High sulfide additives for lubricating oil compositions

Abstract

The present disclosure provides a method for preparing a sulfurized alkylphenate product in conjunction with a neutralized and optionally overbased additive to achieve a high sulfurization ratio of sulfurized alkylphenate to unsulfurized alkylphenate / phenol.

Description

[Technical Field]

[0001] This disclosure relates, in general, to lubricating oil compositions having a high level of sulfidation and additives therefor. [Background technology]

[0002] Metal salts of alkylphenol sulfides, also known as alkylphenates, tend to be useful lubricant additives. These additives can function as cleaning agents and / or dispersants, and can also provide alkaline bases that help neutralize acids generated during vehicle operation. Unsulfurized alkylphenates tend to have reduced utility and are less desirable in lubricants for several reasons. As such, additive manufacturers try to minimize the levels of unsulfurized alkylphenates and / or alkylphenols in their additives. However, current methods have one or more drawbacks when trying to minimize the levels of unsulfurized alkylphenates / phenol variants, when the additives are also over-basified. [Overview of the project]

[0003] According to one embodiment, a process for preparing an alkylphenate sulfide product to achieve a high sulfidation ratio of alkylphenate sulfide to unsulfurized alkylphenate is described herein. In one approach, the process is to sulfurize an alkylphenol with a sulfur source to provide an alkylphenol sulfide, wherein the alkylphenol may be derived from the alkylation of a phenol, and the molar ratio of the sulfur source to the alkylphenol is about 0.66 to about 3.5 (in other approaches, about 0.67 to about 3.5, or about 0.68 to about 3.5, or about 0.7 to about 3.5), and to neutralize and optionally overbase the alkylphenol sulfide in the presence of a solvent to provide an alkylphenate sulfide composition, wherein the neutralization and optional overbasement are carried out at a temperature not exceeding about 140°C to achieve a sulfidation ratio of about 500:1 or higher, and to obtain an alkylphenate sulfide product, the process is to sulfurize the alkylphenol The post-treatment of the nate composition is carried out at a temperature not exceeding about 140°C in order to maintain a sulfurization ratio of about 500:1 or higher, and in some embodiments, the alkyl phenate sulfide product has less than about 0.2 weight percent of unsulfurized alkyl phenate and / or unsulfurized alkylphenol, less than about 0.1 weight percent, less than about 0.08 weight percent of unsulfurized alkyl phenate and / or unsulfurized alkylphenol, less than about 0.06 weight percent of unsulfurized alkyl phenate and / or unsulfurized alkylphenol, less than about 0.04 weight percent of unsulfurized alkyl phenate and / or unsulfurized alkylphenol, or less than about 0.03 weight percent of unsulfurized alkyl phenate and / or unsulfurized alkylphenol.

[0004] In other approaches or embodiments, the processes described in the preceding paragraph may be combined in any combination thereof with one or more optional features, embodiments, or process steps. Such optional features and embodiments may include one or more of the following: the sulfur source comprises elemental sulfur, sulfur monochloride, sulfur dichloride, hydrogen sulfide, sulfur dioxide, sulfide hydrate, or a combination thereof, and / or the molar ratio of the sulfur source to alkylphenol is about 0.68 to about 3.5, and / or the molar ratio of the sulfur source to alkylphenol is about 0.The ratio is 7 to approximately 2, and / or the sulfur source is sulfur monochloride, and / or the solvent is another solvent having a boiling point of about 100°C or less at about 1000 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 a combination thereof, and / or neutralization and / or optional overbasification comprises contacting alkylphenol sulfide 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 a combination thereof. and / or neutralization and / or optional overbasification are carried out in the presence of a carbonating agent at a temperature not exceeding approximately 140°C, and / or post-treatment includes one or more of the following: vacuum stripping, sparging, distillation, filtration, degassing, evaporation, wipe-film evaporation, centrifugation, dilution, liquid-liquid extraction, membrane separation, chromatography, adsorption, supercritical extraction, or a combination thereof, and all post-treatment is carried out at a temperature not exceeding approximately 140°C, and / or the process is The residual unsulfurized alkylphenate is not removed during sulfidation, neutralization, and / or optional overbasification, and / or the temperature of neutralization and optional overbasification, as well as the temperature of the post-treatment, does not exceed approximately 100°C, and / or the sulfidation ratio of the alkylphenate sulfide product is approximately 5000:1 to approximately 500:1, and / or the sulfidation ratio of the alkylphenate sulfide product is approximately 3500:1 to approximately 1000:1, and / or the alkylphenate sulfide product has a total base number of approximately 100 to approximately 400 mg KOH / g as measured by the method of ASTM D-2896, and / or the alkylphenate sulfide product is approximately 0.The product contains less than 2 weight percent of unsulfurized alkylphenate or unsulfurized alkylphenol, and / or the sulfidation is carried out at a temperature of about 0 to about 250°C, and at a temperature of about 40 to about 120°C, and / or the sulfidation is carried out in the absence of a base, and / or the sulfurized alkylphenol is neutralized and overbasicated, and / or the alkylation of the phenol is by one or more oligomers obtained from an olefin, and / or the olefin includes ethylene, propylene, butylene, isobutylene, pentene, or a combination thereof.

[0005] In other embodiments, alkyl phenate sulfide products are described herein, and these alkyl phenate sulfide products are prepared by the methods described in either of the embodiments in the preceding two paragraphs.

[0006] In other embodiments, a metal phenate cleaner having a high sulfidation ratio of alkyl phenate sulfide to unsulfided alkyl phenate is provided. In one approach, the metal phenate cleaner is obtained from a sulfur source and an alkylphenol, with a molar ratio of sulfur source to alkylphenol of about 0.66 to about 3.5 (in other approaches, about 0.67 to about 3.5 or about 0.68 to about 3.5 or about 0.7 to about 3.5), and weighing about 50 to about 400 mg as measured by the ASTM D-2896 method. The compound comprises an alkyl phenate sulfide having a total base number of KOH / g, an alkali or alkali metal up to about 100,000 ppm and an alkali or alkali metal up to about 65,000 ppm and sulfur up to about 65,000 ppm, and, in some embodiments, unsulfurized alkyl phenate and / or unsulfurized alkylphenol in amounts of about 900 ppm or less, about 800 ppm or less, about 700 ppm or less, about 600 ppm or less, about 500 ppm or less, about 400 ppm or less, or about 300 ppm or less, with a sulfidation ratio of about 500:1 to about 5500:1.

[0007] In further embodiments, the metal phenate cleaner may include embodiments having several optional features in any combination. These optional features and embodiments include one or more of the following: The metal is calcium, and the metal phenate cleaner contains approximately 35,000 ppm to approximately 100,000 ppm of calcium, and / or the metal phenate cleaner contains at least approximately 25,000 ppm of sulfur, and / or the metal phenate cleaner contains at least approximately 30,000 ppm of sulfur, and / or the sulfidation ratio is approximately 1200:1 to approximately 5000:1, and / or the alkyl phenate is derived from the alkylation of phenol by one or more C6-C36 alkylene groups, and / or the alkylene group is an oligomer, and / or the oligomer is derived from ethylene, propylene, butylene, isobutylene, pentene, or a combination thereof, and / or the alkyl sulfide phenate cleaner contains approximately 90 to approximately 250 mg when measured by the ASTM D-2896 method. It has a total base number of KOH / g and / or the alkyl phenate sulfide has less than 50 percent alkyl substitution at the ortho position.

[0008] In further embodiments, lubricating oil compositions are described herein, each comprising any embodiment of a metal phenate as described herein and one or more base oils of lubricating viscosity.

[0009] In yet another embodiment, the use of low-temperature processing as described in any embodiment of the methods herein is provided for forming metal phenate detergents and / or alkyl sulfide phenate products having a sulfide ratio of about 500:1 or more, and in some embodiments, is provided for forming unsulfurized alkyl phenate and / or unsulfurized alkylphenol in amounts less than about 0.2 weight percent, less than about 0.1 weight percent, less than about 0.08 weight percent, unsulfurized alkyl phenate and / or unsulfurized alkylphenol in amounts less than about 0.06 weight percent, unsulfurized alkyl phenate and / or unsulfurized alkylphenol in amounts less than about 0.04 weight percent, or less than about 0.03 weight percent.

[0010] The following definitions of terms are provided to clarify the meaning of specific terms used herein.

[0011] The terms “oil composition,” “lubricating composition,” “lubricating oil composition,” “lubricating oil,” “lubricating oil composition,” “lubricating composition,” “completely formulated lubricating oil composition,” and “lubricant” are considered synonymous and fully interchangeable terms, and refer to a finished lubricating product comprising a primary amount of base oil and a small amount of additive composition.

[0012] As used herein, the terms “additive package,” “additive concentrate,” and “additive composition” are considered to be synonymous and fully interchangeable terms referring to a portion of a lubricating oil composition excluding the main amount of base oil stock mixture.

[0013] The term "overbasic" refers to metal salts such as sulfonates, carboxylates, salicylates, and / or phenates in which the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level greater than 100% (i.e., such salts may contain more than 100% of the theoretical amount of metal required to convert an acid to its "standard salt" or "neutral salt"). The expression "metallic ratio," often abbreviated as MR, is used to indicate the ratio of the total stoichiometric equivalents of metal in an overbasic salt to the stoichiometric equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the metallic ratio is 1, but in overbasic salts, the MR is greater than 1. These are generally referred to as overbasic, highly basic, or ultrabasic salts and may be salts of organic sulfur acids, carboxylic acids, salicylates, sulfonates, and / or phenols.

[0014] 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.

[0015] As used herein, the terms “hydrocarbyl,” “hydrocarbyl substituent,” or “hydrocarbyl group” are used in their ordinary sense as is well known to those skilled in the art. Specifically, they refer to a group having carbon atoms directly bonded to the rest of the molecule and having primarily hydrocarbon characteristics. Each hydrocarbyl group is independently selected from hydrocarbon substituents, the substituted hydrocarbon substituents comprising one or more of the following: halo, hydroxyl, alkoxy, mercapto, nitro, nitroso, amino, pyridyl, furyl, imidazolyl, oxygen, and nitrogen, and two or fewer non-hydrocarbon substituents present for every 10 carbon atoms in the hydrocarbyl group.

[0016] As used herein, the terms “hydrocarbilene substituent” or “hydrocarbilene group” are used in their ordinary sense as is well known to those skilled in the art. Specifically, they refer to groups that are directly bonded to the rest of the molecule by carbon atoms at two locations on the molecule and that have primarily hydrocarbon characteristics. Each hydrocarbilene group is independently selected from divalent hydrocarbon substituents, the substituted divalent hydrocarbon substituents include halo groups, alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, hydroxyl groups, alkoxy groups, mercapto groups, nitro groups, nitroso groups, amino groups, pyridyl groups, furyl groups, imidazolyl groups, oxygen, and nitrogen, and two or fewer non-hydrocarbon substituents are present for every 10 carbon atoms in the hydrocarbilene group.

[0017] As used herein, the term “weight percentage” means the percentage of the listed ingredient relative to the total weight of the composition, unless otherwise explicitly stated.

[0018] As used herein, the terms “soluble,” “oil-soluble,” and “dispersible” may indicate, but do not necessarily, that a compound or additive is soluble, soluble, miscible, or suspendable in oil in any proportion. However, the aforementioned terms mean that they are soluble, suspendable, soluble, or stably dispersible in oil to a degree sufficient to exert their intended effect, for example, in an environment where oil is used. Furthermore, if desired, it may be possible to incorporate other additives to incorporate a higher level of specific additive properties.

[0019] As used herein, the term "TBN" is used to express the total base number in mg KOH / g when measured by the method of ASTM D2896.

[0020] As used herein, the term "lime" refers to calcium hydroxide, calcium oxide, and similar compounds, also known as slaked lime or hydrated lime, for example.

[0021] As used herein, the term “alkyl” refers to a linear, branched, cyclic, and / or substituted saturated chain portion comprising about 1 to about 100 carbon atoms. As used herein, the term “alkenyl” refers to a linear, branched, cyclic, and / or substituted unsaturated chain portion comprising about 3 to about 10 carbon atoms. As used herein, the term “aryl” refers to monocyclic and polycyclic aromatic compounds that may contain alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and / or heteroatoms including but not limited to nitrogen, oxygen, and sulfur.

