Lubricating oil composition for improving low speed pre-ignition

Abstract

To provide lubricating compositions configured to improve low-speed pre-ignition with lower levels of phosphorus, and to provide methods of lubricating a spark-ignition engine.SOLUTION: There are provided lubricating compositions and methods of lubricating a spark-ignition engine that are effective in improving low-speed pre-ignition (LSPI) through the selection of lubricant elemental relationships rather than through the addition of supplemental fluid additives. This relationship has added advantage of improving low speed ignition (LSPI) independent of the underlying base oil quality in some circumstances. The lubricating compositions herein include one or more base oils of lubricating viscosity, one or more phosphorus-containing additives that provide low levels of phosphorus, and a detergent system that provides calcium and / or magnesium having a specific relationship between a calcium sulfate ash content and a low phosphorus content.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to lubricating compositions, and in particular to lubricating compositions configured to improve low speed pre-ignition at lower levels of phosphorus. [Background technology]

[0002] Automotive manufacturers continue to seek improvements in efficiency, fluid life, and fuel economy, which in turn increases the requirements for engines, lubricants, and their components. Today's engines are often becoming smaller, lighter, and more efficient with technologies designed to improve fuel economy, performance, and power output. These requirements also mean that the performance of engine oils must evolve to meet the higher demands of such modern engines and the corresponding performance standards associated with their unique uses and applications. Due to such stringent demands on engine oils, lubricant manufacturers often tailor lubricants and their additives to meet certain performance requirements for industry and / or manufacturer applications. Typically, industry standards and / or automotive manufacturers require certain performance standards, where a lubricant designed for one use or application may not meet all performance specifications of a different use or application.

[0003] For example, the American Petroleum Institute (API) sets standards for passenger car motor oils designed to meet the needs and performance characteristics of various passenger vehicle manufacturers. Recent updates to the API standards include a performance test for an undesirable phenomenon typically characterized as low-speed pre-ignition (LSPI), which is considered a form of combustion that results in ignition of the air-fuel mixture in the combustion chamber before the desired spark. LSPI is evaluated according to the Sequence IX Low-Speed ​​Pre-Ignition Test described in ASTM D8291-21a. Turbocharged or supercharged engines are often prone to LSPI, a pre-ignition event that can include high-pressure spikes, premature combustion, and / or knock. Premature ignition in the combustion chamber before the spark plug fires can cause abnormal combustion and high cylinder pressure. LSPI events can result in knocking sounds or other abnormal characteristics from uncontrolled pressure increases in the cylinder. LSPI events are undesirable, and recent API specifications set LSPI performance standards for passenger car motor oils. Traditional solutions to unwanted LSPI events are unsatisfactory because fluid manufacturers tend to address the LSPI problem by adding auxiliary fluid components, which often impose other constraints on the additive package in the fluid, not to mention that the auxiliary additives may in some instances have other unintended effects. Summary of the Invention

[0004] In one approach or embodiment, the present disclosure relates to a lubricating composition for spark ignition engines to provide good LSPI performance at low levels of phosphorus. In one aspect of this embodiment, the lubricating composition includes one or more base oils of lubricating viscosity, one or more phosphorus-containing additives providing the lubricating composition with about 500 ppm or less of phosphorus, and a detergent system providing one or more calcium-containing detergents and optionally one or more magnesium-containing detergents, the detergent system being substantially free of sodium-containing detergents, wherein the lubricating composition has a calcium content such that the lubricating composition has a calculated calcium sulfate ash content of about 0.2 weight percent or less, and a weight ratio of the phosphorus content to the calcium sulfate ash content of at least about 0.1.

[0005] In other approaches or embodiments, the lubricating composition of the preceding paragraph may include one or more optional features or embodiments in any combination. These optional features or embodiments may include one or more of the following: the weight ratio of phosphorus content to calcium sulfate ash content is from about 0.1 to about 0.3, and / or the lubricating composition has a total calculated sulfated ash (SASH) content of about 1 weight percent or less, and / or the lubricating composition has a total calculated sulfated ash content (SASH) of about 0.8 weight percent or less, and / or the lubricating composition has a total calculated sulfated ash content (SASH) of about 0.and / or wherein not more than about 30 weight percent of the total calculated sulfated ash content (SASH) is provided by a calcium sulfate ash content; and / or wherein the lubricating composition further comprises one or more silicon-containing compounds providing from about 3 to about 20 ppm of silicon; and / or wherein the one or more silicon-containing compounds provide from about 5 to about 15 ppm of silicon; and / or wherein the weight ratio of the calcium sulfate ash content to the silicon content is not more than about 250; and / or wherein the silicon-containing compounds are selected from the group consisting of organosilane compounds, fluorosilicone compounds, polydimethylsilicone compounds, and the like. and / or the detergent system comprises a calcium-containing detergent and a magnesium-containing detergent, and / or the detergent system comprises a calcium sulfonate and optionally a magnesium sulfonate, and / or the calcium sulfonate and optional magnesium sulfonate are each overbased, and each meets ASTM standards. D2896, and / or the detergent system does not include a phenate-based detergent; and / or the one or more base oils of lubricating viscosity are selected from API Group I base oils, API Group II base oils, API Group III base oils, or combinations thereof; and / or the one or more base oils of lubricating viscosity are selected from API Group I base oils, API Group II base oils, or combinations thereof; and / or the lubricating composition exhibits 5 or fewer average events according to the Sequence IX Low Speed ​​Pre-Ignition Test of ASTM D8291 and / or exhibits 8 or fewer maximum events according to the Sequence IX Low Speed ​​Pre-Ignition Test of ASTM D8291; and / or the one or more phosphorus-containing additives provide from about 200 to about 400 ppm phosphorus.

[0006] In yet a further approach or embodiment, provided herein is a method of lubricating a spark ignition engine with a low phosphorus content lubricant. In one aspect, the method includes lubricating a crankcase of the spark ignition engine with a lubricating composition comprising: (i) one or more base oils of lubricating viscosity; (ii) one or more phosphorus-containing additives providing the lubricating composition with about 500 ppm or less of phosphorus; (iii) a detergent system providing one or more calcium-containing detergents and optionally one or more magnesium-containing detergents, the detergent system being substantially free of sodium-containing detergents; (iv) a calcium content such that the lubricating composition has a calculated calcium sulfate ash content of about 0.2 weight percent or less; and (v) a weight ratio of the phosphorus content to the calcium sulfate ash content of at least about 0.1, wherein the lubricating composition exhibits 5 or fewer average events according to the Sequence IX Low Speed ​​Pre-Ignition Test of ASTM D8291 and / or 8 or fewer maximum events according to the Sequence IX Low Speed ​​Pre-Ignition Test of ASTM D8291.

[0007] In further approaches or embodiments, the method of the preceding paragraph may include one or more optional steps, features, or embodiments, in any combination, including more and more of: the weight ratio of the phosphorus content to the calcium sulfate ash content is about 0.1 to about 0.3; and / or the lubricating composition further comprises one or more silicon-containing compounds providing the lubricating composition with about 3 to about 20 ppm of silicon; and / or the weight ratio of the calcium sulfate ash content to the silicon content is less than or equal to about 250. The methods herein may include any of the embodiments of the lubricating compositions described in the Summary of the Invention.

[0008] In still yet another approach or embodiment, the present application further includes the use of lubricating compositions having low levels of phosphorus to achieve passing LSPI according to ASTM D8291. In an aspect, the use includes lubricating the crankcase of a spark-ignition engine with a lubricating composition comprising: (i) one or more base oils of lubricating viscosity; (ii) one or more phosphorus-containing additives providing the lubricating composition with about 500 ppm or less of phosphorus; (iii) a detergent system providing one or more calcium-containing detergents and optionally one or more magnesium-containing detergents, the detergent system being substantially free of sodium-containing detergents; (iv) the lubricating composition comprising a calculated calcium sulfate ash content of about 0.2 weight percent or less; and (v) a weight ratio of the phosphorus content to the calcium sulfate ash content of at least about 0.1; and the lubricating composition exhibits 5 or fewer average events according to the Sequence IX Low-Speed ​​Pre-Ignition Test of ASTM D8291 and / or 8 or fewer maximum events according to the Sequence IX Low-Speed ​​Pre-Ignition Test of ASTM D8291. The uses herein may include any of the embodiments of the lubricating compositions described in the Summary of the Invention. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present disclosure relates to lubricating compositions and methods of lubricating spark-ignition engines that are effective in improving low-speed pre-ignition through the selection of lubricant elemental relationships rather than through the addition of supplemental fluid additives, with the added benefit that this relationship, in some circumstances, improves low-speed pre-ignition (LSPI) independently of the underlying base oil quality. In one approach or embodiment, the lubricating compositions herein comprise one or more base oils of lubricating viscosity, one or more phosphorus-containing additives providing no more than about 500 ppm phosphorus, a detergent system providing calcium and / or magnesium that is substantially free of sodium-containing detergents, a calcium content providing no more than 0.2 weight percent calcium sulfate ash (Ca-SASH) as determined by ASTM D874 and / or preferably as calculated herein, and a specified weight ratio of phosphorus content to calcium sulfate ash content in the lubricant of at least about 0.1 (preferably from about 0.1 to about 0.3). In yet other embodiments, the lubricants herein may also have a unique relationship between calcium sulfate ash and silicon in the lubricant, with the weight ratio of calcium sulfate ash content to silicon content being about 250:1 or less (in some approaches, from about 100:1 to about 250:1).

[0010] Surprisingly, such discovered elemental relationships in the lubricants herein, particularly at least the phosphorus content relative to the calcium SASH content, help achieve a low number of average and / or total LSPI events while maintaining a calcium content in the fluid, even at lower total phosphorus than traditionally used in such lubricants. Previously, it was known that calcium tends to be detrimental to LSPI (given the associated calcium sulfate ash content), and it was generally accepted that relatively high levels of phosphorus are beneficial to LSPI. Meanwhile, the lubricants herein defy this conventional practice by (1) lowering the amount of total phosphorus and (2) maintaining a calcium content in the lubricant that unexpectedly achieves desired LSPI performance when the elemental relationships relating phosphorus content, calcium ash content, and / or silicon content are maintained within the ranges described herein.

[0011] In some embodiments, the lubricating compositions herein having the elemental relationships discovered above exhibit 5 or fewer average LSPI events (and by other approaches, 4 or fewer average events, 3 or fewer average events, 2 or fewer average events, or 1 or fewer average LSPI event) according to the Sequence IX Slow Speed ​​Pre-Ignition Test of ASTM D8291. In other embodiments, the lubricating compositions herein exhibit 8 or fewer total LSPI events (and by other approaches, 7 or fewer total events, 6 or fewer total events, 5 or fewer total events, 4 or fewer total events, 3 or fewer total events, or 2 or fewer total events) according to the Sequence IX Slow Speed ​​Pre-Ignition Test of ASTM D8291.

[0012] Phosphorus-containing additives The lubricating compositions herein include small amounts of one or more phosphorus-containing additives to provide the lubricant with about 500 ppm or less of total phosphorus, and in other embodiments, about 450 ppm or less of total phosphorus, about 400 ppm or less of total phosphorus, about 350 ppm or less of total phosphorus, about 300 ppm or less of total phosphorus, or about 250 ppm or less of total phosphorus. In other approaches, the phosphorus-containing additive provides about 200 to about 500 ppm of total phosphorus, about 200 to about 450 ppm of total phosphorus, about 200 to about 400 ppm of total phosphorus, about 200 to about 350 ppm of total phosphorus, about 200 to about 300 ppm of total phosphorus, or about 200 to about 250 ppm of total phosphorus. The lubricants herein achieve good LSPI results at low levels of total phosphorus, even though higher levels of total phosphorus were previously thought to be necessary to achieve desired LSPI performance.

