Boric acid detergent and lubricating applications thereof

Abstract

To provide a boron-containing detergent.SOLUTION: Disclosed herein is an overbased alkaline earth metal hydrocarbyl-substituted salicylate detergent comprising both carbonate and borate moieties and exhibiting the following characteristics: a basicity index of at least 3.8; a ratio of a soap content with respect to boron by mass% is greater than 55 mmol / kg; a soap content of at least 330 mmol / kg; a TBN, measured according to ASTM D2896, of at least 220 mg KOH / g; and a mass ratio of borate with respect to carbonate from 0.75 to 6.0, wherein the alkaline earth metal comprises calcium and / or magnesium, and the hydrocarbyl substitution comprises 9 to 30 carbon atoms. Methods of making the boron-containing salicylate detergent, specifically to be package-stable, are also disclosed, as well as package-stable lubricant additive package concentrates and lubricating oil compositions containing the same.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to boron-containing detergents, in general, and more specifically, to boric and carbonated overbasic salicylate detergents. This disclosure also relates to boron-containing detergents that preferably exhibit package stability, as well as lubricant additive package concentrates that exhibit package stability, and to methods for producing lubricating oil compositions containing such boron-containing detergents. [Background technology]

[0002] Boron can be introduced into lubricant formulations in various ways, either mixed with detergents or as an independent molecule; however, most of these forms for introducing higher levels of boron are unstable in the formulation of additive packages and / or in the preparation of formulations. Traditionally, these difficulties have been mitigated by using boron-containing dispersants. However, apart from using relatively small amounts of boron, the use of boron-containing dispersants means a greater load of the dispersant on the additive package or formulation, which can negatively affect the viscosity of the base stock / lubricant, especially as the formulation moves towards lower viscosity. It is extremely difficult to add even larger amounts of boron to the dispersant while maintaining the ability of the boron to dissociate and migrate to the lubricating surface during operation, thereby promoting the formation of a tribofilm.

[0003] While boron-containing detergents exist, they are still less stable than boron-containing dispersants, and the boron they contain tends to be practically unusable / inert. Surprisingly, it has been found that by carefully borizing certain detergents, it becomes possible to add relatively large amounts of readily available boron, even in known unstable situations (e.g., instability arising from the interaction of salicylate detergents with certain organic friction modifiers), while maintaining the relative stability of the package / formulation. By controlling not only the borooxidation process but also specific aspects of the detergent itself, it is possible to improve stable and useful boron-containing detergents, as well as additive package concentrates and formulations that contain relatively stable and readily available boron and do not suffer from significant viscosity drawbacks. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] U.S. Patent No. 4,873,009 [Patent Document 2] U.S. Patent No. 3,254,025 [Patent Document 3] U.S. Patent No. 3,502,677 [Patent Document 4] U.S. Patent No. 4,857,214 [Patent Document 5] U.S. Patent No. 4,798,684 [Patent Document 6] U.S. Patent No. 5,084,197 [Patent Document 7] U.S. Patent No. 8,048,833 [Patent Document 8] U.S. Patent No. 10,731,101 [Patent Document 9] U.S. Patent No. 2,719,125 [Patent Document 10] U.S. Patent No. 2,719,126 [Patent Document 11] U.S. Patent No. 3,087,937 [Patent Document 12] U.S. Patent No. 2,760,933 [Patent Document 13] U.S. Patent No. 2,836,564 [Patent Document 14] Strength Patent No. 3,663,561 [Patent Document 15] U.S. Patent No. 4,702,850 [Patent Document 16] U.S. Patent No. 5,840,663 [Patent Document 17] U.S. Patent Application Publication No. 2009 / 0005277 Specification [Patent Document 18] U.S. Patent No. 4,263,152 [Patent Document 19] U.S. Patent No. 4,285,822 [Patent Document 20] U.S. Patent No. 4,283,295 [Patent Document 21] U.S. Patent No. 4,272,387 [Patent Document 22] U.S. Patent No. 4,265,773 [Patent Document 23] U.S. Patent No. 4,261,843 [Patent Document 24] U.S. Patent No. 4,259,195 [Patent Document 25] U.S. Patent No. 4,259,194 [Patent Document 26] International Publication No. 94 / 06897 [Patent Document 27] U.S. Patent No. 1,815,022 [Patent Document 28] U.S. Patent No. 2,015,748 [Patent Document 29] U.S. Patent No. 2,191,498 [Patent Document 30] U.S. Patent No. 2,387,501 [Patent Document 31] U.S. Patent No. 2,655,479 [Patent Document 32] U.S. Patent No. 2,666,746 [Patent Document 33] U.S. Patent No. 2,721,877 [Patent Document 34] U.S. Patent No. 2,721,878 [Patent Document 35] U.S. Patent No. 3,250,715 [Patent Document 36] U.S. Patent No. 10,584,300 [Patent Document 37] U.S. Patent No. 5,380,508 [Patent Document 38] U.S. Patent Application Publication No. 2015 / 0005208 [Non-patent literature]

[0005] [Non-Patent Document 1] American Petroleum Institute (API) publication, "Engine Oil Licensing and Certification System," Industrial Services Section, 14th edition, December 1996, Appendix 1, December 1998. [Non-Patent Document 2] Klamann, “Lubricants and Related Products”, Wiley VCH, 1984. [Non-Patent Document 3] M. Belzer, Journal of Tribology, 1992, Vol. 114, pp. 675–682. [Non-Patent Document 4] M. Belzer and S. Jahanmir, Lubrication Science, 1988, Vol. 1, pp. 3–26. [Non-Patent Document 5] CV Smallheer and R. Kennedy Smith, "Lubricant Additives", 1967, pp.1-11 [Overview of the project]

[0006] Accordingly, this disclosure relates to a perbasic alkaline earth metal hydrocarbyl-substituted salicylate detergent comprising both a carbonate portion and a borate portion. The perbasic alkaline earth metal hydrocarbyl-substituted salicylate detergent advantageously exhibits the following characteristics: a basicity index of at least 3.8; a ratio of soap content to boron in mass% greater than 55 mmol / kg; a soap content of at least 330 mmol / kg; a total base number (TBN) measured according to ASTM standard (ASTM) D2896 of at least 220 mgKOH / g; and a mass ratio of borate to carbonate of 0.75 to 6.0. Here, the alkaline earth metal comprises calcium and / or magnesium, and the number of carbon atoms in the hydrocarbyl substituent is 9 to 30. Additionally, or alternatively, overbasic alkaline earth metal hydrocarbyl-substituted salicylate detergents also exhibit at least three, at least four, or all five of the following characteristics: basicity index is 9.0 or less; soap content ratio to boron in mass% is less than 300 mmol / kg; TBN measured according to ASTM D2896 is at most 500 mgKOH / g; soap content is at most 550 mmol / kg; hydrocarbyl substituent is C 14 -C 24It contains an alkyl or alkenyl moiety. Additionally or alternatively, the overbasic alkaline earth metal hydrocarbyl-substituted salicylate detergent may exhibit one or more of the following characteristics: the boron content according to ASTM D4951 is at least 3.2% by mass; the mass ratio of borate to carbonate is 1.0 to 5.0; the alkaline earth metal content according to ASTM D4951 is at least 7.0% by mass; and the mass ratio of alkaline earth metal to boron is 1.5 to 5.5. In certain embodiments, the overbasic calcium salicylate detergent exhibits all of the following characteristics: basicity index is 5.0-8.3; soap content ratio to boron is 70-275 mmol / kg in mass%; TBN is 265-350 mgKOH / g as measured according to ASTM D2896; combined calcium and magnesium content is 7.0-12.5% ​​by mass according to ASTM D4951; boron content is 3.5-6.8% by mass according to ASTM D4951; soap content is 350-520 mmol / kg; the mass ratio of alkaline earth metals to boron is 1.7-4.5; the mass ratio of borate to carbonate is 1.6-3.0; and the hydrocarbyl substituent is C 14 -C 19 Contains an alkyl or alkenyl moiety.

[0007] This disclosure also relates to a method for producing a substantially package-stable overbasic alkaline earth metal hydrocarbyl-substituted salicylate detergent comprising both a carbonate portion and a borate portion. The method comprises the steps of: providing an oil-soluble or oil-dispersible, overbasic but unboroded alkaline earth metal hydrocarbyl-substituted salicylate detergent, the detergent being produced by reacting a mineral oil solution of acid with a stoichiometric excess amount of a neutralizing agent containing an alkaline earth metal carbonate or bicarbonate at a high temperature (e.g., 60-200°C) for a time sufficient to form an overbasic but unboroded alkaline earth metal hydrocarbyl-substituted salicylate detergent, optionally in the presence of an accelerator. The detergent has a basicity index of at least 3.5, a soap content of at least 330 mmol / kg, an alkaline earth metal content of at least 7.0% by mass as measured according to ASTM D4951, and a TBN of at least 240 mg KOH / g according to ASTM D2896. The alkaline earth metal includes calcium and / or magnesium. This overbasic but unborodized alkaline earth metal hydrocarbyl-substituted salicylate detergent contains a carbonate moiety, with the hydrocarbyl substituent having 9 to 30 carbon atoms. In an organic diluent medium containing an aprotic hydrocarbon solvent and a C1-C4 primary alcohol, and optionally, but preferably intentionally, water-free, this overbasic but unborodized alkaline earth metal hydrocarbyl-substituted salicylate detergent product is mixed with a boron source at a temperature below 100°C to form a reaction mixture. This reaction mixture is heated to a temperature above 100°C (e.g., 105°C to 225°C) at a heating rate of less than 3°C / min in a borooxidation step to form a crude borooxidized detergent product. Optionally, additional aprotic hydrocarbon solvent may be added to form another crude borooxidized detergent product. It is possible to remove the diluent and most of the water formed during the borooxidation process to form a perbasic alkaline earth metal hydrocarbyl-substituted salicylate detergent according to this disclosure.In some embodiments, the aprotic hydrocarbon solvent includes benzene, xylene, toluene, mesitylene, naphthalene, cyclohexane, cyclooctane, heptane, octane, decane, dodecane, or combinations thereof. In some embodiments, the boron source includes orthoboric acid, metaboric acid, tetraboric acid, monoammonium borate, diammonium borate, triammonium borate, C1-C4 alkyl borate, di-C1-C4 alkyl hydrogen borate, tri-C1-C4 alkyl borate, or combinations thereof.

[0008] This disclosure also relates to a lubricant additive package concentrate comprising: less than 40% by mass of a Group I, Group II, and / or Group III lubricant base stock; at least 0.5% by mass of a boron-containing overbasic calcium salicylate detergent manufactured in accordance with and / or the methods of this disclosure; at least one ashless dispersant; at least one antioxidant; at least one friction modifier; and optionally one or more additional detergents, corrosion inhibitors, anti-wear agents, seal swelling agents, defoamers, extreme pressure agents, viscosity modifiers, and pour point depressants. The at least one friction modifier in the lubricant additive package concentrate may include a substantially sulfur-free ashless organic friction modifier and / or a substantially nitrogen-free and substantially sulfur-free ashless organic friction modifier. Advantageously, the lubricant additive package concentrate can exhibit package stability for at least 12 weeks at approximately 60°C. This disclosure also relates to a lubricating oil composition comprising: at least 70% by mass of a lubricating oil base stock comprising one or more base stocks from Group I, Group II, Group III, and / or Group IV; and at least 5% by mass of a lubricant additive package concentrate in accordance with this disclosure.

[0009] The Disclosure also relates to a lubricating oil composition comprising: at least 85% by mass of a lubricating oil base stock comprising one or more base stocks from Group I, Group II, Group III, and / or Group IV; at least 0.05% by mass of a boron-containing overbasic calcium salicylate detergent manufactured in accordance with and / or the methods of the Disclosure; at least one ashless dispersant; at least one antioxidant; at least one friction modifier; and optionally, one or more additional detergents, corrosion inhibitors, anti-wear agents, seal swelling agents, adhesives, demulsifiers, defoamers, extreme pressure agents, viscosity modifiers, and pour point depressants. The cleaning agents, additive package concentrates, and lubricating oil compositions described herein are disclosed as being particularly useful for engine lubrication applications such as passenger car motor oil (PCMO) and high-load diesel (HDD) engines. However, they may also be found to be useful as lubricants in other applications, such as coolants for at least some of the electrical or electronic components of the powertrains (transmissions, etc.) of those vehicles, hybrid electric drive or fully electric drive powertrains, two-stroke and / or four-stroke marine engine lubricants, small (e.g., motorcycle, landscaping vehicle) engine lubricants as fuel additives / addpacks / compositions for vehicles or stationary engines, and functional (e.g., hydraulic) fluid applications. [Modes for carrying out the invention]

[0010] The term “comprising” or any synonym specifies the presence of the described feature, process, integer, or component, but does not exclude the presence or addition of one or more other features, processes, integers, components, or groups thereof; it is essentially a synonym for the term “including.” The expression “consisting of” or “basically from” or its synonyms may be encompassed by “comprising” or its synonyms, where “basically from” is semi-exclusive and allows for the inclusion of substances that do not significantly affect the characteristics of the composition to which it applies. The term "main mass" refers to more than 50% by mass of the composition, for example, more than 60% by mass, more than 70% by mass, 80-99% by mass, or 80-99.9% by mass, based on the mass of the composition. The term "small amount" means 50% by mass or less of the composition, based on the mass of the composition; for example, 40% by mass or less, 30% by mass or less, 20% to 0.1% by mass, or 20% to 0.001% by mass. The terms "mass%" and "mass-based%" mean, unless otherwise specified, the mass percentage of an ingredient relative to the mass of the composition (usually measured in grams), or are referred to as weight percentage ("weight%", "wt%", "weight-based%", or "%w / w").

[0011] For example, the term "active ingredient" (also referred to as "ai" or "AI") in additive components refers to a material that is neither a diluent nor a solvent / eluent. As used herein, the terms “oil-soluble” and “oil-dispersible,” or their synonyms, do not necessarily indicate that the compound or additive is soluble, dissolvable, miscible, or suspendable in an oily medium in all proportions. However, these terms mean, for example, that the compound or additive is relatively soluble or stably dispersible in the oily medium to a degree sufficient to exert its intended effect in the environment in which the medium is used. Furthermore, other components / additives may be incorporated to increase the level of incorporation of specific components / additives as needed.

[0012] The terms “base,” “part,” and “radical,” as well as their synonyms, are used interchangeably in this specification. The term "hydrocarbon" refers to a compound of a hydrogen atom and a carbon atom. A "heteroatom" is an atom other than carbon or hydrogen. When referring to "hydrocarbons," and especially "refined hydrocarbons," the hydrocarbon may also contain small amounts of one or more heteroatoms or heteroatom-containing groups (halo, especially chloro and / or fluoro, amino, amide, alkoxy, carbonyl, carboxyl, mercapto, alkylmercapto, nitrile, nitro, nitroso, sulfoxy, sulfonyl, etc.) (for example, here the heteroatom(s) does not substantially alter the hydrocarbon properties of the hydrocarbon). The term "hydrocarbyl" means a group containing a hydrogen atom and a carbon atom. Preferably, unless otherwise specified, this group consists primarily of a hydrogen atom and a carbon atom, and more preferably, of only a hydrogen atom and a carbon atom. As used herein, the term "hydrocarbyl" particularly includes "alkyl," "alkenyl," "alkynyl," "aryl," "alkalyl," and "aralkyl." A hydrocarbyl group may contain one or more heteroatoms other than carbon and hydrogen, provided that they do not affect the basic hydrocarbyl properties of the group. Those skilled in the art will recognize suitable groups (e.g., halo, especially chloro and / or fluoro, amino, amide, alkoxy, carbonyl, carboxyl, mercapto, alkylmercapto, nitrile, nitro, nitroso, sulfoxy, sulfonyl, etc.). The term "alkyl" refers to a radical of carbon and hydrogen (e.g., C1-C1). 30This means that alkyl groups in a compound are usually directly bonded to the compound via covalent bonds. Unless otherwise specified, alkyl groups may be linear (unbranched), branched, cyclic, acyclic, or partially cyclic / acyclic. Representative examples of aliphatic (saturated) alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, dimethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, docosyl, and triacontyl.

[0013] The term "alkenyl" refers to a carbon-hydrogen radical having at least one double bond (e.g., C2-C2). 30 This means that the alkenyl group in the compound is usually directly bonded to the compound via a covalent bond. Unless otherwise specified, the alkenyl group may be linear (non-branched), branched, cyclic, acyclic, or partially cyclic / acyclic. The term "alkylene" refers to a divalent hydrocarbon radical, which may be linear (non-branched), branched, cyclic, acyclic, or partially cyclic / acyclic. It typically exhibits divalentity due to covalent bonding at two different positions within the radical (or its "terminus"). Representative examples of alkylenes include, but are not limited to, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, 1-methylethylene, 1-ethylethylene, 1-ethyl-2-methylethylene, 1,1-dimethylethylene, and 1-ethylpropylene. The term "alkynyl" refers to a radical of carbon and hydrogen having at least one carbon-carbon triple bond (e.g., C2-C2). 30 ) means. The term "aryl" refers to a group containing at least one aromatic ring, such as cyclopentadiene, phenyl, naphthyl, and anthracenyl. Aryl groups are found in all hydrocarbons (e.g., C5-C5). 40) can be, but it is known that aryl groups can sometimes contain heteroatoms such as nitrogen (e.g., pyridine). The aryl group may contain one or more hydrocarbyl group substituents (if the hydrocarbyl group is "alkyl", the hydrocarbyl group substituent is considered to be an "aralkyl" group in this specification), a heteroatom, or a heteroatom-containing group. For clarity, an alkyl group having an aryl substituent is referred to herein as an "alkalyl" group, and an aryl group having an alkyl substituent is referred to herein as an "aralkyl" group.

[0014] The term "substituted" means that an atom (usually a hydrogen atom in this specification) has been replaced by another part, such as a hydrocarbyl group, a heteroatom, or a heteroatom-containing group. The term "halogen" or "halo" refers to an atom or radical of Group 17 of the periodic table, such as fluoro, chloro, bromo, and / or iodine. The term "ash-free" in relation to additives means that the additive does not contain metal atoms. In this context, boron is not considered a metal atom. The term "effective amount" in relation to additives or other functional components of a composition means, for example, in a lubricating oil composition, an amount of such additive / functional component sufficient to provide the desired functional / technical effect. The term "ppm" means one part per million of total mass. The terms "wppm" and "mass ppm" are considered interchangeable.

[0015] The term "Total Base Number," also known as "TBN," is interchangeable with the term "Base Number," for example, in relation to additive components or lubricating oil compositions. Unless otherwise specified, TBN is measured according to ASTM D2896 and expressed in units of mgKOH / g. The term "Total Acid Number," also known as "TAN," which is used in relation to additive components or lubricating oil compositions, refers to the total acid number, for example, and is measured according to ASTM D664. "Phosphorus content" is usually expressed in mass percent or ppm and is measured according to ASTM D5185 unless otherwise specified. "Sulfur content" is usually expressed in mass percent or ppm and is measured according to ASTM D2622 unless otherwise specified.

