where one or more ring atoms are heteroatoms (e.g., N, O, S, or a combination thereof). Examples of heterocycloalkyl groups include piperidyl, piperadyl, tetrahydropyranyl, tetrahydrofuryl, 1,4-dioxolanyl, 1,4-dithianyl, 1,3-dioxolanyl, oxazolidyl, isoxazolidyl, morpholinyl, thiomorpholyl, octahydrobenzofuryl, octahydroclomenyl, octahydrothioclomenyl, octahydroindolyl, octahydropyrindinyl, decahydroquinolinyl, octahydrobenzo[b]thiophenyl, 2-oxa-bicyclo[2.2.2]octyl, 1-aza-bicyclo[2.2.2]octyl, 3-aza-bicyclo[3.2.1]octyl, and 2,6-dioxa-tricyclo[3.3.1.0]nonyl. Monocyclic heterocycloalkyl groups can be fused with a phenyl moiety to form structures such as tetrahydroisoquinoline, which would be classified as heteroaryls.

[0136] As used herein, the “heteroaryl” group refers to a monocyclic, bicyclic, or tricyclic ring system having 4 to 15 ring atoms, where one or more ring atoms are heteroatoms (e.g., N, O, S, or a combination thereof), and the monocyclic ring system is aromatic, or at least one of the rings in the bicyclic or tricyclic ring system is aromatic. Heteroaryl groups include benzo-fusion ring systems having 2 to 3 rings. For example, a benzo-fusion group includes a benzo fused with one or two 4 to 8-membered heterocyclic aliphatic moieties (e.g., indolidyl, indolyl, isoindolyl, 3H-indolyl, indlinyl, benzo[b]furyl, benzo[b]thiophenyl, quinolinyl, or isoquinolinyl). Some examples of heteroaryls are pyridyl, 1H-indazolyl, furyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl, tetrazolyl, benzofuryl, isoquinolinyl, benzthiazolyl, xanthene, thioxanthene, phenothiazine, dihydroindole, benzo[1,3]dioxole, benzo[b]furyl, benzo[b]thiophenyl, indazolyl, benzimidazolyl, benzthiazolyl, prill, cinnolyl, quinolyl, quinazolyl, cinnolyl, phthalazyl, quinazolyl, quinoxalil, isoquinolyl, 4H-quinolidyl, benzo-1,2,5-thiadiazole, or 1,8-naphthilidyl.

[0137] Examples of monocyclic heteroaryls, though not limited to them, include furyl, thiophenyl, 2H-pyrrolyl, pyrrolyl, oxazolyl, tazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, 1,3,4-thiadiazolyl, 2H-pyranyl, 4H-planyl, pyridyl, pyridazyl, pyrimidyl, pyrazolyl, pyrazyl, or 1,3,5-triazyl. Monocyclic heteroaryls are numbered according to standard chemical nomenclature.

[0138] Examples of bicyclic heteroaryls include indolidyl, indolyl, isoindolyl, 3H-indolyl, indolinyl, benzo[b]furyl, benzo[b]thiophenyl, quinolinyl, isoquinolinyl, indolidinyl, isoindolyl, indolyl, benzo[b]furyl, bexo[b]thiophenyl, indazolyl, benzimimidazyl, benzthiazolyl, prinyl, 4H-quinolidyl, quinolyl, isoquinolyl, cinnolyl, phthalazyl, quinazolyl, quinoxalyl, 1,8-naphthilidyl, or pteridyl. Bicyclic heteroaryls are numbered according to standard chemical nomenclature.

[0139] As used herein, the term “processing rate” refers to the weight percentage of a component in the final lubricant or passenger car motor oil.

[0140] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) may be determined using a Waters gel permeation chromatography (GPC) instrument or similar instrument, along with Waters Empower Software or similar software. The GPC instrument may be provided with a Waters separation module and a Waters refractive index detector (or similar optional instrument). GPC operating conditions may include a guard column, four Agilent PLgel columns (300 × 7.5 mm length, 5 μm particle size, and pore size in the range of 100–10000 Å), and a column temperature of approximately 40°C. Unstabilized HPLC-grade tetrahydrofuran (THF) may be used as the solvent at a flow rate of 1.0 mL / min. The GPC instrument may be calibrated with commercially available poly(methyl methacrylate) (PMMA) standards having a narrow molecular weight distribution in the range of 960–1,568,000 g / mol. Calibration curves can be extrapolated for samples with a mass of less than 500 g / mol. The sample and PMMA standard can be dissolved in THF and prepared at a concentration of 0.1–0.5% by weight, and can be used without filtration. GPC measurement is also described in U.S. Patent No. 5,266,223, incorporated herein by reference. The GPC method provides additional molecular weight distribution information; see, for example, "Modern Size Exclusion Liquid Chromatography" by W.W. Yau, J.J. Kirkland and D.D.B. Ly, John Wiley and Sons, New York, 1979, incorporated herein by reference. [Examples]