[0013] The one or more phosphorus-containing compounds may include metal-containing phosphorus-containing compounds and / or ashless phosphorus-containing compounds. Examples of suitable phosphorus-containing compounds include, but are not limited to, thiophosphates, dithiophosphates, metal phosphates, metal thiophosphates, metal dithiophosphates, phosphates, phosphate esters, phosphate esters, phosphites, phosphonates, phosphorus-containing carboxylic acid esters, ethers, or amide salts thereof, and mixtures thereof. In any of the above phosphorus-containing compounds, the compound may have about 5 weight percent to about 20 weight percent phosphorus, or about 5 weight percent to about 15 weight percent phosphorus, or about 8 weight percent to about 16 weight percent phosphorus, or about 6 weight percent to about 9 weight percent phosphorus.

[0014] One class of suitable phosphorus-containing compounds is metal dihydrocarbyl dithiophosphate compounds, such as, but not limited to, zinc dihydrocarbyl dithiophosphate compounds (i.e., zinc dihydrocarbyl dithiophosphate, ZDDP). When the phosphorus-containing compound is a metal thiophosphate or metal dithiophosphate, such as ZDDP, it can contain 5 to about 10 weight percent metal, about 6 to about 9 weight percent metal, about 8 to about 18 weight percent sulfur, about 12 to about 18 weight percent sulfur, or about 8 to about 15 weight percent sulfur. Suitable metal dihydrocarbyl dithiophosphates can include dihydrocarbyl dithiophosphate metal salts, where the metal can be an alkali metal, alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, zirconium, zinc, or a combination thereof; preferably, the metal is zinc.

[0015] When the phosphorus-containing compound is ZDDP, the alkyl groups on the ZDDP can be derived from primary alcohols, secondary alcohols, phenols, and / or mixtures thereof. For example, all of the alkyl groups on the ZDDP can be derived from secondary alcohols such as methyl isobutyl carbinol, or from mixtures of secondary alcohols such as methyl isobutyl carbinol and isopropyl alcohol. In some cases, the alkyl groups on the ZDDP can be derived from mixtures of primary and secondary alcohols such as 2-ethylhexanol, isobutanol, and isopropanol. The ZDDP can contain about 6 to about 10 weight percent phosphorus, about 6 to about 9 weight percent zinc, and about 12 to about 18 weight percent sulfur.

[0016] Examples of such ZDDPs include zinc O,O-di(C 1~14 -Alkyl)dithiophosphate; (Mixed O,O-bis(sec-butyl and isooctyl))dithiophosphate; Zinc-O,O-bis(branched and linear C 3~8-Alkyl)dithiophosphate;Zinc O,O-bis(2-ethylhexyl)dithiophosphate;Zinc O,O-bis(mixed isobutyl and pentyl)dithiophosphate;Zinc mixed O,O-bis(1,3-dimethylbutyl and isopropyl)dithiophosphate;Zinc O,O-diisooctyldithiophosphate;Zinc O,O-dibutyldithiophosphate;Zinc mixed O,O-bis(2-ethylhexyl and isobutyl and isopropyl)dithiophosphate;Zinc O,O-bis(dodecylphenyl)dithiophosphate;Zinc O,O-diisodecyldithiophosphate;Zinc O-(6-methylheptyl)-O-(1-methylbutyl)dithiophosphate zinc O,O-dioctyldithiophosphate; zinc O,O-dipentyldithiophosphate; zinc O-(2-methylbutyl)-O-(2-methylpropyl)dithiophosphate; and zinc O-(3-methylbutyl)-O-(2-methylpropyl)dithiophosphate.

[0017] Such phosphorus-containing compounds have the formula:

[0018] [ka] and In the formula (I), each R independently contains 1 to 18 carbon atoms, or 2 to 12 carbon atoms, or about 3 to 8 carbon atoms. For example, R can be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, methylpentyl, propenyl, or butenyl. The number of carbon atoms in each R group in the above formula is generally about 3 or more, about 4 or more, about 6 or more, or about 8 or more. Each R group can have an average of 3 to 8 carbon atoms. The total number of carbon atoms in each R group can be 5 to about 72, or 12 to about 32. In Formula I, A is a metal, such as aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, zirconium, zinc, or a combination thereof. When the phosphorus-containing compound has the structure shown in Formula I, the compound can have from about 6 to about 9 weight percent phosphorus.

[0019] It is understood in the art that a more accurate representation of the sulfur-zinc coordination array can be represented by the symmetrical array shown below, and that as used herein, the chemical structure of Formula I is interchangeable with Formula I' shown below. It is also understood that the structures shown in Formulas I and I' can exist as monomers, dimers, trimers, or oligomers (e.g., tetramers).

[0020] [ka]

[0021] Dihydrocarbyl dithiophosphate metal salts can be prepared according to known techniques, typically by first forming a dihydrocarbyl dithiophosphate (DDPA) by reacting one or more alcohols or phenols with P2S5, and then neutralizing the resulting DDPA with a metal compound such as zinc oxide. For example, DDPA can be made by reacting a mixture of primary and secondary alcohols with P2S5. In this case, the DDPA contains alkyl groups derived from both primary and secondary alcohols. Alternatively, multiple DDPAs can be prepared, with the alkyl groups on one DDPA derived entirely from secondary alcohols and the alkyl groups on another DDPA derived entirely from primary alcohols. The DDPAs are then blended together to form a mixture of DDPAs with alkyl groups derived from both primary and secondary alcohols.

[0022] Another type of phosphorus-containing compound suitable for the lubricants herein may be an ashless (i.e., metal-free) phosphorus-containing compound. In some embodiments, the ashless phosphorus-containing compound may be a dialkyldithiophosphate ester, amyl acid phosphate, diamyl acid phosphate, dibutyl hydrogen phosphate, dimethyloctadecyl phosphate, salts thereof, and mixtures thereof.

[0023] In some embodiments, exemplary ashless phosphorus-containing compounds have the formula:

[0024] [ka] and wherein R1 is S or O, R2 is -OR", -OH, or -R", R3 is -OR", -OH, or SR'"C(O)OH, R4 is -OR", R'" is a C1 to C3 branched or linear alkyl chain, and R" is a C1 to C18 hydrocarbyl chain of formula II above.

[0025] In some embodiments, the phosphorus-containing compound of Formula II can have R1 as S, R2 as -OR", R3 as S R'"COOH, R4 as -OR", R'" as a C3 branched alkyl chain, and R" as C4. In another embodiment, the phosphorus-containing compound of Formula II can have R1 as O, R2 as -OH, R3 as -OR" or -OH, R4 as -OR", and R" as C5. In yet another embodiment, the phosphorus-containing compound of Formula II can have R1 as O, R2 as OR", R3 as H, R4 as -OR", and R" as C4. In other embodiments, the phosphorus-containing compound of Formula II can have R1 as O, R2 as -R", R3 as -OCH3 or -OH, R4 as -OCH3, and R" as C 18 It may have R'' as

[0026] Detergents The lubricating compositions herein may also include a select detergent system configured in a specific relationship to function in combination with the low phosphorus levels to achieve improved LSPI. In some embodiments, the detergents herein contribute a total base level (TBN) to the lubricating composition of at least about 1 mg KOH / g, at least about 2 mg KOH / g, at least about 3 mg KOH / g, at least about 4 mg KOH / g, or at least about 5 mg KOH / g, and up to about 15 mg KOH / g, up to about 12 mg KOH / g, up to about 10 mg KOH / g, or up to about 8 mg KOH / g, as measured according to ASTM D2896. In embodiments, the detergent systems herein generally include one or more alkali or alkaline metal salts of sulfonates, and preferably contain small amounts, residual levels, or no other detergent additives, such as phenates, calixarates, salixarates, salicylates, carboxylic acids, sulfurized derivatives thereof, or combinations thereof, so long as the relationships described herein are maintained. Preferably, the detergent system of the present invention is substantially free of phenate detergent additives (i.e., less than about 1 weight percent phenate detergent, less than about 0.5 weight percent phenate detergent, less than about 0.1 weight percent phenate detergent, less than about 0.05 weight percent phenate detergent, or no functional amounts of phenate detergent).

[0027] As discussed further below, the detergents herein preferably comprise one or more calcium-containing detergents, one or more optional magnesium-containing detergents, or a combination thereof. Preferably, the detergent is also substantially free of sodium-containing detergents (i.e., less than about 1 weight percent sodium-containing detergents, less than about 0.5 weight percent sodium-containing detergents, less than about 0.1 weight percent sodium-containing detergents, less than about 0.05 weight percent sodium-containing detergents, or no functional amounts of sodium-containing detergents).

[0028] In another approach or embodiment, the detergent systems herein are also configured to maintain low levels of calcium content, measured as calcium sulfate ash (Ca-SASH) according to ASTM D874, or more preferably calculated based on the amount of metal in the lubricant. For example, sulfate ash (SASH) or calcium sulfate ash (Ca-SASH) can be calculated based on the total metallic elements contributing to SASH in the lubricant composition, adjusted by factors for each metallic type. Metals contributing to SASH include (with adjustment factors): barium (1.7), boron (3.22), calcium (3.4), copper (1.252), lead (1.464), lithium (7.92), magnesium (4.95), manganese (1.291), molybdenum (1.5), potassium (2.33), sodium (3.09), and zinc (1.5). Specifically, the ppmw content of each of the metallic elements present in the lubricating oil composition that are considered to contribute to sulfated ash is multiplied by the corresponding factor above, and then each metallic element / factor adjustment product is summed and the total is divided by 10,000 to calculate the weight percent of SASH in the lubricating composition. Unless otherwise specified, all sulfated ash levels herein are calculated using this procedure.

[0029] In some approaches, the detergents herein provide a calcium content contributing to about 0.20 weight percent or less of Ca-SASH, about 0.19 weight percent or less of Ca-SASH, or about 0.18 weight percent or less of Ca-SASH. The lubricant may also have a total sulfated ash content of about 1 weight percent or less, or in other approaches, about 0.8 weight percent or less of a total sulfated ash content, or about 0.7 weight percent or less, when measured according to the calculations therein. In such embodiments, about 30 weight percent or less of the total sulfated ash content is provided by calcium sulfate ash, and in other approaches, about 28 percent or less, or about 25 percent or less of the total sulfated ash content is contributed by calcium sulfate ash.

[0030] Suitable detergents and methods for their preparation are described in more detail in numerous patent publications, such as U.S. Patent No. 7,732,390 and the references cited therein, which are incorporated herein by reference. In some embodiments, the lubricant compositions herein may contain from about 0.1 to about 5 weight percent of any individual and / or total detergent additive, from about 0.15 to about 3 weight percent in another approach, and from about 0.15 to 2.6 weight percent in yet another approach, so long as the detergent additive satisfies the calcium, magnesium, SASH content, sulfonate amount, and / or other relationships described herein.