[0016] With respect to preparations containing additive packages and / or combinations of additive components (e.g., derived from dilutions of additive packages), “package stability” as used herein shall be evaluated over a period of approximately 12 weeks. Samples shall be collected in accordance with the guidelines specified in ASTM D4057. Measurements shall be performed weekly, for example, by examining a sample placed in a 100 mL graduated centrifuge tube. The first division of this centrifuge tube shall not exceed 0.05% of its volume. Measurements shall include visual evaluations, such as haze, phase separation, aggregation / suspension, gelation, “fish eye”, precipitation, and wax formation. Unless otherwise noted, measurements in week 0 shall be performed at ambient temperature (e.g., approximately 15°C to 30°C), and all measurements in other weeks shall be performed in an oven at approximately 60°C ± 5°C (samples shall be temporarily removed from the oven for visual evaluation and then returned to the oven until the final measurement in week 12). Under certain circumstances (which should always be noted), initial reading anomalies (e.g., week 0) may be updated after approximately 24 hours (updates are usually indicated by an asterisk and comment). Visual evaluations should generally be performed under both natural and relatively bright light to ensure accurate assessment. If necessary, a suitable solvent and / or cloth wipe may be applied to the outside of the container to ensure clear visibility. Acceptable package stability may be judged subjectively under certain circumstances, but compositions exhibiting package stability may typically be evaluated using only visual indicators of clear and bright ("CB") or slight haze ("SH"), and the absence of trace precipitate ("tsed"), small precipitate ("MTS"), or no precipitate at all. Some mixtures of additives (and diluents) may not be stable at additive package concentrations, but nevertheless become stable when sufficiently diluted in the formulation, i.e., exhibit "formulation stability." Compositions that do not exhibit package stability are generally undesirable because increasing the amount of diluent tends to necessitate the inclusion of several additive components, and the inclusion of components that exhibit package instability may, in some cases, lead to inconsistent composition stability and / or composition storage stability problems.

[0017] It should be understood that various essential, optimal, and conventional additive components of use may react under the conditions of formulation, blending, storage, and / or use, and that this disclosure also includes products that can or may be obtained as a result of any or all of such reactions. Furthermore, it should be understood that any upper and lower limits of the quantities, ranges, and / or ratios described herein may be combined independently. It should be further understood that any elements and / or preferred features disclosed in any aspect of this disclosure may be considered as elements and / or preferred features disclosed in any other aspect of this disclosure. Accordingly, any elements and / or preferred (and / or advantageous) features disclosed in one aspect of this disclosure may be combined independently with other elements and / or preferred (and / or advantageous) features disclosed in the same or different aspects of this disclosure.

[0018] Method for manufacturing a boron-containing, overbasic alkaline earth metal cleaning agent While there are various different methods for producing boron-containing overbasic alkaline earth metal cleaning agents, the method of the present invention described herein for producing a substantially package-stable overbasic alkaline earth metal hydrocarbyl-substituted salicylate cleaning agent containing both a carbonate and a borate portion has been found to advantageously promote package stability when the resulting cleaning agent is mixed with other additives to form a lubricant additive package. First, we can provide oil-soluble or oil-dispersible, overbasic but non-boronized alkaline earth metal hydrocarbyl-substituted salicylate detergents. The non-boronized detergent can advantageously exhibit minimum (and / or optionally maximum) basicity index, minimum (and / or optionally maximum) soap content, minimum (and / or optionally maximum) calcium content, minimum (and / or optionally maximum) TBN, etc., for example: the basicity index is at least 3.5; the soap content is at least 330 mmol / kg; the alkaline earth metal content, measured according to ASTM D4951, is at least 7.0% by mass; and the TBN, according to ASTM D2896, is at least 240 mg KOH / g. The alkaline earth metals in the non-boronized detergent can advantageously include calcium and / or magnesium. The non-boronized detergent can also advantageously include a carbonate moiety that can promote the overbasification of the alkaline earth metals in the detergent (without being constrained by theory). In non-boronized detergents, hydrocarbyl substituents can contain 9 to 30 carbon atoms.

[0019] The non-boronized detergent may be a commercially available non-boronized detergent component, or it may simply be prepared in advance by another method. Thus, the TBN of the non-boronized detergent specified above may be based on a detergent component in which the active ingredient can be less than 100% (for example, having about 25-60% by mass of diluents and / or non-detergent compounds), or the TBN may be calculated for the active ingredient portion of the detergent only (ignoring any diluents and / or non-detergent compounds incorporated into the detergent component). Unless otherwise specified, the TBN values ​​in this specification are usually determined based on the detergent component (e.g., including diluents). Strictly speaking, the "basicity index" in detergent components is defined as the ratio of basic compounds to acidic compounds in the detergent. However, it is effective to calculate the basicity index as the equivalent ratio of total alkaline earth metal compounds to the total amount of organic acid compounds. Those skilled in the art understand that in pre-mixed (arbitrarily diluted) detergents, this is frequently equivalent to the molar (concentration) ratio of total alkaline earth metals to total soap. Therefore, the "basicity index" in such detergents can be interchangeably referred to as the "metal ratio."

[0020] Overbasic but unboronized alkaline earth metal hydrocarbyl-substituted salicylate detergents can be produced by any suitable method, preferably a method that yields a detergent containing a carbonate portion. In one such exemplary method, a mineral oil solution of acid can be reacted with a stoichiometric excess amount of a neutralizing agent, preferably containing an alkaline earth metal carbonate or bicarbonate, at a temperature of about 60°C to about 200°C, optionally in the presence of an accelerator, for a sufficient time to form an overbasic but unboronized alkaline earth metal hydrocarbyl-substituted salicylate detergent. The resulting product may be filtered. When used in a neutralization step, the incorporation of a considerably excess amount of salt / base may be assisted by an "accelerator". Examples of compounds useful as accelerators include, but are not limited to, phenolic substances such as phenol, naphthol, alkylphenol, thiophenol, alkylphenol sulfide, and condensation products of formaldehyde and phenolic substances; alcohols such as methanol, 2-propanol, octanol, Cellosolve® alcohol, Carbitol® alcohol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol; amines such as aniline, phenylenediamine, phenothiazine, phenyl-β-naphthylamine, and dodecylamine; and combinations thereof. Subsequently, the aforementioned overbasic but non-boronized alkaline earth metal hydrocarbyl-substituted salicylate detergent can be mixed with a boron source in an organic diluent at an appropriate temperature of less than 100°C to form a reaction mixture. The organic diluent may contain aprotic hydrocarbon solvents and C1-C4 primary alcohols, but advantageously, little or no water may be added intentionally. "Intentionally omitting water" should be understood as excluding water that may be trapped in the solvent or primary alcohol diluent or overbasic detergent (e.g., as impurities absorbed from a humid environment, or as impurities moderately / strongly bound to carbonates and / or alkaline earth metal ions / dipoles, etc.), as well as water that can be considered treated water from, for example, boric acid decomposition, carbonate binding, and / or other elements of overbasic (but non-boronized) detergent formation.

[0021] The aprotic hydrocarbon solvent may preferably include benzene, xylene, toluene, mesitylene, naphthalene, cyclohexane, cyclooctane, heptane, octane, decane, dodecane, or combinations thereof (in particular xylene, toluene, heptane, or combinations thereof). The boron source may preferably include orthoboric acid, metaboric acid, tetraboric acid, monoammonium borate, diammonium borate, triammonium borate, dihydrogen dihydrogen C1-C4 alkyl borate, dihydrogen dihydrogen C1-C4 alkyl borate, tri-C1-C4 alkyl borate, or combinations thereof (in particular orthoboric acid, metaboric acid, dihydrogen dihydrogen C1-C4 alkyl borate, dihydrogen dihydrogen C1-C4 alkyl borate, tri-C1-C4 alkyl borate, or combinations thereof). The boron source may be added in this manner or formed in situ (for example, in the case of dihydrogen dihydrogen borate C1-C4 alkyl, hydrogen borate di-C1-C4 alkyl, and tri-C1-C4 alkyl borate, a C1-C4 primary alcohol in the medium may be at least partially reacted with, for example, orthoboric acid and / or metaboric acid to provide a reactive boron source in situ). Subsequently, the reaction mixture containing boron and the detergent may be heated in a borooxidation process at a sufficiently gentle heating rate, e.g., less than 5°C / min, less than 3°C / min, or less than 2°C / min, to a sufficiently high temperature, e.g., greater than 100°C to 275°C, or 105°C to 225°C, to form a crude borooxidation detergent product. Optionally, in some embodiments, additional aprotic hydrocarbon solvents may be added to replenish any initially added aprotic hydrocarbon solvents that may have evaporated due to the increased reaction temperature. Even with the addition of additional solvents, the mixture is still treated as forming a crude borooxidation detergent product.

[0022] Subsequently, a high proportion of the diluent and water formed during the boroxidation process can be removed by known purification techniques such as high-temperature / reduced-pressure evaporation of volatile substances, product phase separation / crystallization, and washing, to form an overbasic and borated alkaline earth metal hydrocarbyl-substituted salicylate washing agent according to this disclosure. Without being bound by theory, it is possible that a reaction may occur in the same step in which a carbonate portion is introduced into the detergent, thereby enabling the overbasification of alkaline earth metals in the detergent. However, in this disclosure, the carbonation / alkaline earth metal overbasification step is defined as a separate step from the boron introduction step (e.g., borolysis), and is performed before that step. Even the step of preparing a detergent with pre-added neutral or alkaline earth metals, and the subsequent step of introducing boron simultaneously into the alkaline earth metal content, which is intentionally increased through additional carbonation / alkaline earth metal inclusion, are still separate steps from the separately sequenced steps of the first carbonation / addition with alkaline earth metals and the second borolysis (introducing a boron-containing species into the already overbasified product of the first step). According to this disclosure, it is considered advantageous to have the alkaline earth metal loading process and the boron introduction process separate and sequentially sequenced to achieve one or more (unexpected) desirable results, for example, in alkaline earth metal retention, boron retention, detergent / component stability, additive detergent properties, down-the-line detergent-containing additive package stability, further down-the-line detergent-containing formulation stability, detergent-containing formulation performance upon addition, and / or detergent-containing formulation performance over time.

[0023] Boric acid-containing overbasic alkaline earth metal cleaning agent Boron-containing overbasic alkaline earth metal hydrocarbyl-substituted salicylate detergents according to this disclosure comprise both the carbonate and borate portions derived from the overbasication of alkaline earth metals. They may also be manufactured according to the methods described herein. Boron-containing overbasic alkaline earth metal hydrocarbyl-substituted salicylate detergents according to this disclosure are advantageous in exhibiting one or more, two or more, three or more, four or more, five or more, six or more, seven or more, eight or more, or all nine of the following characteristics:

[0024] Basicity index (metal ratio). The basicity index of the boron-containing overbasic salicylate detergent according to the present invention can be at least 3.5, for example, at least 3.6, at least 3.8; at least 4.0, at least 4.3, at least 4.7, at least 5.0, at least 5.3, or at least 5.7, and / or 12 or less, for example, 10 or less, 9.5 or less, 9.0 or less, 8.8 or less, 8.5 or less, 8.3 or less, or 8.0 or less. Therefore, the basicity indices are 3.5~12, 3.5~10, 3.5~9.5, 3.5~9.0, 3.5~8.8, 3.5~8.5, 3.5~8.3, 3.5~8.0, 3.6~12, 3.6~10, 3.6~9.5, 3.6~9.0, 3.6~8.8, 3.6~8.5, 3.6~8.3, 3.6~8.0, 3.8~12, 3.8~10, 3.8~9.5, 3 0.8~9.0, 3.8~8.8, 3.8~8.5, 3.8~8.3, 3.8~8.0, 4.0~12, 4.0~10, 4.0~9.5, 4.0~9.0, 4.0~8.8, 4.0~8.5, 4.0~8.3, 4.0~8.0, 4.3~12, 4.3~10, 4.3~9.5, 4.3~9.0, 4.3~8.8, 4.3~8.5, 4.3~8.3, 4.3~ 8.0, 4.7~12, 4.7~10, 4.7~9.5, 4.7~9.0, 4.7~8.8, 4.7~8.5, 4.7~8.3, 4.7~8.0, 5.0~12, 5.0~10, 5.0~9.5, 5.0~9.0, 5.0~8.8, 5.0~8.5, 5.0~8.3, 5.0~8.0, 5.3~12, 5.3~10, 5.3~9.5, 5.3~9.0, It is possible to have a baseness index of 5.3-8.8, 5.3-8.5, 5.3-8.3, 5.3-8.0, 5.7-12, 5.7-10, 5.7-9.5, 5.7-9.0, 5.7-8.8, 5.7-8.5, 5.7-8.3, or 5.7-8.0 (in particular, the baseness index can be at least 3.8, at least 5.0, 9.0 or less, 3.8-9.0, or 5.0-8.3).

[0025] Soap content. The soap content of the boron-containing overbasic salicylate detergent according to the present invention may be at least 300 mmol / kg, for example, at least 320 mmol / kg, at least 330 mmol / kg, at least 350 mmol / kg, at least 370 mmol / kg, at least 390 mmol / kg, at least 400 mmol / kg, or at least 420 mmol / kg, and / or the soap content may be at most 600 mmol / kg, for example, at most 570 mmol / kg, at most 550 mmol / kg, at most 530 mmol / kg, at most 520 mmol / kg, at most 500 mmol / kg, or at most 480 mmol / kg. Therefore, the soap content is as follows: 300 mmol / kg~600 mmol / kg, 300 mmol / kg~570 mmol / kg, 300 mmol / kg~550 mmol / kg, 300 mmol / kg~530 mmol / kg, 300 mmol / kg~520 mmol / kg, 300 mmol / kg~500 mmol / kg, 300 mmol / kg~480 mmol / kg, 320 mmol / kg~600 mmol / kg, 320 mmol / kg~570 mmol / kg, 320 mmol / kg~550 mmol / kg, 320 mmol / kg~530 mmol / kg, 320 mmol / kg~520 mmol / kg, 320 mmol / kg~500 mmol / kg, 320 mmol / kg~480 mmol / kg, 330 mmol / kg~600 mmol / kg. ol / kg, 330mmol / kg~570mmol / kg, 330mmol / kg~550mmol / kg, 330mmol / kg~530mmol / kg, 330mmol / kg~5 20mmol / kg, 330mmol / kg~500mmol / kg, 330mmol / kg~480mmol / kg, 350mmol / kg~600mmol / kg, 350mmol / kg kg~570mmol / kg, 350mmol / kg~550mmol / kg, 350mmol / kg~530mmol / kg, 350mmol / kg~520mmol / kg, 350m mol / kg~500mmol / kg, 350mmol / kg~480mmol / kg, 370mmol / kg~600mmol / kg, 370mmol / kg~570mmol / kg,370mmol / kg~550mmol / kg, 370mmol / kg~530mmol / kg, 370mmol / kg~520mmol / kg, 370mmol / kg~500mmol / kg , 370mmol / kg~480mmol / kg, 390mmol / kg~600mmol / kg, 390mmol / kg~570mmol / kg, 390mmol / kg~550mmol / kg , 390mmol / kg~530mmol / kg, 390mmol / kg~520mmol / kg, 390mmol / kg~500mmol / kg, 390mmol / kg~480mmol / k g, 400mmol / kg~600mmol / kg, 400mmol / kg~570mmol / kg, 400mmol / kg~550mmol / kg, 400mmol / kg~530mmol / k It is possible to set the soap content to g, 400 mmol / kg~520 mmol / kg, 400 mmol / kg~500 mmol / kg, 400 mmol / kg~480 mmol / kg, 420 mmol / kg~600 mmol / kg, 420 mmol / kg~570 mmol / kg, 420 mmol / kg~550 mmol / kg, 420 mmol / kg~530 mmol / kg, 420 mmol / kg~520 mmol / kg, 420 mmol / kg~500 mmol / kg, or 420 mmol / kg~480 mmol / kg (in particular, the soap content can be at least 330 mmol / kg, at least 370 mmol / kg, at most 550 mmol / kg, 350 mmol / kg~520 mmol / kg, or 370 mmol / kg~500 mmol / kg).

[0026] The ratio of soap content to the mass percent of boron. In the boron-containing perbasic salicylate detergent according to the present invention, the ratio of soap content to the mass percent of boron may be greater than 50 mmol / kg, for example, greater than 55 mmol / kg, greater than 58 mmol / kg, greater than 61 mmol / kg, greater than 64 mmol / kg, greater than 67 mmol / kg, or greater than 70 mmol / kg, and / or the ratio of soap content to the mass percent of boron may be less than 300 mmol / kg, for example, less than 275 mmol / kg, less than 250 mmol / kg, less than 225 mmol / kg, less than 200 mmol / kg, less than 175 mmol / kg, or less than 150 mmol / kg. Therefore, the ratio of soap content to boron mass% is as follows: 50 mmol / kg~300 mmol / kg, 50 mmol / kg~275 mmol / kg, 50 mmol / kg~250 mmol / kg, 50 mmol / kg~225 mmol / kg, 50 mmol / kg~200 mmol / kg, 50 mmol / kg~175 mmol / kg, 50 mmol / kg~150 mmol / kg, 55 mmol / kg~300 mmol / kg, 55 mmol / kg~275 mmol / kg, 55 mmol / kg~250 mmol / kg, 55 mmol / kg~225 mmol / kg, 55 mmol / kg~200 mmol / kg, 55 mmol / kg~175 mmol / kg, 55 mmol / kg~150 mmol / kg, 58 mmol / kg~300 mmol / kg, 58 mmol / kg g~275mmol / kg, 58mmol / kg~250mmol / kg, 58mmol / kg~225mmol / kg, 58mmol / kg~200mmol / kg, 58mmol / kg~1 75mmol / kg, 58mmol / kg~150mmol / kg, 61mmol / kg~300mmol / kg, 61mmol / kg~275mmol / kg, 61mmol / kg~250m mol / kg, 61mmol / kg~225mmol / kg, 61mmol / kg~200mmol / kg, 61mmol / kg~175mmol / kg, 61mmol / kg~150mmol / kg, 64mmol / kg~300mmol / kg, 64mmol / kg~275mmol / kg, 64mmol / kg~250mmol / kg, 64mmol / kg~225mmol / kg,64mmol / kg~200mmol / kg, 64mmol / kg~175mmol / kg, 64mmol / kg~150mmol / kg, 67mmol / kg~300mmol / kg, 67mmol / kg~275mmol / kg, 67mmol / kg~250mmol / kg, 67mmol / kg~225mmol / kg, 67mmol / kg~200mmol / kg, 67mmol / kg~175mmol / kg, 67mmol / kg~150mmol / kg, 70mmol / kg~300mmol / kg, 70mmol / kg~275 The possible concentrations are mmol / kg, 70 mmol / kg to 250 mmol / kg, 70 mmol / kg to 225 mmol / kg, 70 mmol / kg to 200 mmol / kg, 70 mmol / kg to 175 mmol / kg, or 70 mmol / kg to 150 mmol / kg (in particular, the ratio of soap content to boron mass% can be greater than 55 mmol / kg, less than 300 mmol / kg, 55 mmol / kg to 300 mmol / kg, 70 to 275 mmol / kg, or 55 mmol / kg to 200 mmol / kg).

[0027] Total base number (TBN) measured according to ASTM D2896. The TBN of the boron-containing overbasic salicylate detergent according to the present invention is at least 220 mg KOH / g, for example, at least 235 mg KOH / g, at least 250 mg KOH / g, at least 265 mg KOH / g, or at least 280 mg KOH / g, and / or the TBN can be at most 500 mg KOH / g, for example, at most 470 mg KOH / g, at most 440 mg KOH / g, at most 410 mg KOH / g, at most 380 mg KOH / g, at most 350 mg KOH / g, or at most 320 mg KOH / g.Therefore, TBN is 220mgKOH / g~500mgKOH / g, 220mgKOH / g~470mgKOH / g, 220mgKOH / g~440mgKOH / g, 220mgKOH / g~410mgKOH / g, 220mgKOH / g~380mgKOH / g, 220mgKOH / g~350mgKOH / g, 220mgKOH / g~320mgKOH / g, 235mgKOH / g~500mgKOH / g, 235mgKOH / g~470mgKOH / g, 235mgKOH / g~440mg gKOH / g, 235mgKOH / g~410mgKOH / g, 235mgKOH / g~380mgKOH / g, 235mgKOH / g~350mgKOH / g, 235mgKOH / g~320mgKOH / g, 250mgKOH / g~500mg KOH / g, 250mgKOH / g~470mgKOH / g, 250mgKOH / g~440mgKOH / g, 250mgKOH / g~410mgKOH / g, 250mgKOH / g~380mgKOH / g, 250mgKOH / g~350mgK OH / g, 250mgKOH / g~320mgKOH / g, 265mgKOH / g~500mgKOH / g, 265mgKOH / g~470mgKOH / g, 265mgKOH / g~440mgKOH / g, 265mgKOH / g~410mgKO H / g, 265mgKOH / g~380mgKOH / g, 265mgKOH / g~350mgKOH / g, 265mgKOH / g~320mgKOH / g, 280mgKOH / g~500mgKOH / g, 280mgKOH / g~470mgKOH It is possible to have concentrations of 280mgKOH / g to 440mgKOH / g, 280mgKOH / g to 410mgKOH / g, 280mgKOH / g to 380mgKOH / g, 280mgKOH / g to 350mgKOH / g, or 280mgKOH / g to 320mgKOH / g (in particular, TBN can be at least 220mgKOH / g, at most 500mgKOH / g, 235mgKOH / g to 440mgKOH / g, or 265mgKOH / g to 350mgKOH / g).

