High-sulfurization additives for lubricating oil compositions

Abstract

This disclosure provides a method for preparing sulfidated alkylphenol salt products to achieve a high sulfidation ratio of sulfidated alkylphenol salt to unsulfidated alkylphenol salt / phenol in the context of neutralization and optional over-alkaliening additives. The sulfidated alkylphenol salt products are obtained by sulfidating alkylphenols with a sulfur chloride blend comprising about 40% to about 75% by weight of sulfur dichloride.

Description

[0001] Cross-reference to related applications

[0002] This application is a continuation-in-part of International Application No. PCT / US2023 / 020157, filed April 27, 2023, which claims the priority of U.S. Application No. 63 / 478,724, filed January 6, 2023; U.S. Application No. 63 / 432,757, filed December 15, 2022; U.S. Application No. 63 / 432,752, filed December 15, 2022; and U.S. Application No. 63 / 335,474, filed April 27, 2022, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure generally relates to lubricating oil compositions with high levels of sulfurization and their additives. Background Technology

[0004] Metal salts of sulfurized alkylphenols (also known as alkylphenol salts) are often useful lubricant additives. These additives act as detergents and / or dispersants and also provide a basic base to help neutralize acids generated during vehicle operation. Unsulfurized alkylphenol salts and / or unsulfurized variants of alkylphenols have reduced utility and are often less desirable in lubricants for many reasons. Therefore, additive manufacturers seek to minimize the levels of unsulfurized alkylphenol salts and / or alkylphenols in their additives. However, current methods for preparing such additives have one or more disadvantages when the additive is also over-basicized, in order to minimize the levels of unsulfurized alkylphenol salts / phenol variants. Summary of the Invention

[0005] According to a method or embodiment, this document describes a method for preparing a sulfurized compound for a lubricating composition to achieve a high sulfurization ratio of the sulfurized compound to the residual unsulfurized compound. In one aspect, the method includes sulfurizing an alkylphenol with a sulfur chloride blend to provide a sulfurized alkylphenol, wherein the molar ratio of the sulfur chloride blend to the alkylphenol is from about 0.6:1 to about 0.75:1; and wherein the sulfur chloride blend comprises sulfur monochloride and sulfur dichloride, and wherein the sulfur chloride blend is from about 40 wt% to about 75 wt% sulfur dichloride. In other embodiments, the method further includes neutralizing and optionally over-alkalizing the sulfurized alkylphenol in the presence of a solvent to provide a sulfurized alkylphenol salt composition. The method of any embodiment produces a sulfurized compound (e.g., a sulfurized alkylphenol or a sulfurized alkylphenol salt) wherein the sulfurization ratio of the sulfurized alkylphenol (or sulfurized alkylphenol salt) to the unsulfurized compound (e.g., alkylphenol and / or unsulfurized alkylphenol salt) is about 500:1 or greater.

[0006] In other methods or implementations, the methods in the preceding paragraph may include any combination of optional implementations, features, or method steps.These optional embodiments, features, or method steps may include one or more of the following: wherein the copper corrosion of a lubricant containing a sulfurized alkylphenol salt composition, as measured according to ASTM D6594, is at least about 50% less than that of a lubricant containing a sulfurized alkylphenol salt composition prepared by sulfurizing the same alkylphenol but with a sulfur chloride blend containing 100% sulfur monochloride; and / or wherein the amount of residual organochlorine in the sulfurized compound is about 1500 ppm or less (as per ASTM D6594). D4929 is measured using X-ray fluorescence (XRF) spectroscopy); and / or the neutralization and optional over-alkaliening are carried out at a temperature not exceeding about 140°C; and / or the solvent is one or more solvents having a boiling point of about 100°C or less at about 1000 mbar to about 40 mbar; and / or the solvent is xylene, toluene, octane, butanol, heptane, methanol, acetone, benzene, cyclohexane, cyclopentane, ethanol, hexane, pentane, propanol, water, or combinations thereof; and / or the neutralization and optional over-alkaliening comprises contacting a sulfide alkylphenol with an alkali metal salt or alkaline earth metal salt at a temperature not exceeding about 140°C; and / or the alkali metal salt or alkaline earth metal salt is lithium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, aluminum hydroxide, lithium oxide, magnesium oxide, calcium oxide, barium oxide, or combinations thereof; and / or the neutralization and / or optional over-alkaliening are carried out in the presence of a carbonating agent at a temperature not exceeding about 140°C. The process occurs at a temperature of 0°C; and / or the sulfidated alkylphenol salt composition undergoes one or more post-processing steps, the one or more post-processing steps comprising one or more of the following: vacuum stripping, jetting, distillation, filtration, degassing, evaporation, scraped-film evaporation, centrifugation, dilution, liquid-liquid extraction, membrane separation, chromatography, adsorption, supercritical extraction, or combinations thereof, and wherein each post-processing step is carried out at a temperature not exceeding about 140°C; and / or the method does not remove residual unsulfided compounds between sulfidation, neutralization, and / or optional over-alkalization; and / or the temperature of the neutralization and optional over-alkalization, as well as the temperature of any post-processing step, does not exceed about 100°C; and / or the sulfidation ratio of the sulfidated alkylphenol salt composition is about 5000:1 to about 500:1; and / or the sulfidation ratio of the sulfidated alkylphenol salt composition is about 3500:1 to about 1200:1; and / or the sulfidated alkylphenol salt composition has about 100 mg The total base value is from about 400 mg KOH / g to about 400 mg KOH / g; and / or the sulfidation compound has less than about 0.1% by weight of unsulfided alkylphenol and / or unsulfided alkylphenol salt; and / or the sulfidation occurs at a temperature of about 0°C to about 250°C; and / or the sulfidation occurs at a temperature of about 20°C to about 120°C; and / or the sulfidation occurs in the absence of base; and / or the sulfided alkylphenol is neutralized and over-alkaliened.

[0007] In several other embodiments, sulfurized alkylphenol salt compositions are also described herein, and these compositions can be prepared by any embodiment of the methods described in the preceding two paragraphs. In one specific embodiment, the sulfurized alkylphenol salt composition is prepared by a method comprising the steps of: (1) sulfurizing an alkylphenol with a sulfur chloride blend to provide sulfurized alkylphenol, wherein the molar ratio of the sulfur chloride blend to the alkylphenol is from about 0.6:1 to about 0.75:1; wherein the sulfur chloride blend comprises sulfur monochloride and sulfur dichloride, and wherein the sulfur chloride blend is from about 40 wt% to about 75 wt% sulfur dichloride; and (2) neutralizing and optionally over-alkalizing the sulfurized alkylphenol in the presence of a solvent to provide the sulfurized alkylphenol salt composition.

[0008] In another method or embodiment of this disclosure, a detergent is also described herein comprising a hydroxy aromatic compound or a salt thereof having a high sulfurization ratio of a sulfurized compound to an unsulfurized compound. In one aspect, the detergent comprises an alkyl-substituted sulfur-bridged hydroxy aromatic compound or a salt thereof, wherein the sulfur bridge is derived from a sulfur chloride blend comprising sulfur dichloride and sulfur monochloride, and wherein the blend comprises about 40% to about 75% by weight of sulfur dichloride; and the detergent has a sulfurization ratio of 500:1 to 5500:1 (as described herein) and has no more than about 900 ppm of unsulfurized hydroxy aromatic compound or a salt thereof.

[0009] In other embodiments or methods, the detergent in the preceding paragraph may include optional features or embodiments. Optional features or embodiments of the detergent may include one or more of the following: wherein the alkyl-substituted sulfur-bridged hydroxy aromatic compound or its salt has a molar ratio of the sulfur chloride blend to the alkyl-substituted hydroxy aromatic compound of about 0.6:1 to about 0.75:1; and / or wherein the alkyl-substituted sulfur-bridged hydroxy aromatic compound or its salt has a molar ratio of about 50 mg KOH / g to about 400 mg KOH / g. The total base value of KOH / g; and / or wherein the alkyl-substituted sulfur-bridged hydroxy aromatic compound or salt has a sulfur content of about 40,000 ppm to 65,000 ppm; and / or wherein the sulfurization ratio is about 1200:1 to about 3500:1; and / or wherein the alkyl-substituted sulfur-bridged hydroxy aromatic compound or salt is derived from the alkylation of phenols with one or more oligomers obtained from olefins; and / or wherein the olefins include ethylene, propylene, butene, pentene, or combinations thereof; and / or wherein the alkyl-substituted sulfur-bridged hydroxy aromatic compound or salt has a total base value of about 90 mg KOH / g to about 250 mg KOH / g; and / or wherein the detergent has a residual organochlorine content of about 1500 ppm or less (as measured by X-ray fluorescence (XRF) spectroscopy according to ASTM D4929).

[0010] In another method or embodiment, this document describes a lubricating oil composition comprising, in any embodiment of the detergents, sulfur compounds, and / or alkyl-substituted sulfur-bridged hydroxy aromatic compounds or salts of the present invention, and one or more base oils having a lubricating viscosity. In other embodiments, the lubricating oil composition is suitable for use as a crankcase lubricating oil composition; and / or wherein the crankcase is fueled by gasoline, diesel, or alternative fuels.

[0011] In other methods or embodiments, this document describes the use of a sulfur chloride blend having about 40% to about 75% by weight of sulfur dichloride (and about 25% to 60% by weight of sulfur monochloride) to form a sulfur compound (e.g., any of the sulfurized alkylphenols, sulfurized alkylphenol salts, and / or alkyl-substituted sulfur-bridged hydroxy aromatic compounds or salts thereof as described in this invention), wherein the sulfurization ratio of the sulfurized alkylphenol (or sulfurized alkylphenol salt) to the unsulfurized alkylphenol (and / or unsulfurized alkylphenol salt) is about 500:1 or greater. In other embodiments, this use may optionally further include neutralizing and optionally over-alkalizing the sulfurized alkylphenol in the presence of a solvent to provide a sulfurized alkylphenol salt or a sulfurized alkylphenol salt composition. In still other methods, this use may further include a molar ratio of the sulfur chloride blend to the alkylphenol of about 0.6:1 to about 0.75:1; and / or wherein the sulfur chloride blend comprises sulfur monochloride and sulfur dichloride. In other embodiments, the use of the sulfur chloride blends described herein may also include any optional embodiments and / or optional features as described above in any embodiment of the present invention.

[0012] Further details and advantages of this disclosure will be set forth in part in the following description and / or may be learned by practicing this disclosure. The details and advantages of this disclosure may be realized and obtained by means of the elements and combinations particularly pointed out in the appended claims. It should be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and do not limit the claimed disclosure. Attached Figure Description

[0013] Figure 1 This is a graph based on temperature of residual or unsulfurized alkylphenols, showing the reaction kinetics of alkylphenol regeneration during treatment. Detailed Implementation

[0014] This disclosure provides a method for preparing neutral to over-alkaline and sulfurized alkylphenol salt products to achieve a high sulfurization ratio of sulfurized alkylphenol salt to unsulfurized alkylphenol salt in the context of neutral to over-alkaline additives, such as TBNs having at least about 0 mg KOH / g, at least about 20 mg KOH / g, at least about 50 mg KOH / g, at least about 100 mg KOH / g, and additionally about 150 mg KOH / g to about 400 mg KOH / g, as further discussed below. As noted in the background section, past attempts to achieve high sulfurization levels in this manner have had limited success, and a sulfurization ratio of about 500:1 or higher (i.e., the weight ratio of sulfurized alkylphenol salt to unsulfurized alkylphenol salt and / or unsulfurized alkylphenol) cannot yet be achieved with such TBNs because high alkalinity and / or treatment methods tend to regenerate unsulfurized variants through treatment.

[0015] In one aspect, the methods described herein include first sulfiding an alkylphenol with a sulfur source (preferably a sulfur chloride blend having a selected amount of sulfur dichloride) to provide a sulfidated alkylphenol. In some methods, sulfidation occurs in the absence of a base in the reaction medium. In one method, the alkylphenol is first derived from the alkylation of a phenol with one or more oligomers derived from olefins such as, but not limited to, ethylene, propylene, butene, or mixtures thereof. The sulfidated alkylphenol is then neutralized and optionally over-alkaliened in the presence of a solvent to provide a neutral to over-alkaliened and sulfidated alkylphenol salt product or composition. In some embodiments, neutralization and optional over-alkaliening are carried out at a temperature not exceeding about 140°C (or other temperatures discussed separately below) to achieve a sulfidation ratio of about 500:1 or greater in the composition. Finally, the optionally over-alkalized and sulfidated alkylphenolate compositions may undergo various optional post-treatment steps to obtain neutral to over-alkalized and sulfidated alkylphenolate products, wherein in some embodiments, all post-treatments are carried out at temperatures not exceeding about 140°C (or other temperatures discussed below) to maintain a sulfidation ratio of about 500:1 or greater. In yet another few methods, the methods described herein effectively achieve sulfidation ratios of about 5000:1 to about 500:1, about 4000:1 to about 500:1 in other methods, about 3500:1 to about 500:1 in other methods, about 2000:1 to about 500:1 in other methods, and about 5000:1 to about 1000:1, or about 3400:1 to about 1200:1, or even about 2000:1 to about 1000:1 for neutral to over-alkalized and sulfidated alkylphenolate products. Further details of the products and each treatment step will be described below.

[0016] Alkylation of phenols

[0017] The alkylphenol salt products of this disclosure are first obtained by alkylation of a suitable phenol (or hydroxy aromatic compound) with one or more olefins and / or oligomers derived from olefins. Suitable phenols or hydroxy aromatic compounds include monohydroxy and / or polyhydroxy aromatic hydrocarbons having 1 to 4 hydroxyl groups, and in some methods 1 to 3 hydroxyl groups. Suitable compounds include, but are not limited to, phenols, catechols, resorcinols, hydroquinones, pyrogallols, cresols, and mixtures thereof. Preferred starting compounds include phenols.

[0018] Alkylating agents comprise one or more olefins and / or oligomers derived from olefins selected from ethylene, propylene, butene, isobutene, or mixtures thereof. Suitable olefins include isobutene, propylene trimers and / or tetramers, butene trimers and / or tetramers, to name just a few, but other olefins may be present in the oligomer or alkyl group, such as straight-chain olefins, cyclic olefins, branched olefins other than propylene oligomers, such as butene or isobutene oligomers, arylalkylenes, and mixtures thereof. Alkylation can be carried out in the presence of catalysts such as Lewis acid catalysts, solid acid catalysts, trifluoromethanesulfonic acid, and other acidic molecular sieve catalysts. Exemplary Lewis acid catalysts are known to those skilled in the art and may include aluminum trichloride, aluminum tribromide, aluminum triiodide, boron trifluoride, boron tribromide, boron triiodide, etc. In some methods, the molar ratio of the phenol or hydroxy aromatic compound to one or more oligomers may be from about 10:1 to about 0.5:1, and in other methods from about 5:1 to about 2:1. Oligomeric alkyl groups are typically linked to phenolic or hydroxy aromatic compounds at the ortho and / or para positions, but other substitutions may also be present depending on the application.