[0031] Generally, suitable detergents in the systems herein, subject to the various relationships and metal contents described above, may include linear or branched alkali or alkaline earth metal salts, such as calcium, sodium, or magnesium, of petroleum sulfonic acids and long-chain mono- or di-alkylaryl sulfonic acids in which the aryl groups are benzyl, tolyl, and xylyl, and / or various phenates or phenate derivatives. Examples of suitable detergents include, in addition to the required amount of sulfonate soap, the following detergents: calcium phenate, calcium sulfur-containing phenate, calcium sulfonate, calcium calixarate, calcium salixarate, calcium salicylate, calcium carboxylic acid, calcium phosphate, calcium mono- and / or di-thiophosphate, calcium alkylphenol, calcium sulfur-bound alkylphenol compound, calcium methylene-bridged phenol, magnesium phenate, magnesium sulfur-containing phenate, magnesium sulfonate, magnesium calixarate, magnesium salixarate, magnesium salicylate, magnesium cal ... and low based / neutral and overbased variations of sodium carboxylic acids, magnesium phosphates, magnesium mono- and / or di-thiophosphates, magnesium alkyl phenols, magnesium sulfur-bonded alkyl phenol compounds, magnesium methylene bridged phenols, sodium phenates, sodium sulfur-containing phenates, sodium sulfonates, sodium calixarates, sodium salixarates, sodium salicylates, sodium carboxylic acids, sodium phosphates, sodium mono- and / or di-thiophosphates, sodium alkyl phenols, sodium sulfur-bonded alkyl phenol compounds, or sodium methylene bridged phenols.

[0032] The detergent additives may be neutral, underbased, or overbased, preferably overbased calcium and magnesium detergents, meeting the minimum detergent TBN numbers set forth above, as needed. As will be appreciated, overbased detergent additives are well known in the art and may be alkali or alkaline earth metal overbased detergent additives. Such detergent additives may be prepared by reacting a metal oxide or metal hydroxide with a base material and carbon dioxide gas. The base material is typically an acid, such as an aliphatic-substituted sulfonic acid, aliphatic-substituted carboxylic acid, or aliphatic-substituted phenol.

[0033] The term "overbased" 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 can have conversion levels greater than 100% (i.e., they can contain more than 100% of the theoretical amount of metal required to convert the acid to its "standard" or "neutral" salt). The expression "metal ratio," often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of metal in an overbased salt to the chemical equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the MR is 1, while in overbased salts, the MR is greater than 1. They are commonly referred to as overbased, highly based, or superbased salts and can be salts of organic sulfur acids, carboxylic acids, or phenols.

[0034] As used herein, the term "TBN" is used to represent a total base number in units of "mg KOH / g" as measured by the method of ASTM D2896. Detergents can be neutral or overbased. For example, a neutral detergent may have a total base number (TBN) of up to about 200 mg KOH / gram. In another example, the overbased detergent of the lubricating oil composition herein may have a total base number (TBN) of about 200 mg KOH / gram or more, or about 250 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 overbased detergent may have a metal-to-substrate 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.

[0035] Examples of suitable overbased detergents (so long as they satisfy the calcium, magnesium, SASH, TBN, and other relationships described herein) include, but are not limited to, overbased calcium phenates, overbased calcium sulfur-containing phenates, overbased calcium sulfonates, overbased calcium calixarates, overbased calcium salixarates, overbased calcium salicylates, overbased calcium carboxylic acids, overbased calcium phosphates, overbased calcium mono- and / or dithiophosphates, overbased calcium alkylphenols, overbased calcium sulfur-linked alkyl phenols, and the like. overbased magnesium carboxylic acid, overbased magnesium phosphate, overbased magnesium mono- and / or dithiophosphate, overbased magnesium alkylphenol, overbased magnesium sulfur-linked alkylphenol compound, or overbased magnesium methylene-bridged phenol.

[0036] Optionally, the detergents herein may include low-based or neutral detergents, so long as the other fluid relationships described herein are satisfied. When an optional low-based or neutral detergent is incorporated into the detergent system, the low-based or neutral detergent generally has a TBN of up to 175 mg KOH / g, up to 150 mg KOH / g, up to 100 mg KOH / g, or up to 50 mg KOH / g. The low-based / neutral detergent may include a calcium- or magnesium-containing detergent. Examples of suitable low-based / neutral detergents include, but are not limited to, calcium sulfonate, calcium phenate, calcium salicylate, magnesium sulfonate, magnesium phenate, and / or magnesium salicylate (again, so long as the calcium, magnesium, SASH, TBN, and other relationships described herein are satisfied).

[0037] In some embodiments, detergents used in the lubricants herein comprise at least an overbased calcium sulfonate and / or an overbased magnesium sulfonate, each having a total base number of 150 to 450, or alternatively, about 200 to about 400, or about 200 to about 350. The TBN values ​​above reflect the values ​​of the finished detergent components diluted in base oil. In other embodiments, the TBN of the detergents herein may reflect the neat (i.e., undiluted or oil-free) version of the detergent components. For example, the fluids herein may comprise an overbased calcium sulfonate as an undiluted additive having a TBN of about 300 to about 450, or alternatively, about 380 to about 420, and / or an overbased magnesium sulfonate as an undiluted additive having a TBN of about 500 to about 700, or alternatively, about 600 to about 700.

[0038] In some embodiments, the detergent systems herein have selected levels of calcium-based detergents to control the amount of calcium sulfate ash content (Ca-SASH) in the lubricant, so that the lubricant achieves a selected weight ratio of phosphorus content to calcium sulfate ash content, which has been discovered to be useful for improving LSPI performance when using low levels of total phosphorus. For example, in embodiments herein, the lubricant has a weight ratio of phosphorus content to calcium sulfate ash content (Ca-SASH) of at least about 0.1, and in other approaches, from about 0.1 to about 0.3. As used herein, the weight ratio of phosphorus content to calcium sulfate ash content is the weight percent of phosphorus in the lubricant divided by the weight percent of calcium sulfate ash (calculated as described herein) in the lubricant, as shown in the Examples below.

[0039] silicon-containing compounds In some approaches or embodiments, the lubricating compositions herein may also contain one or more optional silicon-containing compounds. For example, the compositions may contain one or more organosilane compounds, fluorosilicone compounds, polydimethylsiloxane compounds, phenyl-methylpolysiloxane compounds, linear siloxane compounds, cyclic siloxane compounds, branched siloxane compounds, silicone polymers and copolymers, organo-silicone copolymers, and mixtures thereof. In some approaches, such silicon-containing compounds may have a kinematic viscosity of greater than about 20,000 cSt at 25°C, and in some approaches, from about 40,000 to about 80,000 cSt at 25°C.

[0040] For example, suitable organosilane compounds can include, but are not limited to, hydrocarbyl silyl ether compounds, such as those having C6-C20 hydrocarbyl chains. In one approach, exemplary hydrocarbyl silyl ether compounds can be tri-alkoxy(hydrocarbyl)silanes, such as C10-C20 hydrocarbyl trimethoxysilanes, or more preferably, C14-C20 hydrocarbyl trimethoxysilanes, and most preferably, hexadecyl trimethoxysilane. In another approach, suitable silicon-containing compounds can be polysiloxane compounds, including one or more silicone oils or one or more polydimethylsiloxane polymers. In yet another approach, the silicon-containing compounds can be, but are not limited to, hexadecyl trimethoxysilane, octyl triethoxysilane, nonyl triethoxysilane, n-decyl triethoxysilane, undecyl triethoxysilane, and tetradecyl triethoxysilane. Preferably, the silicon-containing compound may be a silicone oil or a polydimethylsiloxane polymer.

[0041] In other embodiments, suitable organosilanes may contain one organic substituent and three hydrolyzable substituents. In still other embodiments, exemplary organosilanes may include, but are not limited to, the following compounds: [2-(3-cyclohexenyl)ethyl]trimethoxysilane, trimethoxy(7-octen-1-yl)silane, isooctyltrimethoxysilane, N-(3-triethoxysilylpropyl)methoxyethoxyethoxyethylcarbamate, N-(3-triethoxysilylpropyl)methoxyethoxyethoxyethylcarbamate, 3-(methacryloyloxy)propyltrimethoxysilane, allyltrimethoxysilane, methyl ... Silane, 3-acryloxypropyltrimethoxysilane, 3-(methacryloyloxy)propyltriethoxysilane, 3-(methacryloyloxy)propylmethyldimethoxysilane, 3-(acryloyloxypropyl)methyl-dimethoxysilane, 9-3-(methacryloyloxy)propyldimethylethoxysilane, 3-(methacryloyloxy)propyldimethylethoxysilane, vinyldimethylethoxysilane, phenyltrimethoxysilane, n-octyltrimethoxysilane, dodecyltrimethoxysilane, isopropyltrimethoxysilane, Octyltrimethoxysilane, octadecyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, vinylmethyldiacetoxysilane, vinylmethyldiethoxysilane, vinyltriacetoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriphenoxysilane, vinyltri-t-butoxysilane, vinyltrisisobutoxysilane, vinyltriisopropenoxysilane, vinyltris(2-methoxyethoxy)silane, styryl Ethyltrimethoxysilane, mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, heptamethyl(2-tris(2-methoxyethoxy)silylethyltrisiloxane) (described in U.S. Patent Application Publication No. 2003 / 0220204), polydimethylsiloxane, arylsilanes, including substituted and unsubstituted arylsilanes, alkylsilanes, including substituted and unsubstituted alkylsilanes, including methoxy- and hydroxy-substituted alkylsilanes, and / or combinations of two or more of the foregoing compounds.

[0042] In some approaches or embodiments, the silicon-containing compound is present in an amount sufficient to provide the lubricating oil composition with from about 3 ppm to about 20 ppm of silicon, and in other approaches, from about 4 ppm to about 18 ppm of silicon, from about 5 ppm to about 15 ppm of silicon, or from about 7 ppm to about 15 ppm of silicon.

[0043] In some embodiments, the lubricating compositions herein may also have a specific weight ratio of calcium sulfate ash content to silicon content, which may also help provide improved LSPI performance when using low levels of total phosphorus herein. For example, in some embodiments, the lubricants herein may have a weight ratio of calcium sulfate ash content to silicon content of 250:1 or less, and in other approaches from about 100:1 to about 250:1, which may help achieve the LSPI improvements described herein at low levels of total phosphorus. As used herein, the weight ratio of calcium sulfate ash content to silicon content is the weight percent of calcium sulfate ash in the lubricant divided by the weight percent of silicon content in the lubricant, as shown in the Examples below.

[0044] Dispersants The lubricating compositions herein may also contain one or more optional dispersants. Dispersants are often known as ashless dispersants because they contain no ash-forming metals prior to incorporation into the lubricant composition and typically do not contribute any ash upon addition to the lubricant. Ashless dispersants are characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long-chain alkenyl succinimides. Examples of N-substituted long-chain alkenyl succinimides include polyisobutylene succinimides in which the number average molecular weight of the polyisobutylene substituent ranges from about 350 to about 50,000, or from about 5000, or from about 3000, or from about 2,000, or from about 1,500, as measured by GPC. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Pat. No. 7,897,696 and U.S. Pat. No. 4,234,435, which are incorporated herein by reference. The alkenyl substituent may be prepared from polymerizable monomers containing from about 2 to about 16, or from about 2 to about 8, or from about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines, typically poly(ethyleneamines).

[0045] In some approaches, preferred amines for dispersants can be selected from polyamines and hydroxylamines. Examples of polyamines that can be used include, but are not limited to, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and higher homologs such as pentaethylamine hexamine (PEHA). In some approaches, so-called heavy polyamines can be used, which are mixtures of polyalkylene-polyamines containing small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine), but primarily oligomers with six or more nitrogen atoms, two or more primary amines per molecule, and more extensive branching than conventional polyamine mixtures. Heavy polyamines preferably include polyamine oligomers containing seven or more nitrogen atoms per molecule and two or more primary amines per molecule.

[0046] In some embodiments, when included, polyisobutylene (PIB) is a preferred reactant for forming the dispersant and may have a terminal double bond content of greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol%. Such PIB is also referred to as highly reactive PIB ("HR-PIB"). HR-PIB having a number average molecular weight in the range of about 800 to about 5000 as determined by GPC is suitable for use in embodiments of the present disclosure. Conventional PIB typically has 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%.