[0028] Boron content in accordance with ASTM D4951. The boron content of the boron-containing perbasic salicylate detergent according to the present invention may be at least 3.0% by mass, for example, at least 3.2% by mass, at least 3.4% by mass, at least 3.5% by mass, at least 3.6% by mass, or at least 3.7% by mass, and / or the boron content may be at most 7.0% by mass, at most 6.8% by mass, at most 6.6% by mass, at most 6.4% by mass, at most 6.2% by mass, or at most 6.0% by mass. Therefore, the boron content is 3.0 mass% to 7.0 mass%, 3.0 mass% to 6.8 mass%, 3.0 mass% to 6.6 mass%, 3.0 mass% to 6.4 mass%, 3.0 mass% ~6.2 mass%, 3.0 mass%~6.0 mass%, 3.2 mass%~7.0 mass%, 3.2 mass%~6.8 mass%, 3.2 mass%~6.6 mass%, 3.2 mass%~6.4 Mass%, 3.2 mass% to 6.2 mass%, 3.2 mass% to 6.0 mass%, 3.4 mass% to 7.0 mass%, 3.4 mass% to 6.8 mass%, 3.4 mass% to 6.6 mass%, 3.4 mass% to 6.4 mass%, 3.4 mass% to 6.2 mass%, 3.4 mass% to 6.0 mass%, 3.5 mass% to 7.0 mass%, 3.5 mass% to 6.8 mass%, 3.5 quality The boron content can be 3.5% to 6.4% by mass, 3.5% to 6.2% by mass, 3.5% to 6.0% by mass, 3.6% to 7.0% by mass, 3.6% to 6.8% by mass, 3.6% to 6.6% by mass, 3.6% to 6.4% by mass, 3.6% to 6.2% by mass, 3.6% to 6.0% by mass, 3.7% to 7.0% by mass, 3.7% to 6.8% by mass, 3.7% to 6.6% by mass, 3.7% to 6.4% by mass, 3.7% to 6.2% by mass, or 3.7% to 6.0% by mass (in particular, the boron content can be at least 3.2% by mass, 3.2% to 6.0% by mass, or 3.5% to 6.8% by mass).

[0029] The properties of overbasic detergents prepared using different starting materials and synthesis methods can be compared based on the mass ratio of borate to carbonate in the boron-containing detergent of the present invention. Depending on the boron source and reaction conditions used, numerous metal borates can be formed. For example, as is well known in the art, the term "calcium borate" includes compounds such as calcium metaborate (CaB2O4), gray borate (CaB3O4(OH)3·H2O), calcium tetraborate (CaB4O7), and mixtures thereof. Since the equivalent amount of boron to calcium varies among these forms, a practical way to characterize the content of these salts in a detergent composition is to quantify the relative contribution of these forms to the total base number (TBN). Those skilled in the art may routinely estimate the total base number (TBN) of a detergent, the contribution of basic soap to this TBN, and the contribution of metal carbonate to the TBN using conventional titration methods. Therefore, the basic borate content can be easily estimated as follows: borate (mgKOH / g) = total base number (mgKOH / g) - basic soap content (mgKOH / g) - metal carbonate (mgKOH / g). From this formula, the mass ratio of borate to carbonate is simply the ratio of the borate content to the carbonate content.

[0030] Those skilled in the art are familiar with titration methods for estimating the borate:carbonate ratio. For example, by digesting a known amount of overbasic detergent with an excess amount of perchloric acid and then titrating with potassium hydroxide, one or two inflection points can be expected. Such a method is known as back titration. The amount of potassium hydroxide required to reach the first inflection point corresponds to the base contribution of the sample, and this amount of potassium hydroxide can be used to calculate the total TBN value. Since the soap used to form the overbasic detergent also contributes to the total base number of the sample, the presence of acid in the mixture after digesting the basic soap with perchloric acid can be determined from the second inflection point. This value can be used to determine the contribution of the basic soap to the total TBN of the detergent. Finally, the metal carbonate content is generally measured by digesting a known amount of overbasic detergent with acid to liberate carbon dioxide. The liberated gas is captured in the solution. The carbonated solution can then be titrated to measure the amount of liberated CO2, and thus the metal carbonate content of the detergent sample. This method allows for the measurement of the total base number (TBN), basic soap content, and metal carbonate content of a detergent sample. As described above, the borate content can be determined by a simple calculation, and therefore the mass ratio of borate to carbonate can be calculated. These measurement methods will be explained below in relation to Example A4.

[0031] The mass ratio of borate to carbonate (usually calculated as a salt). In the boron-containing overbasic salicylate detergent according to the present invention, the mass ratio of borate to carbonate is 0.75~6.0, 0.75~5.5, 0.75~5.0, 0.75~4.5, 0.75~4.0, 0.75~3.5, 0.75~3.0, 1.0~6.0, 1.0~5.5, 1.0~5.0, 1.0~4.5, 1.0~4.0, 1.0~3.5, 1. The ratios can be 0-3.0, 1.3-6.0, 1.3-5.5, 1.3-5.0, 1.3-4.5, 1.3-4.0, 1.3-3.5, 1.3-3.0, 1.6-6.0, 1.6-5.5, 1.6-5.0, 1.6-4.5, 1.6-4.0, 1.6-3.5, or 1.6-3.0 (in particular, the mass ratio of borate to carbonate can be 0.75-6.0, 1.0-5.0, or 1.6-3.0).

[0032] Alkaline earth metals. The boron-containing overbasic salicylate detergent according to the present invention may contain calcium and / or magnesium as alkaline earth metals (one or more). The alkaline earth metal content in the boron-containing overbasic salicylate detergent according to the present invention may be at least 6.0% by mass, at least 6.5% by mass, at least 7.0% by mass, at least 7.5% by mass, or at least 8.0% by mass, and / or the alkaline earth metal content may be at most 13% by mass, at most 12.7% by mass, at most 12.4% by mass, at most 12.1% by mass, at most 11.8% by mass, or at most 11.5% by mass. Therefore, the alkaline earth metal (for example, a combination of calcium and magnesium) content is 6.0% to 13% by mass, 6.0% to 12.7% by mass, 6.0% to 12.4% by mass, 6.0% to 12.1% by mass, 6.0% to 11.8% by mass, 6.0% to 11.5% by mass, 6.5% to 13% by mass, and 6.5% by mass. Amount% ~ 12.7% by mass, 6.5% by mass ~ 12.4% by mass, 6.5% by mass ~ 12.1% by mass, 6.5% by mass ~ 11.8% by mass, 6.5% by mass ~ 11.5% by mass, 7.0 Mass% ~ 13% by mass, 7.0% by mass ~ 12.7% by mass, 7.0% by mass ~ 12.4% by mass, 7.0% by mass ~ 12.1% by mass, 7.0% by mass ~ 11.8% by mass, 7.0 quality It is possible to have a content of % to 11.5 mass%, 7.5 mass% to 13 mass%, 7.5 mass% to 12.7 mass%, 7.5 mass% to 12.4 mass%, 7.5 mass% to 12.1 mass%, 7.5 mass% to 11.8 mass%, 7.5 mass% to 11.5 mass%, 8.0 mass% to 13 mass%, 8.0 mass% to 12.7 mass%, 8.0 mass% to 12.4 mass%, 8.0 mass% to 12.1 mass%, 8.0 mass% to 11.8 mass%, or 8.0 mass% to 11.5 mass% (in particular, the alkaline earth metal content and / or the total content of calcium and magnesium can be at least 7.0 mass%, 7.0 mass% to 12.5 mass%, or 6.5 mass% to 11.8 mass%).

[0033] Hydrocarbyl substitution. In particular, the boron-containing overbased salicylate detergent according to the present invention has 9 to 30 carbon atoms and contains a C 14 -C 24 alkyl or alkenyl moiety, or can have a hydrocarbyl substituent containing a C 14 -C 19 alkyl or alkenyl moiety.

[0034] Mass ratio of alkaline earth metal to boron. In the boron-containing overbased salicylate detergent according to the present invention, the mass ratio of alkaline earth metal to boron is 1.3 to 5.8, 1.3 to 5.5, 1.3 to 5.2, 1.3 to 4.9, 1.3 to 4.7, 1.3 to 4.5, 1.3 to 4.2, 1.3 to 3.9, 1.3 to 3.6, 1.3 to 3.3, 1.5 to 5.8, 1.5 to 5.5, 1.5 to 5.2, 1.5 to 4.9, 1.5 to 4.7, 1.5 to 4.5, 1.5 to 4.2, 1.5 to 3.9, 1.5 to 3.6, 1.5 to 3.3, 1.6 to 5.8, 1.6 to 5.5, 1.6 to 5.2, 1.6 to 4.9, 1.6 to 4.7, 1.6 to 4.5, 1.6 to 4.2, 1.6 to 3.9, 1.6 to 3.6, 1.6 to 3.3, 1.7 to 5.8, 1.7 to 5.5, 1.7 to 5.2, 1.7 to 4.9, 1.7 to 4.7, 1.7 to 4.5, 1.7 to 4.2, 1.7 to 3.9, 1.7 to 3.6, or 1.7 to 3.3 (particularly, 1.3 to 5.8, 1.5 to 5.5, 1.7 to 4.5, or 1.6 to 3.6).

[0035] The compositions and methods described herein use multiple overbased alkaline earth metal hydrocarbyl-substituted salicylate detergents of various specifications for various parameters, but boration can be carried out in any detergent using any valence ion based on, for example, an alkali metal, a Group 13 metal, or an ashless ion (such as an ammonium ion, etc.), regardless of whether it is overbased, neutral, undervased, or whether it contains an alkaline earth metal or not, and can also be carried out in any detergents such as sulfonates, phenates, or carboxylates. Neutral detergents generally contain a stoichiometrically equal amount of (alkaline earth metal) ions relative to the amount of (Lewis) acidic portion present in the detergent. Underbase detergents generally contain a stoichiometrically small amount of (alkaline earth metal) ions relative to the amount of (Lewis) acidic portion present in the detergent. Therefore, neutral and underbase detergents are generally less basic than their overbasic counterparts. For example, the term "overbasic" in relation to detergents is used to indicate that the (alkaline earth metal) ions are present in a stoichiometrically greater amount than the corresponding (Lewis) acidic component.

[0036] In particular, the boron-containing perbasic salicylate detergent according to the present invention may be included in various lubricating oil compositions in amounts appropriate to the application of the lubricant, for example, 0.03 to 6.0% by mass, 0.05 to 0.7% by mass, 0.07 to 2.0% by mass, or 0.10 to 4.0% by mass relative to the total mass of the composition. Additionally or alternatively, the boron-containing perbasic salicylate detergent may be included in the lubricating oil composition in an amount sufficient to impart calcium of 30 to 2000 parts per million by mass (ppm), particularly 45 to 750 ppm, 100 to 1400 ppm, or 500 to 1800 ppm, relative to the mass of the composition. Additionally or alternatively, boron-containing overbasic salicylate detergents may be included in the lubricating oil composition in an amount sufficient to impart 20 to 500 ppm, particularly 30 to 200 ppm, 60 to 350 ppm, or 100 to 450 ppm relative to the mass of the composition. The boron and / or calcium content can be measured according to ASTM D4951.

[0037] Non-calcium salicylate cleaning agents In some embodiments, the additive package and / or lubricating oil composition may further contain detergents other than one or more boron-containing perbasic alkaline earth metal salicylates according to the Disclosure. In other embodiments, the additive package and / or lubricating oil composition may further substantially not contain any other detergents other than the boron-containing perbasic alkaline earth metal salicylates according to the Disclosure. If the lubricating oil composition contains additional detergents, the detergents may be non-borodic alkaline earth metal detergents, such as non-borodic but overbasic alkaline earth metal detergents. These detergents are usually sufficiently oil-soluble or oil-dispersible so that they remain dissolved or dispersed in the oil and can move to the intended site of action by the oil. Other non-borodic detergents are also known in the art and include neutral and overbasic alkaline earth metal (e.g., calcium and / or magnesium) salts containing acidic substances such as sulfonic acids, carboxylic acids, alkylphenols, alkylphenol sulfides, and mixtures thereof. If additional or alternative non-borodic detergents are present, the additional non-borodic detergents may include or be salicylates of neutral or overbasic non-borodic alkaline earth metal salicylates.

[0038] Examples of additional non-boron cleaning agents useful with boron-containing overbasic alkaline earth metal salicylates in the lubricant additive package concentrates and / or lubricating oil compositions of this disclosure include: neutral and / or overbasic salts of substances such as alkaline earth metal phenates; alkaline earth metal phenates (e.g., each aromatic group has one or more aliphatic groups to impart hydrocarbon solubility); alkaline earth metal sulfons (e.g., each sulfonic acid moiety is bonded to an aromatic nucleus, which then typically contains one or more aliphatic substituents to impart hydrocarbon solubility); hydrolyzed phosphosulfides (phosphosul Alkaline earth metal salts of furized olefins (e.g., having 10 to 2000 carbon atoms), and / or hydrolyzed phosphosulfide alcohols and / or aliphatic-substituted phenolic compounds (e.g., 10 to 2000 carbon atoms); alkaline earth metal salts of aliphatic carboxylic acids and / or aliphatic-substituted cycloaliphatic carboxylic acids; non-borodic alkaline earth metal hydrocarbyl-substituted salicylates (e.g., 10 to 1000 carbon atoms); further combinations thereof and / or reaction products; and many other similar alkaline earth metal salts of oil-soluble organic acids are, but are not limited thereto. If necessary, mixtures of two or more different non-salicylic acid neutral and / or overbasic salts may be used (e.g., one or more overbasic calcium phenates and one or more overbasic calcium sulfonates). Optionally, boron-containing neutral or overbasic non-salicylate detergents may be included in the additive package and / or lubricating oil composition in place of, or in addition to, any additional non-borodic detergents.

[0039] Methods for producing oil-soluble neutral and overbasic non-alkaline earth metal cleaning agents are well known to those skilled in the art and have been extensively reported in patent documents. If a combination of boron-containing alkaline earth metal salicylate and additional detergents exists, they may together impart to the lubricating oil composition 30 to 2000 parts per million (ppm), particularly 45 to 750 ppm, 100 to 1400 ppm, or 500 to 1800 ppm of calcium relative to the mass of the composition. Further or alternatively, boron-containing overbasic salicylate detergents may be included in the lubricating oil composition in amounts sufficient to impart to the composition 20 to 500 ppm, particularly 30 to 200 ppm, 60 to 350 ppm, or 100 to 450 ppm, relative to the mass of the composition. The boron and / or calcium content can be measured according to ASTM D5185.

[0040] Lubricant base stock / diluent The lubricating oil base stock / diluent in boron-containing detergent components, boron-containing detergent-containing lubricating additive package concentrates, and / or boron-containing detergent-containing lubricating oil compositions may be any suitable lubricating oil base stock known in the art. Both natural and synthetic lubricating oil base stocks can be suitable base stocks. Natural lubricating oils include animal oils, vegetable oils (e.g., castor oil and lard), petroleum, mineral oils, coal or shale-derived oils, and combinations thereof. A particular natural lubricating oil may contain or be a mineral oil. Suitable mineral oils may include all common mineral oil base stocks, including oils that are naphthenic or paraffinic in their chemical structure. Suitable oils may be refined by conventional methods using acids, alkalis, and clay or other agents such as aluminum chloride, or the oils may be extracted oils produced by solvent extraction using solvents such as phenol, sulfur dioxide, furfural, dichlorodiethyl ether, or a combination thereof. The oils may be subjected to hydrotreatment or hydrorefining, degreasing by cooling or catalytic degreasing, hydrocracking, or a combination of these. Suitable mineral oils may be produced from natural crude oil sources or may consist of isomerized wax materials or residues from other refining processes.

[0041] Examples of synthetic lubricant base stocks include hydrocarbon oils and halo-substituted hydrocarbon oils such as oligomerized, polymerized, and interpolymerized olefins (e.g., polybutylene, polypropylene, propylene, isobutylene copolymers, chlorinated polylactene, poly(1-hexene), poly(1-octene), poly-(1-decene), etc., and mixtures thereof); alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene, etc.); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyl, etc.); alkylated diphenyl ethers, alkylated diphenyl sulfides, and their derivatives, analogs, and homologs, etc.; and combinations thereof and / or reaction products. In some embodiments, the oils derived from this class of synthetic oil base stocks may include, or be, polyalphaolefins (PAOs) containing hydrogenated oligomers of α-olefins, particularly 1-decene oligomers, produced, for example, by a free radical method, a Ziegler catalyst, or a cationic catalyst. These may be, for example, branched or linear α-olefin oligomers having 2 to 16 carbon atoms, and certain non-limiting examples include polypropene, polyisobutene, poly-1-butene, poly-1-hexene, poly-1-octene, poly-1-decene, poly-1-dodecene, and mixtures thereof, and / or interpolymers / copolymers.

[0042] The synthetic lubricant base stock may additionally or alternatively include alkylene oxide polymers, interpolymers, copolymers, and derivatives thereof, in which any (most) terminal hydroxyl groups are modified by esterification, etherification, etc. Examples of synthetic oils in this class include: polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide; alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether with a number-average molecular weight (Mn) of about 1000 daltons, diphenyl ethers of polypropylene glycol with an average Mn of about 1000 to about 1500 daltons); and mono- and poly-carboxylic acid esters thereof (e.g., acetate esters (single or multiple) of tetraethylene glycol, mixed C3-C8 fatty acid esters, 12 Examples include oxo acid diesters (single or multiple), or combinations thereof. Another preferred class of synthetic lubricant base stocks includes esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acid and alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc.) with various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelaate, diisodecyl azelaate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, composite esters formed by reacting 1 mole of sebacate with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid, and combinations thereof. Preferred types of synthetic oil-derived oils in this class are C4-C 12 It may contain alcohol adipine salts. As esters useful as synthetic lubricant base stocks, additionally or alternatively, C5-C 12 Examples include monocarboxylic acids, polyols, and / or polyol ethers, such as neopentyl glycol, trimethylolpropanepentaerythritol, dipentaerythritol, tripentaerythritol, and esters formed from combinations thereof.

[0043] Lubricating oil base stocks may be derived from unrefined oil, refined oil, re-refined oil, or mixtures thereof. Unrefined oils are obtained directly from natural or synthetic sources (e.g., coal, shale, or tar sand bitumen) without further refining or processing. Examples of unrefined oils include shale oil obtained directly from retorting, petroleum obtained directly from distillation, or ester oils obtained directly from esterification, each or a combination thereof may be used without further processing. Refined oils are similar to unrefined oils, except that they are typically processed in one or more refining steps to alter their chemical structure and / or improve one or more properties. Preferred refining techniques include distillation, hydrotreatment, degreasing, solvent extraction, acid or base extraction, filtration, and percolation, all of which are known to those skilled in the art. Re-refined oils may be obtained by processing used oil and / or refined oil in the same manner as that used to obtain the initially refined oil. Such refined oils may also be known as recycled oils or reprocessed oils, and in many cases may be further treated by techniques to remove used additives and oil hydrolysates. Another additional or alternative class of suitable lubricating oil base stocks may include base stocks produced from oligomerization of natural gas feedstocks or isomerization of waxes. These base stocks can be referred to in many ways, but are generally known as gas-to-liquid (GTL) base stocks or Fischer-Tropsch base stocks. Lubricant base stocks in accordance with this disclosure may be of similar or different types, or may be formulations of one or more of the lubricants / base stocks described herein, and this disclosure explicitly intends for formulations of natural and synthetic lubricants (i.e., partially synthetic).