[0141] A better understanding of this disclosure and its many advantages can be made apparent by the following examples. The following examples are illustrative and not limiting in any way to their scope or intent. Those skilled in the art will readily understand that variations of the components, methods, processes, and devices described in these examples can be used. Unless otherwise stated or evident from the context of the discussion through the following examples and this disclosure, all percentages, ratios, and parts described in this disclosure are by weight. Any reference to a standardized test method refers to the version publicly available at the time of this disclosure unless evident from the context of its use in this specification.

[0142] The additive packages and comparative additive packages of the present invention for Comparative Example 1 and Example 1 below were prepared by including the following cleaning agents, metal-containing wear-resistant additives, and / or antioxidants described in each example: • A magnesium sulfonate overbasic cleaning agent with a TBN of approximately 410. • A perbasic calcium sulfonate cleaning agent with approximately 300 TBN. • A perbasic calcium phenate cleaning agent with a TBN of 250. • A neutral calcium sulfonate cleaning agent with a TBN of 50 or less. ZDDP-secondary is zinc dialkyldithiophosphate, derived from one or more secondary alcohols, and contains an alkyl group having an average of 6 or fewer carbon atoms per phosphorus atom. ZDDP-primary is zinc dialkyldithiophosphate, derived from one or more primary alcohols, and contains an alkyl group having an average of 8 or more carbon atoms per phosphorus atom. • Amine-based antioxidant - nonylated diphenylamine. • Phenolic antioxidants - hindered phenolic esters.

[0143] Comparative Example 1 The lubricants in these comparative examples contained the various detergents and base oils listed in the table below. In addition to the components listed in the table below, the comparative additive package in this example also contained other common additives suitable for passenger car motor oil, which were the same for each of the lubricants in Comparative 1 and 2. The only change in the additive package in this example was the components listed in Table 3 below.

[0144] [Table 3]

[0145] [Table 4]

[0146] As shown in Tables 3 and 4, the lubrication method of Comparative 1, which included a lubricant containing a calcium phenate detergent and an API Group III base oil, was able to achieve a passing AES of 9.0 merit according to CEC L-107-19. However, when the calcium phenate detergent was removed from the fluid to produce the lubricant used in Comparative 2, the AES dropped to an unacceptable merit grade of 8.1, even when the API Group III base oil was still used.

[0147] Example 1 In this embodiment, the present invention's additive package and a comparative additive package for lubricants were prepared by changing the detergent system, anti-wear system, and antioxidant system in a lubricant composition containing a majority of API Group II base oil. In addition to the components listed in the table below, the comparative additive package and the present invention's additive package in this embodiment also contained other common additives suitable for passenger car motor oil, which were the same for each evaluated additive package. The only changes in the additive packages of this embodiment were the above components to derive the fluid relationships shown in Table 5 below.

[0148] [Table 5]

[0149] [Table 6]

[0150] [Table 7]

[0151] As shown in Tables 5, 6, and 7, in the case of the method of lubricating a combustion engine using the lubricant composition of Comparative 3, which has a majority of API Group II base oil, the lubrication could not achieve an AES rating of 9.0 or higher. Comparative 3 did not have the correct combination of detergent systems, anti-wear systems, and / or antioxidant systems to overcome the performance degradation of such a large amount of low-quality API Group II base oil. However, in the method of Invention 1, when the detergent system contains a majority of magnesium sulfonate detergent, the method of lubrication using such a lubricant composition was able to achieve an improved AES. In the method of Invention 2, when the anti-wear system contains a majority of dihydrocarbyl dithiophosphate zinc compounds having an average of 8 or more carbon atoms per phosphorus atom, the method of lubrication using such a lubricant composition was also able to achieve an acceptable AES. Finally, in the method of Invention 3, when the antioxidant system contains a majority of phenolic antioxidants, the method of lubrication using such a lubricant composition was also able to achieve an acceptable AES. Methods 1 to 3 of the present invention all contain a majority of API Group II base oil (e.g., base oil having more than about 90 weight percent saturated, less than about 0.03 weight percent sulfur, and a viscosity index of about 120 or less (ASTM D2270)), and improved AES could be achieved by selecting appropriate detergent systems, anti-wear systems, and / or antioxidant systems as shown in Tables 5, 6, and 7.