[0047] HR-PIB having a number-average molecular weight ranging from about 900 to about 3000, as determined by GPC, may be suitable. Such HR-PIB is commercially available or can be synthesized by polymerization of isobutene in the presence of a non-chlorinated catalyst, such as boron trifluoride, as described in U.S. Pat. Nos. 4,152,499 and 5,739,355. When used in the aforementioned thermal ene reaction, HR-PIB can result in higher conversion rates and less precipitate formation in the reaction due to its increased reactivity. A suitable method is described in U.S. Pat. No. 7,897,696. In one embodiment, the present disclosure further includes at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"), which can have an average of about 1.0 to about 2.0 succinic acid moieties per polymer.

[0048] In some approaches, the dispersants in the lubricants herein may optionally be post-treated by conventional methods by reaction with any of a variety of agents. Suitable post-treatment agents include boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds. (See, e.g., U.S. Pat. Nos. 7,645,726, 7,214,649, 8,048,831, and 5,241,003, all of which are incorporated herein by reference in their entirety.)

[0049] The boron compounds used as post-treatment reagents can be selected from boron oxide, boron halides, boric acid, and esters of boric acid in amounts to provide from about 0.1 atomic percentage of boron per mole of nitrogen composition to about 20 atomic percentages of boron for each atomic percentage of nitrogen used. The boron post-treated dispersant can contain from about 0.05 weight percent to about 2.0 weight percent, or in other approaches, from about 0.05 weight percent to about 0.9 weight percent, of boron, based on the total weight of the borate dispersant.

[0050] In another approach, carboxylic acids can also be used as post-treating reagents and can be saturated or unsaturated mono-, di-, or poly-carboxylic acids. Examples of carboxylic acids include, but are not limited to, maleic acid, fumaric acid, succinic acid, and naphthalic diacids (e.g., 1,8-naphthalic diacid). Anhydrides can also be used as post-treating reagents and can be selected from the group consisting of mono-unsaturated anhydrides (e.g., maleic anhydride), alkyl- or alkylene-substituted cyclic anhydrides (e.g., succinic anhydride or glutamic anhydride), and aromatic carboxylic anhydrides (including naphthalic anhydrides, e.g., 1,8-naphthalic anhydride).

[0051] In one embodiment, the process for post-treating a dispersant includes first forming a succinimide product as described above, and then further reacting the succinimide product with a post-treating agent, such as a boron compound, such as boric acid. In some cases, the dispersants herein may be post-treated with more than one post-treating agent. For example, a dispersant may be post-treated with a boron compound, such as boric acid, and also with an anhydride, such as maleic anhydride and / or 1,8-naphthalic anhydride.

[0052] The dispersants may be used in an amount sufficient to provide up to about 20 weight percent of the lubricating composition, with one or more of the dispersants being post-treated to provide the lubricating composition with at least about 40 ppm boron and up to 500 ppm boron. In other approaches, the dispersants may be used in the lubricating composition in an amount of about 0.1 weight percent to about 15 weight percent, or about 0.1 weight percent to about 10 weight percent, or about 0.1 weight percent to about 8 weight percent, or about 1 weight percent to about 10 weight percent, or about 1 weight percent to about 8 weight percent, or about 1 weight percent to about 6 weight percent, based on the final weight of the lubricating oil composition. The dispersants may provide at least about 400 ppm nitrogen and up to about 1,500 ppm nitrogen.

[0053] Base oil or base oil blend: The base oil used in the lubricating compositions herein can be an oil of lubricating viscosity and can be selected from any of API Groups I to V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. In one approach, the base oil of the lubricating compositions herein can be a blend of API Group II base oil combined with API Group III base oil. Surprisingly, even lower quality base oils can be used in the lubricants herein if the above fluid element relationships are followed. The five base oil groups are generally shown in Table 1 below.

[0054] [Table 1]

[0055] Group I, Group II, and Group III are mineral oil process feedstocks. Group IV base oils contain true synthetic molecular species produced by the polymerization of olefinically unsaturated hydrocarbons. Many Group V base oils are also true synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers, and / or polyphenyl ethers, but may also be natural oils such as vegetable oils. Group III base oils are derived from mineral oils, but it should be noted that the rigorous processing these fluids undergo makes their physical properties very similar to some true synthetic oils, such as PAOs. Therefore, oils derived from Group III base oils may be referred to in industry as synthetic fluids. Group II+ may include high viscosity index Group II.

[0056] The base oil blends used in the disclosed lubricating oil compositions can be mineral, animal, vegetable, synthetic, synthetic oil blends, or mixtures thereof. Suitable oils can be derived from hydrocracked, hydrogenated, hydrofinished, unrefined, refined, and rerefined oils, and mixtures thereof.

[0057] Unrefined oils are derived from natural, mineral, or synthetic sources with little or no further purification processing. Refined oils are similar to unrefined oils except that they have been processed in one or more purification steps, which may result in the improvement of one or more properties. Examples of suitable purification techniques include solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Oils refined to edible quality may or may not be useful. Edible oils may also be called white oils. In some embodiments, the lubricating oil composition does not include edible oils or white oils.

[0058] Re-refined oils are also known as reclaimed or reprocessed oils. These oils are obtained using the same or similar processes as refined oils. Often, these oils are further processed by techniques directed to the removal of spent additives and oil breakdown products.

[0059] 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 lubricating oils, such as liquid petroleum oils and solvent- or acid-treated mineral lubricating oils of the paraffinic, naphthenic, or mixed paraffin-naphthenic types. Such oils may be partially or fully hydrogenated, if desired. Oils derived from coal or shale may also be useful.

[0060] Useful synthetic lubricating oils may include hydrocarbon oils such as polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylene, polypropylene, propylene-isobutylene copolymers); poly(1-hexene), poly(1-octene), trimers or oligomers of 1-decene, such as poly(1-decene) (such materials are often referred to as α-olefins), and mixtures thereof; alkyl-benzenes (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.

[0061] Other synthetic lubricating oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans. Synthetic oils can be produced by the Fischer-Tropsch reaction and are typically hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oils can be prepared by the Fischer-Tropsch gas-to-liquid synthesis procedure, as well as other gas-to-liquid oils.

[0062] A major amount of base oil included in the lubricating composition may be selected from the group consisting of Group I, Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, but the major amount of base oil is other than the base oil resulting from the provision of additive components or viscosity index improvers in the composition. In another embodiment, a major amount of base oil included in the lubricating composition may be selected from the group consisting of Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, but the major amount of base oil is other than the base oil resulting from the provision of additive components or viscosity index improvers in the composition.

[0063] The amount of oil of lubricating viscosity present can be the remaining amount 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 oil of lubricating viscosity can be present in the final fluid in a major amount, such as greater than about 50% by weight, greater than about 60% by weight, greater than about 70% by weight, greater than about 80% by weight, greater than about 85% by weight, or greater than about 90% by weight.

[0064] In some approaches or embodiments, the base oil system herein comprises one or more of Group I through Group V base oils and may have a KV100 of about 2 to about 20 cSt, in other approaches about 2 to about 10 cSt, in other approaches about 2.5 to about 6 cSt, in still other approaches about 2.5 to about 3.5 cSt, and in still other approaches about 2.5 to about 4.5 cSt (ASTM D445).

[0065] As used herein, the terms "oil composition," "lubricating composition," "lubricating oil composition," "lubricating oil," "lubricant composition," "fully formulated lubricant composition," "lubricant," and "lubricating and cooling fluid" are considered synonymous and fully interchangeable terms that refer to a finished lubricating product that includes a majority amount of a base oil component and minor amounts of detergents and other optional components.

[0066] Optional Additives: The lubricating oil compositions herein may also contain a number of optional additives in combination with the detergent system, sulfurized additives, and borated detergents as needed to meet performance criteria, which optional additives are described in the following paragraphs.

[0067] Other Dispersants: The lubricating oil composition may optionally contain one or more other dispersants or mixtures thereof. Dispersants are often referred to as ashless dispersants because they do not contain ash-forming metals prior to incorporation into the lubricating oil composition and do not typically contribute ash when added to the lubricant. Ashless dispersants are characterized by polar groups attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long-chain alkenyl succinimides. Examples of N-substituted long-chain alkenyl succinimides include polyisobutylene succinimides in which the number average molecular weight of the polyisobutylene substituent ranges from about 350 to about 50,000, or from about 5,000, or from about 3,000, as measured by GPC. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Pat. No. 7,897,696 or U.S. Pat. No. 4,234,435. The alkenyl substituent may be prepared from polymerizable monomers containing from about 2 to about 16, or from about 2 to about 8, or from about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines, typically poly(ethyleneamines).

[0068] Preferred amines are selected from polyamines and hydroxylamines. Examples of polyamines that can be used include, but are not limited to, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and higher homologs such as pentaethylaminehexamine (PEHA).

[0069] Suitable heavy polyamines are mixtures of polyalkylene-polyamines containing oligomers with six or more nitrogen atoms, two or more primary amines per molecule, and more extensive branching than conventional polyamine mixtures, although they contain small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine). Heavy polyamines preferably include polyamine oligomers containing seven or more nitrogen atoms per molecule and two or more primary amines per molecule. Heavy polyamines contain greater than 28% by weight (e.g., greater than 32% by weight) of total nitrogen and an equivalent weight of 120 to 160 grams of primary amine groups per equivalent.

[0070] In some approaches, suitable polyamines are commonly known as PAMs and contain a mixture of ethyleneamines, with TEPA and pentaethylenehexamine (PEHA) being the major portion of the polyamine, usually less than about 80%.

[0071] Typically, PAM has 8.7-8.9 milliequivalents of primary amine per gram (115-112 gram equivalents per equivalent of primary amine) and a total nitrogen content of about 33-34% by weight. Heavier cuts of PAM oligomers, which are substantially free of TEPA and contain only small amounts of PEHA, but contain primarily oligomers with more than six nitrogen atoms and more extensive branching, may produce dispersants with improved dispersancy.

[0072] In some embodiments, the present disclosure further comprises at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight ranging from about 350 to about 50,000, or from about 5,000, or from about 3,000, as determined by GPC. The polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0073] In some embodiments, when polyisobutylene is included, the polyisobutylene may have a terminal double bond content of greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol%. Such PIB is also referred to as highly reactive PIB ("HR-PIB"). HR-PIB having a number average molecular weight in the range of about 800 to about 5000 as determined by GPC is suitable for use in embodiments of the present disclosure. Conventional PIB typically has 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%.

[0074] HR-PIB having a number-average molecular weight ranging from about 900 to about 3000, as determined by GPC, may be suitable. Such HR-PIB is commercially available or can be synthesized by polymerization of isobutene in the presence of a non-chlorinated catalyst, such as boron trifluoride, as described in U.S. Patent No. 4,152,499 to Boerzel et al. and U.S. Patent No. 5,739,355 to Gateau et al. When HR-PIB is used in the thermal ene reaction, it can result in higher conversion and less precipitate formation during the reaction due to increased reactivity. A suitable method is described in U.S. Patent No. 7,897,696.

[0075] In one embodiment, the present disclosure further includes at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"), which may have an average of about 1.0 to about 2.0 succinic acid moieties per polymer.

[0076] The percent active ingredient of the alkenyl or alkyl succinic anhydride can be determined using chromatographic techniques, which are described in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0077] Polyolefin conversion is calculated from the % active ingredient using the formula in columns 5 and 6 of US Pat. No. 5,334,321.

[0078] Unless otherwise specified, all percentages are weight percent and all molecular weights are number average molecular weights as determined by gel permeation chromatography (GPC) using commercially available polystyrene standards (having number average molecular weights of 180 to about 18,000) as calibration standards.