[0044] Lubricants can be classified as described in the American Petroleum Institute (API) publication "Engine Oil Licensing and Certification System," Industrial Services Section, 14th edition, December 1996, Appendix 1, December 1998, in which lubricants are classified as follows: a) Group I base stocks contain less than 90% saturates and / or more than 0.03% sulfur, and have a viscosity index of 80 or more and less than 120; b) The Group II base stock contains 90% or more saturation and 0.03% or less sulfur, and has a viscosity index of 80 or more and less than 120; c) Group III base stocks contain 90% or more saturation content and 0.03% or less sulfur, and have a viscosity index of 120 or higher; d) The Group IV base stock is polyalphaolefin (PAO); and e) Group V base stocks include all other base stock oils not included in Groups I, II, III, or IV.

[0045] In embodiments of the present disclosure, the lubricating oil base stock may include or be mineral oils or mixtures of mineral oils, particularly mineral oils of Group II and / or Group III (API classification). Additionally or alternatively, the lubricating oil base stock may include or be synthetic oils such as Fischer-Tropsch / GTL oils of any group, polyalphaolefins (Group IV), and / or Group V oils. In embodiments where the viscosity of the desired formulation is very low (e.g., less than 4.0 cSt or less than 3.5 cSt), the lubricating oil base stock may advantageously be a Group IV (polyalphaolefin) base stock or a mixture of Group IV base stocks, or comprise at least 40% by mass (e.g., at least 50%, at least 60%, at least 70%, at least 80%, or at least 90%) of one or more Group IV base stocks.

[0046] In some embodiments, the lubricating oil base stock(s) are individually or collectively measured to have a kinematic viscosity (KV100) at 100°C as measured by ASTM D445 between 1.0 cSt and 40 cSt (e.g., 1.0 cSt to 30 cSt, 1.0 cSt to 20 cSt, 1.0 cSt to 15 cSt, 1.0 cSt to 10 cSt, 1.0 cSt to 8.5 cSt, 1.0 cSt to 7.5 cSt, 1.0 cSt to 6.5 cSt, 1.0 cSt to 5.5 cSt, 1.0 cSt to 5.0 cSt, 1.0 cSt to 4.5 cSt, 1.0 cSt to 4.0 cSt, 1.0 cSt to 3.5 cSt, 1.0 cSt to 3.0 cSt, 1.0 cSt to 2.5 cSt). , 1.0cSt~2.0cSt, 1.5cSt~30cSt, 1.5cSt~20cSt, 1.5cSt~15cSt, 1.5cSt~10cSt, 1.5cSt~8.5cSt, 1.5cSt~7.5cSt, 1.5cSt~6.5cSt, 1.5cSt~5.5 cSt, 1.5cSt~5.0cSt, 1.5cSt~4.5cSt, 1.5cSt~4.0cSt, 1.5cSt~3.5cSt, 1.5cSt~3.0cSt, 1.5cSt~2.5cSt, 2.0cSt~30cSt, 2.0cSt~20cSt, 2.0cS t~15cSt, 2.0cSt~10cSt, 2.0cSt~8.5cSt, 2.0cSt~7.5cSt, 2.0cSt~6.5cSt, 2.0cSt~5.5cSt, 2.0cSt~5.0cSt, 2.0cSt~4.5cST, 2.0cSt~4.0cST, 2.0cSt~3.5cST, 2.0cSt~3.0cST, 2.5cSt~30cST, 2.5cSt~20cSt, 2.5cSt~15cSt, 2.5cSt~10cSt, 2.5cSt~8.5cSt, 2.5cSt~7.5cSt, 2.5cSt~6.5c St, 2.5cSt~5.5cSt, 2.5cSt~5.0cSt, 2.5cSt~4.5cSt, 2.5cSt~4.0cSt, 2.5cSt~3.5cSt, 3.0cSt~30cSt, 3.0cSt~20cSt, 3.0cSt~15cSt, 3.0cSt~ 10cSt, 3.0cSt~8.5cSt, 3.0cSt~7.5cSt, 3.0cSt~6.5cSt, 3.0cSt~5.5cSt, 3.0cSt~5.0cSt, 3.0cSt~4.5cSt, 3.0cSt~4.0cSt, 4.0cSt~30cSt, 4.The cst values ​​are 0cSt to 20cSt, 4.0cSt to 15cSt, 4.0cSt to 10cSt, 4.0cSt to 8.5cSt, 4.0cSt to 7.5cSt, 4.0cSt to 6.5cSt, 4.0cSt to 5.5cSt, or 4cSt to 5.0cSt), and may particularly be 1.5cSt to 40cSt, 2.0cSt to 20cSt, 2.5cSt to 10cSt, or 4.0cSt to 40cSt.

[0047] Non-cleaning agent additives Co-additives commonly found in lubricating oils may optionally be included in additive packages and / or lubricating oil compositions in accordance with this disclosure. Suitable co-additives are known to those skilled in the art. Several examples are described herein.

[0048] Ashless dispersant In some embodiments, the additive package concentrate and / or lubricating oil composition may further contain one or more basic nitrogen-containing ashless dispersants. In fact, when such nitrogen-containing ashless dispersants (one or more) are present, the nitrogen-containing ashless dispersants may advantageously have the following structure (I): [ka] In the formula, R1 and R2 are each independently a hydrocarbyl group (for example, a polyisobutenyl moiety having a number-average molecular weight (Mn) of 500-5000 daltons or 750-2500 daltons, as determined by gel permeation chromatography (GPC) with respect to a linear polystyrene standard, and / or a hydrocarbon group produced by metallocene catalytic polymerization of α-olefin feedstock oil consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-octadecene, or mixtures thereof, particularly 1-octene, 1-decene, 1-dodecene, and mixtures thereof, also known as metallocene-catalyzed poly(α-olefin) or mPAO, and these, linear Mn, determined by GPC based on the standard polystyrene, is 300-20000 daltons, e.g., 400-15000 daltons, 450-10000 daltons, 500-8000 daltons, 650-6500 daltons, 800-5000 daltons, or 900-3000 daltons; in particular, 300-20000 daltons, 500-8000 daltons, or 800-5000 daltons); each R3 is independently a hydrogen, acetyl moiety, or moiety formed by the reaction between ethylene carbonate and >N-R3 (in particular, a hydrogen or acetyl moiety); y is 1-10 (in particular, 3-10), and is the same for all molecules of structure (I), or the average value of all molecules of structure (I) in a mixture of molecules of structure (I).

[0049] Examples of such ashless dispersants include polyisobutenyl succinimide, mPAO-based succinimide, polyisobutenyl succinamide, mPAO-based succinamide, mixed esters / amides of polyisobutenyl-substituted succinic acid, mixed esters / amides of mPAO-substituted succinic acid (mPAOSA), hydroxyesters of polyisobutenyl-substituted succinic acid, hydroxyesters of mPAO-substituted succinic acid, hydrocarbyl-substituted phenol, formaldehyde, and Mannich condensation products of polyamines, as well as reaction products and mixtures thereof. Such basic nitrogen-containing ashless dispersants may be used as lubricant additives, and their preparation methods are extensively described in the patent literature. Examples of ashless dispersants of structure (I) include polyisobutenyl and / or mPAO succinimide and succinamide, where the polyisobutenyl and / or mPAO substituent(s) are long hydrocarbon chains with more than 36 carbon atoms, for example, more than 40. These polyisobutenyl (PIB)-based materials can be readily produced by reacting a polyisobutenyl-substituted dicarboxylic acid material with an amine-functionalized molecule. These mPAO-based materials can be readily produced by reacting mPAO functionalized with a dicarboxylic acid or mPAO functionalized with an anhydride (e.g., reacted maleic acid) with an amine-functionalized molecule. Examples of suitable amines in either or both of these production examples include polyamines such as polyalkylene polyamines, hydroxy-substituted polyamines, polyoxyalkylene polyamines, and combinations thereof. Amine functionality may be imparted by polyalkylene polyamines such as tetraethylenepentamine and pentaethylenehexamine. Mixtures with an average number of nitrogen atoms per polyamine molecule exceeding 7 are also available. These are generally referred to as heavy-chain polyamines or H-PAMs and are commercially available under trade names such as HPA(trademark) and HPA-X(trademark) from Dow Chemical and E-100(trademark) from Huntsman Chemical. Examples of hydroxy-substituted polyamines include N-hydroxyalkyl-alkylene polyamines such as N-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)piperazine, and / or N-hydroxyalkylated alkylenediamine, as described in U.S. Patent No. 4,873,009. Examples of polyoxyalkylene polyamines include polyoxyethylene, polyoxypropylenediamine, and triamines with an average Mn of approximately 200 to 2500 daltons. Some products of this type are commercially available under the trade name Jeffamine(trademark).

[0050] As is well known in the art, the reaction between an amine and a polyisobutenyl-substituted and / or mPAO-functionalized dicarboxylic acid material (preferably alkenyl succinic anhydride or maleic anhydride) can be conveniently carried out by heating the reactants together, for example, in an oil solution. Typically, the reaction temperature may be about 100°C to about 250°C, and the reaction time may be about 1 hour to about 10 hours. The reaction ratio can vary considerably, but generally, a dicarboxylic acid unit content of about 0.1 to about 1.0 equivalents per reaction equivalent of the amine-containing reactant may be used. In particular, when an ashless dispersant is present, examples of ashless dispersants include polyisobutenyl succinimide formed from polyisobutenyl succinic anhydride and polyalkylene polyamines such as tetraethylenepentamine or H-PAM, mPAO-based succinimide formed from succinic anhydride-functionalized mPAO and polyalkylene polyamines such as tetraethylenepentamine or H-PAM, or combinations thereof or reaction products thereof. These dispersants may be further treated (e.g., with secondary nitrogen capping agents such as acetic anhydride and / or ethylene carboxylate, with borolysis / boration agents, and / or phosphorus inorganic acids) as with other dispersants known in the art. Preferred examples are found, for example, in U.S. Patent No. 3,254,025, No. 3,502,677, and No. 4,857,214.

[0051] When used, the ashless dispersant according to structure (I) may be included in an amount of 0.1 to 30% by mass, for example, 0.5 to 25% by mass, or 1.0 to 20% by mass, based on the total mass of the additive package concentrate and / or the lubricating oil composition. While boron oxidation of dispersants is known and sometimes desirable, in certain embodiments, the dispersant(s) of structure (I) may individually (together), and in practice, all components (as a whole) of the additive package concentrate and / or lubricating oil composition according to this disclosure may contain 20 to 500 ppm, particularly 30 to 200 ppm, 60 to 350 ppm, or 100 to 450 ppm relative to the mass of the composition. The boron content can be measured according to ASTM D5185.

[0052] Antioxidants Antioxidants, sometimes called antioxidants, can increase (or decrease) the resistance of lubricant compositions to oxidation. Antioxidants act by binding to and modifying oxidizing agents such as peroxides and other free radical-forming compounds, rendering them harmless, for example, by decomposing the oxidizing agent, or by inactivating oxidation catalysts or accelerators. Oxidative degradation can occur due to sludge in the fluid with increasing usage, varnish-like deposits on metal surfaces, and sometimes increased viscosity.

[0053] A variety of antioxidants useful in lubricating oil compositions. See, for example, Klamann, "Lubricants and Related Products," Wiley VCH, 1984; U.S. Patent No. 4,798,684; and U.S. Patent No. 5,084,197. Examples of suitable antioxidants include, but are not limited to, copper-containing antioxidants, sulfur-containing antioxidants, aromatic amine-containing and / or amide-containing antioxidants, (hindered)phenol antioxidants, dithiophosphates and derivatives, and combinations thereof and specific reaction products. Some antioxidants may be ashless (i.e., they may contain, if any, very few, metal atoms that are not traces or contaminants). In preferred embodiments, one or more antioxidants may be included in additive package concentrates and / or lubricating oil compositions according to the present disclosure. In particular, the lubricating oil compositions of the present disclosure may contain amine antioxidants, (hindered)phenol antioxidants, or combinations thereof.

[0054] Phenol antioxidants may be ashless (metal-free) phenol compounds, or neutral or basic metal salts of specific phenol compounds. Typical phenol antioxidants are hindered phenols containing sterically hindered hydroxyl groups, and hindered phenols include derivatives of dihydroxyaryl compounds in which the hydroxyl groups are in the ortho- or para-position relative to each other. Representative phenol antioxidants include C 6+Examples include alkyl-substituted hindered phenols and alkylene-bonded derivatives of these hindered phenols. Examples of this type of phenol material include, but are not limited to, 2-t-butyl-4-heptylphenol; 2-t-butyl-4-octylphenol; 2-t-butyl-4-dodecylphenol; 2,6-di-t-butyl-4-heptylphenol; 2,6-di-t-butyl-4-dodecylphenol; 2-methyl-6-t-butyl-4-heptylphenol; 2-methyl-6-t-butyl-4-dodecylphenol; and combinations thereof. Other useful hindered monophenol antioxidants include, for example, hindered 2,6-dialkyl-phenolpropionic acid ester derivatives. Bisphenol antioxidants may also be used. Examples of ortho-linked phenols include 2,2'-bis(4-heptyl-6-t-butylphenol); 2,2'-bis(4-octyl-6-t-butylphenol); 2,2'-bis(4-dodecyl-6-t-butylphenol); and combinations thereof. Examples of para-linked bisphenols include 4,4'-bis(2,6-di-t-butylphenol) and / or 4,4'-methylene-bis(2,6-di-t-butylphenol).

[0055] An effective amount of one or more catalytic antioxidants may be used additionally or as a substitute. The catalytic antioxidants may include a) one or more oil-soluble polymetallic organic compounds; and b) one or more substituted N,N'-diaryl-o-phenylenediamine compounds; or c) one or more hindered phenol compounds; or a combination of both b) and c). Catalytic antioxidants are disclosed in U.S. Patent No. 8,048,833. Examples of non-phenol antioxidants include (aromatic)amine antioxidants, which may be used alone or in combination with phenol. A typical example of a non-phenol antioxidant is formula R 4 R 5 R 6Examples include alkylated and non-alkylated aromatic amines such as aromatic monoamines of N, but are not necessarily limited to these. In the formula, R 4 R is an aliphatic, aromatic, or substituted aromatic group. 5 R is an aromatic or substituted aromatic group, 6 is H, alkyl, aryl, or R 7 S(O) x R 8 And in the formula, R 7 R is an alkylene, alkenylene, or aralkylene group, 8 x is an alkyl group, or an alkenyl group, an aryl group, or an alkaryl group, and x is 0, 1, or 2. Aliphatic group R 4 It may contain 1 to 20 carbon atoms (for example, 6 to 12 carbon atoms). The aliphatic group can usually be a saturated aliphatic group. In some embodiments, R 4 and R 5 All of these are aromatic groups or substituted aromatic groups, and the aromatic group may be a fused ring aromatic group such as naphthyl. Aromatic group R 4 and R 5 It may be combined with other groups such as S.

[0056] Typical aromatic amine antioxidants can have alkyl substituents with at least about six carbon atoms. Examples of aliphatic groups include, in particular, hexyl, heptyl, octyl, nonyl, decyl, and combinations thereof. Generally, the number of carbon atoms in the aliphatic group can be about 14 or less. Common types of amine antioxidants useful as lubricant additives include diphenylamine, phenylnaphthylamine, phenothiazine, imidodibenzyl, diphenylphenylenediamine, etc., and combinations thereof. Mixtures of two or more amines are also useful. Polymeric amine antioxidants are also useful. Examples of aromatic amine antioxidants include p,p'-dioctyldiphenylamine; t-octylphenyl-α-naphthylamine; phenyl-α-naphthylamine; p-octylphenyl-α-naphthylamine; bis(nonylphenyl)amine; N-phenylbenzeneamide; etc., and combinations thereof. Sulfur-containing antioxidants can be oil-soluble and / or oil-dispersible, and examples include, but are not limited to, alkylphenol sulfides and / or their alkali / alkaline earth metal salts. A non-limiting example is C4-C sulfide. 25 Olefins (singular or plural), aliphatic sulfides (C7-C) 29 Examples include hydrocarbyl fatty acid esters (one or more), ashless sulfurized phenol antioxidants (one or more), sulfur-containing organic molybdenum compounds (one or more), and combinations thereof. For further information on sulfurized substances useful as antioxidants, see U.S. Patent No. 10,731,101 (e.g., paragraphs 15-22).

[0057] In particular, if antioxidants are present, they may include hindered phenols and / or optionally alkylated diarylamines. If present, one or more antioxidants may be used in aggregate amounts of 0.01 to 10% by mass, for example, 0.05 to 5% by mass, 0.1 to 3% by mass, or 0.5 to 10% by mass.

[0058] Corrosion inhibitor Corrosion inhibitors may be used to reduce metal corrosion and are often alternatively called metal deactivators or metal passivators. Some corrosion inhibitors are also characterized as antioxidants. Suitable corrosion inhibitors include nitrogen and / or sulfur-containing heterocyclic compounds, such as triazoles (e.g., benzotriazole), substituted thiadiazoles, imidazoles, thiazoles, tetrazoles, hydroxyquinolines, oxazolines, imidazolines, thiophenes, indoles, indazoles, quinolines, benzoxazines, dithiols, oxazoles, oxatriazoles, pyridines, piperazines, triazines, and one or more derivatives thereof. A specific corrosion inhibitor is a benzotriazole represented by the following structure: [ka] In the formula, R 10 C1-C may not exist, or may be linear or branched, saturated or unsaturated. 20 It is a hydrocarbyl group or a substituted hydrocarbyl group. 10 The ring structure is essentially alkyl or aromatic and / or may contain heteroatoms such as N, O, or S. Examples of suitable compounds include benzotriazoles, alkyl-substituted benzotriazoles (e.g., tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), aryl-substituted benzotriazoles, alkylaryl-substituted or arylalkyl-substituted benzotriazoles, etc., and combinations thereof. For example, the triazole may include or be an alkylbenzotriazole having 1 to about 20 or 1 to about 8 carbon atoms in the alkyl group. In some embodiments, the corrosion inhibitor may include or be an alkylbenzotriazole.

[0059] Additionally or alternatively, the corrosion inhibitor may include a substituted thiadiazole represented by the following structure: [ka] In the formula, R 11 and R 12 The group is independently a hydrogen or hydrocarbon group, which may be cyclic, alicyclic, aralkyl, aryl, and alkaryl aliphatic or aromatic. These substituted thiadiazoles are derived from the 2,5-dimercapto-1,3,4-thiadiazole (DMTD) molecule. Many derivatives of DMTD have been reported in the Art, and any such compound can be included in the lubricating oil compositions used in this Disclosure. For example, U.S. Patents 2,719,125, 2,719,126, and 3,087,937 describe the preparation of various 2,5-bis-(hydrocarbon dithio)-1,3,4-thiadiazoles. In addition or alternatively, corrosion inhibitors include R 11 and R 12 It may also contain one or more other derivatives of DMTD, such as carboxylic acid esters, to which the sulfur atom of the sulfide may be bonded via a carbonyl group. The preparation of these thioester-containing DMTD derivatives is described, for example, in U.S. Patent No. 2,760,933. DMTD derivatives produced by the condensation of DMTD with a carboxylic acid of an α-halogenated aliphatic monocarboxylic acid having at least 10 carbon atoms are described, for example, in U.S. Patent No. 2,836,564. By this method, R 11 and R 12 hooc-CH(R 13 )- and R 13 DMTD derivatives with a hydrocarbyl group are generated. Further DMTD derivatives generated by amidation or esterification of these terminal carboxylic acid groups may also be useful. The preparation of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole is described, for example, in U.S. Patent No. 3,663,561.