[0152] Where used herein and in the appended claims, the singular forms “a,” “an,” and “the” include multiple references unless explicitly and clearly limited to one. For example, a reference to “antioxidants” includes two or more different antioxidants. Where used herein, the term “includes” and its grammatical variations are intended to be non-limiting so as not to exclude other similar items that may be substituted for or added to the items in the list.

[0153] For the purposes of this specification and the appended claims, unless otherwise indicated, all numbers representing quantities, percentages, or proportions, and other numerical values ​​used herein and in the claims should be understood in all cases as being modified by the term “approximately.” Therefore, unless otherwise indicated, the numerical parameters described herein and in the appended claims are approximations that may vary depending on the desired characteristics sought by this disclosure. Each numerical parameter should be interpreted at least in terms of the number of significant figures reported and by applying common rounding techniques, not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims.

[0154] It should be understood that each component, compound, substituent, or parameter disclosed herein is disclosed for use alone or in combination with any one or more other components, compounds, substituents, or parameters disclosed herein.

[0155] It should be further understood that each range disclosed herein should be interpreted as a disclosure of each specific value within the disclosure range having the same number of significant figures. Therefore, for example, the range 1 to 4 should be interpreted as a clear disclosure of any range of such values, not just the values ​​1, 2, 3, and 4.

[0156] It should be further understood that each lower limit of each range disclosed herein should be interpreted as being disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compound, substituent, or parameter. Therefore, this disclosure should be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or each specific value within each range, or by combining each upper limit of each range with each specific value within each range. That is, it should also be further understood that any range between endpoint values ​​within a broad range is also considered herein. Therefore, the range 1-4 also means ranges such as 1-3, 1-2, 2-4, 2-3, etc.

[0157] Furthermore, any specific amounts / values ​​of components, compounds, substituents, or parameters disclosed in the description or examples should be interpreted as disclosures of either a lower or upper limit of a range, and can therefore be combined with any other lower or upper limit or specific amounts / values ​​in the range for the same component, compound, substituent, or parameter disclosed elsewhere in this application to form a range for that component, compound, substituent, or parameter.

[0158] While specific embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents may emerge that are not currently anticipated or can not be anticipated by the applicants or others skilled in the art. Therefore, the attached claims, as filed and as may be amended, are intended to encompass all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A method for lubricating a combustion engine to pass the M271 EVO combustion engine test of CEC L-107-19, wherein the method is This includes lubricating a combustion engine with a lubricating oil composition, The lubricating oil composition is A base oil with lubricating viscosity having more than 90 weight percent saturated material, less than 0.03 weight percent sulfur, and a viscosity index of 120 or less (ASTM D2270), and more than 50 weight percent hydrogenated mineral oil, (i) less than 5 weight percent of metal from a non-sulfonate detergent, and (ii) a detergent system having a total base number (TBN) of less than 10 mg KOH / gram as measured according to ASTM D2896, giving about 60 to about 85 percent of the TBN of the total lubricating oil composition. An anti-wear system comprising one or more zinc dihydrocarbyl dithiophosphate compounds having an alkyl group derived from a primary alcohol, a secondary alcohol, or a combination thereof, and providing about 200 to about 1000 ppm of phosphorus, An antioxidant system comprising one or more phenolic antioxidant compounds, one or more amine-based antioxidant compounds, or a combination thereof, In order for the lubricating oil composition to achieve a passing average engine sludge grade of 9.0 + / - 0.3 merit or higher according to CEC L-107-19, the following applies: (a) The cleaning agent system contains more than half of one or more overbasic sulfonate cleaning agents. (b) The abrasion-resistant system comprises a majority of zinc dihydrocarbyl dithiophosphate compounds having an average of eight or more carbon atoms per phosphorus atom, and / or (c) The antioxidant system comprises one or more phenolic antioxidant compounds.

2. The method according to claim 1, wherein the lubricating oil composition comprises the detergent system, wherein (a) one or more overbasic magnesium sulfonate detergents constitute a majority, further comprising a magnesium-to-calcium ratio of about 600:1 or more, and providing about 70 to about 85 percent of the total lubricating oil composition TBN as measured according to ASTM D2896.