[0079] In one embodiment, the dispersant may be derived from a polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant may be derived from an olefin maleic anhydride copolymer. As an example, the dispersant may be described as poly-PIBSA. In some embodiments, the dispersant may be derived from an anhydride grafted to an ethylene-propylene copolymer.

[0080] A suitable class of nitrogen-containing dispersants can be derived from olefin copolymers (OCPs), more specifically 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 in U.S. Patent Nos. 7,485,603, 7,786,057, 7,253,231, 6,107,257, and 5,075,383, and / or is commercially available.

[0081] One class of suitable dispersants can 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 more detail in U.S. Pat. No. 3,634,515.

[0082] A suitable class of dispersants may also be high molecular weight esters or half-ester amides. Suitable dispersants may also be post-treated by conventional methods with any of a variety of agents. Among these are boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds. U.S. Patent Nos. 7,645,726, 7,214,649, and 8,048,831 are incorporated herein by reference in their entireties.

[0083] In addition to the carbonate and boric acid post-treatments, any of the compounds may be post-treated or further post-treated with 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. Pat. No. 5,241,003, which is incorporated herein by reference. Such treatments include treatment with inorganic phosphoric acids or anhydrides (e.g., U.S. Pat. Nos. 3,403,102 and 4,648,980); organic phosphorus compounds (e.g., U.S. Pat. No. 3,502,677); phosphorus pentasulfide; boron compounds as already mentioned above (e.g., U.S. Pat. Nos. 3,178,663 and 4,652,387); carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Pat. Nos. 3,708,522 and 4,909,910). 48,386); epoxide polyepoxides or thioepoxides (e.g., U.S. Pat. Nos. 3,859,318 and 5,026,495); aldehydes or ketones (e.g., U.S. Pat. No. 3,458,530); carbon disulfide (e.g., U.S. Pat. No. 3,256,185); glycidol (e.g., U.S. Pat. No. 4,617,137); urea, thiourea, or guanidine (e.g., U.S. Pat. No. 3,312,61 Nos. 9, 3,865,813, and British Patent No. 1,065,595; organic sulfonic acids (e.g., U.S. Pat. No. 3,189,544 and British Patent No. 2,140,811); alkenyl cyanides (e.g., U.S. Pat. Nos. 3,278,550 and 3,366,569); diketene (e.g., U.S. Pat. No. 3,546,243); diisocyanates (e.g., U.S. Pat. No. 3,573,205); alkanesulf ...546,243); ton (e.g., U.S. Pat. No. 3,749,695); 1,3-dicarbonyl compounds (e.g., U.S. Pat. No. 4,579,675); sulfates of alkoxylated alcohols or phenols (e.g., U.S. Pat. No. 3,954,639); cyclic lactones (e.g., U.S. Pat. Nos. 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. Pat. Nos. 4,612,132, 4,647,390, 4,648,886, 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent No. 2,140,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Pat. Nos. 4,614,522, ... Nos. 4,614,603 and 4,666,460; cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132, 4,647,390, 4,646,860, and 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent No. 2,440,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiocarbonates, and the like. olactams, thiolactones, or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460); cyclic carbamates, cyclic thiocarbamates, or cyclic dithiocarbamates (e.g., U.S. Pat. Nos. 4,663,062 and 4,666,459); hydroxyaliphatic carboxylic acids (e.g., U.S. Pat. Nos. 4,482,464, 4,521,318, and 4,713,189); oxidizing agents (e.g., U.S. Pat. No. 4,379,064); combinations of phosphorus pentasulfide and polyalkylene polyamines (e.g., U.S. Pat. Nos. 4,379,064, 4,379,064); , U.S. Pat. No. 3,185,647); combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (e.g., U.S. Pat. Nos. 3,390,086, 3,470,098); combinations of hydrazine and carbon disulfide (e.g., U.S. Pat. No. 3,519,564); combinations of aldehydes and phenols (e.g., U.S. Pat. Nos. 3,649,229, 5,030,249, 5,039,307); combinations of aldehydes and O-diesters of dithiophosphoric acids (e.g., U.S. Pat. No. 3,865,740);Combinations of hydroxyaliphatic carboxylic acids and boric acid (e.g., U.S. Pat. No. 4,554,086); combinations of hydroxyaliphatic carboxylic acids followed by formaldehyde and phenol (e.g., U.S. Pat. No. 4,636,322); combinations of hydroxyaliphatic carboxylic acids followed by aliphatic dicarboxylic acids (e.g., U.S. Pat. No. 4,663,064); combinations of formaldehyde and phenol followed by glycolic acid (e.g., U.S. Pat. No. 4,699,724); combinations of hydroxyaliphatic carboxylic acids or oxalic acid followed by a diisocyanate (e.g., U.S. Pat. No. 4,713,191); inorganic acids or anhydrides of phosphorus or a combination of its partial or total sulfur analogue and a boron compound (e.g., U.S. Pat. No. 4,857,214); a combination of an organic diacid, followed by an unsaturated fatty acid, followed by a nitrosoaromatic amine, optionally followed by a boron compound, and then a glycosylation agent (e.g., U.S. Pat. No. 4,973,412); a combination of an aldehyde and a triazole (e.g., U.S. Pat. No. 4,963,278); a combination of an aldehyde and a triazole, followed by a boron compound (e.g., U.S. Pat. No. 4,981,492); a combination of a cyclic lactone and a boron compound (e.g., U.S. Pat. Nos. 4,963,275 and 4,971,711). The above-mentioned patents are incorporated herein in their entirety.

[0084] Suitable dispersants may have a TBN of from about 10 to about 65 mg KOH / g on an oil-free basis, which equates to about 5 to about 30 TBN when measured on a dispersant sample containing about 50% diluent oil. TBN is measured by the method of ASTM D2896.

[0085] In yet another embodiment, the optional dispersant 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, wherein 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 as determined by GPC using polystyrene as a calibration standard.

[0086] In some approaches, the polyalkylene polyamine used to form the dispersant has the following formula:

[0087] [ka] wherein each R and R' is independently a divalent C1-C6 alkylene linker, and each R1 and R2 is independently hydrogen, a C1-C6 alkyl group, or together with the nitrogen atom to which they are attached form a 5- or 6-membered ring optionally fused to one or more aromatic or non-aromatic rings, and n is an integer from 0 to 8. In another approach, the polyalkylene polyamine is selected from the group consisting of a mixture of polyethylene polyamines having an average of 5 to 7 nitrogen atoms, triethylenetetramine, tetraethylenepentamine, and combinations thereof.

[0088] Dispersants, when present, 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. Alternative amounts of dispersant that may be used may be from about 0.1% to about 15% by weight, or from about 0.1% to about 10% by weight, or from about 0.1% to about 8% by weight, or from about 1% to about 10% by weight, or from about 1% to about 8% by weight, or from 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.

[0089] Antioxidants: The lubricating oil compositions herein may also optionally contain one or more antioxidants. Antioxidant compounds are known and include, for example, phenates, phenate sulfides, sulfurized olefins, phosphosulfurized terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, di-nonyldiphenylamine, octyldiphenylamine, di-octyldiphenylamine), phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, polymeric antioxidants, or mixtures thereof. The antioxidant compounds may be used alone or in combination.

[0090] The hindered phenol antioxidant may contain a secondary butyl group and / or a tertiary butyl group as a steric hindering group. The phenol group may be further substituted with a hydrocarbyl group and / or a bridging group connecting to a second aromatic group. Examples of suitable hindered phenol 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, 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, such as Irganox® L-135 available from BASF, or an addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate. wherein the alkyl group can contain from about 1 to about 18, or from about 2 to about 12, or from about 2 to about 8, or from about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant, which can be an ester, can include Ethanox™ 4716, available from Albemarle Corporation.

[0091] Useful antioxidants may include diarylamines and high molecular weight phenols. In some embodiments, the lubricating oil composition may contain a mixture of diarylamines and high molecular weight phenols, such that each antioxidant may be present in an amount sufficient to provide up to about 5 wt. %, based on the final weight of the lubricating oil composition. In some embodiments, the antioxidant may be a mixture of about 0.3 to about 1.5 wt. % diarylamines and about 0.4 to about 2.5 wt. % high molecular weight phenols, based on the final weight of the lubricating oil composition.

[0092] Examples of 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 olefin can be a Diels-Alder adduct of a diene, such as 1,3-butadiene, and an unsaturated ester, such as butyl acrylate.

[0093] Another class of sulfurized olefins includes sulfurized fatty acids and their esters. The fatty acids are often derived from vegetable or animal oils and typically contain from about 4 to about 22 carbon atoms. Examples of suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof. Often, the fatty acids are derived from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or mixtures thereof. The fatty acids and / or esters may be mixed with an olefin, such as an α-olefin.

[0094] In another alternative embodiment, the antioxidant composition contains a molybdenum-containing antioxidant in addition to the phenolic and / or aminic antioxidants discussed above. When a combination of these three antioxidants is used, preferably the treat rate ratio of the phenol to the amine to the molybdenum-containing component is (0-3):(0-3):(0-3).

[0095] The one or more antioxidants may be present in the range of from about 0% to about 20%, or from about 0.1% to about 10%, or from about 1% to about 5% by weight of the lubricating oil composition.

[0096] Antiwear Agents: The lubricating oil compositions herein may also optionally contain one or more antiwear agents. Examples of suitable antiwear agents include, but are not limited to, metal thiophosphates; metal dialkyldithiophosphates; phosphoric acid esters or salts thereof; phosphoric acid 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) disulfides; and mixtures thereof. A suitable antiwear agent may be molybdenum dithiocarbamate. Phosphorus-containing antiwear agents are more fully described in EP 612839. The metal in the dialkyldithiophosphate salt may be an alkali metal, alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful antiwear agent may be zinc dialkyldithiophosphate.

[0097] Further examples of suitable antiwear agents include titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (e.g., dibutyl phosphite), phosphonates, thiocarbamate-containing compounds such as thiocarbamate esters, thiocarbamate amides, thiocarbamic acid ethers, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides. The tartrates or tartrimides may contain alkyl-ester groups, but the total number of carbon atoms on the alkyl group may be at least 8. In one embodiment, the antiwear agent may include citrate.

[0098] The antiwear agent may be present in a range including from about 0% to about 15%, or from about 0.01% to about 10%, or from about 0.05% to about 5%, or from about 0.1% to about 3% by weight of the lubricating oil composition.

[0099] Boron-Containing Compounds: The lubricating oil compositions herein may optionally contain one or more boron-containing compounds. Examples of boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, and borated dispersants, such as borated succinimide dispersants, as disclosed in U.S. Patent No. 5,883,057. When present, the boron-containing compounds may be used in an amount sufficient to provide up to about 8% by weight of the lubricating oil composition, from about 0.01% to about 7% by weight, from about 0.05% to about 5% by weight, or from about 0.1% to about 3% by weight.

[0100] Additional Detergents: The lubricating oil composition may optionally further comprise one or more neutral, low-based, or overbased detergents, and mixtures thereof. Suitable detergent substrates include phenates, sulfur-containing phenates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, phosphoric acids, mono- and / or di-thiophosphoric acids, alkylphenols, sulfur-bonded alkylphenol compounds, or methylene-bridged phenols. Suitable detergents and methods for their preparation are described in more detail in numerous patent publications, including U.S. Pat. No. 7,732,390 and the references cited therein.