[0060] Certain classes of DMTD derivatives may include mixtures of 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole and 2,5-bis-hydrocarbyldithio-1,3,4-thiadiazole. Such mixtures are sometimes sold under the trade name HiTEC® 4313 and are commercially available from Afton Chemical. In particular, if additive package concentrates and / or lubricating oil compositions exist in accordance with this disclosure, they may include substituted thiadiazoles, substituted benzotriazoles, or combinations thereof. If necessary, corrosion inhibitors may be used in any effective amount, but if used, they are usually used in amounts of about 0.001 to 5.0% by mass relative to the mass of the concentrate / composition, for example, 0.01 to 3.0% by mass, or 0.03 to 1.0% by mass.

[0061] Friction modifier Organic friction modifiers (OFMs; also known as ashless FMs) may be present in additive package concentrates and / or lubricating oil compositions according to this disclosure and are generally known. For example, OFMs may include esters formed by reacting carboxylic acids and / or anhydrides with alkanols and / or amine-based FMs. Other useful friction modifiers may generally include polar end groups (e.g., carboxyl or hydroxyl) covalently bonded to lipophilic hydrocarbon chains. Esters of carboxylic acids and anhydrides with alkanols are described in U.S. Patent No. 4,702,850. Examples of other conventional OFMs can be found in M. Belzer, Journal of Tribology, 1992, Vol. 114, pp. 675–682, and in M. Belzer and S. Jahanmir, Lubrication Science, 1988, Vol. 1, pp. 3–26. Typically, the total amount of organic / ashless friction modifiers in a lubricating oil composition according to this disclosure is 5% by mass or less, for example, 2% by mass or less, or 0.5% by mass or less, relative to the total mass of the composition; optionally, OFM may be included in an amount of at least 0.05% by mass, for example, at least 0.1% by mass or at least 0.2% by mass, relative to the total mass of the composition.

[0062] Examples of friction modifiers that may be useful in the lubricating compositions described herein include alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, glycerol borooxide fatty acid esters, fatty alcohol ethers, and combinations thereof. Examples of alkoxylated fatty acid esters include polyoxyethylene stearate and fatty acid polyglycol esters. These include polyoxypropylene stearate, polyoxybutylene stearate, polyoxyethylene isostearate, polyoxypropylene isostearate, polyoxyethylene palmitate, and combinations thereof. Examples of alkanolamides include diethyl laurate alkanolamide and diethyl palmitate alkanolamide. These include diethyalkanolamide oleate, diethyl stearate alkanolamide, diethyl oleate alkanolamide, polyethoxylated hydrocarbylamide, polypropoxylated hydrocarbylamide, and combinations thereof. Examples of polyol fatty acid esters include, for example, glycerol monooleate, saturated mono-, di-, and tri-glyceride esters, glycerol monostearate, hydroxyl-containing polyol esters, and combinations thereof.

[0063] Examples of glycerol boroside fatty acid esters include, for example, glycerol monooleate borate, saturated mono-, di-, and tri-glyceride borates, glycerol monostearate borate, and combinations thereof. In addition to or instead of glycerol polyols, these esters may include trimethylolpropane, pentaerythritol, sorbitan, and the like. These esters can be polyol monocarboxylic acid esters, polyol dicarboxylic acid esters, and / or, optionally, polyol tricarboxylic acid esters. In particular, OFMs include glycerol monooleate, glycerol dioleate, glycerol trioleate, glycerol monostearate, glycerol distearate, and glycerol tristearate, as well as the corresponding glycerol monopalmitate, glycerol dipalmitate, glycerol tripalmitate, their respective isostearates and linoleates, and combinations thereof. In particular, ethoxylated, propoxylated, and butoxylated fatty acid esters of polyols using glycerol as a base polyol may be useful as OFMs. Examples of fatty alcohol ethers include stearyl ethers, myristyl ethers, and combinations thereof. C3-C 50 Alcohols containing a carbon atom can be ethoxylated, propoxylated, or butoxylated to form the corresponding fatty alkyl ether. The base alcohol portion is stearyl, myristyl, palmityl, C 11 -C 13 It may contain, or be, hydrocarbons, oleyl, isostearyl, etc. Other ashless friction modifiers include derivatives of polyalkylene polyamines and / or ethoxylated long-chain amines. Advantageous derivatives of polyalkylene polyamines include succinimides of the specified structure, or simple amides. The number of carbon atoms in the polyalkylene moiety is preferably 2 to 4.

[0064] Suitable succinimides derived from polyethylene polyamines include succinimides with the following structures: [ka] In the formula, x+y may be between 8 and 15, and z may be an integer between 0 and 5, in particular x+y may be between 11 and 15 (e.g., 13), and z may be between 1 and 3. More broadly, such a friction modifier can be represented by the following general structure: [ka] In the formula, R 14 and R 15 Each of these is independent and can be expressed by the following formula: [ka] In the equation, x+y is between 8 and 15 (in particular between 11 and 15, e.g., 13), and z is an integer between 0 and 1 and 5 (in particular between 1 and 5 or between 1 and 3); each R 16 It is independently hydrogen, the acetyl moiety, or ethylene carbonate and >N-R 16 This is a part formed by a reaction with (especially a hydrogen or acetyl moiety). The preparation of such friction modifiers is described, for example, in U.S. Patent No. 5,840,663.

[0065] The above succinimide may be reacted with acetic anhydride to form a friction modifier, and in this friction modifier, each R is as exemplified by the following structure (where z=1 in the formula). 16 Each of these is an acetyl group independently: [ka] The preparation of this friction modifier can be found, for example, in U.S. Patent Application Publication No. 2009 / 0005277. Post-reactions with other reagents, such as borodic agents, are also known in the art. When such succinimide friction modifiers exist, they may be used in any effective amount.

[0066] An example of an alternative simple amide friction modifier may have the following structure: [ka] In the formula, R 17 and R 18 These may be the same or different alkyl groups. For example, R 17 and R 18 is C 14 ~C 20 It may be an alkyl group, and this alkyl group may be linear or branched, and m can be an integer from 1 to 5. In particular, R 17 and R 18 These can all be derived from isostearic acid, and m may be 4. If such a simple amide exists, it may be used in any effective amount.

[0067] Suitable ethoxylated amine friction modifiers may include, or be, reaction products of primary amines and / or diamines with ethylene oxide. The reaction with ethylene oxide may preferably be carried out using stoichiometric properties such that almost all primary and secondary amines can be converted to tertiary amines. Such amines may have the following exemplary structures: [ka] In the formula, R 19 and R 20 This may be an alkyl group, or an alkyl group containing a sulfur or oxygen bond with approximately 10 to 20 carbon atoms. An example of an ethoxylated amine friction modifier is R 19 and / or R 20Examples of materials include those with 16 to 20 carbon atoms, for example, 16 to 18. These types of materials may be commercially available and may be sold under the trademark names Ethomeen® and Ethoduomeen® by Akzo Nobel. Preferred materials from Akzo Nobel include Ethomeen® T / 12 and Ethoduomeen® T / 13 in particular. If such an ethoxylated amine is present, it may be used in any effective amount.

[0068] In particular, if friction modifiers (one or more) are present, those friction modifiers are glycerol monooleate, triethanolamine (TEEMA) esters (e.g., animal fat esters), R 14 Esters of succinic anhydride having hydrocarbyl substituents (e.g., animal fat esters), R 14 / R 15 Functionalized polyethylene polyamine succinimide, R 19 and / or R 20 It may include or be made of ethoxylated amines having 16 to 20 carbon atoms, or combinations thereof. If present, the useful concentration of the friction modifier may be in the range of 0.01 to 8% by mass, for example, 0.05 to 6.5% by mass, or 0.1 to about 5% by mass. Although organic molybdenum compounds may sometimes be classified as friction modifiers, in this specification they are classified as wear inhibitors and are therefore excluded for calculation purposes from the proportion that reflects the friction modifier component in the additive package and / or lubricating oil composition. Any type of friction modifier may be used alone or in combination with the materials of this disclosure. Additionally or alternatively, mixtures of two or more friction modifiers, or mixtures of friction modifiers with one or more alternative surface active materials may be desirable.

[0069] Abrasion-resistant agent Molybdenum-containing compounds In some embodiments, the additive package and / or lubricating oil composition may further contain one or more oil-soluble or oil-dispersible molybdenum-containing compounds, such as oil-soluble or oil-dispersible organic molybdenum compounds. In other embodiments, the additive package and / or lubricating oil composition may further substantially not contain any oil-soluble or oil-dispersible molybdenum-containing compounds. Non-limiting examples of such oil-soluble or oil-dispersible organic molybdenum compounds include molybdenum dithiocarbamate, molybdenum dithiophosphate, molybdenum dithiophosphinate, molybdenum xanthogenic acid, molybdenum thiooxantogenic acid, molybdenum sulfide, and mixtures thereof, particularly one or more of dialkyldithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum alkylxanthogenic acid, and molybdenum alkylxanthogenic acid, but are not necessarily limited to these. Representative alkylxanthogenic acid molybdenum and alkylthiooxantogenic acid molybdenum compounds are Mo(R 21 OCS2)4 and Mo(R) 21 It may also be expressed using the formula SCS2)4, where each R 21 Each of these may be an organic group independently selected from the group consisting of alkyl, aryl, aralkyl, and alkoxyalkyl groups, generally having 1 to 30 carbon atoms, or 2 to 12 carbon atoms, and may particularly be an alkyl group having 2 to 12 carbon atoms.

[0070] In some embodiments, the oil-soluble or oil-dispersible organic molybdenum compound may contain molybdenum dithiocarbamate, for example, molybdenum dialkyldithiocarbamate, and / or may substantially not contain molybdenum dithiophosphate, particularly molybdenum dialkyldithiophosphate. In some embodiments, any oil-soluble or oil-dispersible molybdenum compound may consist of molybdenum dithiocarbamate, such as molybdenum dialkyldithiocarbamate, and / or molybdenum dithiophosphate, such as molybdenum dialkyldithiophosphate, as the sole source(s) of molybdenum atoms in the composition. In either of these two sets of embodiments, if an oil-soluble or oil-dispersible molybdenum compound is present, the molybdenum compound may basically consist of molybdenum dithiocarbamate, for example, molybdenum dialkyldithiocarbamate, as the sole source of molybdenum atoms in the lubricating oil composition.

[0071] If a molybdenum compound is present, the molybdenum compound may be mononuclear, dinuclear, trinuclear, or tetranuclear, and may particularly include or consist of dinuclear and / or trinuclear molybdenum compounds. A suitable dinuclear or dimeric molybdenum dialkyldithiocarbamate can be represented, for example, by the following formula: [ka] In the formula, R 22 ~R 25 Each of these may independently represent a linear, branched, or aromatic hydrocarbyl group having 1 to 24 carbon atoms, and each of X1 to X4 may independently represent an oxygen atom or a sulfur atom. The four hydrocarbyl groups R 22 ~R 25 They may be the same or different from one another.

[0072] Suitable trinuclear organomolybdenum compounds include those with the formula: Mo3S k L n Q zExamples include those having , and mixtures thereof. In such a trinuclear formula, the three molybdenum atoms may be linked to multiple sulfur atoms (S), and k varies from 4 to 7. Each L may also be a selected organic ligand having a sufficient number of carbon atoms n1 to 4 to make the compound oil-soluble or oil-dispersible. Furthermore, if z is not 0, Q may be selected from the group of neutral electron-donating compounds such as water, amines, alcohols, phosphines, and / or ethers, where z is in the range of 0 to 5 and includes non-stoichiometric (non-integer) values. In such a trinuclear structure, at least 21 total carbon atoms (e.g., at least 25, at least 30, or at least 35) are typically all ligands (L n ) may exist within the combination. However, it is important that the organic group of the ligand can exhibit a sufficient number of carbon atoms in a group to favorably make the compound oil-soluble or oil-dispersible. For example, the number of carbon atoms in each ligand L is generally in the range of 1 to 100, for example, 1 to 30 or 4 to 20. Formula Mo3S k L n Q z Trinuclear molybdenum compounds having the following may advantageously exhibit a cationic core surrounded by an anionic ligand, represented by one or both of the following structures: [ka] Each of these cationic cores may have a net charge of +4 (for example, due to the oxidation state of each Mo atom being +4). Therefore, in order to solubilize these cores, the total charge of all ligands must match, in this case -4. Four monoanionic ligands may be favorable for neutralizing the cores. Without intending to be bound by any theory, two or more trinuclear cores may be bound or interconnected by one or more ligands, and the ligands may be polydentate. This includes cases where a polydentate ligand has multiple attachment sites to a single core. Oxygen and / or selenium may be substituted for some of the sulfur atoms of any of the cores.

[0073] Non-limiting examples of the above-mentioned trinuclear core ligands include dithiophosphates such as dialkyldithiophosphates, xanthates such as alkylxanthates and / or alkylthioxanthates, and dithiocarbamates such as dialkyldithiocarbamates, each of which particularly contains or is a dialkyldithiocarbamate, and combinations thereof, but are not necessarily limited thereto. Additionally or alternatively, the ligands of the trinuclear molybdenum-containing core may independently be one or more of the following formulas:

Chemical formula

[0074] Oil-soluble or oil-dispersible trinuclear molybdenum compounds can be prepared by reacting a molybdenum source such as (NH4)2Mo3S 13 ·n(H2O) with a suitable ligand source such as tetraalkylthiuram disulfide in a suitable liquid(s) / solvent(s). In the formula, n varies between 0 and 2, including non-stoichiometric (non-integer) values. Other oil-soluble or dispersible trinuclear molybdenum compounds are in a suitable solvent(s), (NH4)2Mo3S 13These compounds can be formed during the reaction of a molybdenum source such as n(H2O), a ligand source such as tetraalkylthiuram disulfide, dialkyldithiocarbamide, or dialkyldithiophosphate, and a sulfur extractant such as cyanide ions, sulfite ions, or substituted phosphines. Alternatively, trinuclear molybdenum-sulfur halide salts such as [M']2[Mo3S7A6], where M' is a counterion and A is a halogen such as Cl, Br, or I, may be reacted with a ligand source such as dialkyldithiocarbamide or dialkyldithiophosphate in a suitable liquid / solvent(s) to form oil-soluble or oil-dispersible trinuclear molybdenum compounds. The suitable liquid / solvent(s) may be, for example, aqueous or organic. Other molybdenum precursors include acidic molybdenum compounds. Such compounds may react with basic nitrogen compounds when measured by the ASTM D-664 or D-2896 titration procedure, and may typically be hexavalent. Examples include, but are not limited to, molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide, or similar acidic molybdenum compounds, or combinations thereof. Accordingly, additionally or alternatively, the concentrates and / or compositions of the present disclosure may be conferred with molybdenum, as necessary, by molybdenum / sulfur complexes of basic nitrogen compounds, such as those described in U.S. Patent Nos. 4,263,152, 4,285,822, 4,283,295, 4,272,387, 4,265,773, 4,261,843, 4,259,195, 4,259,194, and / or International Publication No. 94 / 06897, for example.

[0075] If a molybdenum-containing compound is present, it may be included in the lubricating oil composition in amounts of 0.1-2.0% by mass, 0.1-1.5% by mass, 0.2-1.2% by mass, or 0.2-0.8% by mass relative to the total mass of the composition. Additionally or alternatively, if a molybdenum-containing compound is present, it may impart to the lubricating oil composition molybdenum in parts per million by mass of 50-1500, for example, 75-800 ppm, 100-500 ppm, or 300-1200 ppm relative to the total mass of the composition. The molybdenum content can be measured in accordance with ASTM D5185. Molybdenum-containing compounds may have other functions, or may be classified as, for example, antioxidants and / or friction modifiers, but in this specification, molybdenum-containing compounds are classified as anti-wear agents. Accordingly, compositions characterized as substantially free of anti-wear agents should be understood as substantially free of molybdenum-containing compounds, despite having other potential functional additive properties. Similarly, compositions characterized as substantially free of friction modifiers may contain these molybdenum-containing compounds despite being substantially free of friction modifiers. Nevertheless, additive packages and / or lubricating oil compositions containing molybdenum-containing compounds may still be substantially free of other anti-wear agents.

[0076] Zinc-based phosphorus-containing compounds In some embodiments, the additive package and / or lubricating oil composition may further contain one or more zinc-based phosphorus-containing compounds, such as one or more zinc dihydrocarbyl dithiophosphate compounds. Such compounds are known in the art and are often referred to as ZDDP. In other embodiments, the additive package and / or lubricating oil composition may further substantially not contain any zinc-based phosphorus-containing compounds. ZDDP compounds may be prepared according to known techniques, for example, by first forming dihydrocarbyl dithiophosphoric acid (DDPA) by reacting one or more alcohols or phenols with P2S5 and then neutralizing the formed DDPA with a zinc compound. For example, dithiophosphoric acid may be produced by reacting a mixture of a primary alcohol and a secondary alcohol. Alternatively, dithiophosphoric acid characterized in that all hydrocarbyl groups are secondary or all hydrocarbyl groups are primary can be prepared. For the production of zinc salts, any basic or neutral zinc compound may be used, but usually oxides, hydroxides, and carbonates are used. When using commercially available additives, commercially available additives often contain an excess of zinc because a basic zinc compound is used in excess in the neutralization reaction.

[0077] Advantageous zinc dihydrocarbyl dithiophosphates may include, or may be, oil-soluble or oil-dispersible salts of dihydrocarbyl dithiophosphoric acid represented by the following formula:

Chemical formula

[0078] If necessary, one or more ZDDP compounds may be included in the lubricating oil composition in an amount of 0.4 to 5.0% by mass, for example, 0.6 to 3.5%, 1.0 to 3.0%, or 1.2 to 2.5% by mass, relative to the total mass of the composition. Additionally or alternatively, if ZDDP compounds are present, each ZDDP compound may impart phosphorus to the lubricating oil composition at a rate of 300 to 4000 parts per million by mass, for example, 500 to 2500 ppm, 750 to 2000 ppm, or 800 to 1600 ppm, relative to the total mass of the composition. Further additionally or alternatively, if ZDDP compounds are present, the ZDDP compounds may impart zinc to the lubricating oil composition at a rate of 400 to 4500 parts per million by mass, for example, 500 to 3000 ppm, 800 to 2600 ppm, or 1000 to 2200 ppm, relative to the total mass of the composition. The zinc and phosphorus content can be measured according to ASTM D5185, respectively. Additionally or alternatively, zinc dihydrocarbyldithiocarbamate, zinc alkanates (e.g., zinc stearate, zinc isostearate, zinc palmitate, zinc myristate, zinc laurate, zinc caprate, zinc 2-ethylhexanoate, etc.), zinc alkenates (e.g., zinc oleate and / or zinc undecylenate), zinc aryl, aralkyl, and / or alkali compounds (e.g., zinc benzoate, zinc carbolic acid, and / or zinc naphthenate) can be used as abrasion resistant agents.