[0019] vulcanization

[0020] Alkylphenols or alkylhydroxy aromatic compounds are then sulfided by contacting a sulfur source in a manner that effectively achieves a high degree of sulfidation, preferably a sulfur chloride blend as discussed below. In the method, sulfidation typically involves introducing a sulfur bridging group between the alkylphenol or alkylhydroxy aromatic moieties. In some methods, the sulfur bridging is a -Sy- group, where y is an integer from 1 to 4, and in other methods it is an integer from 1 to 3, and in some methods it is an integer from 1 to 2, and / or the total sulfur level is at most about 5%. The sulfur source can be any suitable sulfur or blend thereof, such as elemental sulfur or its halides such as sulfur monochloride or sulfur dichloride, hydrogen sulfide, sulfur dioxide, or sodium sulfide hydrate. Sulfur can be used as molten sulfur or as a solid (powder or granules) or as a solid suspension in a hydrocarbon liquid. In one method, the sulfur source is sulfur monochloride, which those skilled in the art will understand to be S2Cl2 as shown in reaction scheme I below, or sulfur dichloride (SCl2), or a blend thereof. In other methods or embodiments, the sulfur source may preferably be a blend of sulfur dichloride (SCl2) and sulfur monochloride (S2Cl2), and particularly a blend of about 40% to about 75% by weight of sulfur dichloride and about 25% to about 60% by weight of sulfur monochloride. In still other embodiments, the sulfur chloride blend may be about 60% to about 67% by weight of sulfur dichloride and about 33% to about 40% by weight of sulfur monochloride, or about 40% to about 70% by weight of sulfur dichloride and about 30% to about 60% by weight of sulfur monochloride, or about 40% to about 67% by weight of sulfur dichloride and about 33% to about 60% by weight of sulfur monochloride. Scheme I below describes the use of sulfur monochloride for sulfidation at room temperature (20°C to 25°C) for up to approximately 60 minutes (other sulfur sources mentioned herein may also be used in Scheme I, preferably the sulfur chloride blends discussed above), but other sulfidation conditions (such as sulfidation at approximately 0°C to approximately 250°C for approximately 1 hour to approximately 7 hours) may be used as required by the specific application.

[0021] (Option I)

[0022] In optional methods, vulcanization occurs in the absence or lack of an alkali (such as sodium hydroxide, potassium hydroxide, or calcium hydroxide), meaning less than 1% by weight of alkali, less than about 0.5% by weight of alkali, less than about 0.1% by weight of alkali, or even no alkali at all during vulcanization. Preferably, the vulcanization reaction temperature can be from about 0°C to about 250°C, from about 0°C to about 230°C, from about 0°C to about 120°C, from about 40°C to about 120°C, or from about 40°C to about 60°C, or from about 20°C to about 25°C (e.g., room temperature) and / or other ranges within these endpoints as required by the specific application. In some methods, the sulfur source may be combined with a selected alkylphenol (optionally in the presence of a solvent) at temperatures ranging from at least about 0°C, at least about 20°C, at least about 40°C, at least about 60°C, at least about 80°C, at least about 100°C to less than 200°C, less than 180°C, less than about 160°C, less than about 140°C, less than about 120°C, or less than about 100°C, or less than about 80°C, or less than about 60°C, or less than about 40°C, or less than about 30°C. Subsequently, depending on the specific application requirements, the reaction product is subjected to short-term temperature treatments up to about 200°C for 30 to 60 minutes and / or vacuum stripping / distillation at temperatures up to about 200°C for 30 to 60 minutes. Depending on the sulfur source, the sulfidation process may take up to about 8 hours, up to about 6 hours, up to about 4 hours, or less (and preferably about 1 hour). Solvents such as heptane, hexane, xylene, diol, etc., may be present during the reaction. When sulfidation occurs first in the absence of a base, especially when sulfur dichloride is used and particularly when the sulfur chloride blends described herein are used, the reaction is preferentially driven to high sulfidation levels, such as about 500:1 or greater, about 1000:1 or greater, about 2400:1 or greater, and in some methods, intermediate sulfidation ratios of about 5000:1 or less.

[0023] In some methods, the ratio of sulfur source to alkylphenol reactant can be selected to achieve a high level of sulfidation when sulfidation is carried out in the absence of alkali, and in some methods, it also helps to maintain a low level of copper corrosion in the final product when used in lubricants. In one method, depending on the needs of a particular application, the molar ratio of sulfur source (e.g., preferably, a sulfur chloride blend) to alkylphenol or alkylhydroxy aromatic reactant in the sulfidation reaction can be about 0.6 or greater, and in some other methods or embodiments, it is about 0.6 to about 3.5, about 0.65 to about 3.5, about 0.65 to about 3.2, or in other methods or embodiments, it is about 0.65 to about 3.0, or about 0.65 to about 2.0, or about 0.65 to about 1.4, or about 0.65 to about 1.0, or about 0.65 to about 0.75 (or other endpoints covered by such ranges). In other embodiments, the molar ratio of the sulfur source (e.g., preferably, a sulfur chloride blend) to the alkylphenol or alkyl hydroxy aromatic reactant in the sulfidation reaction can be at least about 0.6, at least about 0.62, at least about 0.65, at least about 0.66, at least about 0.67, at least about 0.68, at least about 0.69, at least about 0.7, at least about 0.72, at least about 0.74, at least about 0.76, at least about 0.78, or at least about 0.8 to less than about 3.5, less than about 3.0, less than about 2.5, less than about 2.0, less than about 1.5, less than about 1.0, less than about 0.8, or less than about 0.75, or less than about 0.7, or less than about 0.68. Such a molar ratio of sulfur source (e.g., sulfur chloride blend) to alkylphenol reactant helps to achieve a high sulfidation ratio of about 500:1 or greater in the sulfidation reaction (and in other embodiments, about 500:1 to about 5000:1, or about 500:1 to about 4000:1, or about 500:1 to about 3500:1, or about 500:1 to about 2000:1), and in some methods, subsequent processing steps as described below are allowed to maintain or increase the sulfidation ratio such that the final sulfidated and over-alkalized alkylphenolate products maintain a high sulfidation ratio of sulfidated phenolate to unsulfidated phenolate. In other methods or embodiments, such molar ratios of the sulfur source to alkylphenol described herein can facilitate achieving vulcanization ratios of at least about 500:1, at least about 600:1, at least about 700:1, at least about 800:1, at least about 900:1, at least about 1000:1, at least about 1100:1, or at least about 1200:1 to about 5000:1 or less, about 4500:1 or less, about 4000:1 or less, about 3500:1 or less, about 3000:1 or less, about 2500:1 or less, or about 2000:1 or less. In other embodiments, the molar ratios and resulting vulcanization ratios described herein may also include any other ranges within the said endpoints, depending on the needs of a particular application.In some other methods, the molar ratio of the sulfur chloride blend and the sulfur source to the alkylphenol may help achieve about 0.2% by weight or less, about 0.1% by weight or less, about 0.08% by weight or less, about 0.06% by weight or less, about 0.04% by weight or less, or about 0.03% by weight or less of residual unsulfurized alkylphenol salt and / or unsulfurized alkylphenol, or in some methods, undetectable amounts of residual unsulfurized alkylphenol salt and / or residual unsulfurized alkylphenol.

[0024] Due to the high sulfidation ratio, and in part due to the selected sulfur chloride blend, the method described herein eliminates the need to remove any residual unsulfided alkylphenols after sulfidation and / or after any subsequent process steps, such as neutralization, over-alkalization, and / or post-treatment. Instead, the method described herein minimizes the generation and / or regeneration of any unsulfided variants, and thus avoids the need to remove this undesirable component.

[0025] neutralization

[0026] Following sulfidation, the sulfidated alkylphenol or sulfidated alkylhydroxy aromatic compound, having reached a high sulfidation ratio, is then neutralized to provide a phenolate or salt of the sulfidated alkylphenol or alkylhydroxy aromatic compound. In one method, neutralization is carried out by contacting the sulfidated alkylphenol with a metal base under reaction conditions; in some methods, it is done by contacting it with an accelerator in a liquid hydrocarbon diluent to provide a phenolate or salt of the sulfidated alkylhydroxy aromatic compound. In some cases, the reaction may be carried out under an inert gas, such as nitrogen. If required by certain applications, the metal base may be added at different times during the reaction, either in a single addition or multiple additions. Neutralization may occur via exemplary reaction scheme II as shown below, but other reactions may be carried out as needed, depending on the application, materials, and conditions.

[0027] (Option II)

[0028] Exemplary metal-based reactants include hydroxides, oxides, or alkoxides of metals, such as, but not limited to, alkali metal salts derived from metal bases selected from alkali metal hydroxides, alkali metal oxides, or alkali metal alkoxides, or alkaline earth metal salts derived from metal bases selected from alkaline earth metal hydroxides, alkaline earth metal oxides, or alkaline earth metal alkoxides. Suitable metal-based compounds include lithium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and aluminum hydroxide. Other examples of metal-based compounds include lithium oxide, magnesium oxide, calcium oxide, and barium oxide. In preferred examples, the alkaline earth metal base is lime or calcium hydroxide. Additives may be borated as needed, depending on the application and intended use.

[0029] Neutralization (and the subsequent over-alkalization discussed in more detail below) is carried out in the presence of a solvent or solvent system. In one method, the solvent and / or system is one or more organic compounds with a boiling point less than about 100 °C; in other methods, it is a compound with a boiling point less than about 100 °C at a pressure of about 1000 mbar to about 40 mbar (or, in other methods, about 1000 mbar to about 300 mbar). Suitable examples include xylene, toluene, octane, butanol, heptane, methanol, pentanol, acetone, benzene, cyclohexane, cyclopentane, ethanol, hexane, pentane, propanol, water, or combinations thereof. In one method, the solvent includes one or more of heptane, methanol, water, and combinations thereof, and in one method, based on the total amount of solvent, the solvent system used for neutralization may be about 80% to about 95% by weight of heptane, about 2% to about 10% by weight of methanol, and about 5% to about 15% by weight of water. In another method, the solvent may be a heptane / methanol system, and in some embodiments comprises about 85% to about 95% heptane and about 5% to about 15% methanol. The total amount of solvent used for neutralization may be about 10% to about 80% by weight, based on the total weight of the solvent, base, and alkylphenol / phenolate. In one method, a base and / or alkaline earth metal source may be added in excess as a slurry (such as a premix of a metal base and a solvent) and then reacted with a sulfurized alkylphenol compound.

[0030] In one method, the neutralizing solvent lacks substances with high boiling points, such as solvents with a boiling point of about 100°C or higher at the stated pressure, such as ethylene glycol, propylene glycol, and / or decanol. In optional methods and as used herein, lack of or absence of such compounds means that the solvent contains less than about 10% by weight, less than about 5% by weight, less than about 2% by weight, less than 1% by weight, less than 0.5% by weight of the high-boiling-point solvent, or does not contain the high-boiling-point solvent.

[0031] The neutralization reaction between the metal alkali and the sulfurized alkylphenol is carried out under conditions that effectively maintain the high sulfurization ratio achieved during the sulfurization reaction. In one method, neutralization occurs at low temperatures, such as no higher than about 140°C, in some methods no higher than about 120°C, in others no higher than about 100°C, and in still preferred methods no higher than about 80°C, to maintain the high sulfurization ratio achieved during the previous sulfurization reaction. Neutralization at higher temperatures tends to lead to an increase and / or regeneration of the level of unsulfurized alkylphenol or alkylphenol salts, which reduces the sulfurization ratio, which is undesirable. Instead, the method described herein selects conditions that maintain a high sulfurization level and ratio throughout the treatment. In other methods, neutralization is carried out at temperatures ranging from at least about 20°C, at least about 30°C, at least about 40°C, at least about 50°C, at least about 60°C to less than about 140°C, less than about 130°C, less than about 120°C, less than about 110°C, less than about 100°C, less than about 90°C, or less than about 80°C. The neutralization reaction should occur and last from about 5 minutes to about 60 minutes.

[0032] Over-alkalization

[0033] Next, over-alkalization is optional, but preferred in some embodiments, and is carried out during or alternatively after the above-described neutralization. In one method, the sulfided alkylphenol / alkylphenol salt is over-alkalized by reacting with an excess of metal alkali and / or with an acidic over-alkalizing compound such as, for example, carbon dioxide or boric acid. In another method, over-alkalization is carried out in the presence of a solvent, such as any solvent from the solvent system described above, via carbonation (reaction with carbon dioxide) and neutralization. A convenient carbonation reaction is to pass gaseous carbon dioxide through the reaction mixture. Excess solvent and any water formed during the over-alkalization reaction can be removed, as needed, during or after the reaction by distillation, as discussed further below.

[0034] In one embodiment, an exemplary over-alkaliening reaction may be the reaction of a sulfurized alkylphenol or its salt with an alkali metal or alkaline earth metal such as lime in the presence of carbon dioxide and a solvent system as discussed above. Conveniently, the reaction can be carried out by bubbling gaseous carbon dioxide through the mixture of the reaction and solvent systems. Just as the neutralization temperature is controlled at a low level to maintain a high level of sulfurization, the over-alkaliening temperature is also maintained low to maintain a high level and ratio of sulfurization throughout the over-alkaliening process. For example, the over-alkaliening temperature is not greater than about 140°C, in some methods not greater than about 120°C, in others not greater than about 100°C, and in still preferred methods, at a temperature not greater than about 80°C to maintain a high sulfurization-to-neutralization ratio from the over-alkaliening treatment. Over-alkaliening at higher temperatures also tends to result in a higher level of residual unsulfurized alkylphenol / phenolate or increased regeneration, leading to a lower sulfurization ratio, which is undesirable.

[0035] In other methods, over-alkaliening is carried out at temperatures ranging from at least about 20°C, at least about 30°C, at least about 40°C, at least about 50°C, at least about 60°C to less than about 140°C, less than about 130°C, less than about 120°C, less than about 110°C, less than about 100°C, less than about 90°C, or less than about 80°C. The degree of over-alkaliening can be controlled by the amount of alkali metal or alkaline earth metal added to the reaction mixture, the amount of carbon dioxide and other reactants (if any), and the reaction conditions used during the carbonation process. In the methods, at said temperatures, over-alkaliening, or over-alkaliening via carbonation, occurs for a time sufficient to achieve the desired degree of over-alkaliening or TBN, and in some methods this can be from about 30 minutes to about 180 minutes.

[0036] Following over-alkalization, the over-alkalized and sulfurized alkylphenol salts may have a TBN of about 100 mg KOH / g to about 400 mg KOH / g, or about 150 mg KOH / g to about 400 mg KOH / g, and in other methods about 200 mg KOH / g to about 300 mg KOH / g, and in still other methods about 220 mg KOH / g to about 275 mg KOH / g. Even during over-alkalization, the sulfurized alkylphenol salts maintain a high level of sulfurization compared to unsulfurized alkylphenol salts or alkylphenols, and this sulfurization ratio is maintained at at least about 500:1 after the over-alkalization step and during post-treatment as discussed further below.

[0037] Post-processing

[0038] Following optional over-alkalization, the composition comprising the sulfidated alkylphenol salt is typically subjected to numerous steps to prepare the final sulfidated alkylphenol salt product. However, these post-treatment steps should also be carried out under conditions that effectively maintain a high sulfidation ratio. In this method, all post-treatments are performed at low temperatures to maintain a high sulfidation level relative to the unsulfidated alkylphenol salt and to prevent the regeneration of unsulfidated alkylphenol or phenolate.

[0039] Examples of post-treatments occurring at low temperatures include one or more of the following: vacuum stripping, distillation, jetting, filtration, degassing, evaporation, scraped-film evaporation, centrifugation, dilution, liquid-liquid extraction, membrane separation, chromatography, absorption, supercritical extraction, and / or combinations thereof, wherein all individual and / or combined post-treatments are carried out under conditions that effectively maintain a high level of sulfidation, such as at low temperatures not exceeding about 140°C. Similar to neutralization and over-alkalization, any post-treatment is also carried out at temperatures ranging from at least about 20°C, at least about 30°C, at least about 40°C, at least about 50°C, at least about 60°C to less than about 140°C, less than about 130°C, less than about 120°C, less than about 110°C, less than about 100°C, less than about 90°C, or less than about 80°C.

[0040] The method steps described herein produce over-alkalized and sulfided alkylphenolate products with high sulfidation levels or at least about 500:1, in other methods about 500:1 to about 5000:1, in other methods about 1000:1 to about 5000:1, about 1000:1 to about 3500:1, or even about 1000:1 to about 2000:1, of sulfided alkylphenolate / alkylphenol with a high sulfidation ratio, thereby demonstrating the high level of sulfided alkylphenolate relative to unsulfided alkylphenolate or unsulfided alkylphenol when in neutral to over-alkalized form. In other methods, the additives and methods described herein have less than about 0.2% by weight, less than about 0.1% by weight, less than about 0.08% by weight, less than about 0.05% by weight, or less than about 0.03% by weight of unsulfurized alkylphenol salts / alkylphenols or about 0.01% by weight to about 0.2% by weight (about 0.01% by weight to about 0.1% by weight) or any range thereof of unsulfurized alkylphenol salts / alkylphenols.

[0041] The unique feature of the method presented herein is that it typically does not require the removal of unsulfurized alkylphenol salts or alkylphenols (such as after sulfidation or after any intermediate step) because these method steps and / or the use of the selected sulfur chloride blend do not generate and / or regenerate unsulfurized alkylphenol salts or alkylphenols at any step of the various treatment steps, but rather maintain a high sulfidation level throughout the treatment process. Therefore, the method presented herein avoids the cost and complexity of existing methods that require the removal of residual and / or unsulfurized alkylphenol salts / phenols during intermediate or post-treatment steps.

[0042] Another unique aspect of the method described herein is that the preferred sulfur dichloride blend used in the sulfidation step produces a sulfurized alkylphenol salt product or composition with low levels of residual organochlorides, such as about 1500 ppm or less of chloride, about 1450 ppm or less of chloride, or about 1400 ppm or less of chloride. In other embodiments, the method described herein provides a sulfurized alkylphenol salt product or composition having about 600 ppm to about 1500 ppm of residual chloride, about 700 ppm to about 1450 ppm of residual chloride, or about 800 ppm to about 1400 ppm of residual chloride (or any other range between these indicated endpoints). Chloride content is measured herein by X-ray fluorescence (XRF) spectroscopy according to ASTM D4929.

[0043] Lubricating oil composition

[0044] The optionally over-alkalized and sulfidated alkylphenol salt products described herein can be combined with one or more additional optional additives, or with a major amount of a base oil blend or a base oil blend having a lubricating viscosity (as described below), to produce a lubricating oil composition. In the method, the lubricating oil composition comprises about 50% by weight or more of a base oil blend, about 60% by weight or more, about 70% by weight or more, or about 80% by weight or more to about 95% by weight or less, about 90% by weight or less, or about 85% by weight or less of a base oil blend, which is further discussed below.

[0045] In the method, the lubricating oil composition herein may contain about 0.02% to about 5% by weight, about 0.2% to about 3% by weight in other methods, and about 0.2% to about 2% by weight in other methods, of an alkylphenol salt product or composition optionally over-alkalized and sulfided by the method herein.

[0046] In some methods, the additives prepared by the methods described herein can be used as detergents in lubricating oils to neutralize acids and / or help control rust, corrosion, and deposits. Furthermore, the detergents described herein can also be used in fuels, including but not limited to gasoline, diesel, and biodiesel, for spark, compression, and hybrid engines.

[0047] It is noteworthy that, when measured according to ASTM D6594, the additives prepared by the methods described herein unexpectedly provide low levels of copper corrosion. For example, when measuring the copper corrosion of a lubricant containing a sulfurized alkylphenol salt as described herein according to ASTM D6594, the copper level in the lubricant is at least about 50% lower than that in a lubricant containing the same sulfurized alkylphenol salt but prepared by using a sulfur chloride blend containing 100% sulfur monochloride (preferably, the copper level is at least about 60% lower than that in a lubricant with an additive made from sulfur monochloride, more preferably at least about 70% lower, and most preferably at least about 80% lower than that in a lubricant containing an additive produced from a 100% sulfur monochloride blend). In other embodiments, copper corrosion from lubricants containing sulfurized alkylphenol salts of this disclosure is about 50% to about 90% less (preferably about 60% to about 85%, more preferably about 70% to about 85%, and even more preferably about 75% to about 85%) less than copper corrosion achieved by lubricants containing sulfurized alkylphenol salts prepared with 100% sulfur monochloride. In other methods, lubricants containing sulfurized alkylphenol salt additives of this document may also have about 70 ppm or less of copper when measured according to ASTM D6594, or in other methods, about 60 ppm or less, about 50 ppm or less, about 40 ppm or less, about 30 ppm or less, about 20 ppm or less, or about 10 ppm or less.

[0048] The lubricants, combinations of components, dispersant inhibitor packages and / or individual components described herein are suitable for use in a wide variety of lubricants, such as automotive lubricants and / or greases, internal combustion engine oils, blended engine oils, hybrid motor lubricants, powertrain lubricants, transmission lubricants, gear oils, hydraulic lubricants, tractor hydraulic fluids, metal working fluids, turbine engine lubricants, stationary engine lubricants, tractor lubricants, motorcycle lubricants, power steering fluids, clutch fluids, shaft fluids, wet breakage fluids, etc.

[0049] Suitable engine types may include, but are not limited to, heavy-duty diesel engines, passenger car engines, light-duty diesel engines, medium-speed diesel engines, or marine engines. Internal combustion engines can be diesel-fueled engines, gasoline-fueled engines, natural gas-fueled engines, biofuel engines, hybrid diesel / biofuel engines, hybrid gasoline / biofuel engines, alcohol-fueled engines, hybrid gasoline / alcohol-fueled engines, compressed natural gas (CNG) engines, or mixtures thereof. Diesel engines can be compression-ignition engines. Gasoline engines can be spark-ignition engines. Internal combustion engines can also be used in combination with electrical or battery power sources. Engines constructed in this way are often referred to as hybrid engines. Internal combustion engines can be 2-stroke, 4-stroke, or rotary engines. Suitable internal combustion engines include marine diesel engines (such as those for inland vessels), aviation piston engines, low-load diesel engines, and engines for motorcycles, automobiles, locomotives, and trucks. Engines may be coupled with turbochargers.

[0050] Regardless of the sulfur, phosphorus, or sulfate ash (ASTM D-874) content, the internal combustion engine lubricant composition is suitable for any engine lubricant. The sulfur content of the engine oil lubricant can be about 1% by weight or less, or about 0.8% by weight or less, or about 0.5% by weight or less, or about 0.3% by weight or less, or about 0.2% by weight or less. In one embodiment, the sulfur content can range from about 0.001% by weight to about 0.5% by weight, or from about 0.01% by weight to about 0.3% by weight. The phosphorus content can be about 0.2% by weight or less, or about 0.1% by weight or less, or about 0.085% by weight or less, or about 0.08% by weight or less, or even about 0.06% by weight or less, about 0.055% by weight or less, or about 0.05% by weight or less. In one embodiment, the phosphorus content can be from about 50 ppm to about 1000 ppm, or from about 325 ppm to about 850 ppm. The total sulfate ash content may be about 2% by weight or less, or about 1.5% by weight or less, or about 1.1% by weight or less, or about 1% by weight or less, or about 0.8% by weight or less, or about 0.5% by weight or less. In one embodiment, the sulfate ash content may be about 0.05% by weight to about 0.9% by weight, or about 0.1% by weight or about 0.2% by weight to about 0.45% by weight. In another embodiment, the sulfur content may be about 0.4% by weight or less, the phosphorus content may be about 0.08% by weight or less, and the sulfate ash content may be about 1% by weight or less. In yet another embodiment, the sulfur content may be about 0.3% by weight or less, the phosphorus content may be about 0.05% by weight or less, and the sulfate ash content may be about 0.8% by weight or less.

[0051] Furthermore, the lubricants described in this manual are suitable for meeting one or more industry specifications, such as ILSAC GF-3, GF-4, GF-5, GF-6, PC-11, CF, CF-4, CH-4, CK-4, FA-4, CJ-4, CI-4 Plus, CI-4, API SG, SJ, SL, SM, SN, SN PLUS, ACEA A1 / B1, A2 / B2, A3 / B3, A3 / B4, A5 / B5, C1, C2, C3, C4, C5, E4 / E6 / E7 / E9, Euro 5 / 6, JASO DL-1, Low SAPS, Mid SAPS, or original equipment manufacturer (OEM) specifications, such as Dexos1™, Dexos2™, MB-Approval. 229.1, 229.3, 229.5, 229.51 / 229.31, 229.52, 229.6, 229.71, 226.5, 226.51, 228.0 / .1, 228.2 / .3, 228.31, 228.5, 228.51, 228.61, VW 501.01, 502.00, 503.00 / 503.01, 504.00, 505.00, 505.01, 506.00 / 506.01, 507.00, 508.00, 509.00, 508.88, 509.99, BMW Longlife-01, Longlife-01 FE、Longlife-04、Longlife-12 FE, Longlife-14FE+, Longlife-17 FE+, Porsche A40, C30, Peugeot Citroën Automobiles B71 2290, B712294, B71 2295, B71 2296, B71 2297, B71 2300, B71 2302, B71 2312, B71 2007, B71 2008, Renault RN0700, RN0710, RN0720, Ford WSS-M2C153-H, WSS-M2C930-A, WSS-M2C945-A, WSS-M2C913A, WSS-M2C913-B, WS S-M2C913-C, WSS-M2C913-D, WSS-M2C948-B, WSS-M2C948-A, GM6094-M, Chrysler MS-6395, Fiat 9.55535 G1, G2, M2, N1, N2, Z2, S1, S2, S3, S4, T2, DS1, DSX, GH2, GS1, GSX, CR1, Jaguar Land Rover STJLR.03.5003, STJLR.03.5004, STJLR.03.5005, STJLR.03.5006, STJLR.03.5007, STJLR.51.5122, or any past or future PCMO or HDD specifications not mentioned herein. In some implementations, for passenger car engine oil (PCMO) applications, the phosphorus content in the finished fluid is 1000 ppm or less, or 900 ppm or less, or 800 ppm or less.

[0052] Base oil or base oil blend The base oils used in lubricating oil compositions as described herein may be oils with lubricating viscosity and selected from any of the Group I to Group V base oils as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five base oil groups are generally listed in Table 1 below:

[0053] Table 1

[0054]

[0055] Groups I, II, and III are mineral oil processing feedstocks. Group IV base oils contain truly synthetic molecules produced through the polymerization of olefinic unsaturated hydrocarbons. Many Group V base oils are also truly synthetic products and can include diesters, polyol esters, polyalkylene glycols, alkylated aromatic compounds, polyphosphates, polyethylene ethers, and / or polyphenylene ethers, but can also be naturally occurring oils such as vegetable oils. It should be noted that although Group III base oils are derived from mineral oils, the rigorous processing these fluids undergo results in physical properties very similar to some truly synthetic oils, such as PAO. Therefore, oils derived from Group III base oils can be referred to as synthetic fluids in industry. Group II+ can include high viscosity index Group II oils.

[0056] The base oil blend used in the disclosed lubricating oil composition may be mineral oil, animal oil, vegetable oil, synthetic oil, synthetic oil blends, or mixtures thereof. Suitable oils may be derived from hydrocracked, hydrogenated, hydrorefined, unrefined, refined, and refined oils, as well as mixtures thereof.

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

[0058] Refined oils, also known as recycled oils or reprocessed oils, are obtained using the same or similar processes as refined oils. These oils are typically further processed using techniques aimed at removing waste additives and oil decomposition products.

[0059] Mineral oils may include oils obtained through drilling or oils derived from plants and animals, or any mixture thereof. For example, such oils may include, but are not limited to: castor oil, lard, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricants, such as liquid petroleum and solvent-treated or acid-treated mineral lubricants of alkanes, cycloalkanes, or mixtures of alkane-cycloalkanes. If desired, such oils may be partially or fully hydrogenated. Oils derived from coal or shale may also be available.

[0060] Useful synthetic lubricants may include hydrocarbon oils such as polymeric, oligomeric, or copolymeric olefins (e.g., polybutene, polypropylene, propylene-isobutylene copolymers); trimers or oligomers of poly(1-hexene), poly(1-octene), and 1-decene, such as poly(1-decene), which are commonly referred to as α-olefins, and mixtures thereof; alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene); polyphenylene (e.g., biphenyl, terphenyl, alkylated polyphenylene); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers, and alkylated diphenyl sulfides and their derivatives, analogs, and homologues, or mixtures thereof. Polyα-olefins are typically hydrogenated materials.

[0061] Other synthetic lubricants include phosphoric acid-containing polyol esters, diesters, liquid esters (e.g., diethyl esters of toluene phosphate, trioctyl phosphate, and decanephosphonic acid), or polytetrahydrofurans. Synthetic oils can be produced via the Fischer-Tropsch reaction and are typically hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil can be prepared via a Fischer-Tropsch gas-liquid synthesis process, along with other gas-liquid oils.

[0062] The base oil included in the lubricating composition in a major amount may be selected from Group I, Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, and wherein the base oil in a major amount is different from the base oil produced by providing additive components or viscosity index improvers in the composition. In another embodiment, the base oil included in the lubricating composition in a major amount may be selected from Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, and wherein the base oil in a major amount is different from the base oil produced by providing additive components or viscosity index improvers in the composition.

[0063] The amount of oil with lubricating viscosity may be the balance remaining after subtracting the total amount of performance additives (including viscosity index improvers and / or pour point depressants and / or other pretreatment additives) from 100% by weight. For example, the amount of oil with lubricating viscosity that may be present in the finished fluid may be the main amount, such as greater than about 50% by weight, greater than about 60% by weight, greater than about 70% by weight, greater than about 80% by weight, greater than about 85% by weight, or greater than about 90% by weight.

[0064] Optional additives :

[0065] The lubricating oil compositions described herein may also include, as needed, a number of optional additives in combination with optionally over-alkalized and sulfurized alkylphenol salt products to meet performance criteria. Those optional additives are described in the following paragraphs.

[0066] dispersant Lubricating oil compositions may optionally include one or more dispersants or mixtures thereof. Dispersants are generally referred to as ashless dispersants because they do not contain ash-forming metals before being incorporated into the lubricating oil composition and typically do not provide any ash when added to the lubricant. Ashless dispersants are characterized by polar groups attached to relatively high molecular weight hydrocarbon chains. Typical ashless dispersants include N-substituted long-chain alkenyl succinimides. Examples of N-substituted long-chain alkenyl succinimides include polyisobutylene succinimides, wherein, as measured by GPC, the number average molecular weight of the polyisobutylene substituents is in the range of about 350 to about 50,000, or about 5,000, or about 3,000. Succinimid dispersants and their preparation are disclosed, for example, in U.S. Patent No. 7,897,696 or U.S. Patent No. 4,234,435. The alkenyl substituent can be prepared from polymerizable monomers containing about 2 to about 16, about 2 to about 8, or about 2 to about 6 carbon atoms. Succinimid dispersants are typically polyamines, usually poly(ethylene amine) imides.

[0067] Preferred amines are selected from polyamines and hydroxylamines. Examples of polyamines that may be used include, but are not limited to, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and higher homologues such as pentaethylenehexamine (PEHA).

[0068] Suitable heavy polyamines are mixtures of polyalkylene polyamines containing small amounts of lower polyamine oligomers (such as TEPA and PEHA (pentaethylenehexamine)) but primarily having 6 or more nitrogen atoms per molecule, 2 or more primary amines, and oligomers with more extensive branching than conventional polyamine mixtures. Heavy polyamines preferably comprise polyamine oligomers containing 7 or more nitrogen atoms per molecule and 2 or more primary amines per molecule. Heavy polyamines contain greater than 28% by weight (e.g., >32% by weight) of total nitrogen and 120 g / equivalent to 160 g / equivalent of primary amine groups by equivalent weight.

[0069] In some methods, the appropriate polyamine is often referred to as PAM and contains a mixture of ethylenediamines, in which TEPA and pentaethylenehexamine (PEHA) are the main components of the polyamine, typically less than about 80%.

[0070] Typically, PAM has a primary amine content of 8.7 mEq / g to 8.9 mEq / g (equivalent weight of primary amine is 115 g / equivalent to 112 g / equivalent) and a total nitrogen content of approximately 33 wt% to 34 wt%. Heavier PAM oligomers are cut with almost no TEPA and only a very small amount of PEHA, but mainly contain more than 6 nitrogen atoms and more extensively branched oligomers, which can produce dispersants with improved dispersibility.

[0071] In one embodiment, this disclosure further comprises at least one polyisobutylene succinimide dispersant derived from polyisobutylene with a number average molecular weight in the range of about 350 to about 50,000, about 5,000, or about 3,000, as determined by GPC. The polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0072] In some embodiments, polyisobutylene (when included) may have terminal double bonds in amounts greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol%. Such PIBs are also referred to as highly reactive PIBs (“HR-PIBs”). HR-PIBs with a number-average molecular weight in the range of about 800 to about 5000, as determined by GPC, are suitable for use in embodiments of this disclosure. Conventional PIBs typically have terminal double bonds in amounts less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0073] HR-PIBs with a number-average molecular weight in the range of about 900 to about 3000, as determined by GPC, are suitable. Such HR-PIBs are commercially available or can be synthesized by polymerizing isobutylene in the presence of a non-chlorinated catalyst, such as boron trifluoride, as described in U.S. Patent No. 4,152,499 to Boerzel et al. and U.S. Patent No. 5,739,355 to Gateau et al. When used in the aforementioned thermobutylene reaction, HR-PIBs can increase the conversion rate and reduce the amount of sediment formed in the reaction due to enhanced reactivity. Suitable methods are described in U.S. Patent No. 7,897,696.

[0074] In one embodiment, this disclosure also includes at least one dispersant derived from polyisobutylene succinic anhydride (“PIBSA”). PIBSA may have an average succinic acid fraction of about 1.0 to about 2.0 per polymer.

[0075] Chromatographic techniques can be used to determine the activity percentage of alkenyl or alkyl succinic anhydrides. This method is described in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0076] The conversion percentage of polyolefins is calculated from the activity percentage using the equations in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0077] Unless otherwise stated, all percentages are weight percentages (wt%), and all molecular weights are number average molecular weights determined by gel permeation chromatography (GPC) using commercially available polystyrene standards with a number average molecular weight of 180 to approximately 18,000 as a calibration reference.

[0078] In one embodiment, the dispersant may be derived from polyalphaolefin (PAO) succinic anhydride. In another embodiment, the dispersant may be derived from an olefin maleic anhydride copolymer. For example, the dispersant may be described as polyPIBSA. In one embodiment, the dispersant may be derived from an anhydride grafted onto an ethylene-propylene copolymer.

[0079] Suitable classes of nitrogen-containing dispersants may be derived from olefin copolymers (OCPs), more specifically, ethylene-propylene dispersants which may be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that can react with functionalized OCPs is described in U.S. Patents 7,485,603; 7,786,057; 7,253,231; 6,107,257; and 5,075,383; and / or are commercially available.

[0080] Suitable dispersants can also be Mannich bases. Mannich bases are substances formed by the condensation of alkyl-substituted phenols, polyalkylene polyamines, and aldehydes (such as formaldehyde) with higher molecular weight alkyl groups. Mannich bases are described in more detail in U.S. Patent No. 3,634,515.

[0081] Suitable dispersants can also be high molecular weight esters or hemiesteramides. Suitable dispersants can also be post-treated by conventional methods through reaction with any of a variety of reagents. These include boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydrides, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenolic esters, and phosphorus compounds. US 7,645,726; US 7,214,649; and US 8,048,831 are incorporated herein by reference in their entirety.

[0082] In addition to carbonate and boric acid posttreatments, both compounds can be posttreated or further posttreated using a variety of posttreatment methods designed to improve or impart different properties. Such posttreatments include those outlined in columns 27 through 29 of U.S. Patent No. 5,241,003, which are incorporated herein by reference. Such treatments include treatment with: inorganic phosphorous acid or anhydrous substances (e.g., U.S. Patent Nos. 3,403,102 and 4,648,980); organophosphorus compounds (e.g., U.S. Patent No. 3,502,677); phosphorus pentasulfide; boron compounds as described above (e.g., U.S. Patent Nos. 3,178,663 and 4,652,387); carboxylic acids, polycarboxylic acids, acid anhydrides, and / or acidic halides (e.g., U.S. Patent Nos. 3,708,522 and 4,948,003). 386); epoxides, polyepoxides, or thioepoxides (e.g., U.S. Patent Nos. 3,859,318 and 5,026,495); aldehydes or ketones (e.g., U.S. Patent No. 3,458,530); carbon disulfide (e.g., U.S. Patent No. 3,256,185); glycidyl (e.g., U.S. Patent No. 4,617,137); urea, thiourea, or guanidine (e.g., U.S. Patent Nos. 3,312,619; 3,865,813; and British Patent GB 1,065,595); organic sulfonic acids (e.g., U.S. Patent No. 3,189,544 and British Patent GB 1,065,595). 2,140,811); alkenyl cyanides (e.g., U.S. Patent Nos. 3,278,550 and 3,366,569); dienoketones (e.g., U.S. Patent No. 3,546,243); diisocyanates (e.g., U.S. Patent No. 3,573,205); alkane sulcolepsy (e.g., U.S. Patent No. 3,749,695); 1,3-dicarbonyl compounds (e.g., U.S. Patent No. 4,579,675); sulfates of alkoxylated alcohols or phenols (e.g., U.S. Patent No. 3,954,639); cyclic compounds Lactones (e.g., U.S. Patent Nos. 4,617,138; 4,645,515; 4,668,246; 4,963,275; and 4,971,711); cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Patent Nos. 4,612,132; 4,647,390; 4,648,886; and 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Patent No. 4,971,598 and British Patent GB 2,140,811); hydroxyl-protected chlorodicarbonyloxy compounds (e.g., U.S. Patent No. 4,614,522); lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Patent Nos. 4,614,603 and 4,666,460);Cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Patent Nos. 4,612,132; 4,647,390; 4,646,860; and 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Patent No. 4,971,598 and British Patent GB). 2,440,811); hydroxyl-protected chlorodicarbonyloxy compounds (e.g., U.S. Patent No. 4,614,522); lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Patent Nos. 4,614,603 and 4,666,460); cyclic carbamates, cyclic thiocarbamates, or cyclic dithiocarbamates (e.g., U.S. Patent Nos. 4,663,062 and 4,666,459); hydroxy aliphatic carboxylic acids (e.g., U.S. Patent Nos. 4,482,464; 4,521,318; 4,713,189); oxidized Agents (e.g., U.S. Patent No. 4,379,064); combinations of phosphorus pentasulfide and polyalkylene polyamines (e.g., U.S. Patent No. 3,185,647); combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (e.g., U.S. Patent Nos. 3,390,086; 3,470,098); combinations of hydrazine and carbon disulfide (e.g., U.S. Patent No. 3,519,564); combinations of aldehydes and phenols (e.g., U.S. Patent Nos. 3,649,229; 5,030,249; 5,039,307); combinations of aldehydes and O-diesters of dithiophosphate (e.g., U.S. Patent No. 4,379,064). 3,865,740); combinations of hydroxyaliphatic carboxylic acids and boric acid (e.g., U.S. Patent No. 4,554,086); combinations of hydroxyaliphatic carboxylic acids, then formaldehyde and phenol (e.g., U.S. Patent No. 4,636,322); combinations of hydroxyaliphatic carboxylic acids and then aliphatic dicarboxylic acids (e.g., U.S. Patent No. 4,663,064); combinations of formaldehyde and phenol and then glycolic acid (e.g., U.S. Patent No. 4,699,724); combinations of hydroxyaliphatic carboxylic acids or oxalic acid, and then diisocyanates (e.g., U.S. Patent No. 4,713,191); inorganic acids or anhydrides of phosphorus or Combinations of some or all of their sulfur analogs with boron compounds (e.g., U.S. Patent No. 4,857,214); combinations of organic diacids, then unsaturated fatty acids, then nitrosoaromatic amines, optionally followed by boron compounds, and then ethanolating agents (e.g., U.S. Patent No. 4,973,412); combinations of aldehydes and triazoles (e.g., U.S. Patent No. 4,963,278); combinations of aldehydes and triazoles, then boron compounds (e.g., U.S. Patent No. 4,981,492); combinations of cyclic lactones and boron compounds (e.g., U.S. Patent Nos. 4,963,275 and 4,971,711). The patents mentioned above are incorporated herein by reference in their entirety.

[0083] The TBN of a suitable dispersant can be from about 10 mg KOH / g to about 65 mg KOH / g on an oil-free basis. If measured on a dispersant sample containing about 50% diluted oil, it is equivalent to a TBN of about 5 mg KOH / g to about 30 mg KOH / g. TBN is measured according to the method of ASTM D2896.

[0084] In some other embodiments, the optional dispersant additive may be a hydrocarbon-substituted succinamide or succinimide dispersant. In the method, the hydrocarbon-substituted succinamide or succinimide dispersant is derived from a hydrocarbon-substituted acylated agent reacting with a polyalkylene polyamine, and wherein, as measured by GPC using polystyrene as a calibration reference, the hydrocarbon substituent of the succinamide or succinimide dispersant is a linear or branched hydrocarbon group with a number average molecular weight of about 250 to about 5,000.

[0085] In some methods, the polyalkylene polyamine used to form the dispersant has the formula...

[0086]

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

[0088] If a dispersant is present, it may be sufficient to provide up to about 20% by weight for use, based on the final weight of the lubricating oil composition. Another amount of dispersant that may be used, based on the final weight of the lubricating oil composition, may be about 0.1% to about 15% by weight, or about 0.1% to about 10% by weight, or about 0.1% to about 8% by weight, or about 1% to about 10% by weight, or about 1% to about 8% by weight, or about 1% to about 6% by weight. In some embodiments, the lubricating oil composition utilizes a mixed dispersant system. A single type of dispersant or a mixture of two or more types of dispersants may be used in any desired ratio.

[0089] antioxidantsThe lubricating oil compositions described herein may optionally contain one or more antioxidants. Antioxidant compounds are known and include, for example, phenolates, phenolate sulfides, sulfide olefins, phosphosulfur terpenes, sulfide esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, dinonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine), phenyl-α-naphthylamine, alkylated phenyl-α-naphthylamine, hindered nonaromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, macromolecular antioxidants, or mixtures thereof. Antioxidant compounds may be used alone or in combination.

[0090] Hindered phenolic antioxidants may contain sec-butyl and / or tert-butyl groups as sterically hindered groups. The phenolic group may also be substituted with a hydrocarbon group and / or a bridging group attached to a second aromatic group. Examples of suitable hindered phenolic antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol, or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenolic antioxidant may be an ester and may include, for example, Irganox, which is available from BASF. ™ L-135 may be derived from an addition product of 2,6-di-tert-butylphenol and an alkyl acrylate, wherein the alkyl group may contain about 1 to about 18, or about 2 to about 12, or about 2 to about 8, or about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenolic antioxidant may be an ester and may include Ethanox, available from Albemarle Corporation. ™ 4716.

[0091] Available antioxidants may include diarylamines and high molecular weight phenols. In one embodiment, the lubricating oil composition may contain a mixture of diarylamines and high molecular weight phenols, such that each antioxidant may be sufficient to provide up to about 5% by weight based on the final weight of the lubricating oil composition. In one embodiment, based on the final weight of the lubricating oil composition, the antioxidant may be a mixture of about 0.3% to about 1.5% by weight of diarylamine and about 0.4% to about 2.5% by weight of high molecular weight phenols.

[0092] Examples of suitable olefins that can be vulcanized to form vulcanized olefins include propylene, butene, isobutylene, polyisobutylene, pentene, hexene, hepten, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecadecene, nonadecene, eicosene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecadecene, nonadecene, eicosene, or mixtures thereof, as well as their dimers, trimers, and tetramers, are particularly suitable olefins. Alternatively, the olefin may be a Diels-Alder adduct of a diene (such as 1,3-butadiene) and an unsaturated ester (such as butyl acrylate).

[0093] Another class of sulfurized olefins includes sulfurized fatty acids and their esters. Fatty acids are typically derived from vegetable or animal oils and generally contain about 4 to about 22 carbon atoms. Examples of suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitic acid, or mixtures thereof. Typically, fatty acids are derived from lard, pine oil, peanut oil, soybean oil, cottonseed oil, sunflower oil, or mixtures thereof. Fatty acids and / or esters may be mixed with olefins such as α-olefins.

[0094] In another alternative embodiment, in addition to the phenolic and / or amine antioxidants discussed above, the antioxidant composition also contains a molybdenum-containing antioxidant. When using a combination of these three antioxidants, preferably, the ratio of the phenolic antioxidant to the amine antioxidant to the molybdenum-containing antioxidant is (0 to 2):(0 to 2):(0 to 1).

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

[0096] Anti-wear agent The lubricating oil compositions described herein may optionally contain one or more anti-wear agents. Examples of suitable anti-wear agents include, but are not limited to, metal thiophosphates; metal dialkyl dithiophosphates; phosphate esters or salts thereof; phosphate esters; phosphites; phosphoric acid esters, ethers or amides; sulfurized olefins; compounds containing thiocarbamates, including thiocarbamates, alkylene-coupled thiocarbamates and bis(S-alkyldithiocarbamoyl) disulfides; and mixtures thereof. A suitable anti-wear agent may be molybdenum dithiocarbamate. Phosphorus-containing anti-wear agents are described more fully in European Patent 612 839. The metal in the dialkyl dithiophosphate may be an alkali metal, an alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium or zinc. A suitable anti-wear agent may be zinc dialkyl dithiophosphate.

[0097] Other examples of suitable anti-wear agents include titanium compounds, tartrates, tartrate imides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (such as dibutyl phosphite), phosphonates, and compounds containing thiocarbamates (such as thiocarbamates, thiocarbamate amides, thiocarbamate ethers, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamoyl) disulfides). Tartrates or tartrate imides may contain alkyl ester groups, wherein the total number of carbon atoms in the alkyl groups may be at least 8. In one embodiment, the anti-wear agent may include citrates.

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

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

[0100] Additional cleaning agent The lubricating oil composition may optionally further comprise one or more neutral, low-alkalinity, or over-alkalinity detergents, or mixtures thereof. Suitable detergent matrices include phenolates, sulfur-containing phenolates, sulfonates, calixarates, salicylates, salicylates, carboxylic acids, phosphoric acid, monothiophosphoric acid and / or dithiophosphoric acid, alkylphenols, thiocoupled alkylphenol compounds, or methylene-bridged phenols. Suitable detergents and methods of their preparation are described in more detail in several patent publications, including US 7,732,390 and the references cited therein.

[0101] The detergent matrix can be salted from, but is not limited to, alkali metals or alkaline earth metals such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent is barium-free. In some embodiments, the detergent may contain trace amounts of other metals, such as magnesium or calcium, such as 50 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less, or 10 ppm or less. Suitable detergents may include alkali metal or alkaline earth metal salts of petroleum sulfonic acids and long-chain mono- or dialkyl aryl sulfonic acids, wherein the aryl group is benzyl, tolyl, or xylyl. Examples of suitable detergents include, but are not limited to: calcium phenolate, calcium sulfonate, calcium calixarate, calcium salicylate, calcium carboxylate, calcium phosphate, calcium monothiophosphate and / or calcium dithiophosphate, calcium alkylphenolate, calcium thiocoupled alkylphenolate compound, methylene-bridged calcium phenolate, magnesium phenolate, magnesium sulfonate, magnesium calixarate, magnesium salicylate, magnesium carboxylate, magnesium phosphate, magnesium monothiophosphate and / or magnesium dithiophosphate, magnesium alkylphenolate, magnesium thiocoupled alkylphenolate compound, methylene-bridged magnesium phenolate, sodium phenolate, sodium sulfonate, sodium calixarate, sodium salicylate, sodium carboxylate, sodium phosphate, sodium monothiophosphate and / or sodium dithiophosphate, sodium alkylphenolate, sodium thiocoupled alkylphenolate compound, or sodium methylene-bridged sodium phenolate.

[0102] High-alkalinity detergent additives are well known in the art and can be alkali metal or alkaline earth metal high-alkalinity detergent additives. Such detergent additives are prepared by reacting a metal oxide or metal hydroxide with a matrix and carbon dioxide gas. The matrix is ​​typically an acid, such as aliphatic-substituted sulfonic acids, aliphatic-substituted carboxylic acids, or aliphatic-substituted phenols.

[0103] The term "highly basic" refers to metal salts, such as those containing sulfonates, carboxylates, and phenolates, in which the amount of metal present exceeds the stoichiometric amount. Such salts can have conversion levels exceeding 100% (i.e., they can contain more than 100% of the theoretical amount of metal required to convert an acid to its "normal," "neutral" salt). The expression "metal ratio," often abbreviated as MR, is used to represent the ratio of the total stoichiometric amount of metal in a highly basic salt to the stoichiometric amount of metal in a neutral salt, based on known chemical reactivity and stoichiometry. In normal or neutral salts, the metal ratio is one, while in highly basic salts, MR is greater than one. These are often referred to as highly basic, hyperbasic, or superbasic salts and can be salts of organic sulfuric acids, carboxylic acids, or phenols.

[0104] The total base number (TBN) of the over-alkali detergent in the lubricating oil composition may be about 200 mg KOH / g or greater, or, as in other examples, about 250 mg KOH / g or greater, or about 350 mg KOH / g or greater, or about 375 mg KOH / g or greater, or about 400 mg KOH / g or greater. TBN is measured by the method of ASTM D-2896.

[0105] Examples of suitable high-alkalinity detergents include, but are not limited to: high-alkalinity calcium phenolate, high-alkalinity calcium sulfur-containing phenolate, high-alkalinity calcium sulfonate, high-alkalinity calcium calixarate, high-alkalinity calcium salicylate, high-alkalinity calcium carboxylate, high-alkalinity calcium phosphate, high-alkalinity calcium monothiophosphate and / or calcium dithiophosphate, high-alkalinity calcium alkylphenolate, high-alkalinity calcium sulfur-coupled alkylphenolate, high-alkalinity calcium methylene-bridged phenolate, high-alkalinity magnesium phenolate, high-alkalinity magnesium sulfur-containing phenolate, high-alkalinity magnesium sulfonate, high-alkalinity magnesium calixarate, high-alkalinity magnesium salicylate, high-alkalinity magnesium carboxylate, high-alkalinity magnesium phosphate, high-alkalinity magnesium monothiophosphate and / or magnesium dithiophosphate, high-alkalinity magnesium alkylphenolate, high-alkalinity magnesium sulfur-coupled alkylphenolate, or high-alkalinity magnesium methylene-bridged phenolate.

[0106] The total base value of high-alkalinity calcium phenolate detergents is at least about 150 mg KOH / g, at least about 225 mg KOH / g, from at least about 225 mg KOH / g to about 400 mg KOH / g, from at least about 225 mg KOH / g to about 350 mg KOH / g, or from about 230 mg KOH / g to about 350 mg KOH / g, all as measured by the method of ASTM D-2896. When such detergent compositions are formed in an inert diluent (such as process oil, typically mineral oil), the total base value reflects the alkalinity of the overall composition, which includes the diluent and any other materials that may be present in the detergent composition (such as accelerators, etc.).

[0107] The metal-to-matrix ratio of the highly alkaline detergent can be 1.1:1, 2:1, 4:1, 5:1, 7:1, or 10:1. In some embodiments, the detergent is effective in reducing or preventing rust in the engine or other automotive components, such as transmissions or gears. The detergent may be present in the lubricating composition at about 0% to about 10% by weight, or about 0.1% to about 8% by weight, or about 1% to about 4% by weight, or greater than about 4% to about 8% by weight.

[0108] Extreme pressure agentThe lubricating oil compositions described herein may optionally contain one or more extreme pressure agents. Oil-soluble extreme pressure (EP) agents include sulfur-containing and chlorine-containing sulfur EP agents, chlorinated hydrocarbon EP agents, and phosphorus EP agents. Examples of such EP agents include chlorinated waxes; organosulfurs and polysulfides, such as dibenzyl disulfide, bis(chlorobenzyl) disulfide, dibutyltetrasulfide, methyl oleate sulfurized, alkyl phenol sulfurized, dipentene sulfurized, terpenes sulfurized, and Diels-Alder sulfurized adducts; phosphorus sulfides, such as the reaction products of phosphorus sulfide with turpentine or methyl oleate; phosphites, such as dialkyl phosphites and trialkyl phosphites, for example, dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite; dipentylphenyl phosphite, tridecyl phosphite, distearate phosphite, and polypropylene-substituted phenyl phosphite; metal thiocarbamates, such as zinc dioctyl dithiocarbamate and barium heptaphenolate; amine salts of alkyl and dialkyl phosphates, including, for example, amine salts of the reaction products of dialkyl dithiophosphite with propylene oxide; and mixtures thereof.

[0109] Friction modifier The lubricating oil compositions described herein may optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing and metal-free friction modifiers, and may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amide amines, nitriles, betaine, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerides, sulfurized aliphatic compounds and olefins, sunflower oil, other naturally occurring vegetable or animal oils, dicarboxylic acid esters, esters or metaesters of polyols, and one or more aliphatic or aromatic carboxylic acids.

[0110] Suitable friction modifiers may contain hydrocarbon groups selected from straight-chain, branched, or aromatic hydrocarbon groups or mixtures thereof, and may be saturated or unsaturated. The hydrocarbon groups may consist of carbon and hydrogen or heteroatoms (such as sulfur or oxygen). The hydrocarbon groups may range from about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long-chain fatty acid ester. In another embodiment, the long-chain fatty acid ester may be a monoester, diester, or (tri)glycerol ester. The friction modifier may be a long-chain fatty amide, a long-chain fatty ester, a long-chain fatty epoxide derivative, or a long-chain imidazoline.

[0111] Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers may comprise esters formed by reacting carboxylic acids and anhydrides with alkanols, and generally contain polar terminal groups (e.g., carboxyl or hydroxyl groups) covalently bonded to a lipophilic hydrocarbon chain. Examples of organic ashless and nitrogen-free friction modifiers are generally known as glyceryl monooleate (GMO), which may contain monoesters, diesters, and trimers of oleic acid. Other suitable friction modifiers are described in U.S. Patent No. 6,723,685, the entire contents of which are incorporated herein by reference.

[0112] Amine-based friction modifiers may include amines or polyamines. These compounds may have linear chains, saturated or unsaturated hydrocarbon groups, or mixtures thereof, and may contain about 12 to about 25 carbon atoms. Other examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. These compounds may have linear chains, saturated or unsaturated hydrocarbon groups, or mixtures thereof. They may contain about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

[0113] Amines and amides may be used as is or as adducts or reaction products with boron compounds, such as boron oxide, boron halide, metaborates, boric acid or monoalkyl, dialkyl or trialkyl esters of borate. Other suitable friction modifiers are described in U.S. Patent No. 6,300,291, the entire contents of which are incorporated herein by reference.

[0114] The friction modifier may optionally be present in the range of, for example, from about 0% to about 10% by weight, or from about 0.01% to about 8% by weight, or from about 0.1% to about 4% by weight.

[0115] molybdenum-containing components The lubricating oil compositions described herein may optionally contain one or more molybdenum-containing compounds. Oil-soluble molybdenum compounds may have functional properties as anti-wear agents, antioxidants, friction modifiers, or mixtures thereof. Oil-soluble molybdenum compounds may include molybdenum dithiocarbamate, molybdenum dialkyl dithiophosphate, molybdenum dithiophosphonite, amine salts of molybdenum compounds, molybdenum xanthate, molybdenum thioxanthate, molybdenum sulfide, molybdenum carboxylate, molybdenum alkanolate, trinuclear organomolybdenum compounds, and / or mixtures thereof. Molybdenum sulfide includes molybdenum dithiophosphate. Molybdenum dithiophosphate may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamate, molybdenum dialkyl dithiophosphate, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound may be molybdenum dithiocarbamate.

[0116] Suitable examples of usable molybdenum compounds include commercial substances sold under trademarks such as Molyvan 822 from RT Vanderbilt Co., Ltd. ™ Molyvan ™ A, Molyvan2000 ™ And Molyvan 855 ™ And Sakura-Lube, available from Adeka Corporation. ™ S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710, and mixtures thereof. Suitable molybdenum compositions are described in US 5,650,381; US ​​RE 37,363 E1; US ​​RE 38,929 E1; and US RE 40,595 E1, the entire contents of which are incorporated herein by reference.

[0117] Alternatively, the molybdenum compound can be an acidic molybdenum compound. This includes molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal salts of molybdate, as well as other molybdenum salts such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide, or similar acidic molybdenum compounds. Alternatively, these compositions may provide molybdenum via molybdenum / sulfur complexes of basic nitrogen compounds, as described, for example, in U.S. Patents 4,263,152; 4,285,822; 4,283,295; 4,272,387; 4,265,773; 4,261,843; 4,259,195 and 4,259,194; and WO 94 / 06897, the entire contents of which are incorporated herein by reference.

[0118] Another class of suitable organomolybdenum compounds are trinuclear molybdenum compounds, such as those having the formula Mo3SkLnQz and mixtures thereof, where S represents sulfur, L represents an independently selected ligand having an organic group having a sufficient number of carbon atoms to impart solubility or dispersibility of the compound in oil, n is 1 to 4, k varies from 4 to 7, Q is selected from the group of neutral electron-donating compounds, such as water, amines, alcohols, phosphine, and ethers, and z is in the range of 0 to 5 and includes non-stoichiometric values. A total of at least 21 carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms, may be present in the organic group of all ligands. Further suitable molybdenum compounds are described in U.S. Patent No. 6,723,685, the entire contents of which are incorporated herein by reference.

[0119] Oil-soluble molybdenum compounds may be present in amounts sufficient to provide molybdenum of about 0.5 ppm to about 2000 ppm, about 1 ppm to about 700 ppm, about 1 ppm to about 550 ppm, about 5 ppm to about 300 ppm, or about 20 ppm to about 250 ppm.

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

[0121] In one embodiment, the oil-soluble transition metal-containing compound may function as an anti-wear agent, friction modifier, antioxidant, deposition control additive, or more than one of these functions. In one embodiment, the oil-soluble transition metal-containing compound may be an oil-soluble titanium compound, such as titanium alkoxide (IV). Various Ti (IV) compounds, such as titanium oxide (IV); titanium sulfide (IV); titanium nitrate (IV); titanium alkoxide (IV), such as titanium methoxide, titanium ethanol, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexanoate; and other titanium compounds or complexes, including but not limited to titanium phenolate; titanium carboxylate, such as titanium 2-ethyl-1-3-adipic acid (IV) or titanium citrate or titanium oleate; and titanium (triethanolamine) isopropoxide (IV). Other forms of titanium covered within the disclosed technology include titanium phosphate, such as titanium dithiophosphate (e.g., dialkyl titanium dithiophosphate), and titanium sulfonates (e.g., titanium alkylbenzene sulfonate), or reaction products of titanium compounds reacting with various acidic materials to form salts (such as oil-soluble salts). Titanium compounds can therefore be derived, in particular, from organic acids, alcohols, and glycols. Ti compounds can also exist in dimer or oligomeric forms, containing a Ti-O-Ti structure. Such titanium materials are commercially available or can be readily prepared using suitable synthetic techniques readily apparent to those skilled in the art. They exist in solid or liquid form at room temperature, depending on the specific compound. They are also available in solution form in suitable inert solvents.

[0122] In one embodiment, titanium can be supplied as a Ti-modified dispersant, such as a succinimide dispersant. Such materials can be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbon-substituted succinic anhydride, such as an alkenyl (or alkyl) succinic anhydride. The resulting titanate-succinate intermediate can be used directly, or it can be reacted with any of a number of materials, such as (a) polyamine-based succinimide / amide dispersants having free, condensable --NH functional groups; (b) components of polyamine-based succinimide / amide dispersants, namely alkenyl (or alkyl) succinic anhydrides and polyamines; and (c) hydroxyl-containing polyester dispersants prepared by reacting substituted succinic anhydrides with polyols, amino alcohols, polyamines, or mixtures thereof. Alternatively, the titanate-succinate intermediate can be reacted with other agents, such as alcohols, amino alcohols, ether alcohols, polyether alcohols, or polyols or fatty acids, and the product can be used directly to impart Ti to lubricants, or additionally, further reacted with succinic anhydride dispersants as described herein. As an example, 1 part (molar) of tetraisopropyl titanate can be reacted with about 2 parts (molar) of polyisobutylene-substituted succinic anhydride at 140°C to 150°C for 5 to 6 hours to provide a titanium-modified dispersant or intermediate. The resulting material (30 g) can also be reacted with a mixture of succinimide dispersant from polyisobutylene-substituted succinic anhydride and polyethylene polyamine (127 g + diluent oil) at 150°C for 1.5 hours to produce a titanium-modified succinimide dispersant.

[0123] Another titanium-containing compound can be titanium alkoxide with C6 to C6 atoms. 25 The reaction products of carboxylic acids. The reaction products can be represented by the following formula:

[0124]

[0125] Where n is an integer selected from 2, 3, and 4, and R is a hydrocarbon group containing approximately 5 to approximately 24 carbon atoms, or is represented by the following formula:

[0126]

[0127] Where m+n=4 and n is in the range of 1 to 3, R4 is an alkyl moiety with 1 to 8 carbon atoms, R1 is selected from a hydrocarbon group containing about 6 to 25 carbon atoms, and R2 and R3 are the same or different and are selected from hydrocarbon groups containing about 1 to 6 carbon atoms, or a titanium compound can be represented by the following formula:

[0128]

[0129] Where x is in the range of 0 to 3, R1 is selected from hydrocarbon groups containing about 6 to 25 carbon atoms, R2 and R3 are the same or different and are selected from hydrocarbon groups containing about 1 to 6 carbon atoms, and R4 is selected from H, or C6 to C4. 25 A group composed of carboxylic acid moieties.

[0130] Suitable carboxylic acids may include, but are not limited to, hexanoic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, etc.

[0131] In one embodiment, the oil-soluble titanium compound may be present in the lubricating oil composition in amounts ranging from 0 ppm to 3000 ppm titanium by weight, or from 25 ppm to about 1500 ppm titanium by weight, or from about 35 ppm to 500 ppm titanium by weight, or from about 50 ppm to about 300 ppm titanium by weight.

[0132] Viscosity index improver The lubricating oil compositions described herein may optionally contain one or more viscosity index improvers. Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutylene, hydrogenated styrene-isoprene polymers, styrene / maleate copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, α-olefin maleic anhydride copolymers, polymethyl methacrylates, polyacrylates, polyalkylstyrene, hydrogenated alkenylaryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers may include star polymers, and suitable examples are described in U.S. Publication No. 20120101017A1.

[0133] In addition to or in place of viscosity index improvers, the lubricating oil compositions described herein may optionally contain one or more dispersant viscosity index improvers. Suitable viscosity index improvers may include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with the reaction product of an acylation agent (such as maleic anhydride) and an amine; amine-functionalized polymethacrylates; or esterified maleic anhydride-styrene copolymers reacted with an amine.

[0134] The total amount of viscosity index improver and / or dispersant may be from about 0% to about 20% by weight, from about 0.1% to about 15% by weight, from about 0.1% to about 12% by weight, or from about 0.5% to about 10% by weight of the lubricating oil composition.

[0135] Other optional additives Other additives may be selected to perform one or more functions required for lubrication fluids. Additionally, one or more of the mentioned additives may be multifunctional and provide functions other than those described herein or different from those specified herein.

[0136] The lubricating oil compositions according to this disclosure may optionally contain other performance additives. These other performance additives may be additives other than those specified in this disclosure and / or may include one or more of the following: metal passivators, viscosity index improvers, detergents, ashless TBN accelerators, friction modifiers, anti-wear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, emulsifiers, pour point depressants, sealing swelling agents, and mixtures thereof. Typically, a fully formulated lubricating oil will contain one or more of these performance additives.

[0137] Suitable metal passivating agents may include derivatives of benzotriazole (typically toluenetriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzothiazole; foam inhibitors, including copolymers of ethyl acrylate and 2-ethylhexyl acrylate, and optionally vinyl acetate; demulsifiers, including trialkyl phosphates, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers; and pour point depressants, including maleic anhydride-styrene esters, polymethacrylates, polyacrylates, or polyacrylamide.

[0138] Suitable foam inhibitors include silicon-based compounds, such as siloxanes.

[0139] Suitable pour point depressants may include polymethyl methacrylate or mixtures thereof. The pour point depressant may be present in an amount sufficient to provide about 0% to about 1% by weight, about 0.01% to about 0.5% by weight, or about 0.02% to about 0.04% by weight based on the final weight of the lubricating oil composition.

[0140] Suitable rust inhibitors can be single compounds or mixtures of compounds that have properties that inhibit corrosion of ferrous metal surfaces. Non-limiting examples of useful rust inhibitors include: oil-soluble high molecular weight organic acids, such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and wax acids; and oil-soluble polycarboxylic acids, including dimer and trimer acids, such as those derived from pine fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long-chain α,ω-dicarboxylic acids with molecular weights ranging from about 600 to about 3000, and alkenyl succinic acids in which the alkenyl group contains about 10 or more carbon atoms, such as tetrapropylene succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Another type of available acidic corrosion inhibitor is a half-ester of alkenyl succinic acid having about 8 to about 24 carbon atoms in the alkenyl group with an alcohol (such as polyethylene glycol). Corresponding semiamides of such alkenyl succinic acids are also available. The available rust inhibitors are high molecular weight organic acids.

[0141] If a rust inhibitor is present, it may be used in amounts sufficient to provide about 0% to about 5% by weight, about 0.01% to about 3% by weight, or about 0.1% to about 2% by weight, based on the final weight of the lubricating oil composition.

[0142] Generally, suitable lubricants, including the neutral to over-alkalized and sulfurized alkylphenol salt products described herein, may include additive components in the ranges listed in the table below.

[0143] Table 2: Suitable Lubricating Compositions

[0144]

[0145] Based on the weight of the final lubricating oil composition, the percentages for each component above represent the weight percentage of each component. The remainder of the lubricating oil composition consists of one or more base oils. Additives used to formulate the compositions described herein may be blended into the base oils individually or in various sub-combinations. However, it may be suitable to simultaneously blend all components using an additive concentrate (i.e., additive plus a diluent, such as a hydrocarbon solvent). Fully formulated lubricants typically contain an additive package, referred to herein as a dispersant / inhibitor package or DI package, which will supply the desired characteristics in the formulation.

[0146] The following terminology definitions are provided to clarify the meaning of certain terms as used herein.

[0147] The terms “oil composition,” “lubricating composition,” “lubricating oil composition,” “lubricating oil,” “lubricant composition,” “fully formulated lubricant composition,” and “lubricant” are considered synonymous and fully interchangeable terms, referring to finished lubricating products that contain a major amount of base oil and a small amount of additives.

[0148] As used herein, the terms “additive package,” “additive concentrate,” and “additive composition” are considered synonymous and fully interchangeable terms referring to a portion of a lubricating oil composition that does not include a major amount of the base oil feedstock mixture.

[0149] The term "over-basification" refers to metal salts, such as sulfonates, carboxylates, salicylates, and / or phenolates, in which the metal content exceeds the stoichiometric amount. Such salts can have conversion levels exceeding 100% (i.e., they can contain more than 100% of the theoretical amount of metal required to convert an acid to its "normal," "neutral" salt). The expression "metal ratio," often abbreviated as MR, is used to represent the ratio of the total stoichiometric amount of metal in a highly basic salt to the stoichiometric amount of metal in a neutral salt, based on known chemical reactivity and stoichiometry. In normal or neutral salts, the metal ratio is one, while in highly basic salts, MR is greater than one. These are often referred to as over-basic, hyper-basic, or super-basic salts and can be salts of organic sulfuric acids, carboxylic acids, salicylic acids, sulfonic acids, and / or phenols.

[0150] The term "alkaline earth metals" refers to calcium, barium, magnesium, and strontium, while the term "alkali metals" refers to lithium, sodium, potassium, rubidium, and cesium.

[0151] As used herein, the terms "hydrocarbon group" or "hydrocarbon substituent" or "hydrocarbon substituent" are used in their ordinary sense, as is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly connected to the rest of the molecule and having predominantly hydrocarbon characteristics. Each hydrocarbon substituent is independently selected from hydrocarbon substituents and hydrocarbon substituents containing one or more of a halogen group, hydroxyl group, alkoxy group, mercapto group, nitro group, nitroso group, amino group, pyridyl group, furanyl group, imidazolyl group, oxygen, and nitrogen, and wherein there are no more than two non-hydrocarbon substituents present for every ten carbon atoms in the hydrocarbon group.

[0152] As used herein, the term "hydroalkyl substituent" or "hydroalkyl group" is used in its usual sense, as is well known to those skilled in the art. Specifically, it refers to a group that is directly attached to the remainder of a molecule by two carbon atoms at two positions and is predominantly hydrocarbon-characteristic. Each hydroalkyl group is independently selected from divalent hydrocarbon substituents and contains substituted divalent hydrocarbon substituents such as: halogen groups, alkyl groups, aryl groups, alkylaryl groups, aralkyl groups, hydroxyl groups, alkoxy groups, mercapto groups, nitro groups, nitroso groups, amino groups, pyridyl groups, furanyl groups, imidazolyl groups, oxygen, and nitrogen, and wherein no more than two non-hydrocarbon substituents are present for every ten carbon atoms in the hydroalkyl group.

[0153] Unless otherwise expressly stated, as used herein, the term "weight%" refers to the percentage of the said component by weight of the whole composition.

[0154] The terms “soluble,” “oil-soluble,” or “dispersible” as used herein may, but do not necessarily, mean that a compound or additive is soluble, miscible, or capable of being suspended in oil in all proportions. However, these terms do mean that they are, for example, soluble, suspended, dispersible, or stably dispersed in oil to a degree sufficient to exert their intended effect in an environment where oil is used. Furthermore, if desired, additional additives may be incorporated, allowing for the addition of higher levels of specific additives.

[0155] As used herein, the term "TBN" refers to the total base number in mg KOH / g as measured by ASTM D2896.

[0156] As used in this article, the term "lime" refers to compounds such as calcium hydroxide and calcium oxide, also known as slaked lime or quicklime.

[0157] As used herein, the term "alkyl" refers to a straight-chain, branched, cyclic, and / or substituted saturated chain moiety having about 1 to about 100 carbon atoms. As used herein, the term "alkenyl" refers to a straight-chain, branched, cyclic, and / or substituted unsaturated chain moiety having about 3 to about 10 carbon atoms. As used herein, the term "aryl" refers to monocyclic and polycyclic aromatic compounds, which may include alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halogenated substituents, and / or heteroatoms, including but not limited to nitrogen, oxygen, and sulfur.

[0158] As used herein, the term "sulfurization ratio" refers to the weight ratio of sulfurized alkylphenol salt to unsulfurized alkylphenol salt / unsulfurized alkylphenol. As discussed in more detail below, the methods described herein effectively form and maintain alkylphenol salt additives with high sulfurization ratios. As used herein, when referring to unsulfurized alkylphenol salts or residual unsulfurized alkylphenol salts, both the phenolate and phenolic forms of the compound are considered, as the phenolate form can be readily acidified to phenol.

[0159] The molecular weight of any embodiment described herein can be determined using instruments such as a gel permeation chromatography (GPC) instrument available from Waters, and the data processed using software such as Waters Empower software. The GPC instrument may be equipped with a Waters separation module and a Waters refractive index detector (or similar optional equipment). GPC operating conditions may include a guard column, four Agilent PLgel columns (300 × 7.5 mm in length; 5 µm particle size and pore size range of 100 Å to 10000 Å), and a column temperature of approximately 40 °C. Unstabilized HPLC-grade tetrahydrofuran (THF) can be used as a solvent at a flow rate of 1.0 mL / min. The GPC instrument can be calibrated using commercially available polystyrene (PS) standards with a narrow molecular weight distribution ranging from 500 g / mol to 380,000 g / mol. For samples with a mass less than 500 g / mol, calibration curves can be extrapolated. Samples and PS standards can be dissolved in THF and prepared at concentrations of 0.1 wt% to 0.5 wt%, and used without filtration. GPC measurements are also described in US 5,266,223, which is incorporated herein by reference. GPC methods also provide information on molecular weight distribution; see, for example, WW Yau, JJ Kirkland and DD Bly, “Modern Size Exclusion Liquid Chromatography”, John Wiley and Sons, New York, 1979, which is also incorporated herein by reference.

[0160] Example

[0161] The following examples illustrate exemplary embodiments of this disclosure. In these examples, and elsewhere in this application, all ratios, parts, and percentages are by weight unless otherwise stated. These examples are intended to be presented for illustrative purposes only and are not intended to limit the scope of the invention disclosed herein.

[0162] For comparative examples where the sulfidation ratio is less than 500:1, for example and as described in US 8933022 B2, the concentration of unsulfurized alkylphenol salts is determined by reversed-phase high-performance liquid chromatography (HPLC), such as when the level of unsulfurized alkylphenol salts is at least about 0.3% by weight or greater. In an exemplary HPLC method, the sample is prepared by weighing about 80 mg to 120 mg into a 10 ml volumetric flask, diluting it to the level mark with dichloromethane, and mixing until the sample is completely dissolved. The HPLC system used in the HPLC method includes an HPLC pump, a constant-temperature HPLC column chamber, an HPLC fluorescence detector, and a PC-based chromatographic data acquisition system. An exemplary system is an Agilent 1200 HPLC with ChemStation software or an equivalent. The HPLC column is a Phenomenex Luna C8(2) 150 × 4.6 mm 5 μm 100 Å or an equivalent.

[0163] For the comparative examples, the following system settings were used during analysis: pump flow rate = 1.0 ml / min, maximum pressure = 200 bar, fluorescence wavelength: 225 nm excitation, 313 nm emission: gain = 9, column isotherm temperature = 25 °C, injection volume = 1 μL diluted sample, elution type: gradient, reversed phase, gradient: 0 to 7 minutes 85 / 15 methanol / water to 100% methanol linear gradient, and run time: 17 minutes.

[0164] For comparison samples, the resulting chromatograms typically contain several peaks. Peaks attributable to unsulfurized alkylphenol salts usually elute at early retention times, while peaks attributable to sulfurized alkylphenol salts elute at longer retention times. For quantification, the area of ​​the single largest peak of the unsulfurized alkylphenol salt is measured, and this area is used to determine the total concentration of unsulfurized alkylphenol salt. The area of ​​the selected peak is compared with a calibration curve to determine the weight percentage of unsulfurized alkylphenol salt, thereby determining the amount of sulfurized alkylphenol salt.

[0165] For samples of the present invention with a sulfidation ratio of 500:1 or greater, the above method is generally not sensitive enough to measure such low levels of unsulfured alkylphenol salts / alkylphenols. Instead, measurements are performed in accordance with the above method, but using samples with a target phenol salt concentration of 5 mg / ml, and using liquid chromatography-mass spectrometry (LC-MS) with single-quadruple or triple-quadruple MS or equivalents, modified via an Agilent MS6420 QQQ equipped with an Agilent MSD XT column fitted with an Agilent 1260 LC column, such as a Supelco Ascentis Express RP Amide 2.7u, 100 mm x 2.1 mm ID column or equivalent. For the sample measurements of the present invention, the following system settings are used in the analysis: column temperature 45°C, flow rate 0.3 ml / min, injection volume 3 µl, and run time 22 min. The MS system settings and conditions are as follows: ion source: ESI negative, mode SIM, gas temperature 300°C, gas flow rate 13 L / min, nebulizer 35 psi, capillary 3000 (V), splitter 135, and peak width 0.07. Calibration curves were generated using the MassHunter Quant Program or its equivalent, and the percentage of unsulfured alkylphenols / phenolates in the sample was then calculated to determine the percentage of unsulfured alkylphenols / phenolates.

[0166] Comparative Example 1

[0167] As described in US 8,933,002 B2, Examples 1 and 3 describe the sulfidation, neutralization and over-alkaliening of tetrapropylenephenol with methanol and xylene, but these methods can only achieve a sulfidation ratio of 262:1 (i.e., a residual unsulfided TPP of 0.38).

[0168] As described in Example 1 of Patent '002, a two-step method for the vulcanization of tetrapropenylphenol is illustrated. As described in Patent '002, Step 1 is the vulcanization of tetrapropenylphenol, as follows: 1620 g of tetrapropenylphenol (available from Chevron Oronite Company LLC) is charged into a 4-liter round-bottom flask at room temperature. The tetrapropenylphenol is heated to 110°C over 30 minutes. At 60°C, 14 g of a 50% by weight aqueous solution of potassium hydroxide is added with stirring. Next, 192 g of sulfur flakes (i.e., elemental sulfur) is added at 110°C, and the pressure is reduced to 680 mmHg. The reaction temperature is then increased to 180°C over 30 minutes, and the pressure is slowly reduced to 260 mmHg to promote the release of H₂S. The formed H₂S gas is trapped in a concentrated potassium hydroxide solution located before a vacuum pump. The reaction conditions are maintained for 2 hours and 45 minutes. The pressure is further reduced to 50 mmHg over 15 minutes, and these conditions are maintained for another 3 hours. The sulfurized alkylphenol reaction product is cooled. Patent '002 describes the obtained sulfurized alkylphenol having the following analysis: 6.85% sulfur, 2646 ppm potassium, a viscosity of 65.4 mm² / s at 100°C, and 26.5% TPP (i.e., unreacted tetrapropylene phenol and its calcium salt).

[0169] Next, Example 1 of Patent '002 further describes step 2, which is the distillation of the sulfurized alkylphenol from step 1, as follows: the sulfurized alkylphenol reaction product obtained in step 1 is preheated to about 140°C, and then fed at about 400 g / h to a continuous 0.0385m... 2 In a scraped-film evaporator, the temperature of the evaporator is maintained at approximately 210°C, and the pressure is maintained at approximately 1.5 mbar. Patent '002 then describes the average distillation product having the following analytical properties: sulfur: approximately 10.3%, potassium: approximately 4293 ppm, viscosity at 100°C: approximately 402.8 mm² / s, TPP: 0.31%.

[0170] Then, in Example 3 of the '002 patent, the neutralization, over-alkalization, and post-treatment of the product from Example 1 of the '002 patent were described using methanol and xylene as follows: 243.2 g of quicklime was added together with 243.2 g of methanol and 876 g of xylene into a 5-liter double-jacketed glass reactor. Next, 713.4 g of the sulfurized tetrapropylenephenol from Step 2 of Example 1 of the '002 patent was heated to approximately 80°C and then diluted with 562 g of xylene. The mixture was added to the reactor over 30 minutes while the reaction temperature was increased from room temperature to 30°C. The reaction mixture was then cooled to 25°C over 20 minutes. 29.6 g of a 90 / 10 molar mixture of acetic acid and formic acid was added to the mixture over 2 minutes. Due to the exothermic reaction, the temperature of the reaction mixture was increased from 25°C to 34°C. Then, 24.4 g of CO2 was added over 30 minutes while heating from 34°C to 36°C. Next, 41.6 g of CO2 was introduced over 66 minutes while heating from 36°C to 42°C. A slurry consisting of 60.8 g of quicklime, 60.8 g of methanol, and 334 g of xylene was added to the reactor over 1 minute. Then, an additional 51.4 g of CO2 was added over 64 minutes while heating from 41°C to 46°C. The temperature of the reaction mixture was raised to 65°C over 26 minutes to initiate methanol distillation. The temperature was further raised to 93°C over 60 minutes. The temperature was further raised to 130°C over 30 minutes. 550 g of 130 neutral lubricating oil was added to the reaction mixture. The crude precipitate was measured to be 2.4% by volume. The crude product was centrifuged, and then xylene distillation was carried out over one hour at 170°C and 25 mBar.

[0171] Example 3 of patent '002 then describes the resulting product being degassed at 150°C for 4 hours, and the resulting product containing 9.56% calcium, 4.71% sulfur, 1876 ppm potassium, a kinematic viscosity of 410.2 cSt at 100°C, 273 mg KOH / g TBN, and a reported residual content of 0.38% unsulfurized tetrapropylenephenol (TPP), with a sulfurization ratio of only 262:1.

[0172] Comparative Example 2

[0173] Similar to Comparative Example 1, Example 4 of US 8933002 B2 describes the neutralization and over-alkaliening of tetrapropylenephenol with methanol, but this method only achieves a sulfidation ratio of 178:1. In this example, 609.01 g of sulfidated tetrapropylenephenol (Example 1 of US 8933002) was charged into a 2-liter round-bottom flask. Next, 425.2 g of methanol and 0.2 g of foam inhibitor SI 200 purchased from Dow Corning were added to the reactor. The reaction mixture was heated to 60°C with stirring. During this step, 78.5 g of quicklime was introduced along with 300 g of 100N diluent. At 60°C, 4.6 g of a 50 / 50 mixture of acetic acid and formic acid by weight was added. Neutralization was maintained at 60°C and atmospheric pressure for 210 minutes. The methanol was evaporated by slowly reducing the pressure to 30 mm Hg over approximately 2 hours. During this step, 354 g of lubricating oil was added dropwise. Distillation was carried out at 60°C for one hour at 30 mm Hg. The crude precipitate of the neutralized calcium salt of sulfidated alkyl hydroxy aromatics was measured to be 0.4% by volume. The product was filtered through a Büchner funnel to remove unreacted lime.

[0174] US 8,933,002 further describes the degassing of the obtained product in air at 150°C for 4 hours, and the product has the following analysis: 3.17% calcium, 4.86% sulfur, K: 1827 ppm, kinematic viscosity of 80.8 cSt at 100°C, TBN of 89 mg KOH / g, and the content of unsulfurized tetrapropylenephenol (TPP) is reported to be 0.56%, with a sulfurization ratio of only 178:1.

[0175] Comparative Example 3

[0176] A tetrapropylene calcium phenolate composition having 118 mg KOH / g TBN, approximately 4.26 wt% calcium, and 1.8 wt% unsulfurized tetrapropylene phenol / phenolate obtained from catalytic sulfur monochloride was over-alkalized at 165 °C for 3 hours, and then vacuum distilled at 200 °C for 1 hour. After over-alkalization and distillation, the product had 314 mg KOH / g TBN, but now had 4.4 wt% unsulfurized tetrapropylene phenol / phenol.

[0177] Comparative Example 4

[0178] As described in US 4973411, Example 1 therein describes a sulfurized phenolate product; however, when tested using the measurement method of this application, this method only yields about 0.3 wt% to about 0.5 wt% of residual unsulfurized alkylphenol, and therefore only a sulfurization ratio of about 300:1. Example 1 of the '411 patent uses sulfur dichloride from Sigma Aldrich, having 80 wt% sulfur dichloride and 20 wt% impurities including sulfur monochloride.

[0179] Example 1 of US 4973411 was repeated as follows: Approximately 192 parts by weight of dodecylphenol were added to a 3-liter four-necked reaction flask along with approximately 840 parts by weight of isooctane or heptane. Nitrogen gas was then bubbled through the mixture at a rate of approximately 400 ml / min. Next, approximately 51 parts of the aforementioned sulfur dichloride (80% SCl2 and 20% S2Cl2) were added via a feeding funnel to maintain the reaction temperature close to room temperature. The reactants were stirred for approximately 5 minutes, and then heated to approximately 80°C for half an hour. The reactants were then cooled to approximately 45°C. Next, approximately 216 parts of 100 P light-colored oil, approximately 115 parts of methanol, and approximately 105 parts of Ca(OH)2 were added; the nitrogen gas was stopped, and the mixture was stirred at approximately 55°C to approximately 57°C for one hour. This temperature was maintained, and CO2 was bubbled at a suitable rate between approximately 200 ml / min and approximately 300 ml / min for approximately 77 minutes. Finally, the crude product was filtered, and the solvent was removed under vacuum at approximately 100°C. The replicated product contained approximately 8.8 wt% calcium, approximately 3.4 wt% sulfur, approximately 143 KV100, and 232 mg KOH / g TBN, consistent with the final product reported in the '411 patent.

[0180] Although US 4973411 does not disclose or suggest any effect of the molar ratio between the sulfur source and dodecylphenol, in this embodiment, the molar ratio of the sulfur source provided by 80% by weight sulfur dichloride and 20% by weight sulfur monochloride to dodecylphenol is calculated to be 0.64:1.

[0181] As described above, when the residual unsulfured alkylphenols were evaluated using the test methods of this application (including reversed-phase high-performance liquid chromatography (HPLC) and / or liquid chromatography-mass spectrometry (LC-MS)), the residual unsulfured alkylphenol level from Example 1 of US 4973411 was measured to be 0.39 g / L.

[0182] Example 1

[0183] The results of the low-temperature method of the present invention for producing over-alkali and sulfurized tetrapropylene alkylphenolate products with high sulfurization ratios using the method of this application are shown in the table below. For this embodiment, three different sulfurized tetrapropylene alkylphenols were first prepared as follows by reacting approximately 720 grams of tetrapropylene phenol with approximately 241 grams of sulfur monochloride;

[0184] S1: Tetrapropylenephenol was loaded into a reactor at approximately 100°C, and sulfur monochloride was added dropwise. The temperature was then increased to approximately 180°C and held for approximately 1 hour, followed by increasing to approximately 190°C and holding for approximately 1 hour. Vacuum stripping was then performed at approximately 200°C for approximately 1 hour. The mixture was then cooled to approximately 150°C, and approximately 252 grams of treatment oil were added. After vulcanization, the intermediate vulcanized product had a vulcanization ratio of approximately 499:1.

[0185] S2: Tetrapropylenephenol was loaded into a reactor with approximately 100 g of heptane, and sulfur monochloride was added dropwise at approximately 40°C. The temperature was then increased to approximately 100°C, and full vacuum stripping was performed to distill the heptane over approximately 1 hour. Vacuum stripping was then performed at approximately 200°C for approximately 1 hour. The mixture was then cooled to approximately 150°C, and approximately 252 g of treatment oil was added. After sulfidation, the intermediate sulfidation product had a sulfidation ratio of approximately 1110:1.

[0186] S3: Tetrapropylenephenol was loaded into a vessel with approximately 100 g of heptane, and sulfur monochloride was added dropwise at approximately 40°C. The temperature was then increased to approximately 100°C, and full vacuum stripping was performed to distill the heptane over approximately 1 hour. Approximately 252 g of treatment oil was then added. After sulfidation, the intermediate sulfidation product had a sulfidation ratio of approximately 2499:1.

[0187] Each of the sulfonate-based phenols S1, S2, or S3 was then neutralized with calcium oxide in the presence of the ammonium sulfonate composition, solvent system, and treatment oil shown in Table 4. The neutralized compositions were then over-alkalized in the solvent system by treatment with gaseous carbon dioxide at approximately 208 sccm, as shown in Tables 5 and 6. Table 3 provides characterization of the neutralized and over-alkalized products.

[0188] Table 3 :

[0189]

[0190] Unsulfurized alkylphenols refer to unsulfurized alkylphenol salts and any unsulfurized alkylphenols in the product.

[0191] For example, the vulcanization ratio of sample A is determined by 99.92% of the vulcanized alkylphenol salts and 0.08% of the unvulcanized alkylphenol salts / phenols in the sample, which results in a weight ratio of 99.92:0.08 or 1249:1.

[0192] Table 4: Neutralization

[0193]

[0194] Table 5: Further treatments prior to over-alkalization

[0195]

[0196] Table 6: Over-alkalization

[0197]

[0198] 21g CaO added during the entire peralkalization process

[0199] After over-alkalization, the sample was filtered and vacuum stripped at a temperature not exceeding about 140°C to produce the sulfidated alkylphenol salt products as outlined in Table 3 above.

[0200] Example 2

[0201] Further experiments were conducted to replicate Example 1 of US 8933002 B2 for the vulcanization of tetrapropylenephenol. Vulcanization was performed in step 1 of Example 1 of the '002 patent, and the resulting intermediate product had 6.88% sulfur and 56.8 mm. 2 / s KV100, 1958ppm potassium and 30.4% unsulfurized tetrapropylenephenol content.

[0202] The intermediate product was then distilled using a scraped-film evaporator identical to step 2 of Example 1 of Patent '002' to produce a sulfurized tetrapropylene alkylated phenolate product with a high sulfurization ratio (i.e., a low level of unreacted or unsulfurized tetrapropylenephenol), except that the vacuum was 1100 mTorr and the feed rate was 360 g / h. The resulting product had 10.18% sulfur and a 360 mm... 2 / s of KV100, 3133ppm of potassium and 0.05% of unreacted or unsulfurized tetrapropylenephenol or a high sulfurization ratio of 1999:1.

[0203] Example 3

[0204] Then, in accordance with Example 3 of US 8,933,002 B2, the repeated sulfurized alkylphenols from Example 2 above were neutralized and over-alkalized, except that the solvents were heptane and methanol, and the neutralization, over-alkalization, and post-treatment were carried out at a low temperature not exceeding about 100°C.

[0205] The solvent mixture in this embodiment is approximately 90% heptane and approximately 10% methanol. The crude product from Example 2 above was centrifuged at a temperature not exceeding 100°C, and then degassed at a temperature not exceeding 100°C to form the final sulfided product, which has the following characteristics: 4.24% sulfur, 298.8 mm... 2 / s KV100, 1048ppm potassium, less than 0.03% unsulfurized alkylphenol content (i.e., undetectable amount or sulfidation ratio of 3333:1 or higher), 270.4mgKOH / g TBN and 10.52% calcium content.

[0206] When the results of this embodiment using the heptane / methanol solvent system are compared with those of Comparative Example 2 described above (using the method of US8933002 and methanol / xylene solvent and high-temperature post-treatment), the effects of solvent selection and low-temperature treatment, particularly low-temperature post-treatment, as discovered herein, become apparent. In Comparative Example 2 of the '002 patent, which uses a methanol / xylene solvent system and high-temperature post-treatment, the level of unreacted TPP increases after neutralization, over-alkalization, and post-treatment; however, in this embodiment using the heptane / methanol solvent and low-temperature post-treatment, the level of unreacted TPP in the final product is even further reduced.

[0207] This temperature dependence on the formation of unreacted TPP (i.e., the regeneration of unvulcanized TPP during treatment) is also shown in Figure 1 The figure illustrates the reaction kinetics of temperature-based regeneration of unvulcanized TPP. Figure 1 As shown, when the temperature is maintained at around 100°C and lower (such as around 80°C) during processing, the level of unreacted or unvulcanized TPP does not regenerate.

[0208] Example 4

[0209] Further experiments were conducted using the methods of this application to produce sulfurized tetrapropylene alkylated phenolate products with a high sulfurization ratio (i.e., low levels of unreacted or unsulfurized tetrapropylenephenol), as described in Table 7 below. In this embodiment, the sulfur source used was a mixture of about 67 wt% sulfur dichloride (SCl2) and about 33 wt% sulfur monochloride (S2Cl2), wherein the molar ratio of the sulfur source to tetrapropylenephenol (TPP) differed, and the sulfurization method of Comparative Example 1 was generally used, wherein any post-treatment occurred at a temperature of about 100°C or lower.

[0210] The residual level of unreacted tetrapropylenephenol was measured using LCMS as described above to detect unreacted or unsulfurized alkylphenols in the product, and the results are provided in Table 7 below. The LCMS technique has a detection limit of 0.03 wt%. As shown in Table 7, a sulfur source to alkylphenol ratio of at least 0.7 or higher results in unreacted or unsulfurized tetrapropylenephenol levels that are undetectable in the vulcanized product and / or when combined with the low-temperature treatment disclosed herein.

[0211] Table 7

[0212]

[0213] The compositions of this embodiment may be subjected to any neutralization and / or over-alkalization consistent with this disclosure.

[0214] Example 5

[0215] Various sulfurized compounds suitable for lubricating compositions of engine crankcases were prepared as follows: Approximately 21 g of tetrapropylenephenol and approximately 7 g of processing oil were dissolved in approximately 50 g of heptane and added to a three-necked round-bottom flask equipped with a condenser and purged with nitrogen. Then, approximately 5.9 g of a sulfur chloride blend (from Table 8 below) containing sulfur dichloride (SCl2) and sulfur monochloride (S2Cl2) was slowly added to the mixture in the flask at room temperature (approximately 20°C to approximately 25°C). In this example, the molar ratio of the sulfur chloride blend to the tetrapropylenephenol compound was approximately 0.65:1. Different blends of sulfur dichloride and sulfur monochloride were used, as shown in Table 8 below. After the addition was complete, the mixture was slowly stirred for approximately 60 minutes. The heptane solvent was then removed under vacuum. The resulting product was sulfurized tetrapropylenephenol.

[0216] Next, the sulfurized tetrapropylenephenol was neutralized as follows: Approximately 21 g of sulfurized tetrapropylenephenol was added to a second three-necked round-bottom flask equipped with a condenser, a nitrogen layer, and a heating mantle, along with approximately 4.1 g of calcium hydroxide, approximately 10.6 g of API Group II base oil, approximately 45 g of heptane, and approximately 3.5 g of alkyl sulfonic acid (molecular weight approximately 500). The mixture in the second flask was slowly stirred at room temperature, and approximately 5 g of methanol was added. The mixture was then heated to approximately 64°C and refluxed for approximately 3 hours. The resulting mixture was then filtered to remove the solvent, forming a neutrally sulfurized phenolate product. The neutrally sulfurized phenolate product was evaluated for the presence of residual organochlorides using X-ray fluorescence (XRF) spectroscopy as described in the examples above, and for copper corrosion as a fully formulated crankcase lubricant according to D6594, using ASTM D4929. The results are also provided in Table 8 below.

[0217] Table 8 :

[0218]

[0219] The vulcanization rate is calculated, for example, as follows: Sample A is determined by 99.91% vulcanized alkylphenol salt and 0.09% unvulcanized alkylphenol salt / phenol, which yields a weight ratio of 99.91:0.09 or a ratio of 1110.1:1.

[0220] The percentage improvement in copper corrosion is relative to sample F prepared using 100% sulfur monochloride. For example, the percentage improvement in copper corrosion for sample A is 100 - (65 ppm / 371 ppm). 100) or 82.5%

[0221] As shown in samples B, C, and D in Table 8 above, when sulfur blends containing approximately 40% to approximately 75% by weight of sulfur dichloride (SCl2) (and approximately 60% to approximately 25% by weight of sulfur monochloride (S2Cl2)) are used for sulfurization, the resulting neutral sulfurized alkylphenol salts exhibit 1500 ppm or less of residual chloride, low levels of unsulfurized alkylphenol salts (i.e., high sulfurization ratio), and low levels of copper corrosion compared to neutral sulfurized alkylphenol salts obtained with 100% sulfur monochloride in the sulfur blends. Although sample A exhibits low levels of unsulfurized alkylphenol salts and low copper corrosion, sample A also exhibits high levels of residual chloride, which is undesirable in finished lubricants. Although samples E and F exhibit low levels of residual chloride and low levels of unsulfurized alkylphenol salts, these samples show unacceptably high levels of copper corrosion when used in fully formulated lubricants.

[0222] Although the sulfidated alkylphenol salts of this embodiment are each sulfided and neutralized as described above, when treated with equal soap content, further over-alkaliening of the resulting neutral phenol salts as discussed herein and in the examples will produce substantially the same residual organochlorides, substantially the same sulfidation levels, and / or substantially the same copper corrosion results as shown in Table 8 above.

[0223] It should be noted that, unless explicitly and definitively limited to one indicator, the singular forms “a” and “the” as used in this specification and the appended claims include multiple indicators. Thus, for example, a reference to “antioxidant” includes two or more different antioxidants. As used herein, the term “comprising” and its grammatical variations are intended to be non-limiting, such that the description of an item in the list does not exclude other similar items that may be substituted for or added to the listed items.

[0224] For the purposes of this specification and the appended claims, unless otherwise stated, all figures and other numerical values ​​used in the specification and claims to express quantities, percentages or proportions should be understood to be modified by the term "about" in all cases. Therefore, unless stated to the contrary, the numerical parameters set forth in the following specification and the appended claims are approximations that may vary depending on the desired properties sought to be obtained through this disclosure. To a minimum, and without attempting to limit the application of the equivalence principle to the scope of the claims, each numerical parameter should be interpreted at least according to the number of significant figures reported and by applying general rounding techniques.

[0225] It should be understood that each component, compound, substituent or parameter disclosed herein should be interpreted as disclosed for use alone or in combination with one or more of each other component, compound, substituent or parameter disclosed herein.

[0226] It should also be understood that each range disclosed herein should be interpreted as a disclosure of each specific value within the disclosed range having the same significant digits. Thus, for example, the range 1 to 4 should be interpreted as an explicit disclosure of the values ​​1, 2, 3, and 4, and any range of such values.

[0227] It should also be understood that each lower limit of each range disclosed herein should be interpreted as a combination of each upper limit of each range and each specific value within each range disclosed herein for the same component, compound, substituent, or parameter. Therefore, this disclosure should be interpreted as the disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or with each specific value within each range, or by combining each upper limit of each range with each specific value within each range. That is, it should also be understood that this document also discusses any range between endpoint values ​​within a wide range. Therefore, the range 1 to 4 also means the range 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0228] Furthermore, the specific amounts / values ​​of components, compounds, substituents, or parameters disclosed in this specification or examples should be interpreted as disclosures of a lower or upper limit of a range, and therefore can be combined with any other lower or upper limit or specific amount / value of the range of the same components, compounds, substituents, or parameters disclosed elsewhere in this disclosure to form such a range of components, compounds, substituents, or parameters.

[0229] While specific embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that may not currently be foreseen or likely to be foreseen by the applicant or others skilled in the art are likely to occur. Therefore, the appended claims, as filed and as may be amended, are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A method for preparing a sulfurized compound for a lubricating composition to achieve a high sulfurization ratio of the sulfurized compound to the residual unsulfurized compound, the method comprising: Sulfated alkylphenols are provided by sulfidating alkylphenols with a sulfur chloride blend, wherein the molar ratio of the sulfur chloride blend to the alkylphenol is from about 0.6:1 to about 0.75:1; and The sulfur chloride blend comprises sulfur monochloride and sulfur dichloride, and the sulfur chloride blend is about 40% to about 75% by weight of sulfur dichloride.

2. The method of claim 1 for preparing a sulfurized compound to achieve a high sulfurization ratio of the sulfurized compound to the residual unsulfurized compound, the method further comprising neutralizing and optionally over-alkalizing the sulfurized alkylphenol in the presence of a solvent to provide a sulfurized alkylphenol salt composition.

3. The method for preparing a sulfurized compound according to claim 1 to achieve a high sulfurization ratio of the sulfurized compound to the residual unsulfurized compound, wherein the sulfurization ratio of the sulfurized alkylphenol to the unsulfurized alkylphenol is about 500:1 or greater.

4. The method for preparing a sulfurized compound according to claim 2 to achieve a high sulfurization ratio of the sulfurized compound to the residual unsulfurized compound, wherein the copper corrosion of a lubricant comprising the sulfurized alkylphenol salt composition, as measured according to ASTM D6594, is at least about 50% less than that of a lubricant comprising a sulfurized alkylphenol salt composition prepared by sulfurizing the same alkylphenol but with a sulfur chloride blend containing 100% sulfur monochloride.

5. The method for preparing a sulfidation compound according to claim 2 to achieve a high sulfidation ratio of the sulfidation compound to the residual unsulfidated compound, wherein the amount of residual chloride in the sulfidation compound is about 1500 ppm or less.

6. The method for preparing a sulfur compound according to claim 2 to achieve a high sulfurization ratio of the sulfur compound to the residual unsulfurized compound, wherein the neutralization and optional over-alkaliization are carried out at a temperature not exceeding about 140°C.

7. The method for preparing a sulfidated compound according to claim 2 to achieve a high sulfidation ratio of the sulfidated compound to the residual unsulfidated compound, wherein the solvent is one or more solvents having a boiling point of about 100°C or less at about 1000 mbar to about 40 mbar.

8. The method for preparing a sulfidated compound according to claim 7 to achieve a high sulfidation ratio of the sulfidated compound to the residual unsulfidated compound, wherein the solvent is xylene, toluene, octane, butanol, heptane, methanol, acetone, benzene, cyclohexane, cyclopentane, ethanol, hexane, pentane, propanol, water, or a combination thereof.

9. The method of claim 2 for preparing a sulfurized compound to achieve a high sulfurization ratio of the sulfurized compound to the residual unsulfurized compound, wherein the neutralization and the optional over-alkaliization comprise contacting the sulfurized alkylphenol with an alkali metal salt or an alkaline earth metal salt at a temperature not exceeding about 140°C.

10. The method for preparing a sulfide compound according to claim 9 to achieve a high sulfidation ratio of the sulfide compound to the residual unsulfided compound, wherein the alkali metal salt or alkaline earth metal salt is lithium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, aluminum hydroxide, lithium oxide, magnesium oxide, calcium oxide, barium oxide, or a combination thereof.

11. The method of claim 9 for preparing a sulfur compound to achieve a high sulfurization ratio of the sulfur compound to the residual unsulfurized compound, wherein the neutralization and / or the optional over-alkaliization occur in the presence of a carbonating agent at a temperature not exceeding about 140°C.

12. The method of claim 2 for preparing a sulfurized compound to achieve a high sulfurization ratio of the sulfurized compound to the residual unsulfurized compound, wherein the sulfurized alkylphenol salt composition is subjected to one or more post-processing steps, the one or more post-processing steps comprising one or more of the following: vacuum stripping, jetting, distillation, filtration, degassing, evaporation, scraped membrane evaporation, centrifugation, dilution, liquid-liquid extraction, membrane separation, chromatography, adsorption, supercritical extraction, or combinations thereof, and wherein each post-processing step is carried out at a temperature not exceeding about 140°C.

13. The method of claim 2 for preparing a sulfidation compound to achieve a high sulfidation ratio of the sulfidation compound to residual unsulfidated compounds, wherein the method does not remove residual unsulfidated compounds between the sulfidation, the neutralization, and / or the optional over-alkaliization.

14. The method of claim 2 for preparing a sulfur compound to achieve a high sulfurization ratio of the sulfur compound to the residual unsulfurized compound, wherein the temperature of the neutralization and the optional over-alkalization, as well as the temperature of any post-treatment step, does not exceed about 100°C.

15. The method for preparing a sulfurized compound according to claim 2 to achieve a high sulfurization ratio of the sulfurized compound to the residual unsulfurized compound, wherein the sulfurization ratio of the sulfurized alkylphenol salt composition is about 5000:1 to about 500:

1.

16. The method for preparing a sulfurized compound according to claim 2 to achieve a high sulfurization ratio of the sulfurized compound to the residual unsulfurized compound, wherein the sulfurization ratio of the sulfurized alkylphenol salt composition is about 3500:1 to about 1200:

1.

17. The method for preparing a sulfurized compound according to claim 16 to achieve a high sulfurization ratio of the sulfurized compound to the residual unsulfurized compound, wherein the sulfurized alkylphenol salt composition has a total base number of about 100 mg KOH / g to about 400 mg KOH / g.

18. The method of claim 1 for preparing a sulfurized compound to achieve a high sulfurization ratio of the sulfurized compound to the residual unsulfurized compound, wherein the sulfurized compound has less than about 0.1% by weight of unsulfurized alkylphenol and / or unsulfurized alkylphenol salt.

19. The method of claim 1 for preparing a sulfidated compound to achieve a high sulfidation ratio of the sulfidated compound to the residual unsulfidated compound, wherein the sulfidation occurs at a temperature of about 0°C to about 250°C.

20. The method of claim 1 for preparing a sulfidated compound to achieve a high sulfidation ratio of the sulfidated compound to the residual unsulfidated compound, wherein the sulfidation occurs at a temperature of about 20°C to about 120°C.

21. The method for preparing a sulfidated compound according to claim 1 to achieve a high sulfidation ratio of the sulfidated compound to the residual unsulfidated compound, wherein the sulfidation occurs in the absence of alkali.

22. The method for preparing a sulfurized compound according to claim 2 to achieve a high sulfurization ratio of the sulfurized compound to the residual unsulfurized compound, wherein the sulfurized alkylphenol is neutralized and over-alkalized.

23. A sulfurized alkylphenol salt composition, said sulfurized alkylphenol salt composition being prepared by a method comprising the following steps: Sulfurized alkylphenols are provided by sulfidation of alkylphenols with a sulfur chloride blend, wherein the molar ratio of sulfur chloride to alkylphenols is from about 0.6:1 to about 0.75:1; The sulfur chloride blend comprises sulfur monochloride and sulfur dichloride, and the sulfur chloride blend is approximately 40% to approximately 75% by weight of sulfur dichloride; and The sulfurized alkylphenol is neutralized and optionally over-alkalized in the presence of a solvent to provide the sulfurized alkylphenol salt composition.

24. A detergent comprising a hydroxy aromatic compound or a salt thereof having a high sulfurization ratio of sulfurized to unsulfurized compound, the detergent comprising: Alkyl-substituted sulfur-bridged hydroxy aromatic compounds or salts thereof, wherein the sulfur bridge is derived from a sulfur chloride blend comprising sulfur dichloride and sulfur monochloride, and wherein the blend comprises about 40% to about 75% by weight of sulfur dichloride; and A vulcanization ratio of 500:1 to 5500:1, containing no more than about 900 ppm of unvulcanized hydroxy aromatic compounds or their salts.

25. The detergent of claim 24, wherein the alkyl-substituted sulfur-bridged hydroxy aromatic compound or a salt thereof has a molar ratio of the sulfur chloride blend to the alkyl-substituted hydroxy aromatic compound of about 0.6:1 to about 0.75:

1.

26. The detergent according to claim 24, wherein the alkyl-substituted sulfur-bridged hydroxy aromatic compound or a salt thereof has a total base value of about 50 mg KOH / g to about 400 mg KOH / g.

27. The detergent of claim 24, wherein the alkyl-substituted sulfur-bridged hydroxy aromatic compound or salt has a sulfur content of about 40,000 ppm to 65,000 ppm.

28. The detergent according to claim 27, wherein the sulfidation ratio is from about 1200:1 to about 3500:

1.

29. The detergent of claim 24, wherein the alkyl-substituted sulfur-bridged hydroxy aromatic compound or salt is derived from the alkylation of phenols and one or more oligomers obtained from olefins.

30. The detergent of claim 29, wherein the olefin comprises ethylene, propylene, butene, pentene, or combinations thereof.

31. The detergent according to claim 30, wherein the alkyl-substituted sulfur-bridged hydroxy aromatic compound or salt has a total base value of about 90 mg KOH / g to about 250 mg KOH / g.

32. A lubricating oil composition comprising an alkyl-substituted sulfur-bridged hydroxy aromatic compound or a salt thereof according to claim 24 and one or more base oils having a lubricating viscosity.

33. The lubricating oil composition comprising an alkyl-substituted sulfur-bridged hydroxy aromatic compound or a salt thereof according to claim 32, wherein the lubricating oil composition is suitable for use as a crankcase lubricating oil composition.

34. The lubricating oil composition of claim 33 comprising an alkyl-substituted sulfur-bridged hydroxy aromatic compound or a salt thereof, wherein the crankcase is fueled by gasoline, diesel or an alternative fuel.

Images