3. The method according to claim 2, wherein the lubricating oil composition further comprises a majority of the phosphorus from the dihydrocarbyl dithiophosphate zinc compounds of the wear-resistant system, wherein the lubricating oil composition is provided by one or more dihydrocarbyl dithiophosphate zinc compounds having an average of six or fewer carbon atoms per phosphorus atom.

4. The method according to claim 3, wherein the lubricating oil composition further comprises one or more phenolic antioxidant compounds and one or more amine-based antioxidant compounds in the antioxidant system, and further comprises a ratio of approximately 4:1 to approximately 6:1 (O / N) of ppm oxygen from the phenolic compound to ppm nitrogen from the amine-based compound.

5. The method according to claim 1, wherein the lubricating oil composition comprises (b) a zinc dihydrocarbyl dithiophosphate compound having an average of 8 or more carbon atoms per phosphorus atom, with the majority of the phosphorus being from the zinc dihydrocarbyl dithiophosphate compound of the wear-resistant system.

6. The method according to claim 5, wherein about 90 to about 100 weight percent of the phosphorus from the zinc dihydrocarbyl dithiophosphate compound of the wear-resistant system is provided by the zinc dihydrocarbyl dithiophosphate compound having an average of 8 or more carbon atoms per phosphorus atom.

7. The method according to claim 6, wherein the lubricating oil composition further comprises both calcium and magnesium provided by the detergent system, and has a calcium-to-magnesium ratio of about 0.8:1 to about 1.5:

1.

8. The method according to claim 7, wherein the lubricating oil composition further comprises one or more phenolic antioxidant compounds and one or more amine-based antioxidant compounds in the antioxidant system, and has a weight ratio (O / N) of ppm oxygen to ppm nitrogen provided by the one or more phenolic antioxidant compounds (O / N) of ppm oxygen to ppm nitrogen provided by the one or more amine-based antioxidant compounds.

9. The method according to claim 1, wherein the lubricating oil composition comprises an antioxidant system having (c) a majority of phenolic antioxidant compounds, and further having a weight ratio (O / N) of greater than about 100:1 of oxygen in ppm from the phenolic antioxidant compounds to nitrogen in ppm from the amine antioxidant compounds, and / or the lubricating oil composition further comprises both calcium and magnesium provided by the detergent system, having a detergent calcium to detergent magnesium ratio of at least about 0.8:1 to about 1.5:1, and / or the lubricating oil composition further comprises a majority of the phosphorus from the dihydrocarbyl dithiophosphate zinc compound of the wear-resistant system, provided by a dihydrocarbyl dithiophosphate zinc compound having an average of 6 or fewer carbon atoms per phosphorus atom.

10. The method according to claim 1, wherein the base oil of the lubricating viscosity is a hydrogenated mineral oil of about 75 to about 90 weight percent having more than about 90 weight percent saturated material, less than about 0.03 weight percent sulfur, and a viscosity index of about 120 or less (ASTM D2270), and / or the antioxidant system is substantially free of monoalkylphenolamine antioxidants.

11. The method according to claim 1, wherein the TBN of the cleaning agent system is less than about 5 to about 10 mg KOH / gram, and / or the TBN of the lubricating oil composition is about 7 to about 12 mg KOH / gram as measured according to ASTM D2896, and / or the cleaning agent system is substantially free of phenate cleaning agents, and / or the cleaning agent system essentially consists of a sulfonate cleaning agent that provides calcium, magnesium, or a combination thereof.

12. The method according to claim 1, wherein the lubricating oil composition comprises one or more dispersant olefin copolymer viscosity index improvers in an amount of about 1.3 weight percent or less, and / or the lubricating oil composition substantially contains no dispersant olefin copolymer viscosity index improvers.

13. The method according to claim 1, wherein the lubricating oil composition has at least about 1000 ppm of total nitrogen, and / or the lubricating oil composition contains one or more nitrogen-containing dispersant additives that provide about 600 ppm or more of dispersant nitrogen to the lubricating oil composition.

14. The method according to claim 1, wherein the lubricating oil composition contains less than about 200 ppm of molybdenum and / or the lubricating oil composition contains less than about 150 ppm of boron.

15. The method according to claim 1, wherein the lubricating oil composition substantially does not contain an API Group III base oil.

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