[0079] ashless phosphorus-containing compounds Ashless abrasion resistant agents may be individual compounds or mixtures of compounds. In one embodiment comprising an ashless abrasion resistant mixture of compounds, the ashless abrasion resistant mixture may contain component (i) and component (ii). Component (i) may advantageously have significant abrasion resistance, and component (ii) may or may not have abrasion resistance. The ashless abrasion prevention component (i) may advantageously include a mixture of two or more compounds of structure (I):(II); [ka] In the formula, the group R 35 , R 36 , and R 37 Each of these independently contains, or may contain, a hydrocarbyl group having 1 to 18 carbon atoms and / or a hydrocarbyl group having 1 to 18 carbon atoms in which the alkyl chain is interrupted by a thioether bond. However, R 35 , R 36 , and R 37 At least some of all the groups in the set representing the set together include a hydrocarbyl group having 1 to 18 carbon atoms in which the alkyl chain is interrupted by a thioether bond, or a hydrocarbyl group thereof. The mixture may contain three or more, four or more, or five or more compounds of structure (II). In some embodiments, base R 35 , R 36 , and R 37Each of these independently comprises, or may comprise, a hydrocarbyl (especially alkyl) group having 4 to 10 carbon atoms, and / or a hydrocarbyl (especially alkyl) group having 4 to 10 carbon atoms in which the alkyl chain is interrupted by a thioether bond. However, all R in a set 35 , R 36 , and R 37 At least some of these groups together may include a hydrocarbyl (especially alkyl) group with 4 to 10 carbon atoms in which the hydrocarbyl (especially alkyl) chain is interrupted by a thioether bond, or it may be that hydrocarbyl group. base R 35 , R 36 , and R 37 If the alkyl group contains alkyl groups (where the alkyl chain is not interrupted by a thioether bond), examples include methyl, ethyl, propyl, and butyl, and in particular contains or is butyl.

[0080] base R 35 , R 36 , and R 37 However, when a hydrocarbyl (especially alkyl) chain is interrupted by a thioether bond, an example is the group of the structure -R'-S-R'' where R' may be -(CH2)n-. In the formula, n may be an integer from 2 to 4, and R'' is -(CH2) m - It may also be CH3, and m may be an integer from 1 to 15, for example, from 1 to 7. In particular, in a mixture of compounds of structure (I) containing component (i), at least 10% by mass (e.g., at least 20%, at least 30%, or at least 40%) of the mixture contains a compound of structure (I) in which at least one of R1, R2, and R3 contains or is an alkyl group, where the alkyl chain is interrupted by a thioether bond, and structure (I) is particularly such that R' is -(CH2) n It has the structure -R'-S-R''. In the formula, n may be an integer from 2 to 4, and R'' is -(CH2) m - It may also be CH3, and m may be an integer from 1 to 15, for example, from 1 to 7.

[0081] The gray-free abrasion-resistant component (ii) may advantageously contain one or more compounds having the following structure (III). [ka] In the formula, the group R 38 and R 41 Each of these independently contains an alkyl group having 1 to 12 carbon atoms, or may be such an alkyl group, R 39 and R 40 Each of these independently contains an alkyl bond with 2 to 12 carbon atoms, or may contain such an alkyl bond. In particular, R 38 and R 41 Each is independent of -(CH2) m - CH3 may or may not be included in the formula, where m is an integer from 1 to 15, for example from 1 to 7, and R 39 and R 40 (If present) Each is independent of -(CH2) n The formula may include or not include n, where n is an integer between 2 and 4. The mixture may contain two or more or three or more compounds of structure (III).

[0082] In particular, if compounds of structure (II) (component (i)) and compounds of structure (III) (component (ii)) are present, these compounds may be present in the lubricating oil composition in amounts of 0.04 to 1.0% by mass, for example, 0.05 to 0.8% by mass, 0.05 to 0.5% by mass, or 0.07 to 0.4% by mass, based on the total mass of the composition. Additionally or alternatively, in particular, compounds of structure (II) (component (i)) and compounds of structure (III) (component (ii)) together may impart phosphorus to the lubricating oil composition in amounts of 80 to 800 parts per million by mass, for example, 100 to 700 ppm, 150 to 600 ppm, or 200 to 500 ppm, based on the total mass of the composition. The phosphorus content can be measured according to ASTM D5185. In addition or alternatively, in particular, if a compound of structure (II) (component (i)) and a compound of structure (III) (component (ii)) are present, their mass ratios may be 2:1 to 1:2, 5:3 to 3:5, 3:2 to 2:3, or 4:3 to 3:4. Individual examples of ashless anti-wear agents may contain one or more compounds of structure (II) above, so that even in the absence of structure (III) of component (ii), an alternative mixture of ashless anti-wear agents can easily contain two or more compounds of structure (II) above. The anti-wear agent may additionally or alternatively contain a mixture of one or more ashless anti-wear agents and one or more metal-containing anti-wear agents.

[0083] Anti-foaming agent Antifoaming agents (defoamers) may be advantageously added to additive packages / concentrates and / or lubricating oil compositions according to this disclosure, as needed, for example, to delay the formation of stable foam. Silicones and certain organic polymers are typical defoamers. For example, polysiloxanes such as silicone oil (e.g., polydimethylsiloxane) may provide defoaming properties in appropriate proportions. Defoamers are commercially available and, if present, may be used in small amounts, such as less than 1% by mass, often less than 0.1% by mass.

[0084] Viscosity modifier Viscosity modifiers (also referred to as viscosity index improvers / VII or viscosity improvers) may be included in the lubricating compositions described herein. Viscosity modifiers impart high-temperature and low-temperature operability to the lubricant. These additives may impart shear stability at high temperatures and acceptable viscosity at low temperatures. Suitable viscosity modifiers include high molecular weight hydrocarbons, polyesters, and viscosity modifier dispersants that can function as both viscosity modifiers and dispersants. Typical molecular weights of these polymers can be about 10 to 1500 kilodaltons (kD), for example, about 20 to 1200 kD, or about 50 to 1000 kD.

[0085] Examples of suitable viscosity modifiers include linear or star polymers and copolymers of methacrylates, butadienes, olefins, and / or optionally alkylated styrenes. Polyisobutylene is a commonly used viscosity modifier. Another class of suitable viscosity modifiers is poly(meth)acrylates (e.g., copolymers of alkyl(meth)acrylates of various chain lengths), some of which formulations may also / alternatively function as pour point depressants (see below). Other suitable viscosity modifiers include copolymers of ethylene and propylene, copolymers of ethylene and high carbon number copolymers, and / or hydrogenated block copolymers of styrene and dienes such as butadiene and / or isoprene. Specific examples include polymers based on styrene-isoprene or styrene-butadiene with molecular weights of 50 to 200 kD. Copolymers useful as viscosity modifiers include those marketed under the trade names PARATONE® (e.g., PARATONE® 8921, PARATONE® 68231, and PARATONE® 8941) from Chevron Oronite; HiTEC® (e.g., HiTEC® 5850B) from Afton Chemical; and Lubrizol® 7067C from Lubrizol. Hydrogenated polyisoprene star polymers (including diblocks / multiblock arms containing styrene and isoprene blocks) useful as viscosity modifiers in this specification include those marketed under the trade names SV200® and SV600® from Infineum International Limited. Hydrogenated diene-styrene block copolymers useful as viscosity modifiers in this specification are marketed under the trade name SV50® from Infineum International Limited. Polymers useful as viscosity modifiers in this specification include polymethacrylate or polyacrylate polymers such as linear poly(meth)acrylate polymers available under the trade name Viscoplex® (e.g., Viscoplex® 6-954) from Evonik Industries, or star-shaped polymers available under the trade name Asteric® (e.g., Lubrizol® 87708 and Lubrizol® 87725) from Lubrizol.

[0086] Vinyl aromatic-containing polymers useful as viscosity modifiers in this specification may be derived from vinyl aromatic hydrocarbon monomers such as styrene monomers, e.g., styrene. Exemplary vinyl aromatic-containing copolymers useful in this specification may be represented by general formula A-B, where A is a polymer block mainly derived from a vinyl aromatic hydrocarbon monomer (e.g., styrene), and B is a polymer block mainly derived from a conjugated diene monomer (e.g., butadiene and / or isoprene). When used / necessary, viscosity modifiers may be incorporated into the lubricating oil composition (formulation) in amounts of about 0.01 to about 10% by mass relative to the total mass of the composition / formulation, for example, about 0.1 to about 7% by mass, about 0.1 to about 4% by mass, about 0.2 to about 2% by mass, about 0.2 to about 1% by mass, or about 0.2 to about 0.5% by mass. Viscosity modifiers may be added to the additive package concentrate or mixed into the lubricating formulation during / after dilution, but the above amounts reflect the amount present in the final lubricating formulation, and the corresponding amount that may be present when viscosity modifiers (VM) are added to the additive package concentrate can be easily calculated by assuming, for example, that the concentrate accounts for about 5% to about 20% by mass of the final formulation.

[0087] Viscosity modifier components are typically included as concentrates in base stocks / diluent oils, similar to those in additive package concentrates and / or lubricating oil compositions / formulations. Viscosity modifiers "for transport" can typically contain, in the form of components / concentrates, 20% to 75% by mass of active polymer for polymethacrylate or polyacrylate polymers, or 8% to 25% by mass of active polymer for olefin copolymers, hydrogenated polyisoprene star polymers, or hydrogenated diene-styrene block copolymers.

[0088] Pour point depressant Conventional pour point depressants (PPDs, also known as lubricant flow improvers or LOFIs) may be added to additive packages / concentrates and / or lubricant compositions according to this disclosure, if necessary, for example, to lower the minimum temperature at which the fluid can flow or be poured. Examples of suitable pour point depressants include polymethacrylates, polyacrylates, polyallylamides, condensation products of haloparaffinic waxes and aromatic compounds, vinyl carboxylate polymers, and terpolymers of dialkyl fumarates, vinyl esters of fatty acids, and allyl vinyl ethers. U.S. Patent Nos. 1,815,022, 2,015,748, 2,191,498, 2,387,501, 2,655,479, 2,666,746, 2,721,877, 2,721,878, and 3,250,715 describe pour point depressants and / or preparations thereof. When present in an additive package / concentrate and / or lubricating oil composition in accordance with this disclosure, such additives may be used in amounts of about 0.01 to 5% by mass, for example, about 0.01 to 1.5% by mass.

[0089] Other additives Additive packages / concentrates and / or lubricating oil compositions according to this disclosure may optionally contain other additives known in the art, such as other friction modifiers, other anti-wear agents, demulsifiers, anti-foaming agents, adhesives (e.g., succinic anhydride of hydrocarbyl / oligomer / polymer), extreme pressure agents, seal compatibility (swelling) agents, etc. Various additive categories (genera) and additive compounds (species) are disclosed, for example, in "Lubricant Additives" by CVSmallheer and R. Kennedy Smith, 1967, pp. 1-11.

[0090] Further Embodiments Additionally or alternatively, this disclosure may include one or more of the following embodiments: Embodiment 1. A perbasic alkaline earth metal hydrocarbyl-substituted salicylate detergent comprising both a carbonate portion and a borate portion, and exhibiting the following characteristics: a basicity index of at least 3.8; a ratio of soap content to boron in mass% greater than 55 mmol / kg; a soap content of at least 330 mmol / kg; a TBN of at least 220 mg KOH / g as measured according to ASTM D2896; and a mass ratio of borate to carbonate of 0.75 to 6.0, wherein the alkaline earth metal comprises calcium and / or magnesium, and the number of carbon atoms in the hydrocarbyl substituent is 9 to 30. Embodiment 2. The following characteristics: Basicity index is 9.0 or less; ratio of soap content to boron in mass% is less than 300 mmol / kg; TBN measured according to ASTM D2896 is at most 500 mgKOH / g; soap content is at most 550 mmol / kg; hydrocarbyl substituent is C 14 -C 24 The overbasic calcium salicylate detergent according to Embodiment 1, wherein at least three, at least four, or all five of the following conditions are met: containing an alkyl or alkenyl moiety. Embodiment 3. The overbasic calcium salicylate detergent according to Embodiment 1 or Embodiment 2, wherein the boron content according to ASTM D4951 is at least 3.2% by mass.

[0091] Embodiment 4. An overbasic calcium salicylate detergent according to any one of Embodiments 1 to 3, wherein the mass ratio of borate to carbonate is 1.0 to 5.0. Embodiment 5. An overbasic calcium salicylate detergent according to any one of Embodiments 1 to 4, wherein the alkaline earth metal content according to ASTM D4951 is at least 7.0% by mass. Embodiment 6. An overbasic calcium salicylate cleaning agent according to any one of Embodiments 1 to 5, wherein the mass ratio of alkaline earth metals to boron is 1.5 to 5.5. Embodiment 7. The basicity index is 5.0 to 8.3; the ratio of soap content to boron in mass% is 70 to 275 mmol / kg; the TBN measured according to ASTM D2896 is 265 to 350 mg KOH / g; the combined calcium and magnesium content according to ASTM D4951 is 7.0 to 12.5 mass%; the boron content according to ASTM D4951 is 3.5 to 6.8 mass%; the soap content is 350 to 520 mmol / kg; the mass ratio of alkaline earth metals to boron is 1.7 to 4.5; the mass ratio of borate to carbonate portion is 1.6 to 3.0; and the hydrocarbyl substituent is C 14 -C 19 A perbasic calcium salicylate detergent according to any one of Embodiments 1 to 6, comprising an alkyl or alkenyl moiety.

[0092] Embodiment 8. A method for producing a substantially package-stable overbasic alkaline earth metal hydrocarbyl-substituted salicylate detergent containing both a carbonate portion and a borate portion, comprising the following steps: reacting a mineral oil solution of acid with a stoichiometric excess amount of a neutralizing agent containing an alkaline earth metal carbonate or bicarbonate at a temperature of 60 to 200°C, optionally in the presence of an accelerator, for a time sufficient to form an overbasic but non-boric alkaline earth metal hydrocarbyl-substituted salicylate detergent, wherein the detergent has a basicity index of at least 3.5, a soap content of at least 330 mmol / kg, an alkaline earth metal content of at least 7.0% by mass as measured according to ASTM D4951, and ASTM The detergent exhibits a TBN of at least 240 mg KOH / g according to D2896, wherein the alkaline earth metal comprises calcium and / or magnesium, and this overbasic but unborodized alkaline earth metal hydrocarbyl-substituted salicylate detergent comprises a carbonate portion, with the number of carbon atoms in the hydrocarbyl substituent being 9 to 30; the detergent is prepared in an organic diluent medium containing an aprotic hydrocarbon solvent and C1-C4 primary alcohols but without intentionally added water, and the overbasic but unborodized alkaline earth metal hydrocarbyl-substituted salicylate is prepared in this medium. A step of mixing an acid salt detergent with a boron source at a temperature below 100°C to form a reaction mixture; a step of heating this reaction mixture to a temperature of 105°C to 225°C at a heating rate of less than 3°C / min in a boric acid process to form a crude boric acid detergent product; a step of optionally adding an aprotic hydrocarbon solvent to form another crude boric acid detergent product; a step of removing the diluent and most of the water formed during the boric acid process to form a perbasic alkaline earth metal hydrocarbyl-substituted salicylate detergent according to any one of Embodiments 1 to 7. A method that includes this.

[0093] Embodiment 9. The method according to Embodiment 8, wherein the aprotic hydrocarbon solvent includes benzene, xylene, toluene, mesitylene, naphthalene, cyclohexane, cyclooctane, heptane, octane, decane, dodecane, or a combination thereof; and the boron source includes orthoboric acid, metaboric acid, tetraboric acid, monoammonium borate, diammonium borate, triammonium borate, C1-C4 alkyl dihydrogen borate, di-C1-C4 alkyl hydrogen borate, tri-C1-C4 alkyl borate, or a combination thereof; or both. Embodiment 10. A lubricant additive package concentrate comprising: less than 40% by mass of a group I, group II, and / or group III lubricant base stock; at least 0.5% by mass of a boron-containing overbasic calcium salicylate detergent prepared according to any one of Embodiments 1 to 7 and / or according to the method of Embodiment 8 or 9; at least one ashless dispersant; at least one antioxidant; at least one friction modifier; and optionally one or more additional detergents, corrosion inhibitors, anti-wear agents, seal swelling agents, defoamers, extreme pressure agents, viscosity modifiers, and pour point depressants. Embodiment 11. The lubricant additive package concentrate according to Embodiment 10, wherein at least one friction modifier comprises a substantially sulfur-free ashless organic friction modifier. Embodiment 12. The lubricant additive package concentrate according to Embodiment 10, wherein at least one friction modifier comprises a substantially nitrogen-free and substantially sulfur-free ashless organic friction modifier.

[0094] Embodiment 13. A lubricant additive package concentrate according to any one of Embodiments 10 to 12, exhibiting package stability for at least 12 weeks at approximately 60°C. Embodiment 14. A lubricating oil composition comprising at least 70% by mass of a lubricating oil base stock containing one or more base stocks from Group I, Group II, Group III, and / or Group IV; and at least 5% by mass of a lubricant additive package concentrate as described in any one of Embodiments 10 to 13. Embodiment 15. A lubricating oil composition comprising at least 85% by mass of a lubricating oil base stock containing one or more base stocks from Group I, Group II, Group III, and / or Group IV; at least 0.05% by mass of a boron-containing overbasic calcium salicylate detergent prepared according to any one of Embodiments 1 to 7 and / or according to the method of Embodiment 8 or 9; at least one ashless dispersant; at least one antioxidant; at least one friction modifier; and optionally, one or more additional detergents, corrosion inhibitors, wear inhibitors, seal swelling agents, adhesives, demulsifiers, defoamers, extreme pressure agents, viscosity modifiers, and pour point depressants. Next, the present invention will be described using only non-limiting examples. [Examples]

[0095] Boro Oxide Cleaning Agent Synthesis Comparative Example A1 is the example of boro oxide detergent synthesis described in paragraph 22 of U.S. Patent No. 10,584,300. This example is reproduced herein. A reaction flask equipped with a Dean-Stark trap was loaded with 1 kg of perbasic calcium salicylate having 225 mg KOH / g TBN and 1 kg of xylene. Under nitrogen with stirring, 124 g of boric acid was slowly added at room temperature. The mixture was then heated to 115°C over 2 hours and held at 115°C for 1 hour. The reaction mixture was then heated to 140°C over 90 minutes and held at 140°C for 40 minutes. The reaction mixture was then cooled, centrifuged, and concentrated under vacuum on a rotary evaporator to obtain approximately 1 kg of calcium salicylate borooxide product. Inductively coupled plasma (ICP) analysis (measured according to ASTM D4951) showed that the product contained 3.09% boron and 6.77% calcium by mass. The TBN of this product (measured according to ASTM D2896) was 186 mg KOH / g. The basicity index (metal ratio) of this comparative example was calculated to be approximately 3. The soap content of this product was estimated to be approximately 563 mmol / kg, with a ratio of soap content to boron by mass of approximately 182 mmol / kg. The hydrocarbyl substituents of the product contained a mixture of hydrocarbyl substituents with 14 to 18 carbon atoms.

[0096] Comparative Example A2 is Invention Example 1 of U.S. Patent No. 5,380,508 ("Patent No. 508"). This example is reproduced herein. 200 grams of neutral alkyl salicylate (calcium content: 2.0% by mass) (A), diluted to an effective concentration of approximately 50% by mass with a lubricating oil fraction, 26 g of calcium hydroxide (B), 43.4 g of orthoboric acid (C) (2.0 mol per mol of calcium hydroxide), and 400 g of xylene (F) were placed in a 1000 ml four-neck flask equipped with a condenser and heated to 60°C with stirring. 120 g of methanol (D) and 20 g of water (E) were added to this mixture, and the resulting mixture was heated to reflux temperature (66°C) with stirring and reacted for 4 hours. The reaction mixture was further heated to 140°C over 1.5 hours, and methanol, water, and xylene were removed by distillation. Finally, the reaction product was diluted 2-fold with hexane, filtered to remove any remaining solids, and the hexane was removed by distillation to obtain the desired calcium borate overbasic alkyl salicylate. Note that in this comparative example, a neutral calcium washing agent was used as the starting material, and the calcium overbasication and boroxidation steps were achieved simultaneously. The TBN of this product was 205 mg KOH / g; the boron content was 3.1% by mass; the calcium content was 7.0% by mass; and the hydrocarbyl substituents consisted of a mixture of hydrocarbyl substituents with 16 and 18 carbon atoms.