[0101] The detergent substrate may be salified with an alkali metal or alkaline earth metal, such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent is barium-free. In some embodiments, the detergent may contain trace amounts of other metals, such as magnesium or calcium, in amounts of 50 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less, or 10 ppm or less. Suitable detergents may include alkali metal or alkaline earth metal salts of petroleum sulfonic acids and long-chain mono- or di-alkylaryl sulfonic acids in which the aryl groups are benzyl, tolyl, and xylyl. Examples of suitable detergents include, but are not limited to, calcium phenate, calcium sulfonate, calcium calixarate, calcium salixarate, calcium salicylate, calcium carboxylic acid, calcium phosphate, calcium mono- and / or di-thiophosphate, calcium alkyl phenol, calcium sulfur-bound alkyl phenol compound, calcium methylene bridged phenol, magnesium phenate, magnesium sulfonate, magnesium calixarate, magnesium salixarate, magnesium salicylate, magnesium carboxylic acid, magnesium phosphate, magnesium mono- and / or di-thiophosphate, magnesium alkyl phenol, magnesium sulfur-bound alkyl phenol compound, magnesium methylene bridged phenol, sodium phenate, sodium sulfonate, sodium calixarate, sodium salixarate, sodium salicylate, sodium carboxylic acid, sodium phosphate, sodium mono- and / or di-thiophosphate, sodium alkyl phenol, sodium sulfur-bound alkyl phenol compound, or sodium methylene bridged phenol.

[0102] Overbased detergent additives are well known in the art and can be alkali or alkaline earth metal overbased detergent additives. Such detergent additives can be prepared by reacting a metal oxide or metal hydroxide with a base material and carbon dioxide gas. The base material is typically an acid, such as an aliphatic-substituted sulfonic acid, aliphatic-substituted carboxylic acid, or aliphatic-substituted phenol.

[0103] The term "overbased" refers to metal salts, such as metal salts of sulfonates, carboxylates, and phenates, in which the amount of metal present exceeds the stoichiometric amount. Such salts can have conversion levels greater than 100% (i.e., they can contain more than 100% of the theoretical amount of metal required to convert the acid to its "standard" or "neutral" salt). The expression "metal ratio," often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of metal in an overbased salt to the chemical equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the metal ratio (MR) is 1, while in overbased salts, the MR is greater than 1. They are commonly referred to as overbased, highly based, or superbased salts and can be salts of organic sulfur acids, carboxylic acids, or phenols.

[0104] The overbased detergent of the lubricating oil composition may have a total base number (TBN) of about 200 mg KOH / g or greater, or, as a further example, about 250 mg KOH / g or greater, or about 350 mg KOH / g or greater, or about 375 mg KOH / g or greater, or about 400 mg KOH / g or greater, as measured by the method of ASTM D2896.

[0105] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenate, overbased calcium sulfur-containing phenate, overbased calcium sulfonate, overbased calcium calixalate, overbased calcium salixarate, overbased calcium salicylate, overbased calcium carboxylic acid, overbased calcium phosphate, overbased calcium mono- and / or di-thiophosphate, overbased calcium alkylphenol, overbased calcium sulfur-bound alkylphenol compound, overbased calcium methylene-bridged phenol, overbased magnesium phenate, overbased magnesium sulfonate, overbased magnesium calixalate, overbased magnesium salixarate, overbased magnesium salicylate, overbased magnesium carboxylic acid, overbased magnesium phosphate, overbased magnesium mono- and / or di-thiophosphate, overbased magnesium alkylphenol, overbased magnesium sulfur-bound alkylphenol compound, or overbased magnesium methylene-bridged phenol.

[0106] The overbased calcium phenate detergents have a total base number of at least about 150 mg KOH / g, at least about 225 mg KOH / g, at least about 225 to about 400 mg KOH / g, at least about 225 to about 350 mg KOH / g, or about 230 to about 350 mg KOH / g, all measured by the method of ASTM D 2896. When such detergent compositions are formed in an inert diluent, such as a process oil, usually a mineral oil, the total base number reflects the basicity of the entire composition, including the diluent and any other materials (e.g., accelerators, etc.) that may be included in the detergent composition.

[0107] The overbased detergent may have a metal-to-substrate ratio of 1.1:1 or greater, or 2:1 or greater, or 4:1 or greater, or 5:1 or greater, or 7:1 or greater, or 10:1 or greater. In some embodiments, the detergent is effective in reducing or preventing rust in engines or other automotive components such as transmissions or gears. The detergent in the lubricating composition may be present from about 0 wt % to about 10 wt %, or from about 0.1 wt % to about 8 wt %, or from about 1 wt % to about 4 wt %, or from greater than about 4 wt % to about 8 wt %.

[0108] Extreme Pressure Agents: The lubricating oil compositions herein 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, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenols, sulfurized dipentene, sulfurized terpene, and sulfurized Diels-Alder adducts; phosphorus sulfurized hydrocarbons such as the reaction products of phosphorus sulfide with turpentine or methyl oleate; dihydrocarbyl and trihydrocarbyl phosphites, for example, phosphate esters such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl phenyl phosphite; dipentyl phenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene-substituted phenyl phosphites; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol diacid; amine salts of alkyl and dialkyl phosphates, including, for example, the amine salt of the reaction product of a dialkyl dithiophosphate with propylene oxide; and mixtures thereof.

[0109] Friction Modifiers: The lubricating oil compositions herein may also optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing and metal-free friction modifiers, but may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, 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.

[0110] Suitable friction modifiers may contain hydrocarbyl groups selected from linear, branched, or aromatic hydrocarbyl groups, or mixtures thereof, and may be saturated or unsaturated. The hydrocarbyl groups may be composed of carbon and hydrogen or heteroatoms such as sulfur or oxygen. The 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, a di-ester, or a (tri)glyceride. The friction modifier may be a long-chain fatty amide, a long-chain fatty ester, a long-chain fatty epoxide derivative, or a long-chain imidazoline.

[0111] Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers include esters formed by reacting carboxylic acids and anhydrides with alkanols, and generally may contain polar end groups (e.g., carboxyl or hydroxyl) covalently bonded to an oleophilic 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, the entire contents of which are incorporated herein by reference.

[0112] Aminic friction modifiers may include amines or polyamines. Such compounds may have hydrocarbyl groups that are linear, saturated, unsaturated, or a mixture thereof, and may contain from about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds may have hydrocarbyl groups that are linear, saturated, unsaturated, or a mixture thereof. They may contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

[0113] The amines and amides may be used as such or in the form of 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 its entirety.

[0114] Friction modifiers may optionally be present in ranges such as from about 0% to about 10% by weight, or from about 0.01% to about 8% by weight, or from about 0.1% to about 4% by weight.

[0115] Molybdenum-Containing Component: The lubricating oil compositions herein may also optionally contain one or more molybdenum-containing compounds. The oil-soluble molybdenum compounds may have the functional properties of antiwear agents, antioxidants, friction modifiers, or mixtures thereof. The oil-soluble molybdenum compounds may include molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dithiophosphinates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organo-molybdenum compounds, and / or mixtures thereof. Molybdenum sulfides include molybdenum disulfide. The molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compounds may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound can be a molybdenum dithiocarbamate.

[0116] Suitable examples of molybdenum compounds that can be used include commercially available materials sold under trade names such as Molyvan® 822, Molyvan® A, Molyvan® 2000, and Molyvan® 855 from R.T. Vanderbilt Co., Ltd., and 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. Pat. No. 5,650,381, U.S. Reissue Pat. Nos. 37,363 (E1), 38,929 (E1), and 40,595 (E1), the entire contents of which are incorporated herein by reference.

[0117] Additionally, the molybdenum compound can be an acidic molybdenum compound, including molybdic acid, ammonium molybrate, sodium molybrate, potassium molybrate, and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybrate, MoOCl, MoOBr, MoOCl, molybdenum trioxide, or similar acidic molybdenum compounds. Alternatively, the composition can provide the molybdenum via molybdenum / sulfur complexes of basic nitrogen compounds, as described, for example, in U.S. Pat. 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 WO 94 / 06897, the foregoing patents being incorporated herein by reference in their entireties.

[0118] Another class of suitable organo-molybdenum compounds is the trinuclear molybdenum compounds, e.g., those of the formula Mo3S k L n Q z and mixtures thereof, wherein S represents sulfur, L represents an independently selected ligand having an organic group having a sufficient number of carbon atoms to render 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 donor compounds, e.g., water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5, including non-stoichiometric values. There may be at least 21 total carbon atoms among all of the ligand's organic groups, such as at least 25, at least 30, or at least 35 carbon atoms. Additional suitable molybdenum compounds are described in U.S. Pat. No. 6,723,685, incorporated herein by reference in its entirety.

[0119] The oil-soluble molybdenum compound may be present in an amount sufficient to provide from about 0.5 ppm to about 2000 ppm, from about 1 ppm to about 700 ppm, from about 1 ppm to about 550 ppm, from about 5 ppm to about 300 ppm, or from about 20 ppm to about 250 ppm of molybdenum.

[0120] Transition Metal-Containing Compound: In another embodiment, the oil-soluble compound can be a transition metal-containing compound or metalloid. Transition metals can include, but are not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten, etc. Suitable metalloids include, but are not limited to, boron, silicon, antimony, tellurium, etc.

[0121] In some embodiments, the oil-soluble transition metal-containing compound may function as an anti-wear agent, a friction modifier, an antioxidant, a deposit control additive, or two or more of these functions. In some embodiments, the oil-soluble transition metal-containing compound may be an oil-soluble titanium compound such as a titanium(IV) alkoxide. Among the titanium-containing compounds that may be used in or for preparing the oil-soluble materials of the disclosed technology are various Ti(IV) compounds such as titanium(IV) oxide; titanium(IV) sulfide; titanium(IV) nitrate; titanium(IV) alkoxides, such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, and titanium 2-ethylhexoxide; and other titanium compounds or complexes, such as, but not limited to, titanium phenate; titanium carboxylates, such as titanium(IV) 2-ethyl-1,3-hexanedioate, titanium citrate, or titanium oleate; and titanium(IV) (triethanolaminato)isopropoxide. Other forms of titanium encompassed by the disclosed technology include titanium phosphates, such as titanium dithiophosphates (e.g., dialkyldithiophosphates) and titanium sulfonates (e.g., alkylbenzene sulfonates), or generally reaction products of titanium compounds with various acidic substances to form salts, such as oil-soluble salts. Thus, titanium compounds can be derived from organic acids, alcohols, and glycols, among others. Ti compounds can also exist in dimeric or oligomeric forms containing Ti-O-Ti structures. Such titanium materials are commercially available or can be readily prepared by suitable synthetic techniques apparent to those skilled in the art. They can exist at room temperature as solids or liquids, depending on the particular compound. They can also be provided in solution form in a suitable inert solvent.

[0122] In one embodiment, titanium can be provided as a Ti-modified dispersant, such as a succinimide dispersant. Such materials can be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as an alkenyl-(or alkyl) succinic anhydride. The resulting titanate-succinate intermediate can be used directly or reacted with any of several materials, such as (a) polyamine-based succinimide / amide dispersants having free condensable —NH functional groups; (b) components of polyamine-based succinimide / amide dispersants, i.e., alkenyl-(or alkyl) succinic anhydrides and polyamines; or (c) hydroxy-containing polyester dispersants prepared by reacting a substituted succinic anhydride with a polyol, aminoalcohol, polyamine, or mixtures thereof. Alternatively, the titanate-succinate intermediate can be reacted with other agents, such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product can be used directly to impart Ti to lubricants or further reacted with a succinic dispersant as described above. As an example, one part (mole) of tetraisopropyl titanate can be reacted with approximately two parts (mole) of polyisobutene-substituted succinic anhydride at 140-150°C for 5-6 hours to provide a titanium-modified dispersant or intermediate. The resulting material (30 g) can be further reacted with a succinimide dispersant from a polyisobutene-substituted succinic anhydride and polyethylene polyamine mixture (127 grams + diluent oil) at 150°C for 1.5 hours to produce a titanium-modified succinimide dispersant.

[0123] Another titanium-containing compound is titanium alkoxide and C6-C 25 The reaction product may be a reaction product with a carboxylic acid. The reaction product has the following formula:

[0124] [ka] wherein n is an integer selected from 2, 3, and 4, and R is a hydrocarbyl group containing from about 5 to about 24 carbon atoms, or may be represented by the following formula:

[0125] [ka] where m+n=4, n ranges from 1 to 3, R4 is an alkyl moiety having from 1 to 8 carbon atoms, R1 is selected from hydrocarbyl groups containing from about 6 to 25 carbon atoms, and R2 and R3 are the same or different and are selected from hydrocarbyl groups containing from 1 to 6 carbon atoms. Alternatively, the titanium compound may be represented by the following formula:

[0126] [ka] wherein x ranges from 0 to 3; R1 is selected from hydrocarbyl groups containing about 6 to 25 carbon atoms; R2 and R3 are the same or different and are selected from hydrocarbyl groups containing about 1 to 6 carbon atoms; and R4 is selected from H, C6 to C8 25 and the carboxylic acid moiety of

[0127] Suitable carboxylic acids may include, but are not limited to, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, and the like.

[0128] In certain embodiments, the oil-soluble titanium compound may be present in the lubricating oil composition in an amount to provide from about 0 to about 3000 ppm by weight of titanium, or from 25 to about 1500 ppm by weight of titanium, or from about 35 to about 500 ppm by weight of titanium, or from about 50 to about 300 ppm by weight.

[0129] Viscosity Index Improvers: The lubricating oil compositions herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, hydrogenated styrene-isoprene polymers, styrene / maleic acid ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenylaryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers may include star polymers, suitable examples of which are described in U.S. Patent Application Publication No. 2012 / 0101017(A1).

[0130] The lubricating oil compositions herein may also optionally contain one or more dispersant viscosity index improvers in addition to or instead of a viscosity index improver. Suitable viscosity index improvers may include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with the reaction product of an acylating agent (such as maleic anhydride) and an amine, amine-functionalized polymethacrylates, or esterified maleic anhydride-styrene copolymers reacted with amines.

[0131] The total amount of viscosity index improver and / or dispersant viscosity index improver can be from about 0% to about 20%, from about 0.1% to about 15%, from about 0.1% to about 12%, or from about 0.5% to about 10% by weight of the lubricating oil composition.

[0132] Other optional additives: Other additives may be selected to perform one or more functions required in a lubricating fluid. Additionally, one or more of the aforementioned additives may be multifunctional and may provide functions in addition to or other than those described herein.

[0133] Lubricating oil compositions according to the present disclosure may optionally contain other performance additives. The other performance additives may be in addition to the specific additives of the present disclosure and / or may include one or more of metal deactivators, viscosity index improvers, detergents, ashless TBN boosters, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam suppressants, demulsifiers, emulsifiers, pour point depressants, seal swell agents, and mixtures thereof. Typically, fully formulated lubricating oils will contain one or more of these performance additives.

[0134] Suitable metal deactivators may include derivatives of benzotriazole (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzothiazole; foam suppressors including copolymers of ethyl acrylate, 2-ethylhexyl acrylate, and optionally vinyl acetate; demulsifiers including trialkyl phosphate, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylate, polyacrylate, or polyacrylamide.

[0135] Suitable suds suppressors include silicon-based compounds such as siloxanes.

[0136] Suitable pour point depressants may include polymethyl methacrylate or mixtures thereof. The pour point depressant may be present in an amount sufficient to provide from about 0 wt % to about 1 wt %, from about 0.01 wt % to about 0.5 wt %, or from about 0.02 wt % to about 0.04 wt %, based on the final weight of the lubricating oil composition.

[0137] Suitable rust inhibitors can be a single compound or a mixture of compounds that have the property of inhibiting corrosion of ferrous metal surfaces. Non-limiting examples of rust inhibitors useful 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 dimer and trimer acids such as those produced from tall oil fatty acid, 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 succinic acids in which the alkenyl group contains about 10 or more carbon atoms, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Another useful type of acidic corrosion inhibitor is the half ester of an alkenyl succinic acid having about 8 to about 24 carbon atoms in the alkenyl group with an alcohol, such as a polyglycol. The corresponding half amides of such alkenyl succinic acids are also useful. Useful rust inhibitors are high molecular weight organic acids.

[0138] When present, the rust inhibitor may be used in an amount sufficient to provide from about 0 wt. % to about 5 wt. %, from about 0.01 wt. % to about 3 wt. %, from about 0.1 wt. % to about 2 wt. %, based on the final weight of the lubricating oil composition.

[0139] Generally speaking, suitable lubricants containing detergent metals herein may contain additive components in the ranges listed in the table below.

[0140] [Table 2]

[0141] The percentages of each component above represent the weight percent 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 can be blended into the base oil individually or in various partial combinations. However, it may be preferred to blend all of the components simultaneously using an additive concentrate (i.e., additives plus a diluent such as a hydrocarbon solvent). Fully formulated lubricants conventionally contain an additive package, referred to herein as a dispersant / inhibitor package or DI package, that supplies the characteristics required in the formulation.

[0142] definition For 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. Additionally, 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, M.B. and March, J., John Wiley & Sons, New York: 2001, the entire contents of which are incorporated herein by reference.

[0143] As described herein, compounds can be optionally substituted with one or more substituents as generally illustrated above or as exemplified by the specific classes, subclasses, and species of the present disclosure.

[0144] Unless otherwise clear from the context, the term "major amount" is understood to mean an amount of 50 weight percent or more, for example, about 80 to about 98 weight percent, based on the total weight of the composition, and the term "minor amount" as used herein is understood to mean an amount of less than 50 weight percent, based on the total weight of the composition.

[0145] As used herein, the term "hydrocarbyl group" or "hydrocarbyl" is used in its ordinary sense, as is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character. 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, aliphatic, and alicyclic-substituted aromatic substituents, as well as cyclic substituents in which the ring is completed through another portion of the molecule (e.g., two substituents together form an alicyclic radical); (2) substituted hydrocarbon substituents, i.e., substituents containing non-hydrocarbon groups (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, amino, alkylamino, and sulfoxy) that do not alter the predominantly hydrocarbon substituent in the context of this disclosure; and (3) heterosubstituents, i.e., substituents that, while predominantly hydrocarbon in the context of this disclosure, contain other than carbon atoms in the ring or chain or are otherwise composed of carbon atoms. Heteroatoms include sulfur, oxygen, and nitrogen, and encompass substituents such as pyridyl, furyl, thienyl, and imidazolyl. Generally, no more than two, or as a further example, only one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group, and in some embodiments, there will be no non-hydrocarbon substituents in the hydrocarbyl group.

[0146] As used herein, the term "aliphatic" encompasses the terms alkyl, alkenyl, alkynyl, each of which is optionally substituted as described below.

[0147] As used herein, an "alkyl" group refers to a saturated aliphatic hydrocarbon group containing 1 to 12 (e.g., 1 to 8, 1 to 6, or 1 to 4) carbon atoms. The alkyl group can be straight-chained or branched. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-heptyl, or 2-ethylhexyl. An alkyl group can have one or more substituents, such as halo, phospho, alicyclic [e.g., cycloalkyl or cycloalkenyl], heteroalicyclic [e.g., heterocycloalkyl or heterocycloalkenyl], aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl [e.g., (aliphatic)carbonyl, (alicyclic)carbonyl, or (heteroalicyclic)carbonyl], nitro, cyano, amido [e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylamino], or the like.

[0039] The aryl group may be substituted (i.e., optionally substituted) with an alkylaminocarbonyl, 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, sulfamido, oxo, carboxy, carbamoyl, alicyclicoxy, heterocycloaliphaticoxy, aryloxy, heteroaryloxy, aralkyloxy, heteroarylalkoxy, alkoxycarbonyl, alkylcarbonyloxy, or hydroxy.Some examples of substituted alkyls include, but are not limited to, carboxyalkyl (e.g., HOOC-alkyl, alkoxycarbonylalkyl, and alkylcarbonyloxyalkyl), cyanoalkyl, hydroxyalkyl, alkoxyalkyl, acylalkyl, aralkyl, (alkoxyaryl)alkyl, (sulfonylamino)alkyl (e.g., (alkyl-SO2-amino)alkyl), aminoalkyl, amidoalkyl, (alicyclic)alkyl, or haloalkyl.

[0148] As used herein, an "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 an alkyl group, an alkenyl group can be straight or branched. Examples of alkenyl groups include, but are not limited to, allyl, isoprenyl, 2-butenyl, and 2-hexenyl. Alkenyl groups can have one or more substituents, such as halo, phospho, alicyclic [e.g., cycloalkyl or cycloalkenyl], heteroalicyclic [e.g., heterocycloalkyl or heterocycloalkenyl], aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl [e.g., (aliphatic)carbonyl, (alicyclic)carbonyl, or (heteroalicyclic)carbonyl], nitro, cyano, amido [e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylaminoalkylaminocarbonyl], or heteroarylcarbonylamino. and optionally substituted by alkyl, 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, sulfamido, oxo, carboxy, carbamoyl, alicyclicoxy, heteroalicyclicoxy, aryloxy, heteroaryloxy, aralkyloxy, heteroaralkoxy, alkoxycarbonyl, alkylcarbonyloxy, or hydroxy. Some examples of substituted alkenyls include, but are not limited to, cyanoalkenyl, alkoxyalkenyl, acylalkenyl, hydroxyalkenyl, aralkenyl, (alkoxyaryl)alkenyl, (sulfonylamino)alkenyl (e.g., (alkyl-SO2-amino)alkenyl), aminoalkenyl, amidoalkenyl, (alicyclic)alkenyl, or haloalkenyl.

[0149] As used herein, an "alkynyl" 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 having at least one triple bond. Alkynyl groups can be straight-chained or branched. Examples of alkynyl groups include, but are not limited to, propargyl and butynyl. Alkynyl groups can be substituted with one or more groups, such as aroyl, heteroaroyl, 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 sulfinyl], sulfonyl [e.g., aliphatic -SO2-, aliphatic amino-SO2-, or alicyclic -SO2-], amido [e.g., aminocarbonyl, alkylaminocarbonyl, alkylcarbonylamino, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, cycloalkylcarbonylamino, aryl aminocarbonyl, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (cycloalkylalkyl)carbonylamino, heteroaralkylcarbonylamino, heteroarylcarbonylamino, or heteroarylaminocarbonyl], urea, thiourea, sulfamoyl, sulfamido, 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.

[0150] As used herein, an "amino" group refers to an -NR X R Y In the formula, R X and R Yis 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. When the term "amino" is not a terminal group (e.g., alkylcarbonylamino), it is not -NR X - represented by R X is as defined above.

[0151] As used herein, a "cycloalkyl" group refers to a saturated carbocyclic monocyclic or bicyclic (fused or bridged) ring of 3 to 10 (e.g., 5 to 10) carbon atoms. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, cubyl, 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.

[0152] As used herein, a "heterocycloalkyl" group refers to a 3- to 10-membered mono- or bicyclic (fused or bridged) (e.g., 5- to 10-membered mono- or bicyclic) saturated ring structure in which one or more of the ring atoms is a heteroatom (e.g., N, O, S, or combinations thereof). Examples of heterocycloalkyl groups include piperidyl, piperazyl, tetrahydropyranyl, tetrahydrofuryl, 1,4-dioxolanyl, 1,4-dithianyl, 1,3-dioxolanyl, oxazolidyl, isoxazolidyl, morpholinyl, thiomorpholyl, octahydrobenzofuryl, octahydrochromenyl, octahydrothiochromenyl, 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.

[0153] As used herein, a "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 ring in the bicyclic or tricyclic ring system is aromatic. Heteroaryl groups include benzo-fused ring systems having 2 to 3 rings. For example, a benzo-fused group includes benzo fused to one or two 4- to 8-membered heterocyclic aliphatic moieties (e.g., indolyl, indolyl, isoindolyl, 3H-indolyl, indolinyl, benzo[b]furyl, benzo[b]thiophenyl, quinolinyl, or isoquinolinyl). Some examples of heteroaryl 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, puryl, cinnolyl, quinolyl, quinazolyl, cinnolyl, phthalazyl, quinazolyl, quinoxalyl, isoquinolyl, 4H-quinolidyl, benzo-1,2,5-thiadiazole, or 1,8-naphthyridyl.

[0154] Monocyclic heteroaryls include, but are not limited to, furyl, thiophenyl, 2H-pyrrolyl, pyrrolyl, oxazolyl, thazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, 1,3,4-thiadiazolyl, 2H-pyranyl, 4H-pyranyl, pyridyl, pyridazyl, pyrimidyl, pyrazolyl, pyrazyl, or 1,3,5-triazyl. Monocyclic heteroaryls are numbered according to standard chemical nomenclature.

[0155] Bicyclic heteroaryls include indolizyl, indolyl, isoindolyl, 3H-indolyl, indolinyl, benzo[b]furyl, benzo[b]thiophenyl, quinolinyl, isoquinolinyl, indolizinyl, isoindolyl, indolyl, benzo[b]furyl, bexo[b]thiophenyl, indazolyl, benzimidazyl, benzthiazolyl, purinyl, 4H-quinolizyl, quinolyl, isoquinolyl, cinnolyl, phthalazyl, quinazolyl, quinoxalyl, 1,8-naphthyridyl, or pteridyl. Bicyclic heteroaryls are numbered according to standard chemical nomenclature.

[0156] As used herein, the term "treat rate" refers to the weight percent of a component in a lubricating and cooling fluid.

[0157] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined using a gel permeation chromatography (GPC) instrument from Waters or similar equipment and Waters Empower Software or similar software. The GPC instrument can be equipped with a Waters Separation Module and a Waters Refractive Index Detector (or similar optional equipment). GPC operating conditions can include a guard column, four Agilent PLgel columns (300 x 7.5 mm long, 5 μm particle size, and pore size range 100-10,000 Å), and a column temperature of approximately 40°C. Unstabilized HPLC-grade tetrahydrofuran (THF) can be used as the solvent at a flow rate of 1.0 mL / min. The GPC instrument can be calibrated with commercially available poly(methyl methacrylate) (PMMA) standards with narrow molecular weight distributions ranging from 960 to 1,568,000 g / mol. The calibration curve can be extrapolated for samples with masses less than 500 g / mol. Samples and PMMA standards can be dissolved in THF at concentrations of 0.1 to 0.5% by weight and used without filtration. GPC measurements are also described in U.S. Pat. No. 5,266,223, which is incorporated herein by reference. The GPC method also provides molecular weight distribution information. See, for example, W.W. Yau, J.J. Kirkland, and D.D. Bly, "Modern Size Exclusion Liquid Chromatography," John Wiley and Sons, New York, 1979, which is incorporated herein by reference. [Example]

[0158] A better understanding of the present disclosure and its many advantages may be clarified with the following examples. The following examples are illustrative and not limiting in scope or spirit. Those skilled in the art will readily understand that variations of the components, methods, steps, and devices described in these examples can be used. Unless otherwise specified or apparent from the context of the following examples and discussion throughout this disclosure, all percentages, ratios, and parts described in this disclosure are by weight.

[0159] The inventive and comparative lubricating compositions were subjected to the Sequence IX Low Speed ​​Pre-Ignition (LSPI) test of ASTM D8291-21a. The inventive and comparative lubricating compositions contained a detergent system, an antiwear system, and an antifoam additive to provide the lubricant elements as shown in Table 3 below. Each lubricating composition in this example contained the same amounts of other additives, including dispersants, antioxidants, organomolybdenum additives, ashless antiwear additives, pour point depressants, and viscosity index modifiers. The additives were blended into the same base oil, including a blend of API Group II and API Group III base oils. Therefore, the only material change in each of the lubricants was the amount of additive and antifoam in the detergent system.

[0160] [Table 3] * Calculated as described herein ** Wt% Phosphorus / wt% Ca-SASH (i.e., C1 is 236 ppm / 10000 / 0.27) *** wt% Ca-SASH / wt% Silicon (i.e., C1 is 0.27 / (7 ppm / 10000))

[0161] In the detergent system of Table 3, calcium was provided by a calcium sulfonate detergent having a TBN of about 307 (413 neat TBN), and magnesium was provided by a magnesium sulfonate having a TBN of 400 (680 neat TBN). Phosphorus was provided by a zinc dialkyldithiophosphate, and the alkyl group was provided by a secondary alcohol. Silicon was provided by a polydimethylsiloxane antifoam agent.

[0162] Each of the inventive and comparative lubricating compositions in Table 3 was subjected to the Sequence IX Low Speed ​​Pre-Ignition (LSPI) test of ASTM D8291-21a, and the results are provided in Table 4 below.

[0163] [Table 4]

[0164] As shown in Table 4 above, none of the comparative fluids achieved passing the Sequence IX LSPI requirements for passenger car motor oils having the lower levels of phosphorus shown in Table 3. In contrast, the lubricants of the present invention having lower levels of phosphorus achieved passing the Sequence IX LSPI requirements when the recited ratios of phosphorus to calcium SASH and / or calcium SASH to silicon were maintained.

[0165] It should be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless expressly and unambiguously limited to one referent. Thus, for example, a reference to an "antioxidant" includes two or more different antioxidants. As used herein, the term "comprises" and grammatical variations thereof are intended to be open-ended such that the recitation of items in a list does not exclude other similar items that may be substituted for or added to the listed items.

[0166] For purposes of this specification and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages, or proportions, and other numerical values ​​used in the specification and claims should be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0167] It is understood that each component, compound, substituent, or parameter disclosed herein should be construed as disclosed for use alone or in combination with one or more of any and all other components, compounds, substituents, or parameters disclosed herein.

[0168] It is further understood that each range disclosed herein should be construed as a disclosure of each specific value within the disclosed range having the same number of significant digits. Thus, for example, a range of 1 to 4 should be construed as an explicit disclosure of not only the values ​​1, 2, 3, and 4, but also any range of such values.

[0169] 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 for the same component, compound, substituent, or parameter. Thus, the present 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. In other words, it is also further understood that any range between the endpoints within a broad range is also contemplated herein. Thus, a range of 1 to 4 also means ranges of 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0170] Furthermore, a specific amount / value of a component, compound, substituent, or parameter disclosed in the description or examples should be construed as a disclosure of either a lower or upper limit of a range and, therefore, can be combined with any other lower or upper limit of a range or specific amount / value for the same component, compound, substituent, or parameter disclosed elsewhere in this application to form a range for that component, compound, substituent, or parameter.

[0171] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents may occur that are not presently anticipated or presently unforeseeable to Applicants or others skilled in the art. Accordingly, the appended claims as filed, and the appended claims as they may be amended, are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. 1. A lubricating composition for a spark ignition engine, said lubricating composition comprising: one or more base oils of lubricating viscosity; one or more phosphorus-containing additives providing the lubricating composition with 500 ppm or less of phosphorus; a detergent system providing one or more overbased calcium-containing detergents and optionally one or more magnesium-containing detergents, the detergent system containing less than 1 weight percent of a sodium-containing detergent or no sodium-containing detergents; and one or more silicon-containing compounds providing 3 to 20 ppm of silicon to the lubricating composition; a calcium content such that the lubricating composition provides a calculated calcium sulfate ash content of 0.19 weight percent or less; a weight ratio of phosphorus content to calcium sulfate ash content of at least 0.1; no more than 30 weight percent of the total calculated SASH content is provided by said calcium sulfate ash content; the overbased calcium-containing detergent has a total base number (TBN) of at least 250 mg KOH / g as determined by ASTM D2896; A lubricating composition having a weight ratio of calcium sulfate ash content to silicon content of 250 or less.

2. 2. The lubricating composition of claim 1, wherein the weight ratio of the phosphorus content to the calcium sulfate ash content is from 0.1 to 0.3, and / or the lubricating composition has a total calculated sulfated ash content (SASH) of 0.8 weight percent or less, and / or the lubricating composition has a total calculated sulfated ash content (SASH) of 0.7 weight percent or less.

3. 3. The lubricating composition of claim 2, wherein the lubricating composition has a total calculated sulfated ash content (SASH) of 1 weight percent or less.

4. 10. The lubricating composition of claim 1, wherein the one or more silicon-containing compounds provide 5 to 15 ppm silicon.

5. 2. The lubricating composition of claim 1, wherein the silicon-containing compound is selected from organosilane compounds, fluorosilicone compounds, polydimethylsiloxane compounds, phenyl-methylpolysiloxane compounds, linear siloxane compounds, cyclic siloxane compounds, branched siloxane compounds, silicone polymers and copolymers, organo-silicone copolymers, silicone oils, or combinations thereof.

6. 2. The lubricating composition of claim 1, wherein the detergent system comprises the calcium-containing detergent and the magnesium-containing detergent, and / or the detergent system comprises a calcium sulfonate and optionally a magnesium sulfonate, and / or the detergent system is free of phenate-based detergents.

7. 7. The lubricating composition of claim 6, wherein the calcium sulfonate and the optional magnesium sulfonate are each overbased, each having a total base number (TBN) of at least 250 mg KOH / g as determined by ASTM D2896.

8. 10. The lubricating composition of claim 1, wherein the one or more base oils of lubricating viscosity are selected from API Group I base oils, API Group II base oils, API Group III base oils, or combinations thereof; and / or the one or more base oils of lubricating viscosity are selected from API Group I base oils, API Group II base oils, or combinations thereof.

9. 10. The lubricating composition of claim 1, wherein the lubricating composition exhibits an average event of 5 or less according to the Sequence IX Slow Speed ​​Pre-ignition Test of ASTM D8291 and / or a maximum event of 8 or less according to the Sequence IX Slow Speed ​​Pre-ignition Test of ASTM D8291.

10. 10. The lubricating composition of claim 1, wherein the one or more phosphorus-containing additives provide 200 to 400 ppm phosphorus.

11. 1. A method of lubricating a spark ignition engine, said method comprising: lubricating a crankcase of a spark ignition engine with a lubricating composition; (v) a calcium content providing a calculated calcium sulfate ash content of 0.19 weight percent or less; and (vi) a weight ratio of phosphorus content to calcium sulfate ash content of at least 0.1, wherein 30 weight percent or less of a total calculated SASH content is provided by the calcium sulfate ash content, and the overbased calcium-containing detergent has a content of at least 250 mg as determined by ASTM D2896. KOH / g total base number (TBN), and a weight ratio of calcium sulfate ash content to silicon content of 250 or less; The method, wherein the lubricating composition exhibits 5 or fewer average events according to the Sequence IX Slow Speed ​​Pre-ignition Test of ASTM D8291 and / or 8 or fewer maximum events according to the Sequence IX Slow Speed ​​Pre-ignition Test of ASTM D8291.

12. 12. The method of claim 11, wherein the weight ratio of the phosphorus content to the calcium sulfate ash content is between 0.1 and 0.3.

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