[0022] The term "sulfidation ratio" refers to the weight ratio of alkylphenate sulfide to unsulfided alkylphenate / unsulfided alkylphenol. As will be discussed in more detail below, the methods described herein are effective in forming and maintaining alkylphenate additives with a high sulfidation ratio. When used herein, if unsulfided alkylphenate or residual unsulfided alkylphenate is referred to, both the phenate and phenolic forms of the compound are intended, since the phenate form can be readily acidified to phenol.

[0023] The molecular weight of any embodiment described herein may be determined using a gel permeation chromatography (GPC) instrument or similar instrument available from Waters, and data processed with Waters Empower Software or similar software. The GPC instrument may be provided with a Waters separation module and a Waters refractive index detector (or similar optional instrument). GPC operating conditions may include a guard column, four Agilent PLgel columns (300 × 7.5 mm in length, 5 μm in particle size, and pore sizes ranging from 100 to 10,000 Å), and a column temperature of approximately 40°C. Unstabilized HPLC-grade tetrahydrofuran (THF) may be used as the solvent at a flow rate of 1.0 mL / min. The GPC instrument may be calibrated with commercially available polystyrene (PS) standards having a narrow molecular weight distribution ranging from 500 to 380,000 g / mol. Calibration curves can be extrapolated for samples with a mass of less than 500 g / mol. The sample and PS standard can be dissolved in THF and prepared at a concentration of 0.1–0.5% by weight, and can be used without filtration. GPC measurement is also described in U.S. Patent No. 5,266,223, which is incorporated herein by reference. The GPC method provides additional molecular weight distribution information. See, for example, WWYau, JJKirkland and DDBly, "Modern Size Exclusion Liquid Chromatography," John Wiley and Sons, New York, 1979, which is incorporated herein by reference.

[0024] Additional details and benefits of this disclosure are partially described below and / or may be acquired through the practice of this disclosure. These details and benefits may be realized and achieved through the elements and combinations specifically indicated in the attached claims. It should be understood that both the above general description and the following detailed description are illustrative and descriptive only and do not limit the claimed disclosure. [Brief explanation of the drawing]

[0025] [Figure 1] A graph of residual or unsulfurized alkylphenol based on temperature, showing the kinetics of alkylphenol regeneration during processing.

BRIEF DESCRIPTION OF THE INVENTION

[0026] The present disclosure relates to a method for preparing neutral to overbased and sulfurized alkylphenate products to achieve a high sulfurization ratio of sulfurized alkylphenate to unsulfurized alkylphenate in relation to neutral to overbased additives, such as additives having a TBN of at least about 0, at least about 20, at least about 50, at least about 100, or otherwise about 150 to about 400 as further contemplated below. As described in the background art, past attempts to achieve high levels of sulfurization in such situations have met with limited success and have not been able to achieve a sulfurization ratio (i.e., the weight ratio of sulfurized alkylphenate to unsulfurized alkylphenate) of 500:1 or greater at such TBNs, because the high alkalinity and / or processing methods tend to regenerate unsulfurized variants throughout the manufacturing process.

[0027] In one embodiment, the method herein comprises first sulfiding an alkylphenol with a sulfur source to obtain an alkylphenol sulfide. In some approaches, the sulfidation occurs in the absence of a base in the reaction medium. In one approach, the alkylphenol is derived from the alkylation of a phenol with one or more oligomers obtained from an olefin (e.g., ethylene, propylene, butylene, or a mixture thereof). The alkylphenol sulfide is then neutralized and optionally overbasidized in the presence of a solvent to provide a neutral to overbasidized and alkylphenol sulfide composition. Neutralization and optional overbasidization are carried out at a temperature not exceeding about 140°C to achieve a sulfidation ratio of about 500:1 or higher in the composition. Finally, the optional overbasidized and alkylphenol sulfide composition is subjected to various post-treatment steps to obtain a neutral to overbasidized and alkylphenol sulfide product, all post-treatments carried out under conditions such as a temperature not exceeding about 140°C to maintain a sulfidation ratio of about 500:1 or higher. Further approaches are also effective in achieving neutral-to-overbasication and sulfidation ratios of alkylphenate sulfide products of approximately 5000:1 to 500:1, approximately 4000:1 to 500:1, approximately 3500:1 to 500:1, approximately 2000:1 to 500:1, approximately 5000:1 to 1000:1, or approximately 3400:1 to 1200:1, or even approximately 2000:1 to 1000:1. Further details of each process step are described below.

[0028] Alkylation of phenols The alkylphenate products of this disclosure are first obtained by alkylating one or more olefins and / or oligomers derived from olefins of a preferred phenol (or hydroxyaromatic) compound. Preferred phenol or hydroxyaromatic compounds include monohydroxy and / or polyhydroxyaromatic hydrocarbons having 1 to 4, and in some approaches, 1 to 3, hydroxyl groups. Preferred compounds include, but are not limited to, phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, and mixtures thereof. Preferred starting compounds include phenol.

[0029] Examples of alkylating agents include one or more olefins and / or oligomers derived from olefins selected from ethylene, propylene, butylene, isobutylene, or mixtures thereof. Suitable olefins include, to name just a few, isobutylene, propylene trimers and / or tetramers, but other olefins, such as linear olefins, cyclic olefins, branched olefins other than propylene oligomers, such as butylene or isobutylene oligomers, arylalkylenes, and mixtures thereof, may be present in the oligomer or alkyl group. Alkylation can be carried out in the presence of a catalyst such as a Lewis acid catalyst, a solid acid catalyst, trifluoromethanesulfonic acid, and other acidic molecular sieve catalysts. Exemplary Lewis acid catalysts, known to those skilled in the art, may include aluminum trichloride, aluminum tribromide, aluminum triiodide, boron trifluoride, boron tribromide, and boron triiodide. In some approaches, the molar ratio of the phenol or hydroxyaromatic compound to one or more oligomers is about 10:1 to about 0.5:1, while in other approaches it may be about 5:1 to about 2:1. The oligomeric alkyl group is generally bonded to the phenol or hydroxyaromatic compound at the ortho and / or para positions, but other substituents may be present depending on the application.

[0030] sulfide Alkylphenols or alkylhydroxyaromatic compounds are then sulfurized by contacting them with a sulfur source in a manner effective in achieving a high degree of sulfurization. In some approaches, sulfurization generally involves introducing sulfur crosslinking groups between the alkylphenol or alkylhydroxyaromatic moieties. In some approaches, the sulfur crosslinking group is a -Sy- group, where y is an integer from 1 to 4, in other approaches from 1 to 3, and in some approaches from 1 to 2, and / or has a total sulfur level of up to about 5 percent. The sulfur source can be any suitable sulfur, e.g., sulfur monochloride or sulfur dichloride, hydrogen sulfide, sulfur dioxide, and sodium sulfide hydrate, e.g., elemental sulfur or its halides. Sulfur can be used either as molten sulfur, as a solid (powder or fine particles), or as a solid suspension in a hydrocarbon liquid. In one approach, the sulfur source is sulfur monochloride, which those skilled in the art will understand to be S2Cl2 as shown in the following reaction scheme I. In other approaches, the sulfur source may be a blend of sulfur dichloride (SCl2) and sulfur monochloride (S2Cl2), particularly a blend of about 60–67 weight percent sulfur dichloride and about 33–40 weight percent sulfur monochloride. Scheme I shows sulfurization at room temperature (20–25°C) for about 60 minutes using sulfur monochloride (other sulfur sources may also be used), but other sulfurization conditions (e.g., about 0°C–250°C for about 1–7 hours) may be used as needed for specific applications.

[0031] [ka]

[0032] In this approach, sulfidation occurs in the absence or lack of a base such as sodium hydroxide, potassium hydroxide, or calcium hydroxide, meaning that there is less than 1 weight percent of base, less than about 0.5 weight percent of base, less than about 0.1 weight percent of base, or even no base at all during sulfidation. Preferably, the sulfidation reaction temperature may be about 0°C to about 250°C, about 0°C to about 230°C, about 0°C to about 120°C, about 40°C to about 120°C, or about 40°C to about 60°C, and / or other ranges within such endpoints as required for a particular application. In some approaches, the sulfur source may be combined (optionally in the presence of a solvent) with a selected alkylphenol 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. The reaction product may then be subjected to a short temperature hold of 30 to 60 minutes up to about 200°C, and / or vacuum stripping / distillation at temperatures of 30 to 60 minutes up to about 200°C, as required for the specific application. The sulfidation process may last up to about 8 hours, up to about 6 hours, up to about 4 hours, or less, depending on the sulfur source. Solvents such as heptane, hexane, xylene, and glycol may be present during the reaction. When sulfidation occurs initially without a base, especially when sulfur dichloride is used, the reaction is preferentially driven to high levels of sulfidation, e.g., intermediate sulfidation ratios of about 500:1 or higher, about 1000:1 or higher, about 2400:1 or higher, and in some approaches, about 5000:1 or lower.

[0033] In some approaches, the ratio of the sulfur source to the alkylphenol reactant may be selected to achieve a high level of sulfidation when sulfidation is carried out in a base-deficient environment, and in some approaches, it may also be selected to help maintain a low level of copper corrosion in the final product when used in lubricants. In one approach, the molar ratio of the sulfur source to the alkylphenol or alkylhydroxyaromatic reactant in the sulfidation reaction may be about 0.66 or greater, in other approaches or embodiments it may be about 0.66 to about 3.5, about 0.67 to about 3.5, about 0.68 to about 3.5, or in yet another approach or embodiment it may be about 0.7 to about 3.5, or about 0.7 to about 2.0, or about 0.7 to about 1.4, or even further about 0.7 to about 1.0, depending on the requirements of the particular application. In other embodiments, the molar ratio of the sulfur source to the alkylphenol or alkylhydroxyaromatic reactant in the sulfurization reaction may be 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, or less than 1.0. Such molar ratios of sulfur source to alkylphenol reactant help achieve high sulfidation ratios of about 500:1 or higher in the sulfidation reaction (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 approaches, subsequent processing steps, such as those described below, maintain or increase the sulfidation ratio so that the final sulfided and overbasicated alkylphenate product maintains a high sulfidation ratio of sulfided phenate to unsulfided phenate.In other approaches or embodiments, such molar ratios of sulfur sources to alkylphenols as specified herein may help achieve sulfidation ratios in the range 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 sulfidation ratios as specified herein may also include any other range within the indicated endpoints as needed for a particular application. Furthermore, other approaches can help achieve residual unsulfurized alkylphenates and / or unsulfurized alkylphenols with a molar ratio of sulfur source to alkylphenols of approximately 0.2 weight percent or less, approximately 0.1 weight percent or less, approximately 0.08 weight percent or less, approximately 0.06 weight percent or less, approximately 0.04 weight percent or less, or approximately 0.03 weight percent or less, or in amounts undetectable by some approaches.

[0034] Due to the high sulfurization ratio, the method described herein does not require the removal of residual unsulfurized alkylphenols after sulfurization and / or after any subsequent process steps such as neutralization, overbasication, and / or post-treatment. Rather, the method described herein minimizes the generation and / or regeneration of any unsulfurized variants and thus avoids the need to remove such undesirable components.

[0035] Neutralization Following sulfidation, the alkylphenol sulfide or alkylhydroxyaromatic sulfide, which already has a high sulfidation rate, is neutralized to provide a phenate or salt of the alkylphenol sulfide or alkylhydroxyaromatic sulfide. In one approach, neutralization is carried out by contacting the alkylphenol sulfide with a metal base under reactive conditions, while in several approaches, it is done in a liquid hydrocarbon diluent containing an accelerator to provide a phenate or salt of the alkylhydroxyaromatic sulfide. In some cases, the reaction can be carried out under an inert gas such as nitrogen. The metal base may be added at various points in the reaction, either as a single addition or in multiple additions, if required for a particular application. Neutralization may occur via the exemplary reaction scheme II shown below, but other reactions may proceed as needed, depending on the application, materials, and conditions.

[0036] [ka]

[0037] Examples of metal-base reactants include, but are not limited to, alkali metal salts derived from metal bases selected from alkali hydroxides, alkali oxides, or alkali alkoxides, or alkaline earth metal salts derived from metal bases selected from alkaline earth hydroxides, alkaline earth oxides, or alkaline earth alkoxides, as well as metal hydroxides, oxides, or alkoxides. Suitable metal-base compounds include lithium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and aluminum hydroxide. Other examples of metal-base 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 use.

[0038] Neutralization (and subsequent overbasication, which will be discussed further below) is carried out in the presence of a solvent or solvent system. In one approach, the solvent and / or system is one or more organic compounds having a boiling point below about 100°C, and in another approach, a compound having a boiling point below about 100°C at a pressure of about 1000 to about 40 mbar (in the other approach, about 1000 to about 300 mbar). Preferred examples include xylene, toluene, octane, butanol, heptane, methanol, pentanol, acetone, benzene, cyclohexane, cyclopentane, ethanol, hexane, pentane, propanol, water, or combinations thereof. In one approach, the solvent comprises one or more of heptane, methanol, water, and combinations thereof, and in another approach, the solvent system for neutralization may be about 80 to about 95 weight percent heptane, about 2 to about 10 weight percent methanol, and about 5 to about 15 weight percent water, based on the total amount of solvent. In another approach, the solvent may be a heptane / methanol system, and in some embodiments, it may contain about 85 to about 95 percent heptane and about 5 to about 15 percent methanol. The total amount of solvent for neutralization may be about 10 to about 80 percent by weight, based on the total weight of the solvent, base, and alkylphenol / phenate. In one approach, a source of alkali metal and / or alkaline earth metal may be added in excess as a slurry (e.g., a preliminary mixture of the metal base and solvent) and then reacted with the alkylphenol sulfide compound.

[0039] In one approach, the neutralizing solvent lacks substances with higher boiling points, such as ethylene glycol, propylene glycol, and / or decanol, and similar solvents, which have a boiling point of about 100°C or higher at the described pressure. In this specification, where an optional method is used, lacking or not containing 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 described high-boiling point solvent, or does not contain any of them.

[0040] The neutralization reaction between a metal base and alkylphenol sulfide is carried out under conditions effective in maintaining the high sulfide ratio achieved during the sulfidation reaction. Conventionally, to maintain the high sulfide ratio achieved during the sulfidation reaction, one approach involves neutralization at temperatures below approximately 140°C, some approaches at temperatures below approximately 120°C, others at temperatures below approximately 100°C, and more preferably at temperatures below approximately 80°C. Neutralizing at higher temperatures tends to result in increased levels and / or regeneration of unsulfidated alkylphenol or alkylphenate, which reduces the sulfide ratio, and this is undesirable. Rather, the methods herein select conditions to maintain high sulfide levels and ratios throughout the process. In other approaches, neutralization takes place at temperatures in the range of 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 take about 5 to about 60 minutes.

[0041] Overbasication Next, overbasification is optional, but preferred in some embodiments, and is carried out either during or after neutralization. In one approach, alkylphenol sulfide / alkylphenate is overbasified by reacting with an excess metal base and / or by reacting with an acidic overbasic compound, such as carbon dioxide or boric acid. In another approach, overbasification is via carbonation (reaction with carbon dioxide) in the presence of a solvent, for example, one of the solvents from the solvent system described above, with neutralization. One convenient carbonation reaction is to pass gaseous carbon dioxide through the reaction mixture. Excess solvent and any water formed during the overbasification reaction can be removed as needed by distillation either during or after the reaction, as will be further discussed below.

[0042] In one embodiment, an exemplary overbasication reaction may involve reacting an alkylphenol sulfide or a salt thereof with an alkali metal or alkaline earth metal, such as lime, in the presence of carbon dioxide and the solvent system already discussed above. Conveniently, the reaction can be carried out by bubbling gaseous carbon dioxide through the reaction and solvent system mixture. Just as the neutralization temperature is controlled to a low level to maintain a high sulfidation level, the overbasication temperature is also kept low to maintain a high sulfidation level and ratio throughout the overbasication. For example, the overbasication temperature is about 140°C or less, about 120°C or less in some approaches, about 100°C or less in other approaches, and about 80°C or less in more preferred approaches, in order to maintain a high sulfidation ratio from sulfidation during the overbasication treatment and from neutralization. Performing overbasication at higher temperatures also tends to result in higher levels or increased regeneration of residual unsulfurized alkylphenol / phenate, which leads to an undesirable decrease in the sulfidation ratio.

[0043] In other approaches, overbasication is also carried out at temperatures in the range of 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 overbasication can be controlled by the amount of alkali metal or alkaline earth metal, the amount of carbon dioxide and other reactants (if present) added to the reaction mixture, and the reaction conditions used during the carbonation process. In some approaches, overbasication or overbasication via carbonation occurs for a sufficient amount of time to achieve the desired degree of overbasication or TBN, which in some approaches may be about 30 minutes to about 180 minutes at the temperatures described.

[0044] After overbasication, the overbasicated alkylphenates may have a TBN of about 100–400, or about 150–400, about 200–300 in other approaches, and about 220–275 in yet other approaches. Even when overbasicated, the alkylphenates maintain a high level of sulfurization compared to unsulfurized alkylphenates or alkylphenols, and this sulfurization ratio is maintained at at least about 500:1 after the overbasication step and during post-treatment, as will be further discussed below.

[0045] Post-processing Following optional overbasification, compositions containing alkyl phenates are often subjected to several steps to prepare the final alkyl phenate product. However, such post-treatment steps should also be carried out using conditions effective in maintaining a high sulfidation ratio. In this approach, all post-treatment is carried out at low temperatures to maintain a high level of sulfidation relative to the unsulfurized alkyl phenate and to avoid regeneration of the unsulfurized alkylphenol or phenate.

[0046] Examples of post-treatments performed at low temperatures include vacuum stripping, distillation, sparging, filtration, degassing, evaporation, wiped-film evaporation, centrifugation, dilution, liquid-liquid extraction, membrane separation, chromatography, absorption, supercritical extraction, and / or combinations thereof, all of which are performed individually and / or in combination under conditions effective in maintaining high sulfurization levels, such as low temperatures not exceeding approximately 140°C. As with neutralization and overbasification, any post-treatment is also performed at temperatures in the range of at least approximately 20°C, at least approximately 30°C, at least approximately 40°C, at least approximately 50°C, at least approximately 60°C to less than approximately 140°C, less than approximately 130°C, less than approximately 120°C, less than approximately 110°C, less than approximately 100°C, less than approximately 90°C, or less than approximately 80°C.

[0047] The methods and steps of this specification produce overbasication and alkylphenate sulfide products having a high sulfation ratio of alkylphenate sulfide / alkylphenol to unsulfurized alkylphenate / alkylphenol of at least about 500:1, in other approaches about 500:1 to about 5000:1, in yet other approaches about 1000:1 to about 5000:1, about 1000:1 to about 3500:1, or even further about 1000:1 to about 2000:1, which demonstrates a high level of alkylphenate sulfide relative to unsulfurized alkylphenate or unsulfurized alkylphenol when in a neutral to overbasic form. In other approaches, the additives and methods herein include unsulfurized alkylphenate / alkylphenol in amounts less than about 0.2 weight percent, less than about 0.1 weight percent, less than about 0.08 weight percent, less than about 0.05 weight percent, or less than about 0.03 weight percent, or unsulfurized alkylphenate / alkylphenol in amounts of about 0.01 to about 0.2 weight percent or any range within that range.

[0048] A unique feature of the method of the present invention is that the method steps do not generate and / or regenerate unsulfurized alkylphenates or alkylphenols in any of the various process steps, but rather maintain a high level of sulfurization throughout the entire process, so generally there is no need to remove unsulfurized alkylphenates or alkylphenols (after sulfurization or after any intermediate step, for example). As such, the method described herein thus avoids the cost and complexity of conventional methods that required the removal of residues and / or unsulfurized alkylphenates / phenols either in an intermediate or post-treatment step of the process.

[0049] lubricating oil composition The optionally overbasicated and sulfurized alkylphenate products described herein, in combination with one or more further optionally selected additives, may be combined with a major amount of base oil blend or a base oil blend of lubricating viscosity (as described below) to produce lubricating oil compositions. In this approach, the lubricating oil composition comprises about 50 weight percent or more of base oil, about 60 weight percent or more, about 70 weight percent or more, or about 80 weight percent to about 95 weight percent, about 90 weight percent or less, or about 85 weight percent or less of the base oils further considered below.

[0050] In one approach, the lubricating oil compositions described herein may contain, in a base oil or base oil blend, about 0.02 to about 5 weight percent, in another approach, about 0.2 to about 3 weight percent, and in yet another approach, about 0.2 to about 2 weight percent of optionally over-basidized and sulfurized alkylphenate products in the base oil or base oil blend.

[0051] In some approaches, the additives described herein can be used as detergents in lubricating oils to neutralize acids and / or to help control rust, corrosion, and deposits. In addition, the detergents described herein may also be used in fuels including, but not limited to, gasoline, diesel, and biodiesel for spark, compression, and hybrid engines.

[0052] The lubricants, combinations of components, dispersant inhibitor packages, and / or individual components described herein may be suitable for use in various types of lubricants, such as automotive lubricants and / or greases, internal combustion engine oils, hybrid engine oils, electric engine lubricants, drivetrain 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, axle fluids, and wet brake fluids.

[0053] Suitable engine types may include, but are not limited to, heavy-duty diesels, passenger car engines, light-duty diesels, medium-speed diesels, or marine engines. Internal combustion engines may be diesel-fueled engines, gasoline-fueled engines, natural gas-fueled engines, biofuel-fueled engines, diesel / biofuel-blended engines, gasoline / biofuel-blended engines, alcohol-fueled engines, gasoline / alcohol-fuel-blended engines, compressed natural gas (CNG)-fueled engines, or mixtures thereof. Diesel engines may be compression-ignition engines. Gasoline engines may be spark-ignition engines. Internal combustion engines may also be used in combination with electric or battery power sources. Engines configured in this way are generally known as hybrid engines. Internal combustion engines may be two-stroke, four-stroke, or rotary engines. Suitable internal combustion engines include marine diesel engines (such as those for inland vessels), aircraft piston engines, low-load diesel engines, and engines for motorcycles, automobiles, locomotives, and trucks. Engines may be coupled with turbochargers.

[0054] Lubricant compositions for internal combustion engines may be suitable for any engine lubricant, regardless of sulfur, phosphorus, or sulfated ash (ASTM D-874) content. The sulfur content of the engine oil lubricant may 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 may be in the range of about 0.001% by weight to about 0.5% by weight, or about 0.01% by weight to about 0.3% by weight. The phosphorus content may 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 may be about 50 ppm to about 1000 ppm, or about 325 ppm to about 850 ppm. The total sulfated 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 sulfated 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 sulfated 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 sulfated ash content may be about 0.8% by weight or less.

[0055] Furthermore, the lubricants described herein meet one or more industry specification requirements 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 Dexos1 (trademark), Dexos2 (trademark), 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-14 FE+, Longlife-17 FE+, Porsche A40, C30, Peugeot Citroen Automobiles B71 2290, B71 2294, 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, WSS-M2C913-C, WSS-M2C913-D, WSS-M2C948-B, WSS-M2C948-A, GM 6094-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.It may be suitable for meeting the original equipment manufacturer's specifications such as 5005, STJLR.03.5006, STJLR.03.5007, STJLR.51.5122, or past or future PCMO or HDD specifications not described herein. In some embodiments for passenger car motor oil (PCMO) applications, the amount of phosphorus in the final fluid is 1000 ppm or less, or 900 ppm or less, or 800 ppm or less.

[0056] Base oil or base oil blend: The base oil used in the lubricating oil compositions herein may be an oil of lubricating viscosity and is selected from any of the base oils in Groups I to V, as specified in the American Petroleum Institute (API) Base Oil Interoperability Guidelines. The five base oil groups are generally shown in Table 1 below.

[0057] [Table 1]

[0058] Groups I, II, and III are mineral oil process raw materials. Group IV base oils contain true synthetic molecular species produced by the polymerization of olefinic unsaturated hydrocarbons. Many Group V base oils are also true synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers, and / or polyphenyl ethers, but may also be natural oils such as vegetable oils. It should be noted that Group III base oils are derived from mineral oils, but due to the rigorous processing these fluids undergo, their physical properties become very similar to those of some true synthetic oils such as PAO. Therefore, oils derived from Group III base oils can be referred to as synthetic fluids in industry. Group II+ may include high viscosity index Group II.

[0059] The base oil blends used in the disclosed lubricating oil compositions may be mineral oils, animal oils, vegetable oils, synthetic oils, synthetic oil blends, or mixtures thereof. Suitable oils may be derived from hydrocracking, hydrotapping, hydrofinishing, unrefined oils, refined oils, and re-refined oils, as well as mixtures thereof.

[0060] Unrefined oils are derived from natural, mineral, or synthetic sources that undergo little to no further refining. Refined oils are similar to unrefined oils except that they have been processed through one or more refining steps that may result in an improvement in one or more properties. Examples of preferred refining techniques include solvent extraction, secondary distillation, acid or base extraction, filtration, and osmosis. Oils refined to a quality suitable for consumption may or may not be useful. Edible oils are sometimes called white oils. In some embodiments, lubricating oil compositions do not contain edible oils or white oils.

[0061] Refined oil is also known as recycled oil or reprocessed oil. These oils are obtained in the same way as refined oil using the same or similar processes. Often, these oils are further treated by techniques that target the removal of spent additives and oil degradation products.

[0062] Mineral oils may include oils obtained by drilling, or from plants and animals, or any mixture thereof. For example, such oils may include, but are not limited to, castor oil, lard, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricants, such as liquid petroleum, and paraffinic, naphthenic, or mixed paraffinic-naphthenic type solvent-treated or acid-treated mineral lubricants. Such oils may be partially or fully hydrogenated, if desired. Oils derived from coal or shale may also be useful.

[0063] Useful synthetic lubricants include hydrocarbon oils, for example, polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylene, polypropylene, propylene isobutylene copolymer); trimers or oligomers of poly(1-hexene), poly(1-octene), and 1-decene, for example, poly(1-decene) (such materials are often referred to as α-olefins), and mixtures thereof; alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers, and alkylated diphenyl sulfides, as well as their derivatives, analogs, and homologs, or mixtures thereof. Polyalphaolefins are typically hydrogenated materials.

[0064] Other synthetic lubricants include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl esters of decanephosphonic acid), or polymeric tetrahydrofurans. Synthetic oils may be produced by the Fischer-Tropsch reaction and are typically hydrogenated isomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil may be prepared by the Fischer-Tropsch gas-liquid synthesis procedure and other gas-liquid oils.

[0065] In another embodiment, the main amount of base oil contained in the lubricating composition may be selected from the group consisting of Group I, Group II, Group III, Group IV, Group V, and any combination of two or more of the aforementioned, but the main amount of base oil is other than base oil resulting from the provision of additive components or viscosity index modifiers in the composition.

[0066] The amount of oil with lubricating viscosity present may be the difference remaining after subtracting the total amount of performance additives, including viscosity index improvers and / or pour point depressants and / or other top-treatment additives, from 100% by weight. For example, the amount of oil with lubricating viscosity that may be present in the final fluid may be the main amount, e.g., more than about 50% by weight, more than about 60% by weight, more than about 70% by weight, more than about 80% by weight, more than about 85% by weight, or more than about 90% by weight.

[0067] Optional additives: The lubricating oil compositions described herein may also include several optional additives, which may be combined with optional overbasication and alkyl phenate sulfide products as necessary to meet performance requirements. These optional additives are described in the following paragraphs.

[0068] Dispersants: Lubricating oil compositions may optionally contain one or more dispersants or mixtures thereof. Dispersants are often known as ashless dispersants because they do not contain metals that form ash before being mixed into the lubricating oil composition and do not typically contribute to ash when added to the lubricant. Ashless dispersants are characterized by polar groups being bonded to relatively high molecular weight hydrocarbon chains. Typical ashless dispersants include N-substituted long-chain alkenyl succinimides. An example of an N-substituted long-chain alkenyl succinimide is polyisobutylene succinimide, in which the number-average molecular weight of the polyisobutylene substituent is in the range of about 350 to about 50,000, or about 5,000, or about 3,000, as measured by GPC. Succinimide dispersants and their preparations are disclosed, for example, in U.S. Patent No. 7,897,696 or U.S. Patent No. 4,234,435. Alkenyl substituents can be prepared from polymerizable monomers containing about 2 to about 16 carbon atoms, or about 2 to about 8 carbon atoms, or about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines (typically poly(ethyleneamine)).

[0069] Preferred amines are selected from polyamines and hydroxyamines. Examples of polyamines that can be used include, but are not limited to, higher homologues such as diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and pentaethylamine hexamine (PEHA).

[0070] A suitable heavy polyamine is a polyalkylene-polyamine mixture containing small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine), but mainly containing six or more nitrogen atoms, two or more primary amines per molecule, and oligomers having a broader branching range than conventional polyamine mixtures. The heavy polyamine preferably contains polyamine oligomers containing seven or more nitrogen atoms per molecule and two or more primary amines per molecule. The heavy polyamine contains more than 28% by weight (e.g., more than 32% by weight) of total nitrogen and 120 to 160 grams of primary amine groups per equivalent weight.

[0071] In some approaches, preferred polyamines are commonly known as PAMs and contain a mixture of ethyleneamines, with TEPA and pentaethylenehexamine (PEHA) being the main components of the polyamine, usually less than 80%.

[0072] Typically, PAMs contain 8.7–8.9 milliequivalents of primary amine per gram (115–112 gram equivalents per primary amine equivalent) and a total nitrogen content of approximately 33–34% by weight. Heavier cuts of PAM oligomers, which are substantially TEPA-free and contain very small amounts of PEHA, but mainly contain oligomers with more than 6 nitrogen atoms and broader branching, can produce dispersants with improved dispersibility.

[0073] In embodiments, the disclosure further includes at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight in the range of about 350 to about 50,000, or about 5,000, or about 3,000, as determined by GPC. Polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0074] In some embodiments, if polyisobutylene is included, the polyisobutylene may have a terminal double bond content exceeding 50 mol%, 60 mol%, 70 mol%, 80 mol%, or 90 mol%. Such PIBs are also called highly reactive PIBs ("HR-PIBs"). HR-PIBs having a number-average molecular weight in the range of about 800 to about 5000 as determined by GPC are suitable for use in embodiments of this disclosure. Conventional PIBs typically have a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0075] When determined by GPC, HR-PIBs having a number-average molecular weight in the range of approximately 900 to approximately 3000 may be preferred. Such HR-PIBs are commercially available or can be synthesized by polymerization of isobutene in the presence of a non-chlorinating catalyst such as boron trifluoride, as described in U.S. Patent No. 4,152,499 by Boerzel, et al. and U.S. Patent No. 5,739,355 by Gateau, et al. When HR-PIBs are used in the above-mentioned thermal ene reaction, they may result in a higher conversion rate and less precipitate formation during the reaction due to increased reactivity. A preferred method is described in U.S. Patent No. 7,897,696.

[0076] In one embodiment, the disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride, "PIBSA". PIBSA may have an average succinic acid moiety of about 1.0 to about 2.0 per polymer.

[0077] The percentage of active ingredients in alkenyl or alkyl succinic anhydride can be determined using chromatographic techniques. This method is described in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0078] The conversion percentage of polyolefins is calculated from the active ingredient percentage using the formulas in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0079] Unless otherwise stated, all percentages are weight percentages, and all molecular weights are number-average molecular weights determined by gel permeation chromatography (GPC) using commercially available polystyrene standards (with a number-average molecular weight of 180 to approximately 18,000 as a calibration standard).

[0080] In one embodiment, the dispersant may be derived from polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant may be derived from olefin maleic anhydride copolymer. As an example, the dispersant may be described as poly-PIBSA. In an embodiment, the dispersant may be derived from an anhydride grafted onto an ethylene-propylene copolymer.

[0081] A suitable class of nitrogen-containing dispersants can be derived from olefin copolymers (OCPs), more specifically from ethylene-propylene dispersants that can be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that can be reacted with functionalized OCPs is described and / or commercially available in U.S. Patents Nos. 7,485,603, 7,786,057, 7,253,231, 6,107,257, and 5,075,383.

[0082] One class of suitable dispersants may also be Mannich bases. Mannich bases are materials formed by the condensation of higher molecular weight alkyl-substituted phenols, polyalkylene polyamines, and aldehydes such as formaldehyde. Mannich bases are described in detail by U.S. Patent No. 3,634,515.

[0083] A suitable class of dispersants may also be high molecular weight esters or semi-esteramides. Suitable dispersants may also be post-treated by conventional methods with any of a variety of agents. These include boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydride, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds. U.S. Patents 7,645,726, 7,214,649, and 8,048,831 are incorporated herein by reference in their entirety.

[0084] In addition to the post-treatment of carbonates and boric acid, each compound may be post-treated or further post-treated by a variety of post-treatments designed to improve or impart different properties. Such post-treatments include those summarized in columns 27-29 of U.S. Patent No. 5,241,003, which is incorporated herein by reference. Such treatments include: inorganic phosphoric acid or anhydride (e.g., U.S. Patents No. 3,403,102 and No. 4,648,980); organophosphorus compounds (e.g., U.S. Patent No. 3,502,677); phosphorus pentasulfide; boron compounds as already described above (e.g., U.S. Patents No. 3,178,663 and No. 4,652,387); carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Patents No. 3,708,522 and No. 4,9 48,386); Epoxy polyepoxyates or thioepoxides (e.g., U.S. Patents 3,859,318 and 5,026,495); Aldehydes or ketones (e.g., U.S. Patent 3,458,530); Carbon disulfide (e.g., U.S. Patent 3,256,185); Glycidol (e.g., U.S. Patent 4,617,137); Urea, thiourea, or guanidine (e.g., U.S. Patent 3,312,61 Patent No. 9, No. 3,865,813, and British Patent No. 1,065,595); Organic sulfonic acids (e.g., U.S. Patent No. 3,189,544 and British Patent No. 2,140,811); Alkenyl cyanides (e.g., U.S. Patents No. 3,278,550 and No. 3,366,569); Diketene (e.g., U.S. Patent No. 3,546,243); Diisocyanates (e.g., U.S. Patent No. 3,573,205); Alkansul Tons (e.g., U.S. Patent No. 3,749,695); 1,3-dicarbonyl compounds (e.g., U.S. Patent No. 4,579,675); alkoxylated alcohols or phenolic sulfates (e.g., U.S. Patent No. 3,954,639); cyclic lactones (e.g., U.S. Patents No. 4,617,138, 4,645,515, 4,668,246, 4,963,275, and 4,971,711);Cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Patent 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 No. 2,140,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Patent No. 4,614,522); lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. National Patents No. 4,614,603 and No. 4,666,460); cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Patents No. 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 No. 2,440,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Patent No. 4,614,522); lactam , 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); hydroxyaliphatic carboxylic acids (e.g., U.S. Patents Nos. 4,482,464, 4,521,318 and 4,713,189); oxidizing agents (e.g., U.S. Patent No. 4,379,064); combinations of phosphorus pentasulfide and polyalkylene polyamines (e.g. (e.g., U.S. Patent No. 3,185,647); combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (e.g., U.S. Patents No. 3,390,086 and 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. Patents No. 3,649,229, 5,030,249 and 5,039,307); combinations of aldehydes and O-diesters of dithiophosphate (e.g., U.S. Patent No. 3,865,740);Combinations of hydroxyaliphatic carboxylic acids and boric acid (e.g., U.S. Patent No. 4,554,086); combinations of hydroxyaliphatic carboxylic acids followed by formaldehyde and phenol (e.g., U.S. Patent No. 4,636,322); combinations of hydroxyaliphatic carboxylic acids and followed by aliphatic dicarboxylic acids (e.g., U.S. Patent No. 4,663,064); combinations of formaldehyde and phenol, followed by glycolic acid (e.g., U.S. Patent No. 4,699,724); combinations of hydroxyaliphatic carboxylic acids or oxalic acid followed by diisocyanates (e.g., U.S. Patent No. 4,713,191); inorganic acids or anhydrides of phosphorus or combinations of partially or entirely sulfur analogs and boron compounds (e.g., U.S. Patent No. 4,857,214); combinations of organic diacids, followed by unsaturated fatty acids, followed by nitroso aromatic amines, optionally followed by boron compounds, and followed by glycolating agents (e.g., U.S. Patent No. 4,973,412); combinations of aldehydes and triazoles (e.g., U.S. Patent No. 4,963,278); combinations of aldehydes and triazoles followed by boron compounds (e.g., U.S. Patent No. 4,981,492); combinations of cyclic lactones and boron compounds (e.g., U.S. Patents No. 4,963,275 and 4,971,711). Hereinafter, the aforementioned patents are incorporated herein in their entirety.

[0085] A suitable dispersant may have a TBN of approximately 5 to 30 TBN when measured in a dispersant sample containing approximately 50% diluted oil, and may be a dispersant of approximately 10 to 65 mg KOH / g on an oil-free basis. TBN is measured by the method of ASTM D2896.

[0086] In further embodiments, the optional dispersion additive may be a hydrocarbyl-substituted succinamide dispersant or succinimide dispersant. In some approaches, the hydrocarbyl-substituted succinamide dispersant or succinimide dispersant may be derived from a hydrocarbyl-substituted acylating agent reacted with a polyalkylene polyamine, where the hydrocarbyl substituent of the succinamide dispersant or succinimide dispersant is a linear or branched hydrocarbyl group having a number average molecular weight of about 250 to about 5,000 when measured by GPC using polystyrene as the calibration standard.

[0087] In some approaches, the polyalkylene polyamine used to form the dispersant is given by the following formula:

[0088] [ka] (wherein each R and R' is independently a divalent C1-C6 alkylene linker, each R1 and R2 independently forms a 5-membered or 6-membered ring by being optionally fused with one or more aromatic or non-aromatic rings together with hydrogen, a C1-C6 alkyl group, or a nitrogen atom to which they are bonded, and n is an integer from 0 to 8). Another approach involves selecting polyalkylene polyamines from the group consisting of mixtures of polyethylene polyamines having an average of 5-7 nitrogen atoms, triethylenetetramine, tetraethylenepentaamine, and combinations thereof.

[0089] If present, the dispersant may be used in an amount sufficient to provide up to about 20% by weight, based on the final weight of the lubricating oil composition. Other amounts of dispersant that can be used may be about 0.1% to about 15% by weight, or about 0.1% to about 10% by weight, about 0.1% to about 8% by weight, or about 1% to about 10% by weight, or about 1% to about 8% by weight, or about 1% to about 6% by weight, based on the final weight of the lubricating oil composition. In some embodiments, the lubricating oil composition utilizes a mixed dispersant system. A single type or a mixture of two or more types of dispersants in any desired ratio may be used.

[0090] Antioxidants: The lubricating oil compositions described herein may optionally contain one or more antioxidants. Known antioxidant compounds include, for example, phenates, phenate sulfides, sulfurized olefins, phosphosulfur terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, di-nonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine), phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, polymeric antioxidants, or mixtures thereof. Antioxidant compounds may be used alone or in combination.

[0091] Hindered phenol antioxidants may contain secondary butyl groups and / or tertiary butyl groups as sterically hindering groups. The phenol group may be further substituted with a hydrocarbyl group and / or a crosslinking group bonded to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester, but may include, for example, Irganox® L-135 available from BASF or an addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, where the alkyl group may contain about 1 to about 18 carbon atoms, or about 2 to about 12 carbon atoms, or about 2 to about 8 carbon atoms, or about 2 to about 6 carbon atoms, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant may be an ester, but may include Ethanox® 4716 available from Albemarle Corporation.

[0092] Useful antioxidants may include diarylamines and high molecular weight phenols. In embodiments, the lubricating oil composition may contain a mixture of diarylamines and high molecular weight phenols, so that each antioxidant may be present in an amount sufficient to provide up to about 5% by weight, based on the final weight of the lubricating oil composition. In embodiments, 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 phenol, based on the final weight of the lubricating oil composition.

[0093] Suitable olefins that can be sulfurized to form sulfurized olefins include propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof, as well as their dimers, trimers, and tetramers, are particularly useful olefins. Alternatively, the olefins may be Diels-Alder adducts of dienes such as 1,3-butadiene and unsaturated esters such as butyl acrylate.

[0094] Another class of sulfurized olefins includes sulfurized fatty acids and their esters. Fatty acids are often obtained from vegetable or animal oils and typically contain about 4 to about 22 carbon atoms. Suitable examples of fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof. Often, fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or mixtures thereof. Fatty acids and / or esters can be mixed with olefins such as α-olefins.

[0095] In another alternative embodiment, the antioxidant composition also contains a molybdenum-containing antioxidant in addition to the phenolic and / or amine antioxidants discussed above. When a combination of these three antioxidants is used, the ratio of phenol to amine to molybdenum content is preferably (0-2):(0-2):(0-1).

[0096] One or more antioxidants may be present in the lubricating oil composition in an amount ranging from about 0% to about 20% by weight, or from about 0.1% to about 10% by weight, or from about 1% to about 5% by weight.

[0097] Anti-wear agents: The lubricating oil compositions described herein may also optionally contain one or more anti-wear agents. Examples of suitable anti-wear agents include, but are not limited to, metal thiophosphates; metal dialkyldithiophosphates; phosphate esters or salts thereof; phosphate esters; phosphites; phosphorus-containing carboxylic acid esters, ethers, or amides; sulfurized olefins; thiocarbamate-containing compounds such as thiocarbamate esters, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfide; and mixtures thereof. A suitable anti-wear agent may be molybdenum dithiocarbamate. Phosphorus-containing anti-wear agents are fully described in European Patent No. 612839. The metal in the dialkyldithiophosphate salt may be alkali metals, alkaline earth metals, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful anti-wear agent may be zinc dialkyldithiophosphate.

[0098] Further examples of suitable abrasion resistant agents include titanium compounds, tartrates, taltrimids, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, phosphates (e.g., dibutylphosphite), phosphonates, thiocarbamate-containing compounds such as thiocarbamate esters, thiocarbamate amides, thiocarbamate ethers, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides. Tartrates or taltrimids may contain alkyl ester groups, where the total number of carbon atoms on the alkyl group is at least 8. In one embodiment, the abrasion resistant agent may include citrates.

[0099] 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.

[0100] 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, borate fatty amines, borate epoxides, borochemicals, and borochemical dispersants such as succinimide borooxide dispersants, as disclosed in U.S. Patent No. 5,883,057. If present, boron-containing compounds may be used in amounts sufficient to provide a maximum of about 8% by weight, about 0.01% to about 7% by weight, about 0.05% to about 5% by weight, or about 0.1% to about 3% by weight of the lubricating oil composition.

[0101] Additional detergents: The lubricating oil composition may optionally further contain one or more neutral detergents, low-basic detergents, or over-basic detergents, and mixtures thereof. Suitable detergent substrates include phenates, sulfur-containing phenates, sulfonates, calixalates, salixalates, salicylates, carboxylic acids, phosphoric acids, mono- and / or di-thiophosphates, alkylphenols, sulfur-linked alkylphenol compounds, or methylene-crosslinked phenols. Suitable detergents and methods for preparing them are described in detail in numerous patent publications, including U.S. Patent No. 7,732,390 and the references cited therein.

[0102] The detergent substrate may, but is not limited to, alkali metals or alkaline earth metals such as calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent does not contain barium. In some embodiments, the detergent may contain trace amounts of other metals such as magnesium or calcium in amounts 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 include alkali metal salts or alkaline earth metal salts of petroleum sulfonic acid and long-chain mono- or di-alkylaryl sulfonic acid whose aryl group is benzyl, tolyl, or xylyl. Suitable detergents include, but are not limited to, calcium carbonate, sulfur-containing calcium carbonate, calcium sulfonate, calcium calixalate, calcium salixalate, calcium salicylate, calcium carboxylate, calcium phosphate, mono- and / or di-thiophosphate calcium, calcium alkylphenol, calcium sulfur-linked alkylphenol compounds, calcium methylene crosslinked phenol, magnesium carbonate, sulfur-containing magnesium carbonate, magnesium sulfonate, magnesium calixalate, magnesium salixalate, magnesium salicylate, magnesium carboxylate, magnesium phosphate, mono- and / or di-thiophosphate magnesium, magnesium alkylphenol, magnesium sulfur-linked alkylphenol compounds, magnesium methylene crosslinked phenol, sodium carbonate, sulfur-containing sodium carbonate, sodium sulfonate, sodium calixalate, sodium salixalate, sodium salicylate, sodium carboxylate, sodium phosphate, mono- and / or di-thiophosphate sodium, sodium alkylphenol, sodium sulfur-linked alkylphenol compounds, or sodium methylene crosslinked phenol.

[0103] Overbasic detergent additives are well known in the art and may be alkaline or alkaline earth metal overbasic detergent additives. Such detergent additives can be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas. The substrate is typically an acid, such as an aliphatic-substituted sulfonic acid, aliphatic-substituted carboxylic acid, or aliphatic-substituted phenol.

[0104] The term "overbasic" refers to metal salts such as sulfonic acids, carboxylic acids, and phenolic acid metal salts in which the amount of metal present exceeds the stoichiometric amount. Such salts can have a conversion level greater than 100% (i.e., such salts may contain more than 100% of the theoretical amount of metal required to convert the acid to its "standard salt" or "neutral salt"). The expression "metallic ratio," often abbreviated as MR, is used to indicate the ratio of the total stoichiometric equivalents of metal in an overbasic salt to the stoichiometric equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the metallic ratio is 1, but in overbasic salts, the MR is greater than 1. They are generally referred to as overbasic, highly basic, or ultrabasic salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.

[0105] The overbasic detergent in the lubricating oil composition may have a total base number (TBN) of approximately 200 mg KOH / gram or more, or, as further examples, approximately 250 mg KOH / gram or more, or approximately 350 mg KOH / gram or more, or approximately 375 mg KOH / gram or more, or approximately 400 mg KOH / gram or more. The TBN is measured by the method of ASTM D-2896.

[0106] Suitable examples of perbasic detergents include, but are not limited to, perbasic calcium phenate, perbasic calcium sulfur-containing phenate, perbasic calcium sulfonate, perbasic calcium calixalate, perbasic calcium salixalate, perbasic calcium salicylate, perbasic calcium carboxylic acid, perbasic calcium phosphate, perbasic calcium mono- and / or di-thiophosphate, perbasic calcium alkylphenol, perbasic calcium sulfur-bonded alkylphenol compound, perbasic calcium methylene crosslinked phenol, perbasic magnesium phenate, perbasic magnesium sulfur-containing phenate, perbasic magnesium sulfonate, perbasic magnesium calixalate, perbasic magnesium salixalate, perbasic magnesium salicylate, perbasic magnesium carboxylic acid, perbasic magnesium phosphate, perbasic magnesium mono- and / or di-thiophosphate, perbasic magnesium alkylphenol, perbasic magnesium sulfur-bonded alkylphenol compound, or perbasic magnesium methylene crosslinked phenol.

[0107] Overbasic phenate calcium detergents, when measured according to the ASTM D-2896 method, have a total base number of at least about 150 mg KOH / g, at least about 225 mg KOH / g, at least about 225 mg KOH / g to about 400 mg KOH / g, at least about 225 mg KOH / g to about 350 mg KOH / g, or about 230 mg KOH / g to about 350 mg KOH / g. When such a detergent composition is formed in an inert diluent, such as process oil, usually mineral oil, the total base number reflects the basicity of the overall composition, including the diluent and any other materials that may be included in the detergent composition (e.g., accelerators).

[0108] The over-basic detergent may have a metal-to-substrate ratio of 1.1:1 or greater, or 2:1 or greater, or 4:1 or greater, or 5:1 or greater, or 7:1 or greater, or 10:1 or greater. In some embodiments, the detergent is effective in reducing or preventing rust in the engine or other automotive parts such as the transmission or gears. The detergent may be present in the lubricating composition in amounts of 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 more than about 4% to about 8% by weight.

[0109] Extreme pressure agents: The lubricating oil compositions described herein may optionally contain one or more extreme pressure agents. Oil-soluble extreme pressure (EP) agents include sulfur and chlorosulfur-containing EP agents, chlorinated hydrocarbon EP agents, and phosphorus EP agents. Examples of such EP agents include chlorinated waxes; organic sulfides and polysulfides such as dibenzyl disulfide, bis(chlorobenzyl) disulfide, dibutyltetrasulfide, methyl sulfide esters of oleic acid, alkylphenol sulfides, dipentene sulfides, terpenes sulfides, and Diels-Alder sulfide adducts; phosphorus sulfide hydrocarbons such as reaction products of phosphorus sulfide with terpentine or methyl oleate; phosphate esters such as dihydrocarbyl and trihydrocarbyl phosphite, e.g., dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, and pentylphenyl phosphite; dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene-substituted phenyl phosphite; metal thiocarbamates such as zinc dioctyl dithiocarbamate and barium heptylphenol dioate; amine salts of alkyl and dialkyl phosphates, e.g., amine salts of reaction products of dialkyldithiophosphate and propylene oxide; and mixtures thereof.

[0110] Friction modifiers: The lubricating oil compositions described herein may also optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing and metal-free friction modifiers, but are not limited to imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated etheramines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerol esters, sulfurized fatty compounds and olefins, sunflower oil, other naturally occurring vegetable or animal oils, dicarboxylic acid esters, esters or partial esters of polyols with one or more aliphatic or aromatic carboxylic acids, and the like.

[0111] Suitable friction modifiers may contain hydrocarbyl groups selected from linear, branched, or aromatic hydrocarbyl groups, or mixtures thereof, and may be saturated or unsaturated. Hydrocarbyl groups may consist of carbon and a heteroatom such as hydrogen or sulfur or oxygen. Hydrocarbyl groups may range from about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long-chain fatty acid ester. In other embodiments, the long-chain fatty acid ester may be a mono-ester, di-ester, or (tri)glyceride. 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.

[0112] Other suitable friction modifiers may include organic, ashless (metal-free), and nitrogen-free organic friction modifiers. Such friction modifiers may contain esters formed by reacting a carboxylic acid and an anhydride with an alkanol, and may generally contain polar end groups (e.g., carboxyl or hydroxyl) covalently bonded to a lipophilic hydrocarbon chain. An example of an organic ashless nitrogen-free friction modifier is generally known as glycerol monooleate (GMO), which may contain mono-, di-, and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Patent No. 6,723,685, which is incorporated herein by reference in its entirety.

[0113] Amineral friction modifiers may include amines or polyamines. Such compounds may have linear hydrocarbyl groups that are either saturated or unsaturated, or a mixture thereof, and may contain about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated etheramines. Such compounds may have linear hydrocarbyl groups that are either saturated or unsaturated, or a mixture thereof. These may contain about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated etheramines.

[0114] Amines and amides may be used on their own or as adducts or reaction products with boron compounds such as boron oxide, boron halides, metaborates, boric acid, or mono-, di-, or tri-alkylborates. Other suitable friction modifiers are described in U.S. Patent No. 6,300,291, which is incorporated herein by reference in its entirety.

[0115] The friction modifier may be optionally present in a range such as approximately 0% to 10% by weight, approximately 0.01% to 8% by weight, or approximately 0.1% to 4% by weight.

[0116] Molybdenum-containing components: The lubricating oil compositions described herein may also optionally contain one or more molybdenum-containing compounds. Oil-soluble molybdenum compounds may have the functional properties of anti-wear agents, antioxidants, friction modifiers, or mixtures thereof. Oil-soluble molybdenum compounds may include molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum dithiophosphinate, amine salts of molybdenum compounds, molybdenum xanthate, molybdenum thioxanthate, molybdenum sulfide, molybdenum carboxylate, molybdenum alkoxide, trinuclear organic molybdenum compounds, and / or mixtures thereof. Examples of molybdenum sulfide include molybdenum disulfide. Molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound may be a molybdenum dithiocarbamate.

[0117] Preferred examples of molybdenum compounds that can be used include Molyvan 822®, Molyvan® A, Molyvan 2000®, and Molyvan 855® from RTVanderbilt Co., Ltd., as well as commercially available materials and mixtures thereof sold under trade names such as Sakura-Lube® S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 from Adeka Corporation. Preferred molybdenum components are described in U.S. Patent No. 5,650,381, U.S. Reissue Patents No. 37,363(E1), No. 38,929(E1), and No. 40,595(E1), which are incorporated herein by reference in their entirety.

[0118] Additionally, the molybdenum compounds may be acidic molybdenum compounds. These include molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates, as well as other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide, or similar acidic molybdenum compounds. Alternatively, compositions can provide molybdenum by 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 International Publication No. 94 / 06897, the aforementioned patent documents are incorporated herein by reference in their entirety.

[0119] Another class of preferred organomolybdenum compounds are trinuclear molybdenum compounds and mixtures thereof, such as compounds of the formula Mo3SkLnQz, where S represents sulfur, L represents an independently selected ligand having a sufficient number of carbon atoms to make the organic group soluble or dispersible in oil, n is 1 to 4, k varies from 4 to 7, Q is selected from the group of neutral electron-donating compounds such as water, amines, alcohols, phosphines, and ethers, and z is in the range of 0 to 5, including non-stoichiometric values. In all ligand organic groups, there may be at least 21 total carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms. Additional preferred molybdenum compounds are described in U.S. Patent No. 6,723,685, which is incorporated herein by reference in whole.

[0120] Oil-soluble molybdenum compounds may be present in amounts sufficient to provide molybdenum in concentrations of approximately 0.5 ppm to 2000 ppm, 1 ppm to 700 ppm, 1 ppm to 550 ppm, 5 ppm to 300 ppm, or 20 ppm to 250 ppm.

[0121] Transition metal-containing compounds: In another embodiment, the oil-soluble compound may be a transition metal-containing compound or a metalloid. Transition metals may include, but are not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten, and the like. Preferred metalloids may include, but are not limited to, boron, silicon, antimony, tellurium, and the like.

[0122] In embodiments, oil-soluble transition metal-containing compounds may function as a wear inhibitor, friction modifier, antioxidant, adhesion control additive, or one or more of these functions. In embodiments, oil-soluble transition metal-containing compounds may be oil-soluble titanium compounds such as titanium(IV) alkoxides. Titanium-containing compounds that may be used in or for the preparation of oil-soluble materials in the art of this disclosure include, but are not limited to, various Ti(IV) compounds such as titanium(IV) oxide; titanium(IV) sulfide; titanium(IV) nitrate; titanium(IV) alkoxides, e.g., titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide; and other titanium compounds or complexes, e.g., titanium phenate; titanium carboxylates, e.g., titanium(IV) 2-ethyl-1,3-hexanedioate or titanium citrate or titanium oleate; and titanium(IV) (triethanolamine) isopropoxide. Other forms of titanium included in the disclosed technology include titanium phosphates such as titanium dithiophosphates (e.g., dialkyldithiophosphates) and titanium sulfonates (e.g., alkylbenzene sulfonates), or reaction products of titanium compounds that form salts, such as oil-soluble salts, with various acidic materials. Therefore, titanium compounds can be derived from organic acids, alcohols, and glycols, among other things. Ti compounds may also exist in dimer or oligomeric forms containing a Ti-O-Ti structure. Such titanium materials are commercially available or readily prepared by appropriate synthetic techniques evident to those skilled in the art. Depending on the specific compound, they may exist as solids or liquids at room temperature. They may also be provided in solution form in a suitable inert solvent.

[0123] In one embodiment, titanium may be supplied as a Ti-modified dispersant, such as a succinimide dispersant. Such a material may be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as alkenyl-(or alkyl) succinic anhydride. The resulting titanate-succinate intermediate may be used directly or reacted with any of several materials, such as (a) a polyamine-based succinimide / amide dispersant having a free, condensable -NH functional group; (b) a component of a polyamine-based succinimide / amide dispersant, i.e., alkenyl-(or alkyl) succinic anhydride and a polyamine; or (c) a hydroxy-containing polyester dispersant prepared by the reaction of substituted succinic anhydride with a polyol, amino alcohol, polyamine, or a mixture thereof. Alternatively, the titanate-succinate intermediate may be reacted with other agents such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product may be used directly to impart Ti to the lubricating oil, or it may be further reacted with a succinic acid dispersant as described above. As an example, to provide a titanium-modified dispersant or intermediate, 1 part (mol) of tetraisopropyl titanate may be reacted with about 2 parts (mol) of polyisobutene-substituted succinic anhydride at 140-150°C for 5-6 hours. The resulting material (30 g) may be further reacted at 150°C for 1.5 hours with a succinimide dispersant from a mixture of polyisobutene-substituted succinic anhydride and polyethylene polyamine (127 g + diluent oil) to produce a titanium-modified succinimide dispersant.

[0124] Another titanium-containing compound is titanium alkoxide and C6-C6 25 It may be a reaction product with a carboxylic acid. The reaction product is given by the following formula:

[0125] [ka] It can be represented by (wherein n is an integer selected from 2, 3, and 4, and R is a hydrocarbyl group containing about 5 to about 24 carbon atoms) or by the following formula:

[0126] [ka] (wherein m+n=4, n is in the range of 1 to 3, R4 is an alkyl moiety having 1 to 8 carbon atoms, R1 is selected from hydrocarbyl groups containing approximately 6 to 25 carbon atoms, and R2 and R3 are the same or different and selected from hydrocarbyl groups containing 1 to 6 carbon atoms) or the titanium compound may be represented by the following formula:

[0127] [ka] (In the formula, x is in the range of 0 to 3, R1 is selected from hydrocarbyl groups containing approximately 6 to 25 carbon atoms, R2 and R3 are the same or different and selected from hydrocarbyl groups containing approximately 1 to 6 carbon atoms, and R4 is H, C6 to C) 25 It can be represented by (selected from the group consisting of any of the carboxylic acid moieties).

[0128] Suitable carboxylic acids may include, but are not limited to, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, and neodecanoic acid.

[0129] In embodiments, the oil-soluble titanium compound may be present in the lubricating oil composition in amounts to provide about 0 to about 3000 ppm by weight of titanium, or 25 to about 1500 ppm by weight of titanium, or about 35 ppm to about 500 ppm by weight of titanium, or about 50 ppm to about 300 ppm by weight of titanium.

[0130] Viscosity Index Modifiers: The lubricating oil compositions described herein may also optionally contain one or more viscosity index modifiers. Suitable viscosity index modifiers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, styrene-isoprene polymers, styrene / maleate copolymers, styrene-butadiene copolymers, styrene-isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrated alkenylaryl conjugated diene copolymers, or mixtures thereof. Viscosity index modifiers may include star polymers, but a preferred example is described in U.S. Patent Application Publication No. 20120101017(A1).

[0131] The lubricating oil compositions described herein may optionally contain, in addition to or instead of viscosity index modifiers, one or more dispersant viscosity index modifiers. Suitable viscosity index modifiers include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with reaction products of acyling agents (such as maleic anhydride) and amines, amine-functionalized polymethacrylates, or esterified maleic anhydride-styrene copolymers reacted with amines.

[0132] The total amount of viscosity index improvers and / or dispersible viscosity index improvers may be about 0% to about 20% by weight, about 0.1% to about 15% by weight, about 0.1% to about 12% by weight, or about 0.5% to about 10% by weight of the lubricating oil composition.

[0133] Other optional additives: Other additives may be selected to perform one or more functions required of the lubricating fluid. Furthermore, one or more of the aforementioned additives may be polyfunctional and may provide functions in addition to those described herein, or other functions.

[0134] The lubricating oil compositions according to this disclosure may optionally include other performance additives. These other performance additives may be additions to the specific additives of this disclosure and / or may include one or more of the following: metal deactivators, viscosity index modifiers, detergents, ashless TBN boosters, friction modifiers, anti-wear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index modifiers, extreme pressure agents, antioxidants, foam inhibitors, deemulsifiers, emulsifiers, pour point depressants, seal swelling agents, and mixtures thereof. Typically, a complete lubricating oil will contain one or more of these performance additives.

[0135] Suitable metal deactivators include derivatives of benzotriazole (typically toltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzothiazole; foam inhibitors comprising copolymers of ethyl acrylate, 2-ethylhexyl acrylate, and optionally vinyl acetate; demulsifiers comprising trialkyl phosphates, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers; and pour point depressants comprising esters of maleate-styrene anhydride, polymethacrylate, polyacrylate, or polyacrylamide.

[0136] Suitable foam inhibitors include silicon-based compounds such as siloxanes.

[0137] Suitable pour point depressants 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.

[0138] Suitable rust inhibitors may be a single compound or a mixture of compounds having properties that inhibit corrosion of iron metal surfaces. Non-limiting examples of useful rust inhibitors as used herein include oil-soluble high molecular weight organic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid, as well as oil-soluble polycarboxylic acids including dimeric and trimeric acids such as those derived from tall oil fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long-chain alpha- and omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000, and alkenyl succinates containing about 10 or more carbon atoms in the alkenyl group, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Another useful type of acidic corrosion inhibitor is a semi-ester of alkenyl succinic acid having about 8 to about 24 carbon atoms in the alkenyl group with an alcohol such as polyglycol. The corresponding semiamides of such alkenyl succinic acids are also useful. Useful rust inhibitors are high molecular weight organic acids.

[0139] If present, rust inhibitors may be used in an amount 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.

[0140] Generally speaking, suitable lubricating oils containing neutral to overbasic alkylphenate sulfide products as used herein may contain additive components within the range listed in the table below.

[0141] [Table 2]

[0142] The percentages of each component listed above represent the weight percentage of each component based on the weight of the final lubricating oil composition. The remainder of the lubricating oil composition consists of one or more base oils. The additives used in formulating the compositions described herein may be blended with the base oils individually or in various partial combinations. However, it may be preferable to blend all the components simultaneously using an additive concentrate (i.e., the additive plus a diluent such as a hydrocarbon solvent). A fully formulated lubricating oil conventionally contains an additive package, referred herein as a dispersant / inhibitor package or DI package, which provides the properties required in the formulation. [Examples]

[0143] The following embodiments illustrate exemplary embodiments of the present disclosure. In these embodiments and elsewhere in this application, all ratios, parts, and percentages are by weight unless otherwise indicated. These embodiments are presented for illustrative purposes only and are not intended to limit the scope of the inventions disclosed herein.

[0144] For comparative examples with a sulfidation ratio of less than 500:1, the concentration of unsulfurized alkylphenate was measured, for example, by reversed-phase high-performance liquid chromatography (HPLC) as described in U.S. Patent No. 8,933,022(B2), when the level of unsulfurized alkylphenate was at least about 0.3 weight percent or higher. In the exemplary HPLC method, samples were prepared by weighing about 80–120 mg into a 10 mL volumetric flask, diluting with methylene chloride to the level mark, and mixing until the sample was completely dissolved. The HPLC system used in the HPLC method included an HPLC pump, an HPLC column compartment with thermostat, an HPLC fluorescence detector, and a PC-based chromatography data acquisition system. The exemplary system was an Agilent 1200 HPLC or equivalent with ChemStation software. The HPLC column was a Phenomenex Luna C8(2) 150 × 4.6 mm 5 μm 100 Å or equivalent.

[0145] For the comparative example, the analysis was performed using the following system settings: pump flow rate = 1.0 mL / min, maximum pressure = 200 bar, fluorescence wavelength: 225 excitation 313 emission: gain = 9, column thermostat temperature = 25°C, injection size = 1 μL diluted sample, elution type: gradient, reversed phase, gradient: 0-7 mins, switching from 85 / 15 methanol / water to 100% methanol linear gradient, run time: 17 mins.

[0146] For the comparative samples, the resulting chromatographs typically contain several peaks. Peaks due to unsulfurized alkylphenates typically elute with short retention times, while peaks due to sulfurized alkylphenates elute with longer retention times. For quantification purposes, the area of ​​a single maximum peak of unsulfurized alkylphenate was measured, and this area was used to determine the total concentration of unsulfurized alkylphenate. By comparing the area of ​​the selected peak with the calibration curve, the weight percentage of unsulfurized alkylphenate can be determined, and then the amount of sulfurized alkylphenate can be determined.

[0147] For samples of the present invention with a sulfidation ratio of 500:1 or higher, the above method is generally not sensitive enough to measure such low levels of unsulfided alkylphenate / alkylphenol. Rather, the measurement was consistent with the above method but modified using liquid chromatography-mass spectrometry (LC-MS) with single-quadruple or triple-quadruple MS or homogenized components via Agilent MS 6420 QQQ and Agilent MSD XT or an Agilent MSD XT with an Agilent 1260 LC column such as a Supelco Ascentis Express RP Amide 2.7u, 100 mm × 2.1 mm ID column, as follows. For the measurement of samples of the present invention, the following system settings were used in the analysis: column temperature 45°C, flow rate 0.3 mL / min, injection volume 3 μl, and run time 22 minutes. The MS system settings and conditions were as follows: Ion source: ESI negative, mode SIM, gas temperature 300°C, gas flow rate 13 l / min, nebulizer 35 psi, capillary 3000(v), fragmenter 135, and peak width 0.07. The percentage of unsulfurized alkylphenol / alkylphenate was determined using MassHunter Quant Program or an equivalent to generate a calibration curve, and then the percentage of unsulfurized alkylphenol / phenate in the sample was calculated.

[0148] Comparative Example 1 As described in U.S. Patent No. 8,933,002(B2), Examples 1 and 3 describe the sulfurization, neutralization, and overbasification of tetrapropenylphenol with methanol and xylene, but such methods could only achieve a sulfurization ratio of 262:1 (i.e., 0.38 residual unsulfurized TPP).

[0149] As described in Example 1 of the '002 patent, a two-step process for the sulfurization of tetrapropenylphenol is described. As described in the '002 patent, step 1 was the sulfurization of tetrapropenylphenol as follows: 1620 g of tetrapropenylphenol (available from Chevron Oronite Company LLC) was packed into a 4 liter round-bottom flask at room temperature. The tetrapropenylphenol was heated to 110°C for 30 minutes. At 60°C, 14 g of 50 wt% aqueous potassium hydroxide solution was added with stirring. Next, 192 g of sulfur flakes (i.e., elemental sulfur) were added at 110°C and the pressure was reduced to 680 mmHg. The reaction temperature was then raised to 180°C for 30 minutes and the pressure was slowly reduced to 260 mmHg to promote H2S release. The formed H2S gas was captured in a concentrated potassium hydroxide solution located before a vacuum pump. The reaction conditions were maintained for 2 hours and 45 minutes. The pressure was further reduced to 50 mmHg over 15 minutes and held under these conditions for a further 3 hours. The alkylphenol sulfide reaction product was cooled. The '002 patent states that the obtained alkylphenol sulfide had the following analysis: 6.85 percent sulfur, 2646 ppm potassium, a viscosity of 65.4 mm² / s at 100°C, and 26.5 percent TPP (i.e., unreacted tetrapropenylphenol and its calcium salt).

[0150] Next, Example 1 of the '002 patent further describes step 2, which is distillation of alkylphenol sulfide from step 1, as follows: After preheating the alkylphenol sulfide reaction product obtained in step 1 to about 140°C, continuously 0.0385m 2 The wiped film evaporator was supplied at approximately 400 g / hour. The evaporator temperature was maintained at approximately 210°C and the pressure at approximately 1.5 mbar. Patent '002 states that the average distillation product had the following analytical characteristics: approximately 10.3% sulfur, approximately 4293 ppm potassium, a viscosity of approximately 402.8 mm² / s at 100°C, and 0.31% TPP.

[0151] Next, in Example 3 of the '002 patent, the neutralization, overbasing, and work-up of the product from Example 1 of the '002 patent was described using methanol and xylene as follows: 243.2 g of slaked lime was added to a 5-liter double-jacketed glass reactor together with 243.2 g of methanol and 876 g of xylene. Next, 713.4 g of tetrapropenylphenol sulfide from step 2 of Example 1 of the '002 patent was heated to about 80°C and then diluted with 562 g of xylene. The mixture was added to the reactor over 30 minutes while raising the reaction temperature 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 this mixture over 2 minutes. The temperature of the reaction mixture rose from 25°C to 34°C due to an exothermic reaction. Next, 24.4 g of CO2 was added over 30 minutes while heating from 34°C to 36°C. Then, 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 slaked lime, 60.8 g of methanol, and 334 g of xylene was added to the reactor over 1 minute. Next, 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 start 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 at 2.4 vol%. After centrifuging the crude product, xylene distillation was carried out at 170°C and 25 mBar for 1 hour.

[0152] Subsequently, Example 3 of the '002 patent states that the obtained product was degassed at 150°C for 4 hours, and that the obtained product contained 9.56 percent calcium, 4.71 percent sulfur, 1876 ppm potassium, a kinematic viscosity of 410.2 cSt at 100°C, 273 mg KOH / g TBN, and a residual content of unsulfurized tetrapropenylphenol (TPP) of 0.38%, which is only a sulfidation ratio of 262:1.

[0153] Comparative Example 2 Similar to Comparative Example 1, Example 4 of U.S. Patent No. 8,933,002 (B2) describes the neutralization and overbasication of tetrapropenylphenol with methanol, but such a method could only achieve a sulfidation ratio of 178:1. In this example, 609.01 g of sulfurized tetrapropenylphenol (Example 1 of U.S. Patent No. 8,933,002) was packed into a 2-liter round-bottom flask. Next, 425.2 g of methanol and 0.2 g of foam inhibitor SI200, available 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 slaked lime was introduced along with 300 g of 100 N diluent oil. At 60°C, 4.6 g of a 50 / 50 weight ratio mixture of acetic acid and formic acid was added. Neutralization was maintained at 60°C and atmospheric pressure for 210 minutes. Methanol was evaporated by slowly reducing the pressure to 30 mmHg over approximately 2 hours. During this process, 354 g of lubricating oil was added dropwise. The distillation was maintained at 30 mmHg and 60°C for 1 hour. The crude precipitate of the neutralized calcium salt of alkylhydroxyaromatic sulfide was measured at 0.4 vol%. The product was filtered through a Buchner filter to remove unreacted lime.

[0154] U.S. Patent No. 8,933,002 further states that the obtained product was degassed in air at 150°C for 4 hours, and that the product had the following analysis: 3.17% calcium, 4.86% sulfur, K: 1827 ppm, kinematic viscosity of 80.8 cSt at 100°C, and TBN of 89 mg KOH / g, with an unsulfurized tetrapropenylphenol (TPP) content of 0.56%, which represented a sulfidation ratio of only 178:1.

[0155] Comparative Example 3 A tetrapropylene calcium phenate composition having 118 TBN, approximately 4.26 wt percent calcium, and 1.8 wt percent unsulfurized tetrapropylene phenol / phenate obtained from catalyzed sulfur monochloride was overbasticated at 165°C for 3 hours and then vacuum distilled at 200°C for 1 hour. After overbastication and distillation, the product, which had 314 TBN, now had 4.4 wt percent unsulfurized tetrapropylene phenate / phenol.

[0156] Comparative Example 4 As described in U.S. Patent No. 4,973,411, Example 1 describes a sulfide phenate product, but such a method, when tested using the measurement method of this application, achieves only about 0.3 to about 0.5 weight percent of residual unsulfurized alkylphenol, and therefore only achieves a sulfide ratio of about 300:1. Example 1 of the '411 patent utilized sulfur dichloride from Sigma Aldrich, along with impurities containing 80 weight percent sulfur dichloride and 20 percent sulfur monochloride.

[0157] Example 1 of U.S. Patent No. 4,973,411 was replicated as follows: Approximately 192 parts by weight of dodecylphenol packing was added to a 3-liter four-necked flask along with approximately 840 parts by weight of isooctane or heptane. Nitrogen gas was then bubbled into the mixture at a rate of approximately 400 mL / min. Next, approximately 51 parts of the above sulfur dichloride (80% SCl2 and 20% S2Cl2) were added via an addition funnel to maintain the reaction temperature near room temperature. The reaction mixture was stirred for approximately 5 minutes, and then heated to approximately 80°C for half an hour. The reaction mixture was then cooled to approximately 45°C. Next, approximately 216 parts of 100P light-colored oil were added, along with approximately 115 parts methanol and approximately 105 parts Ca(OH)2. The introduction of nitrogen gas was stopped, and the mixture was stirred at approximately 55°C to approximately 57°C for 1 hour. The temperature was maintained, and CO2 was bubbling at an appropriate rate of approximately 200–300 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 had approximately 8.8 wt percent calcium, approximately 3.4 wt percent sulfur, and approximately 143 kV100 and 232 TBN, which was consistent with the final product reported in the '411 patent.

[0158] U.S. Patent No. 4,973,411 does not disclose or suggest any effect of the molar ratio between the sulfur source and dodecylphenol, but in this example, the molar ratio of the sulfur source provided from 80 wt percent sulfur dichloride and 20 wt percent sulfur monochloride to dodecylphenol was calculated to be 0.64:1.

[0159] As described above, when the residual unsulfurized alkylphenol was evaluated using the test method of this application, which includes either reverse-phase high-performance liquid chromatography (HPLC) and / or liquid chromatography-mass spectrometry (LC-MS), the residual unsulfurized alkylphenol level in Example 1 of U.S. Patent No. 4,973,411 was measured to be 0.39 weight percent.

[0160] Example 1 The results of the low-temperature process of the present invention for producing overbasication and sulfurized tetrapropylene alkylated phenate products having a high sulfurization ratio are shown in the table below. In this example, three different sulfurized tetrapropylene alkylated phenols were first prepared by reacting about 720 grams of tetrapropylene phenol with about 241 grams of sulfur monochloride as follows.

[0161] S1: Tetrapropylenephenol was packed into a kettle, sulfur monochloride was added dropwise at approximately 100°C, the temperature was then raised to approximately 180°C and held for approximately 1 hour, then raised to approximately 190°C and held for approximately 1 hour, then vacuum stripping was performed at approximately 200°C for approximately 1 hour, the mixture was then cooled to approximately 150°C, and approximately 252 grams of process oil were added. After sulfidation, the intermediate sulfidation product had a sulfidation ratio of approximately 499:1.

[0162] S2: Tetrapropylenephenol was packed into a kettle with approximately 100 grams of heptane, and sulfur monochloride was added dropwise at approximately 40°C. The temperature was then raised to approximately 100°C, and heptane was distilled for approximately 1 hour by performing complete vacuum stripping. Vacuum stripping was then performed at approximately 200°C for approximately 1 hour, followed by cooling to approximately 150°C and the addition of approximately 252 grams of process oil. After sulfidation, the intermediate sulfide product had a sulfidation ratio of approximately 1110:1.

[0163] S3: Tetrapropylenephenol was packed into a kettle with approximately 100 grams of heptane, and sulfur monochloride was added dropwise at approximately 40°C. The temperature was then raised to approximately 100°C, and heptane was distilled for approximately 1 hour by performing complete vacuum stripping. Subsequently, approximately 252 grams of process oil was added. After sulfidation, the intermediate sulfide product had a sulfidation ratio of approximately 2499:1.

[0164] Next, each tetrapropylenephenol sulfide S1, S2, or S3 was neutralized with calcium oxide in the presence of the ammonium sulfonate composition, solvent system, and process oil described in Table 4. The neutralized compositions were then overbasicated in the solvent system by treatment with approximately 208 sccm of gaseous carbon dioxide, as shown in Tables 5 and 6. Table 3 provides the properties of the neutralized overbasic products.

[0165] [Table 3] * Unsulfurized alkylphenol refers to both the unsulfurized alkylphenate and any unsulfurized alkylphenol in the product. ** For example, the sulfidation ratio of sample A was determined from 99.92% alkyl phenate sulfide and 0.08% unsulfided alkyl phenate / phenol in the sample, resulting in a weight ratio of 99.92:0.08 or 1249:1.

[0166] [Table 4]

[0167] [Table 5]

[0168] [Table 6] * 21g of CaO was added during the overbasication process.

[0169] After overbasication, the samples were filtered and subjected to vacuum stripping at a temperature not exceeding approximately 140°C to produce the alkyl phenate sulfide products summarized in Table 3 above.

[0170] Example 2 Further experiments were carried out to reproduce Example 1 of U.S. Patent No. 8,933,002 (B2) regarding the sulfidation of tetrapropenylphenol. According to the sulfidation in Step 1 of Example 1 of the '002 patent, the obtained intermediate product had 6.88 percent sulfur, 56.8 mm 2 / s of KV100, 1958 ppm of potassium, and a content of 30.4 percent of unsulfided tetrapropenylphenol.

[0171] Then, distillation using a wiped film evaporator consistent with Step 2 of Example 1 of the '002 patent was performed on the intermediate product, and a sulfurized tetrapropylene alkylated phenate product with a high sulfidation ratio (i.e., a low level of unreacted or unsulfided tetrapropylene phenol) was produced, except that the vacuum was 1100 mTorr and the feed rate was 360 g / hour. The obtained product had 10.18 percent sulfur, 360 mm 2 / s of KV100, 3133 ppm of potassium, and a content of 0.05% of unreacted or unsulfided tetrapropylene phenol or a high sulfidation ratio of 1999:1.

[0172] Example 3 Then, in accordance with Example 3 of U.S. Patent No. 8,933,002 (B2), except that the solvents were heptane and methanol and the neutralization, overbasing, and post-treatment were carried out at a low temperature not exceeding about 100°C, the sulfurized alkylphenol replicated from Example 2 above was neutralized and overbased.

[0173] The solvent mixture for this example was about 90% heptane and about 10% methanol. The crude product of Example 2 above was centrifuged at a temperature not exceeding 100°C, and then the product was degassed at a temperature not exceeding 100°C to form a final sulfurized product having 4.24% sulfur, 298.8 mm 2 / s of KV100, 1048 ppm of potassium, a content of less than 0.03% of unsulfided alkylphenol (i.e., an undetectable amount or a sulfidation ratio of 3333:1 or more), a TBN of 270.4, and a calcium content of 10.52 percent.

[0174] Comparing the results of this example using the heptane / methanol solvent system with those of Comparative Example 2 (using the method of U.S. Patent No. 8,933,002 and methanol / xylene solvent and high-temperature post-treatment), the effects of solvent selection and low-temperature treatment, particularly the low-temperature post-treatment discovered herein, can be demonstrated. In Comparative Example 2 using the methanol / xylene solvent system and high-temperature post-treatment of Patent No. 8,933,002, the level of unreacted TPP increased after neutralization, overbasication, and post-treatment, whereas in this example using the heptane / methanol solvent and low-temperature post-treatment, the level of unreacted TPP further decreased in the final product.

[0175] This temperature dependence on the formation of unreacted TPP (i.e., regeneration of unsulfurized TPP during processing) is also shown in the graph in Figure 1, which illustrates the reaction kinetics of unsulfurized TPP regeneration based on temperature. As shown in Figure 1, if the temperature is maintained below approximately 100°C (e.g., approximately 80°C) during processing, the level of unreacted or unsulfurized TPP is not regenerated.

[0176] Example 4 Further experiments were conducted using the method of this application to produce sulfurized tetrapropylene alkylated phenate products having a high sulfurization ratio (i.e., low levels of unreacted or unsulfurized tetrapropylenephenol), as shown in Table 7 below. In these examples, the sulfur source used was a mixture of about 67 wt percent sulfur dichloride (SCl2) and about 33 wt percent sulfur monochloride (S2Cl2), with different molar ratios of sulfur source to tetrapropylenephenol (TPP), generally using the sulfurization method of Comparative Example 1, with any post-treatments carried out at temperatures below about 100°C.

[0177] Residual levels of unreacted tetrapropylenephenol were measured using LCMS as discussed 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 weight percent. As shown in Table 7, a sulfur source ratio of at least 0.7 or more alkylphenols results in undetectable levels of unreacted or unsulfurized tetrapropylenephenol in the sulfurization product, and / or in combination with the low-temperature treatment disclosed herein.

[0178] [Table 7]

[0179] Any neutralization and / or overbasification consistent with the present disclosure can be performed on the compositions of this embodiment.

[0180] As used herein and in the appended claims, the singular forms “a,” “an,” and “the” include multiple references unless explicitly and clearly limited to one. For example, a reference to “antioxidants” includes two or more different antioxidants. Where used herein, the term “includes” and its grammatical variations are intended to be non-limiting so as not to exclude other similar items that may be substituted for or added to the items in the list.

[0181] For the purposes of this specification and the appended claims, unless otherwise indicated, all numbers representing quantities, percentages, or proportions, and other numerical values ​​used herein and in the claims should be understood in all cases as being modified by the term “approximately.” Therefore, unless otherwise indicated, the numerical parameters described in the following specification and the appended claims are approximations that may vary depending on the desired characteristics sought by this disclosure. At a minimum, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be interpreted at least in terms of the number of significant figures reported and by applying common rounding techniques.

[0182] It should be understood that each component, compound, substituent, or parameter disclosed herein is disclosed for use alone or in combination with any one or more other components, compounds, substituents, or parameters disclosed herein.

[0183] It should be further understood that each range disclosed herein should be interpreted as a disclosure of each specific value within the disclosure range having the same number of significant figures. Therefore, for example, the range 1–4 should be interpreted as a clear disclosure of any range of such values, not just the values ​​1, 2, 3, and 4.

[0184] It should be further understood that each lower limit of each range disclosed herein should be interpreted as being disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compound, substituent, or parameter. Therefore, this disclosure should be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range, or 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 further understood that any range between endpoint values ​​within a broad range is also considered herein. Therefore, the range 1-4 also means ranges such as 1-3, 1-2, 2-4, 2-3, etc.

[0185] Furthermore, any specific amounts / values ​​of components, compounds, substituents, or parameters disclosed in detail or examples should be interpreted as disclosures of either a lower or upper limit of a range, and can therefore be combined with any other lower or upper limit or specific amounts / values ​​in the range for the same component, compound, substituent, or parameter disclosed elsewhere in this application to form a range for that component, compound, substituent, or parameter.

[0186] While specific embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents may emerge that are not currently anticipated or can not be anticipated by the applicants or others skilled in the art. Accordingly, the attached claims filed and any modified attached claims are intended to encompass all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A process for preparing alkyl sulfide phenate products to achieve a high sulfidation ratio of alkyl sulfide phenate to unsulfide alkyl phenate, To provide alkylphenol sulfide, the alkylphenol is sulfurized with a sulfur source, wherein the alkylphenol is derived from the alkylation of phenol, and the molar ratio of the sulfur source to the alkylphenol is about 0.66 to about 3.

5. To provide an alkylphenate sulfide composition, the alkylphenol sulfide is neutralized and optionally overbasified in the presence of a solvent, wherein the neutralization and optionally overbasification are performed at a temperature not exceeding approximately 140°C to achieve a sulfidation ratio of approximately 500:1 or higher, and A process comprising post-treating the alkyl sulfide phenate composition to obtain the alkyl sulfide phenate product, wherein the post-treatment is performed at a temperature not exceeding approximately 140°C in order to maintain the sulfide ratio at approximately 500:1 or higher.

2. A process for preparing an alkylphenate sulfide according to claim 1, wherein the sulfur source comprises elemental sulfur, sulfur monochloride, sulfur dichloride, hydrogen sulfide, sulfur dioxide, sulfide hydrate, or a combination thereof.

3. A process for preparing an alkylphenate sulfide according to claim 1, wherein the solvent is one or more solvents having a boiling point of about 100°C or less at a bar of about 1000 to about 40 mbar.

4. A process for preparing an alkylphenate sulfide according to claim 3, wherein the solvent is about 85 to about 95 weight percent heptane and about 5 to about 15 weight percent methanol.

5. A process for preparing an alkylphenate sulfide according to claim 1, wherein the neutralization and / or the optional overbasication comprises contacting the alkylphenol sulfide with an alkali metal salt or alkaline earth metal salt at a temperature not exceeding about 140°C, the alkali metal salt or alkaline earth metal salt being 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.

6. A process for preparing an alkylphenate sulfide according to claim 1, wherein the process does not remove residual unsulfurized alkylphenate during the sulfidation, neutralization, and / or optional overbasification.

7. A process for preparing the alkyl sulfide phenate according to claim 1, wherein the alkyl sulfide phenate product has a total base number of about 100 to about 400 mg KOH / g when measured by the ASTM D-2896 method.

8. A process for preparing an alkylphenate sulfide according to claim 1, wherein the sulfidation is carried out in the absence of a base and / or the alkylphenol sulfide is neutralized and overbasicated.

9. A process for preparing the alkyl sulfide phenate according to claim 1, wherein the alkyl sulfide phenate product has less than about 0.2 weight percent of unsulfide alkyl phenate and / or unsulfide alkylphenol.

10. Alkylphenate sulfide product prepared by the method described in claim 1.

11. A metal phenate detergent having a high sulfidation ratio of alkyl phenate to unsulfurized alkyl phenate or unsulfurized alkylphenol, Alkylphenate sulfide obtained from a sulfur source and alkylphenol, having a total base number of approximately 50 to approximately 400 mg KOH / g as measured by the ASTM D-2896 method, wherein the molar ratio of the sulfur source to the alkylphenol is approximately 0.66 to approximately 3.5, and It contains up to approximately 100,000 ppm of alkali or alkali metals and up to approximately 65,000 ppm of sulfur, A metal phenate cleaning agent comprising unsulfurized alkyl phenate and / or unsulfurized alkylphenol at a concentration of approximately 900 ppm or less, with a sulfidation ratio of approximately 500:1 to approximately 5500:

1.

12. The metal phenate cleaning agent according to claim 11, wherein the alkylphenate is derived from the alkylation of a phenol by one or more C6-C36 alkylene groups, and / or the alkylene group is an oligomer, and / or the oligomer is derived from ethylene, propylene, butylene, isobutylene, pentene, or a combination thereof.

13. The metal phenate cleaning agent according to claim 11, wherein the alkyl sulfide phenate has a total base number of about 90 to about 250 mg KOH / g when measured by the ASTM D-2896 method.

14. The metal phenate cleaning agent according to claim 11, wherein the alkyl sulfide phenate has less than 50 percent alkyl substitution at the ortho position.

15. A lubricating oil composition comprising the metal phenate detergent described in claim 11 and one or more base oils having a lubricating viscosity.

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