[0097] According to Patent No. 508, observation of the calcium borate overbasic alkyl salicylate obtained in this manner using a transmission electron microscope revealed that the particle size of the overbasic component, calcium borate, was 50 angstroms or less. Furthermore, 5% by mass of water and 1% by mass of methanol were added to this calcium borate overbasic alkyl salicylate to obtain a mixture. This mixture was stirred at 93.5°C for 24 hours using an apparatus specified in ASTM D2619 to precipitate the overbasic component, calcium borate, which was then dispersed in the mixture. After centrifugation, the precipitated calcium borate was recovered. The recovered calcium borate was measured using an X-ray analyzer and found to be metaborate calcium. Table A of Patent No. 508 also shows that for this detergent, the calculated base number is 200 (205 when measured according to ASTM D664), the calcium content is 7.0% by mass, the boron content is 3.1% by mass, and the calculated B / Ca molar ratio is 1.6 (the B / Ca molar ratio analysis value in 2.1 is based on the addition of excess methanol and water in an attempt to detach and isolate calcium borate from the detergent, and in standard measurements of inorganic content, the entire reaction product is measured without separating the inorganic part from the (semi-)organic part of the detergent component).

[0098] Comparative Example A3 is Comparative Example 2 of U.S. Patent No. 5,380,508 ("Patent No. 508"). This example is reproduced herein. 200 grams of the same neutral alkyl calcium salicylate (A) used in Comparative Example A1, 26 g of calcium hydroxide (B), 43.4 g of orthoboric acid (C) (2.0 mol per mole of calcium hydroxide), and 400 g of xylene (F) were placed in a 1000 ml four-neck flask equipped with a condenser and heated to 60°C with stirring. 120 g of methanol was added to this mixture, and the resulting mixture was heated under stirring to reflux temperature (66°C) and reacted for 4 hours to obtain the reaction product. The reaction product was further heated to 140°C over 1.5 hours, and methanol, reaction water, and xylene were removed by distillation. Finally, the reaction product was diluted 2-fold with hexane, filtered to remove any remaining solids, and the hexane was removed by distillation to obtain calcium borate overbasic alkyl salicylate. However, the calcium borate overbasic alkyl salicylate obtained in this way gelled and was found to be unsuitable for general use as an additive in petroleum products. The hydrocarbyl substituents of the product consisted of a mixture of hydrocarbyl substituents with 16 and 18 carbon atoms.

[0099] In Example A4, a reaction flask was loaded with approximately 395 g of overbasic (carbonated) calcium salicylate with a TBN of approximately 350 mg KOH / g, a soap content exceeding 500 mmol / kg, and a basicity index of approximately 6, approximately 395 g of xylene, and approximately 156 g of methanol. This mixture was heated to approximately 40°C with stirring, and approximately 178 g of boric acid was added under nitrogen over approximately 1 hour. The temperature was then further increased to approximately 140°C over approximately 135 minutes. The reaction mixture was then cooled to below approximately 100°C, further diluted with approximately 262 g of xylene, and then cooled further. After cooling, the mixture was centrifuged and vacuum concentrated in a rotary evaporator at approximately 140°C for approximately 2 hours (to remove diluent, reaction water, and other volatile components) to obtain the borodic overbasic calcium salicylate product. ICP analysis (measured according to ASTM D4951) showed that the product contained approximately 5.14% by mass of boron and approximately 10.51% by mass of calcium. The TBN of this borooxide product (measured according to ASTM D2896) was approximately 298 mg KOH / g, and the basicity index (metal ratio) was approximately 5.84. The product had a soap content ratio of 87 mmol / kg to boron by mass, a soap content of 443 mmol / kg, and a borate to carbonate mass ratio of 1.6. The hydrocarbyl substituents of the product consisted of a mixture of hydrocarbyl substituents with 14 to 18 carbon atoms.

[0100] The mass ratio of borate to carbonate, 1.6, in Example A4 was measured as follows. First, the total base number (TBN) of the detergent sample was measured to be 291 mg KOH / g. As is well known in the art, ASTM D2896 is a suitable method. Next, the contribution of basic soap to TBN was measured by titration. A known amount of detergent was diluted in a 70:28:2 (by volume) mixed solvent of cyclohexane / isopropyl alcohol (IPA) / water and digested with 0.5 M ethanol perchloric acid. When the resulting solution was titrated with 0.1 M KOH solution, two inflection points EP1 and EP2 were obtained on the titration curve. Alternatively, TBN can be determined using point EP1 from the following formula.

number

number

number

number

[0101] Example A5 was the same as Example A4, except for the purpose of increasing the boron content. In Example A5, the reaction flask was loaded with approximately 395 g of overbasic (carbonated) calcium salicylate, approximately 395 g of xylene, and approximately 204 g of methanol, all having a TBN of approximately 350 mg KOH / g, a soap content exceeding 500 mmol / kg, and a basicity index of approximately 6. This mixture was heated to approximately 40°C with stirring, and approximately 241 g of boric acid was added under nitrogen over approximately 1 hour. The temperature was then further increased to approximately 140°C over approximately 135 minutes. The reaction mixture was then cooled to below approximately 100°C, further diluted with approximately 262 g of xylene, and then cooled further. After cooling, the mixture was centrifuged and vacuum concentrated in a rotary evaporator at approximately 140°C for approximately 2 hours (to remove diluent, reaction water, and other volatile components) to obtain the borooxidized overbasic calcium salicylate product. ICP analysis (measured according to ASTM D4951) showed that the product contained approximately 5.7% by mass of boron and approximately 10.2% by mass of calcium. The TBN of this borooxide product (measured according to ASTM D2896) was approximately 285 mg KOH / g, and the basicity index (metal ratio) was approximately 5.89. The product had a soap content ratio of 75 mmol / kg to boron by mass; a soap content of 429 mmol / kg; a borate to carbonate mass ratio of 3.0; a boron content of 5.7% by mass; and a calcium content of 10.2% by mass. The hydrocarbyl substituents of the product consisted of a mixture of hydrocarbyl substituents with 14 to 18 carbon atoms.

[0102] Example A6 was the same as Examples A4 and A5, except for the purpose of slightly reducing the boron content. Accordingly, in Example A6, the reaction flask was loaded with approximately 500 g of overbasic (carbonated) calcium salicylate, approximately 395 g of xylene, and approximately 105 g of methanol, all of which similarly had a TBN of approximately 350 mg KOH / g, a soap content exceeding 500 mmol / kg, and a basicity index of approximately 6. This mixture was heated to approximately 40°C with stirring, and approximately 113 g of boric acid was added over approximately 1 hour under nitrogen. The temperature was then further increased to approximately 140°C over approximately 135 minutes. The reaction mixture was then cooled to below approximately 100°C, further diluted with approximately 151 g of xylene, and then cooling was continued. After cooling, the mixture was centrifuged and vacuum concentrated in a rotary evaporator at approximately 140°C for approximately 2 hours (to remove diluent, reaction water, and other volatile components) to obtain a borodilated, overbasic calcium salicylate product. ICP analysis (measured according to ASTM D4951) showed that the product contained approximately 3.8% by mass of boron and approximately 11.6% by mass of calcium. The TBN of this borodilated product (measured according to ASTM D2896) was approximately 314 mg KOH / g, and the basicity index (metal ratio) was approximately 5.72. The product had a soap content ratio of 123 mmol / kg to boron by mass; a soap content of 469 mmol / kg; and a borate to carbonate mass ratio of 0.8. The hydrocarbyl substituents of the product consisted of a mixture of hydrocarbyl substituents with 14 to 18 carbon atoms.

[0103] Example A7 was the same as Example A6, except for the purpose of further reducing the boron content. In Example A7, the reaction flask was loaded with approximately 1.5 kg of overbasic (carbonated) calcium salicylate, which had a TBN of approximately 350 mg KOH / g, a soap content exceeding 500 mmol / kg, and a basicity index of approximately 6, approximately 1185 g of xylene, and approximately 316 g of methanol. This mixture was heated to approximately 40°C with stirring, and approximately 340 g of boric acid was added under nitrogen over approximately 1 hour. The temperature was then further increased to approximately 140°C over approximately 135 minutes. The reaction mixture was then cooled to below approximately 100°C, further diluted with approximately 452 g of xylene, and then cooling was continued. After cooling, the mixture was centrifuged and vacuum concentrated in a rotary evaporator at approximately 140°C for approximately 2 hours (to remove diluent, reaction water, and other volatile components) to obtain a borodilated, overbasic calcium salicylate product. ICP analysis (measured according to ASTM D4951) showed that the product contained approximately 3.6% by mass of boron and approximately 11.8% by mass of calcium. The TBN of this borodilated product (measured according to ASTM D2896) was approximately 312 mg KOH / g, and the basicity index (metal ratio) was approximately 5.81. The product had a soap content ratio of 133 mmol / kg to boron by mass; the soap content was 480 mmol / kg. The hydrocarbyl substituents of the product consisted of a mixture of hydrocarbyl substituents with 14 to 18 carbon atoms.

[0104] Example A8 was similar to Examples A4, A5, A6, and A7, except that the TBN was similarly about 350 mg KOH / g, but the soap content was different, less than 400 mmol / kg, and the basicity index was also different, about 8. Approximately 900 g of different overbasic (carbonated) calcium salicylate was loaded into a reaction flask with approximately 711 g of xylene and approximately 195 g of methanol. This mixture was heated to about 40°C with stirring, and approximately 217 g of boric acid was added under nitrogen over approximately 1 hour. The temperature was then further increased to about 140°C over approximately 135 minutes. The reaction mixture was then cooled to below approximately 100°C, further diluted with approximately 273 g of xylene, and then cooling was continued. After cooling, the mixture was centrifuged and vacuum concentrated in a rotary evaporator at approximately 140°C for approximately 2 hours (to remove diluent, reaction water, and other volatile components) to obtain the borodic overbasic calcium salicylate product. ICP analysis (measured according to ASTM D4951) showed that the product contained approximately 3.9% by mass of boron and approximately 11.9% by mass of calcium. The TBN of this borooxide product (measured according to ASTM D2896) was approximately 310 mg KOH / g, and the basicity index (metal ratio) was approximately 7.95. The product had a soap content ratio of 89 mmol / kg to boron by mass; a soap content of 348 mmol / kg; and a borate to carbonate mass ratio of 0.8. The hydrocarbyl substituents of the product consisted of a mixture of hydrocarbyl substituents with 14 to 18 carbon atoms.

[0105] Comparative Example A9 was similar to Example A8, except that approximately 901 g of a different overbasic (carbonated) calcium salicylate, with a TBN of approximately 225 mg KOH / g, a soap content exceeding 600 mmol / kg, and a basicity index of approximately 3, was loaded into a reaction flask with approximately 711 g of xylene and approximately 111 g of methanol. This mixture was heated to approximately 40°C with stirring, and approximately 106 g of boric acid was added under nitrogen over approximately 1 hour. The temperature was then further increased to approximately 140°C over approximately 135 minutes. The reaction mixture was then cooled to below approximately 100°C, further diluted with approximately 257 g of xylene, and then cooled further. After cooling, the mixture was centrifuged and vacuum concentrated in a rotary evaporator at approximately 140°C for approximately 2 hours (to remove diluent, reaction water, and other volatile components) to obtain the borodic overbasic calcium salicylate product. ICP analysis (measured according to ASTM D4951) showed that the product contained approximately 1.7% by mass of boron and approximately 7.1% by mass of calcium. The TBN of this borooxide product (measured according to ASTM D2896) was approximately 212 mg KOH / g, and the basicity index (metal ratio) was approximately 3.56. The product had a soap content ratio of 359 mmol / kg to boron by mass; a soap content of 611 mmol / kg; and a borate to carbonate mass ratio of 1.3. The hydrocarbyl substituents of the product consisted of a mixture of hydrocarbyl substituents with 14 to 18 carbon atoms.

[0106] Comparative Example A10 was similar to Example A9, except that approximately 1 kg of the same overbasic (carbonated) calcium salicylate, with a TBN of approximately 225 mg KOH / g, a soap content exceeding 600 mmol / kg, and a basicity index of approximately 3, was loaded into a reaction flask with approximately 790 g of xylene and approximately 188 g of methanol. This mixture was heated to approximately 40°C with stirring, and approximately 185 g of boric acid was added under nitrogen over approximately 1 hour. The temperature was then further increased to approximately 140°C over approximately 135 minutes. The reaction mixture was then cooled to below approximately 100°C, further diluted with approximately 337 g of xylene, and then cooled further. After cooling, the mixture was centrifuged and vacuum concentrated in a rotary evaporator at approximately 140°C for approximately 2 hours (to remove diluent, reaction water, and other volatile components) to obtain the borodic overbasic calcium salicylate product. ICP analysis (measured according to ASTM D4951) showed that the product contained approximately 2.9% by mass of boron and approximately 7.5% by mass of calcium. The TBN of this borooxide product (measured according to ASTM D2896) was approximately 202 mg KOH / g, and the basicity index (metal ratio) was approximately 3.01. The product had a soap content ratio of 206 mmol / kg to boron by mass; a soap content of 597 mmol / kg; and a borate to carbonate mass ratio of 2.1. The hydrocarbyl substituents of the product consisted of a mixture of hydrocarbyl substituents with 14 to 18 carbon atoms.

[0107] In Comparative Example A11, a reaction flask was loaded with approximately 606 g of nearly neutral calcium salicylate with a TBN of approximately 64 mg KOH / g, a soap content exceeding 500 mmol / kg, and a basicity index of approximately 6, approximately 500 g of xylene, approximately 130 g of methanol, and approximately 23 g of water. This mixture was heated to approximately 40°C with stirring, and approximately 178 g of boric acid was added under nitrogen over approximately 1 hour. The temperature was then further increased to approximately 140°C over approximately 135 minutes. During the temperature increase, when the temperature reached approximately 60°C, approximately 284 g of a group I lubricating oil base stock with a KV100 of approximately 5 cSt was added. The reaction mixture was then cooled, centrifuged, and vacuum concentrated in a rotary evaporator at approximately 140°C for approximately 2 hours (to remove diluents, reaction water, and other volatile components) to obtain the calcium salicylate borooxide product. ICP analysis (measured according to ASTM D4951) showed that the product contained approximately 1.8% by mass of boron and approximately 2.3% by mass of calcium. The TBN of this borooxide product (measured according to ASTM D2896) was approximately 60 mgKOH / g, and the basicity index (metal ratio) was approximately 1.21. The product had a soap content ratio of 234 mmol / kg to boron by mass; the soap content was 421 mmol / kg. The hydrocarbyl substituents of the product consisted of a mixture of hydrocarbyl substituents with 14 to 18 carbon atoms.

[0108] In Example A12, a reaction flask was loaded with approximately 1000 g of overbasic (carbonated) magnesium salicylate, which had a TBN of approximately 340 mg KOH / g, a soap content exceeding 400 mmol / kg, and a basicity index of approximately 7.5, approximately 790 g of xylene, and approximately 233 g of methanol. This mixture was heated to approximately 40°C with stirring, and approximately 183 g of boric acid was added under nitrogen over approximately 1 hour. The temperature was then further increased to approximately 140°C over approximately 135 minutes. The reaction mixture was then cooled to below approximately 100°C, further diluted with approximately 337 g of xylene, and then cooled further. After cooling, the mixture was centrifuged and vacuum concentrated in a rotary evaporator at approximately 140°C for approximately 2 hours (to remove diluent, reaction water, and other volatile components) to obtain the borodic overbasic magnesium salicylate product. ICP analysis (measured according to ASTM D4951) showed that the product contained approximately 1.7% by mass of boron and approximately 7.2% by mass of magnesium. The TBN of this boro oxide product (measured according to ASTM D2896) was approximately 301 mg KOH / g, and the basicity index (metal ratio) was approximately 6.71. The product had a soap content ratio of 240 mmol / kg to boron by mass; a soap content of 408 mmol / kg; and a borate to carbonate mass ratio of 1.3. The hydrocarbyl substituents of the product consisted of a mixture of hydrocarbyl substituents with 14 to 18 carbon atoms.

[0109] In Example A13, a reaction flask was loaded with approximately 800 g of overbasic (carbonated) calcium salicylate, which similarly had a TBN of approximately 350 mg KOH / g, a soap content exceeding 500 mmol / kg, and a basicity index of approximately 6, and approximately 458 g of xylene. This mixture was heated to approximately 80°C with stirring, and a mixture of approximately 1104 g of methanol containing approximately 191 g of boric acid was added under nitrogen over approximately 1 hour. Some distillation of the solvent was observed during the addition. The temperature was then further increased to approximately 140°C over approximately 45 minutes. The reaction mixture was then cooled to below approximately 100°C, further diluted with approximately 668 g of xylene, and then cooled further. After cooling, the mixture was centrifuged and vacuum concentrated in a rotary evaporator at approximately 140°C for approximately 2 hours (to remove diluent, reaction water, and other volatile components) to obtain the borodic overbasic calcium salicylate product. ICP analysis (measured according to ASTM D4951) showed that the product contained approximately 3.0% by mass of boron and approximately 11.3% by mass of calcium. The TBN of this borooxide product (measured according to ASTM D2896) was approximately 308 mgKOH / g, and the basicity index (metal ratio) was approximately 5.8. The product had a soap content ratio of 164 mmol / kg to boron by mass; the soap content was 487 mmol / kg. The hydrocarbyl substituents of the product consisted of a mixture of hydrocarbyl substituents with 14 to 18 carbon atoms.

[0110] Additive Package Stability – Comparison of Boron-Based and Non-Boron-Based Cleaning Agents To test the effect of the cleaning agent boric acid on package stability, several variations of passenger car motor oil (PCMO) Adpack were prepared. Furthermore, given the well-known Adpack destabilizing interactions between salicylate-based cleaning agents and certain organic components (broadly classified as ashless organic friction modifiers for simplicity), normally unstable combinations of salicylate-based cleaning agents and the aforementioned ashless organic friction modifiers were also tested to investigate the effect of the cleaning agent boric acid. The package stability was tested as defined herein by exposing the samples to air at approximately 60°C in an oven for at least 12 weeks. The data shown in the table below includes observations at week 0 (initial), week 4, week 7, and week 12. The initial test at week 0 was performed at room temperature (approximately 20-25°C), while all other data points were tested in an oven at 60°C after the required number of weeks had elapsed. In the table below, "CB" means clear and transparent, "SH" means slight haze, "H" means haze, "VH" means significant haze, "F" means aggregation, usually expressed as a percentage (higher percentage indicates more widespread aggregation), "PS" means phase separation, usually expressed as a percentage (higher percentage indicates more widespread phase separation), "G" means gel, usually expressed as a percentage (higher percentage indicates more widespread gelation), "tsed" means trace precipitate, and "MTS" means small precipitate. In Examples and Comparative Examples B1-B12, the base additive package contained a mixture of overbasic (non-borodic) magnesium salicylate and overbasic (non-borodic) calcium salicylate cleaning agent components, a mixture of borated polyisobutenyl succinic anhydride-polyamine (PIBSA-PAM) and a non-borodic PIBSA-PAM dispersant component, a zinc-containing anti-wear component, a combination of aromatic amine and hindered phenol antioxidant components, a benzotriazole corrosion inhibitor component, an adhesive component, an antifoaming agent component, and a diluent / base stock. The additive package components were basically pure (containing little or no diluent), or the active ingredients were encapsulated in a diluted form, and may contain as much as 60% diluent / inactive components.

[0111] To investigate stability issues, the base additive package was modified in various ways, most notably by adding and / or substituting one or more overbasic or borodic overbasic calcium salicylate components, adding ashless organic friction modifiers, or both. In this series of examples, when multiple detergents were added, they were substituted for each other to approximate the molar amounts of alkaline earth metals (e.g., calcium salicylate was substituted for magnesium salicylate), or to approximate the molar amount of a specific alkaline earth metal (e.g., calcium salicylate borodate was substituted for a larger amount of non-borodic calcium salicylate to approximate the calcium content). Ashless organic friction modifiers were simply added, as they were not originally present in the base additive package, and did not substitute for any other components (even diluent components). In this series of examples, the amounts of unmodified additive package components were kept constant, but the processing rate was adjusted to account for the differences in the amount of additives resulting from substitution / addition. In this way, fully formulated lubricating oil compositions prepared by diluting the additive package with additional diluents / base stocks (and optionally other components) contain similar amounts of metals, phosphorus, sulfur (but not boron additionally present in the boro oxide detergent, nor oxygen and optionally nitrogen present in the ashless organic friction modifier), detergents (one or more), dispersants (one or more), anti-wear agents, antioxidants (one or more), corrosion inhibitors, adhesives, and defoamers.

[0112] [Table 1] In Table 1 above, Comparative Example B1 uses the overbasic (carbonated but not borodic) calcium salicylate detergent used as a reactant in Examples A4 to A7, which have a relatively high soap content, while Comparative Example B2 uses the overbasic (carbonated but not borodic) calcium salicylate detergent used as a reactant in Example A8, which has a low soap content. The TBN of both detergent components is almost the same. Examples B3 and B4 are identical to Comparative Examples B1 and B2, respectively, except that the former further contains a glycerol monooleate friction modifier component (which may contain a reaction product of approximately 1.5 equivalents of oleic acid and approximately 1 equivalent of glycerol). As can be seen from the package stability results in Table 1, the calcium salicylate detergents of Comparative Examples B1 and B2 exhibited comparable stability in the additive package, while the addition of the ashless organic friction modifiers of Examples B3 and B4 appeared to result in package instability in both cases (as gelation or haze).

[0113] [Table 2] * The packaging exhibited significant haze upon arrival (at room temperature), but it quickly cleared up when the temperature rose to approximately 60°C. In Table 2 above, Examples B5 and B6 utilize borooxidation variations of the overbasic calcium salicylate cleaning agents of Comparative Examples B1 and B2, respectively (the borooxidation products of Examples A7 and A8). Similar to Examples B3 and B4 in Table 1, Examples B7 and B8 in Table 2 are identical to Examples B5 and B6, except that the former further contains a glycerol monooleate friction modifier component (which includes the reaction product of approximately 1.5 equivalents of oleic acid and approximately 1 equivalent of glycerol). As can be seen from the package stability results, the salicylic acid borooxide detergents of Examples B5 and B6 exhibit nearly equivalent stability to each other in the additive package shown in Table 2, and equivalent stability to the non-borooxide analogs of Comparative Examples B1 and B2 in Table 1. However, unlike Table 1, Table 2 shows different results when the ashless organic friction modifier is added to the salicylic acid borooxide detergent. The salicylic acid borooxide analog of Example B8 with a low soap content actually appeared to be inferior to the non-borooxide counterpart of Example B4 (based on overall high aggregation and significant haze at short / long time intervals). Surprisingly, however, the borooxide analog in the salicylic acid detergent with a relatively high soap content of Example B7 showed considerably improved package stability compared to the non-borooxide counterpart of Example B3, and would probably even be equivalent in stability to the counterpart of Example B5 without the ashless organic friction modifier. Since the instability of salicylate detergents and certain ashless organic friction modifiers is well known, it is expected that the reliability of package stability, which can at least partially overcome, if not (almost) completely overcome, the instability drawbacks when combining salicylate detergents and ashless organic friction modifiers, will be unexpectedly added by the borooxidation treatment.

[0114] [Table 3] Table 3 shows that Examples B3 and B7 are identical to those in Tables 1 and 2, respectively, and reflect non-borodic and borodic variations of calcium salicylate detergent components with relatively high soap content, as well as a glycerol monooleate friction modifier. Examples B9 and B10 reflect non-borodic calcium salicylate with relatively high soap content, as well as other ashless / organic friction modifiers, specifically triethanolamine fat ester (TEEMA) and octadecenyl succinic anhydride (ODSA). Examples B11 and B12 reflect borodic analogs of salicylate detergents and the same ashless organic friction modifiers as in Examples B9 and B10. As can be seen from the package stability results in Table 3, in Examples B7 and B11, packages containing salicylate borooxide and ashless organic friction modifiers were more stable at high temperatures over time compared to the combinations with non-salicylate borooxides in Examples B3 and B9, respectively. Since the combination of non-salicylate borooxide and TEEMA (Example B10) did not show significant package instability, it is natural that no improvement was observed in the combination of borooxide analog and TEEMA (Example B12). However, it should be noted that in additive packages that were not particularly unstable initially, the reliability of package stability for borooxide detergents may be lost. In fact, the package stability of the borooxide detergent combination was not significantly inferior to that of the non-borooxide combination. This indicates both that the instability of ashless organic friction modifier-salicylate detergent packages is not necessarily inherent, and that the additive package of borooxide detergents may universally exhibit package stability with several different types of ashless organic friction modifiers.

[0115] In Examples and Comparative Examples B13-B25, the base additive packages contained a perbasic (non-borodic) calcium salicylate cleaning agent component, a non-borodic PIBSA-PAM dispersant component, a zinc-containing anti-wear agent component, a molybdenum-containing anti-wear agent component, a combination of aromatic amine and hindered phenol antioxidant components, a benzotriazole corrosion inhibitor component, an adhesive component, an anti-foaming agent component, and a diluent / base stock. The additive package components were basically pure (containing little to no diluent), or in a diluted form with the active ingredient encapsulated, sometimes containing as much as 60% diluent / inactive components. To investigate stability issues, the base additive package was modified by adding and / or substituting one or more overbasic or borated detergent components and one or more overbasic detergent components. In this series of examples, when multiple detergents were added, they were substituted for each other (e.g., calcium salicylate was substituted for another calcium salicylate, calcium sulfonate for calcium salicylate, or calcium borodate salicylate for non-borodate calcium salicylate) to make the mass of the detergents approximately equal on an alkaline earth metal-free basis. In this series of examples, the amount of unmodified additive package components was kept the same, but the processing rate was adjusted to account for the difference in the amount of additives due to substitution / addition.

[0116] [Table 4] In Table 4 above, Comparative Example B13 utilizes the overbasic (carbonated but not borodic) calcium salicylate detergent used as a reactant in Example A8, which has a low (moderate) soap content, while Comparative Example B14 utilizes the overbasic (carbonated but not borodic) calcium salicylate detergent used as a reactant in Examples A4 to A7, which have a relatively high soap content. The TBN of both non-borodic detergent components is almost the same. Examples B15, B16, and B17 are identical to Comparative Example B14, except that the overbasic borodic detergent products of Examples A4 to A6 are replaced with non-borodic detergents. Example B18 utilizes the borodic overbasic calcium salicylate detergent product of Example A8 (an analogue of the non-borodic counterpart reproduced in Comparative Example B13). As can be seen from the package stability results in Table 4, even in the absence of ashless OFM (Comparative Example B14), non-borodic, overbasic calcium salicylate detergents may exhibit some stability issues in additive packages containing molybdenum-containing anti-wear agents. However, the calcium salicylate detergents of Examples B15-B17 exhibit comparable and acceptable additive package stability compared to Comparative Example B13 and in contrast to their non-borodic detergent analogues of Comparative Example B14. Calcium salicylate detergent of Example B18

[0117] [Table 5] In Table 5 above, Comparative Example B19 utilizes a very high soap content overbasic (carbonated but not borooxidized) calcium salicylate detergent, which was used as a reactant in Comparative Examples A9 and A10, while Comparative Examples B20 and B21 utilize similar borooxidized overbasic calcium salicylate detergent products as in Comparative Examples A9 and A10, respectively. As can be seen from the package stability results in Table 5, borooxidation helps improve package instability under certain conditions, but it does not universally improve package stability. Relatively unstable non-borooxidized detergents (Comparative Example B19) can have their stability improved somewhat by borooxidation under certain conditions (in the case of Comparative Example B20), but not under all conditions (in the case of Comparative Example B21), even under conditions with very high soap content, but not completely. The basicity indices of the non-borooxidized and borooxidized detergents in Comparative Examples B19-B21 are 2.9-3.0. As shown in Table 4, the calcium salicylate detergents with relatively low soap content and relatively high basicity indices in Comparative Example B13 and Example B18 (non-borooxidized and borooxidized, respectively) both show comparable and acceptable package stability, but the calcium salicylate detergents with relatively high soap content and low basicity indices in Comparative Examples B19-B21 in Table 5 universally exhibit inferior package stability. Surprisingly, and without being constrained by theory, at least when done via the boroxidation of detergents, the basicity index appears to be relatively more important than soap content in addressing package stability issues.

[0118] [Table 6] In Table 6 above, Comparative Example B22 utilizes the overbasic (carbonated but not borodic) magnesium salicylate detergent used as a reactant in Example A12, and Example B23 utilizes a similar borodic overbasic magnesium salicylate detergent product as in Example A12. Comparative Examples B24 and B25 utilize an overbasic (carbonated but not borodic) calcium sulfonate detergent (approximately 300 mg KOH / g TBN, less than 250 mmol soap content, and a basicity index of approximately 14) and its borodic analogue, respectively. Although the borodication method for this calcium sulfonate detergent is not specifically described herein, it was carried out using the same procedure and under the same conditions as detailed herein for salicylate detergents (both the present invention and the comparative examples). Table 6 shows that Comparative Example B22 and Example B23 exhibited similar behavior to Comparative Examples B13 and Example B14. Neither of the overbasic salicylate detergents caused significant package stability problems, and borolysis did not cause any package stability issues. However, the case of calcium sulfonate is different. Even in situations where the package stability of non-borodic overbasic calcium sulfonate was relatively high (Comparative Example B24), the borodicated example showed significant gelation even at the time of initial additive package formulation (week 0) (Comparative Example B25). Other unpublished data have shown that borolysis according to the method described herein does indeed cause package instability in overbasic alkaline earth metal sulfonates, and that package instability is not present in the absence of borolysis. While there are many other potential effects available to those skilled in the art to obtain package stability other than borolysis of detergents, the repeated negative results with sulfonate detergents may indicate that borolysis presents a more fundamental difficulty in maintaining package stability of sulfonate detergents.

[0119] Performance of compounding additive packages containing salicylate boro Comparative Examples C1 to C4 correspond to Invention Examples 1 to 4 described in Table 1 of JX Nippon's U.S. Patent Application Publication No. 2015 / 0005208 ('208'). Paragraphs

[0147] to

[0149] of '208' describe a "drive valve system monitoring friction test" that measures friction torque at an oil temperature of approximately 100°C and a rotational speed of approximately 350 rpm. Although '208' has been normalized for Comparative Example B2, it should be noted that Invention Examples 1 to 4 showed friction torque improvement rates in the range of approximately 3.0 to 9.5%, while the boron-free salicylate detergent-containing composition of Comparative Example 1 showed a torque improvement rate of approximately 6.9%. Instead, if we were to measure the friction torque improvement rate of Publication No. 208 compared to the boron-free Comparative Example 1, the formulations with high boron content (Examples 3 and 4) would worsen the friction torque, while the formulations with low boron content (Examples 1 and 2) would show only slight improvement. This seems like a very misleading result, as it is believed that increasing the boron content improves friction torque. Without being bound by theory, we can hypothesize that the cleaning agents with high boron content in Publication No. 208 contain boron species that are difficult / unavailable to use, or boron species in a chemical form that cannot adequately contribute to the friction tribofilm surface.

[0120] It is noteworthy that paragraphs

[0075] to

[0076] of Publication No. 208 teach that lubricant compositions with a detergent-metal ratio exceeding 3.3 are not only undesirable because they tend to reduce friction torque behavior, but that a detergent-metal ratio of 1.9 or less (with a lower limit of 1.01 considering blending lubricity and engine "startability") is most preferable. Readers of Publication No. 208 should understand that only Invention Example 1 satisfies this most preferable metal ratio, and that the same composition has the highest normalized friction torque measurement. Although not a direct comparison, Example C5 utilized an additive package composition containing similar components to Example B5 (prepared according to Example A13), including borodilated, overbasic calcium salicylate as described in this disclosure. To evaluate friction torque, Comparative Example C6 utilized an additive package composition similar to Example C5, except that it contained unborodilated, overbasic calcium salicylate, as described in Publication No. 208. Relative formulation measurements are shown in Table 4 below. "Detergent boron content" should be understood as the amount of boron in the final formulation attributable solely to the borodilated detergent component.

[0121] [Table 7] In Comparative Example C6 and Example C5, friction torque reduction was measured at approximately 80°C and an engine speed of approximately 650 rpm. The torque reduction in Table 7 was normalized by the formulation of Comparative Example C6. Although the conditions differ from those used in Publication No. 208, it should be understood that the absolute value of torque reduction was typically (usually dramatically) reduced due to both the lower boron content and the test temperature (which are included in all aggregate measurements under both sets of conditions). Thus, quantitative evaluation under equal conditions and in the same formulation space is not available, but the relatively large torque reduction shown by the calcium salicylate borooxide-containing formulation of Example C5 compared to its other identical non-calcium salicylate borooxide-containing formulation of Comparative Example C6 is considered surprising and unexpected.

[0122] All documents referenced herein are incorporated herein by reference and, to the extent consistent with this document, include any priority documents and / or test procedures. As is evident from the above general description and specific embodiments, the forms of this disclosure have been illustrated and described, but various modifications can be made without departing from the spirit and scope of the disclosure of the present invention. Accordingly, the present invention is not necessarily intended to be limited by such modifications.

Claims

1. Contains both carbonate and borate moieties and has the following characteristics: a basicity index of at least 3.8; a ratio of soap content to boron in mass % of more than 55 mmol / kg; a soap content of at least 330 mmol / kg; a TBN of at least 220 mg KOH / g, as measured in accordance with ASTM D2896; and A borate to carbonate mass ratio of 0.75 to 6.0 1. An overbased alkaline earth metal hydrocarbyl-substituted salicylate detergent having the formula: An overbased alkaline earth metal hydrocarbyl-substituted salicylate detergent wherein the alkaline earth metal comprises calcium and / or magnesium and the hydrocarbyl substituent has from 9 to 30 carbon atoms.

2. Features include: the basicity index is 9.0 or less; the ratio of soap content to boron in mass % is less than 300 mmol / kg; said TBN, measured in accordance with ASTM D2896, being at most 500 mg KOH / g; the soap content is at most 550 mmol / kg; and The hydrocarbyl substituent is C 14 -C 24 Contains an alkyl or alkenyl moiety:

10. The overbased calcium salicylate detergent of claim 1, wherein at least three, at least four, or all five of the following are satisfied:

3. 10. The overbased calcium salicylate detergent of claim 1, having a boron content of at least 3.2 wt.% according to ASTM D4951.

4. 2. The overbased calcium salicylate detergent of claim 1, wherein the weight ratio of borate to carbonate is from 1.0 to 5.

0.

5. 10. The overbased calcium salicylate detergent of claim 1, having an alkaline earth metal content of at least 7.0 wt. % according to ASTM D4951.

6. 2. The overbased calcium salicylate detergent of claim 1, wherein the weight ratio of alkaline earth metal to boron is from 1.5 to 5.

5.

7. the basicity index is 5.0 to 8.3; the ratio of soap content to boron in mass % is 70 to 275 mmol / kg; TBN measured according to ASTM D2896 is 265 to 350 mg KOH / g; a combined calcium and magnesium content of 7.0 to 12.5 wt. % according to ASTM D4951; a boron content of 3.5 to 6.8 wt. % according to ASTM D4951; The soap content is 350 to 520 mmol / kg; the mass ratio of alkaline earth metal to boron is 1.7 to 4.5; the mass ratio of borate to carbonate moieties is 1.6 to 3.0; The hydrocarbyl substituent is C 14 -C 19 10. The overbased calcium salicylate detergent of claim 1, which includes an alkyl or alkenyl moiety.

8. 1. A method for producing a substantially package-stable overbased alkaline earth metal hydrocarbyl-substituted salicylate detergent containing both carbonate and borate moieties, comprising the steps of: providing an oil-soluble or oil-dispersible overbased but non-borated alkaline earth metal hydrocarbyl-substituted salicylate detergent prepared by reacting a mineral oil solution of an acid with a stoichiometric excess of a neutralizing agent comprising an alkaline earth metal carbonate or bicarbonate, optionally in the presence of a promoter, at a temperature of from 60 to 200°C for a time sufficient to form an overbased but non-borated alkaline earth metal hydrocarbyl-substituted salicylate detergent, said detergent having a basicity index of at least 3.5, a soap content of at least 330 mmol / kg, an alkaline earth metal content of at least 7.0 wt. % as measured in accordance with ASTM D4951, and a pH of at least 10. D2896 of at least 240 mg KOH / g, said alkaline earth metal comprising calcium and / or magnesium, said overbased but non-borated alkaline earth metal hydrocarbyl-substituted salicylate detergent comprising a carbonate moiety and wherein the hydrocarbyl substituent has from 9 to 30 carbon atoms; Aprotic hydrocarbon solvents and C 1 -C 4 combining said overbased, but non-borated, alkaline earth metal hydrocarbyl-substituted salicylate detergent with a boron source in an organic diluent medium comprising a primary alcohol but no intentionally added water at a temperature below 100°C to form a reaction mixture; heating the reaction mixture to a temperature of 105°C to 225°C at a heating rate of less than 3°C / min during boration to form a crude borated detergent product; Optionally, adding more aprotic hydrocarbon solvent, thereby again forming a crude borated detergent product; and removing the dilution medium and most of the water formed during the boration process to form the overbased alkaline earth metal hydrocarbyl-substituted salicylate detergent of claim 1. A method comprising:

9. the aprotic hydrocarbon solvent comprises benzene, xylene, toluene, mesitylene, naphthalene, cyclohexane, cyclooctane, heptane, octane, decane, dodecane, or a combination thereof; The boron source may be orthoboric acid, metaboric acid, tetraboric acid, monoammonium borate, diammonium borate, triammonium borate, dihydrogen borate C 1 -C 4 Alkyl, hydrogen borate di-C 1 -C 4 Alkyl, borate tri-C 1 -C 4 alkyl, or a combination thereof The method of claim 8.

10. 1. A lubricant additive package concentrate comprising: less than 40 wt. % Group I, Group II, and / or Group III lubricant base stocks; 10. At least 0.5% by weight of a boron-containing overbased calcium salicylate detergent according to any one of claims 1 to 7 and / or prepared according to the method of claims 8 or 9; at least one ashless dispersant; at least one antioxidant; at least one friction modifier; and Optionally, one or more of additional detergents, corrosion inhibitors, antiwear agents, seal swell agents, antifoam agents, extreme pressure agents, viscosity modifiers, and pour point depressants.

1. A lubricant additive package concentrate comprising:

11. 11. The lubricant additive package concentrate of claim 10, wherein the at least one friction modifier comprises a substantially sulfur-free ashless organic friction modifier.

12. 11. The lubricant additive package concentrate of claim 10, wherein the at least one friction modifier comprises a substantially nitrogen-free, substantially sulfur-free, ashless organic friction modifier.

13. 11. The lubricant additive package concentrate of claim 10, exhibiting package stability at about 60°C for at least 12 weeks.

14. 1. A lubricating oil composition comprising: at least 70 wt. % of a lubricating oil base stock comprising one or more of Group I, Group II, Group III, and / or Group IV base stocks; and 11. At least 5 wt. % of the lubricant additive package concentrate of claim 10.

1. A lubricating oil composition comprising:

15. 1. A lubricating oil composition comprising: at least 85 wt. % of a lubricating oil base stock comprising one or more of Group I, Group II, Group III, and / or Group IV base stocks; 10. At least 0.05% by weight of the boron-containing overbased calcium salicylate detergent of claim 1; at least one ashless dispersant; at least one antioxidant; at least one friction modifier; and Optionally, one or more of additional detergents, corrosion inhibitors, antiwear agents, seal swell agents, tackifiers, demulsifiers, antifoam agents, extreme pressure agents, viscosity modifiers, and pour point depressants.

1. A lubricating oil composition comprising: