Highly sulfurized 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] The present disclosure relates generally to lubricating oil compositions having high levels of sulfurization and additives therefor. [Background technology]

[0002] Metal salts of sulfurized alkylphenols, also known as alkylphenates, tend to be useful lubricating oil additives. These additives can function as detergents and / or dispersants, and can also provide an alkaline base to help neutralize acids generated during the operation of a vehicle. Unsulfurized versions of alkylphenates tend to have reduced utility and are less desirable in lubricants for a number of reasons. As such, additive manufacturers seek to minimize the levels of unsulfurized alkylphenates and / or alkylphenols in their additives. However, current methods have one or more drawbacks when attempting to minimize the levels of unsulfurized alkylphenate / phenol variants when the additive is also overbased. Summary of the Invention

[0003] According to one embodiment, a process for preparing a sulfurized alkylphenate product to achieve a high sulfurization ratio of sulfurized alkylphenate to unsulfurized alkylphenate is described herein. In one approach, the process includes sulfurizing an alkylphenol with a sulfur source to provide a sulfurized alkylphenol, where the alkylphenol may be derived from the alkylation of a phenol, and the molar ratio of the sulfur source to the alkylphenol is from about 0.66 to about 3.5 (in other approaches, from about 0.67 to about 3.5, or from about 0.68 to about 3.5, or from about 0.7 to about 3.5); neutralizing and optionally overbasing the sulfurized alkylphenol in the presence of a solvent to provide a sulfurized alkylphenate composition, where the neutralization and optional overbasing are performed at a temperature not exceeding about 140° C. to achieve a sulfurization ratio of about 500:1 or greater; and neutralizing and optionally overbasing the sulfurized alkylphenol in the presence of a solvent to provide a sulfurized alkylphenate product. and post-treating the sulfurized alkylphenate composition, the post-treating being conducted at a temperature not exceeding about 140° C. to maintain a sulfurization ratio of about 500:1 or greater, and in some embodiments the sulfurized alkylphenate product having less than about 0.2 weight percent unsulfurized alkylphenate and / or unsulfurized alkylphenol, less than about 0.1 weight percent, less than about 0.08 weight percent unsulfurized alkylphenate and / or unsulfurized alkylphenol, less than about 0.06 weight percent unsulfurized alkylphenate and / or unsulfurized alkylphenol, less than about 0.04 weight percent unsulfurized alkylphenate and / or unsulfurized alkylphenol, or less than about 0.03 weight percent unsulfurized alkylphenate and / or unsulfurized alkylphenol.

[0004] In other approaches or embodiments, the process of the preceding paragraph may be combined with one or more optional features, embodiments, or process steps, in any combination thereof. 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 the alkylphenol is from about 0.68 to about 3.5, and / or the molar ratio of the sulfur source to the alkylphenol is from about 0.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 the neutralization and / or optional overbasing comprises contacting the sulfurized alkylphenol with an alkali metal or alkaline earth metal salt at a temperature not exceeding about 140° C., and / or the alkali metal 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 the neutralization and / or optional overbasing is carried out in the presence of a carbonation agent at a temperature not exceeding about 140° C.; and / or the post-treatment comprises one or more of vacuum stripping, sparging, distillation, filtration, degassing, evaporation, wiped film evaporation, centrifugation, dilution, liquid-liquid extraction, membrane separation, chromatography, adsorption, supercritical extraction, or combinations thereof, all post-treatments being carried out at a temperature not exceeding about 140° C.; and / or the process comprises and / or the temperature of the neutralization and optional overbasing and post-treatment does not exceed about 100° C.; and / or the sulfurized alkylphenate product has a sulfurization ratio of from about 5000:1 to about 500:1; and / or the sulfurized alkylphenate product has a sulfurization ratio of from about 3500:1 to about 1000:1; and / or the sulfurized alkylphenate product has a total base number of from about 100 to about 400 mg KOH / g as measured by the method of ASTM D-2896; and / or the sulfurized alkylphenate product has a total base number of from about 0.5 mg KOH / g to about 1.5 mg KOH / g as measured by the method of ASTM D-2896.The sulfurized alkylphenol has less than 2 weight percent unsulfurized alkylphenate or unsulfurized alkylphenol, and / or the sulfurization is carried out at a temperature of about 0 to about 250° C., the sulfurization is carried out at a temperature of about 40 to about 120° C., and / or the sulfurization is carried out in the absence of a base, and / or the sulfurized alkylphenol is neutralized and overbased, and / or the alkylation of the phenol is with one or more oligomers derived from an olefin, and / or the olefin comprises ethylene, propylene, butylene, isobutylene, pentene, or a combination thereof.

[0005] In other embodiments, a sulfurized alkylphenate product is described herein, wherein the sulfurized alkylphenate product is prepared by a method described by any embodiment of the previous two paragraphs.

[0006] In another embodiment, a metal phenate detergent is provided having a high sulfurization ratio of sulfurized alkylphenate to unsulfurized alkylphenate. In one approach, the metal phenate detergent is derived from a sulfur source and an alkylphenol, the molar ratio of the sulfur source to the alkylphenol being from about 0.66 to about 3.5 (in other approaches, from about 0.67 to about 3.5, or from about 0.68 to about 3.5, or from about 0.7 to about 3.5), and the molar ratio of the sulfur source to the alkylphenol is from about 50 to about 400 mg / kg, as measured by the method of ASTM D-2896. and up to about 100,000 ppm alkali or alkaline metal and up to about 65,000 ppm sulfur, and in some embodiments up to about 900 ppm unsulfurized alkylphenate and / or unsulfurized alkylphenol, up to about 800 ppm or less, up to about 700 ppm or less, up to about 600 ppm or less, up to about 500 ppm or less, up to about 400 ppm or less, or up to about 300 ppm or less unsulfurized alkylphenate and / or unsulfurized alkylphenol, and a sulfurization ratio of about 500:1 to about 5500:1.

[0007] In yet other embodiments, the metal phenate detergent may include embodiments having several optional features in any combination. The optional features and embodiments include one or more of the following: and / or the metal phenate detergent has from about 35,000 ppm to about 100,000 ppm of calcium, and / or the metal phenate detergent has at least about 25,000 ppm of sulfur, and / or the metal phenate detergent has at least about 30,000 ppm of sulfur, and / or the sulfurization ratio is from about 1200:1 to about 5000:1, and / or the alkyl phenate is derived from the alkylation of phenol with one or more C6 to C36 alkylene groups, and / or the alkylene groups are oligomers, and / or the oligomers are derived from ethylene, propylene, butylene, isobutylene, pentene, or combinations thereof, and / or the sulfurized alkyl phenate detergent has a sulfur content of from about 90 to about 250 mg as measured by the method of ASTM D-2896. and / or the sulfurized alkylphenate has less than about 50 percent alkyl substitution in the ortho position.

[0008] In yet another embodiment, a lubricating oil composition is described herein, the lubricating oil composition comprising any embodiment of the metal phenate as described in this Summary and one or more base oils of lubricating viscosity.

[0009] In yet another aspect, the use of low temperature processing as described in any of the aspects of the methods herein is provided to form metal phenate detergent and / or sulfurized alkylphenate products having a sulfurization ratio of about 500:1 or greater, and in some aspects to form less than about 0.2 weight percent unsulfurized alkylphenate and / or unsulfurized alkylphenol, less than about 0.1 weight percent, less than about 0.08 weight percent unsulfurized alkylphenate and / or unsulfurized alkylphenol, less than about 0.06 weight percent unsulfurized alkylphenate and / or unsulfurized alkylphenol, less than about 0.04 weight percent unsulfurized alkylphenate and / or unsulfurized alkylphenol, or less than about 0.03 weight percent unsulfurized alkylphenate and / or unsulfurized alkylphenol.

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

[0011] The terms "oil composition," "lubricant composition," "lubricating oil composition," "lubricant," "lubricating oil composition," "lubricating composition," "fully formulated lubricating oil composition," and "lubricant" are considered to be synonymous and fully interchangeable terms and refer to a finished lubricating product that contains a major amount of a base oil and a minor amount of an additive composition.

[0012] As used herein, the terms "additive package," "additive concentrate," and "additive composition" are considered to be synonymous and fully interchangeable terms that refer to that portion of a lubricating oil composition that excludes a major amount of a base oil stock blend.

[0013] The term "overbased" refers to metal salts, such as metal salts of sulfonates, carboxylates, salicylates, and / or phenates, in which the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level of more 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", "neutral salt"). The expression "metal ratio", often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of the metal in an overbased salt to the chemical equivalents of the metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the metal ratio is 1, while in overbased salts the MR is greater than 1. These are generally referred to as overbased, high based, or superbased 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 term "hydrocarbyl" or "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense, as known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having a predominantly hydrocarbon character. Each hydrocarbyl group is independently selected from hydrocarbon substituents, the substituted hydrocarbon substituents containing one or more of halo, hydroxyl, alkoxy, mercapto, nitro, nitroso, amino, pyridyl, furyl, imidazolyl, oxygen, and nitrogen, and no more than two non-hydrocarbon substituents are present for every 10 carbon atoms in the hydrocarbyl group.

[0016] As used herein, the term "hydrocarbylene substituent" or "hydrocarbylene group" is used in its ordinary sense, which is well known to those skilled in the art. Specifically, it refers to a group that is directly attached to the remainder of the molecule by carbon atoms at two locations in the molecule and has a predominantly hydrocarbon character. Each hydrocarbylene group is independently selected from divalent hydrocarbon substituents, where the substituted divalent hydrocarbon substituents include halo, alkyl, aryl, alkylaryl, arylalkyl, hydroxyl, alkoxy, mercapto, nitro, nitroso, amino, pyridyl, furyl, imidazolyl, oxygen, and nitrogen, and no more than two non-hydrocarbon substituents are present for every 10 carbon atoms in the hydrocarbylene group.

[0017] As used herein, unless expressly stated otherwise, the term "weight percent" means the percentage that the recited component represents relative to the weight of the entire composition.

[0018] The terms "soluble", "oil-soluble" or "dispersible" used herein may, but do not necessarily, indicate that a compound or additive is soluble, dissolvable, miscible, or can be suspended in oil in any proportion. However, the terms mean that they are, for example, soluble, suspendable, soluble, or stably dispersible in oil to a sufficient degree to exert their intended effect in the environment in which the oil is used. Furthermore, if desired, the incorporation of other additives may also allow the incorporation of higher levels of the specific additive.

[0019] As used herein, the term "TBN" is used to indicate the Total Base Number in mg KOH / g as measured by the method of ASTM D2896.

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

[0021] The term "alkyl" as used herein refers to straight, branched, cyclic, and / or substituted saturated chain moieties of about 1 to about 100 carbon atoms. The term "alkenyl" as used herein refers to straight, branched, cyclic, and / or substituted unsaturated chain moieties of about 3 to about 10 carbon atoms. The term "aryl" as used herein 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 "sulfurization ratio" is the weight ratio of sulfurized alkylphenate to unsulfurized alkylphenate / unsulfurized alkylphenol. As discussed in more detail below, the methods herein are effective in forming and maintaining alkylphenate additives having high sulfurization ratios. As used herein, when referring to unsulfurized alkylphenate or residual unsulfurized alkylphenate, both the phenate and phenol forms of the compound are intended, since the phenate form can be readily acidified to phenol.

[0023] The molecular weight of any embodiment herein may be determined using a gel permeation chromatography (GPC) instrument obtained from Waters or similar instrumentation 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 instrumentation). GPC operating conditions may include a guard column, four Agilent PLgel columns (length 300×7.5 mm, particle size 5μ, and pore size ranging from 100 to 10000 Å), and a column temperature of about 40° C. Non-stabilized 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 with narrow molecular weight distributions ranging from 500 to 380,000 g / mol. The calibration curve may be extrapolated for samples with masses less than 500 g / mol. Samples and PS standards are dissolved in THF and prepared at a concentration of 0.1-0.5 wt.% and can be used without filtration. GPC measurements are also described in U.S. Pat. No. 5,266,223, which is incorporated herein by reference. The GPC method additionally provides molecular weight distribution information. See, for example, W.W. Yau, J.J. Kirkland and D.D. Ly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979, which is incorporated herein by reference.

[0024] Additional details and advantages of the disclosure will be set forth in part in the following description and / or may be learned by practice of the disclosure. The details and advantages of the disclosure may be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure as claimed. [Brief description of the drawings]

[0025] [Figure 1] 1 is a graph of residual or unsulfurized alkylphenols based on temperature showing the kinetics of alkylphenol regeneration during processing. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] The present disclosure provides methods for preparing neutral to overbased and sulfurized alkylphenate products to achieve high sulfurization ratios of sulfurized alkylphenate to unsulfurized alkylphenate in conjunction with 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, as further discussed below, from about 150 to about 400. As noted in the Background, past attempts to achieve high levels of sulfurization in such situations have had limited success and have not been able to achieve sulfurization ratios of about 500:1 or greater (i.e., weight ratios of sulfurized alkylphenate to unsulfurized alkylphenate) at such TBNs due to high alkalinity and / or processing methods that tend to regenerate the unsulfurized variants throughout the manufacturing process.

[0027] In one aspect, the method herein includes first sulfurizing an alkylphenol with a sulfur source to obtain a sulfurized alkylphenol. In some approaches, sulfurization 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., but not limited to, ethylene, propylene, butylene, or mixtures thereof). The sulfurized alkylphenol is then neutralized and, optionally, overbased in the presence of a solvent to provide a neutral to overbased and sulfurized alkylphenate composition. The neutralization and optional overbasing are carried out at a temperature not exceeding about 140° C. to achieve a sulfurization ratio of about 500:1 or greater in the composition. Finally, the optional overbased and sulfurized alkylphenate composition is subjected to various post-treatment steps to obtain a neutral to overbased and sulfurized alkylphenate product, all post-treatments being carried out under conditions such as a temperature not exceeding about 140° C. to maintain a sulfurization ratio of about 500:1 or greater. In yet other approaches, the methods herein are effective to achieve sulfurization ratios of neutral to overbased and sulfurized alkylphenate products of from about 5000:1 to about 500:1, in other approaches from about 4000:1 to about 500:1, in other approaches from about 3500:1 to about 500:1, in other approaches from about 2000:1 to about 500:1, in still other approaches from about 5000:1 to about 1000:1, or from about 3400:1 to about 1200:1, or even from about 2000:1 to about 1000:1. Further details of each process step are provided below.

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

[0029] The alkylating agent includes one or more olefins selected from ethylene, propylene, butylene, isobutylene, or mixtures thereof, and / or oligomers derived from olefins. Suitable olefins include isobutylene, propylene trimer and / or tetramer, butylene trimer and / or tetramer, to name just a few, but other olefins may be present in the oligomer or alkyl group, such as linear olefins, cyclic olefins, branched olefins other than propylene oligomers, such as butylene or isobutylene oligomers, aryl alkylenes, and mixtures thereof. The alkylation may 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 are known to those skilled in the art and may include aluminum trichloride, aluminum tribromide, aluminum triiodide, boron trifluoride, boron tribromide, boron triiodide, and the like. In some approaches, the molar ratio of the phenol or hydroxyaromatic compound to the one or more oligomers can be from about 10:1 to about 0.5:1, and in other approaches can be from about 5:1 to about 2:1. The oligomeric alkyl groups are typically attached to the phenol or hydroxyaromatic compound at the ortho and / or para positions, although other substituents may be present depending on the application.

[0030] sulfide The alkylphenol or alkylhydroxyaromatic compound is then sulfurized by contacting it with a sulfur source in a manner effective to achieve a high degree of sulfurization. In the approach, the sulfurization generally introduces a sulfur bridging group between the alkylphenol or alkylhydroxyaromatic moieties. In some approaches, the sulfur bridge is a -Sy- group, where y is an integer between 1 and 4, in other approaches between 1 and 3, in some approaches between 1 and 2, and / or has a total sulfur level of up to about 5 percent. The sulfur source can be any suitable sulfur, such as sulfur monochloride or dichloride, hydrogen sulfide, sulfur dioxide, and sodium sulfide hydrate, for example, elemental sulfur or its halides. The sulfur can be used either as molten sulfur, or as a solid (powder or particulate), or as a solid suspension in a hydrocarbon liquid. In one approach, the sulfur source is sulfur monochloride, and one skilled in the art can react with sulfur monochloride to obtain S as shown in Reaction Scheme I below. 2 Cl 2 In another approach, the sulfur source is sulfur dichloride (SCl 2 ) and sulfur monochloride (S 2 Cl 2 ), particularly a blend of about 60 to about 67 weight percent sulfur dichloride and about 33 to about 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 can be used as well), although other sulfurization conditions can be used (such as about 0° C. to about 250° C. for about 1 hour to about 7 hours) as needed for a particular application.

[0031] [ka]

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

[0033] In some approaches, the ratio of sulfur source to alkylphenol reactant may be selected to achieve a high level of sulfurization when sulfurization is carried out in the absence of base, and in some approaches may also be selected to help maintain a low level of copper corrosion in the final product when used in a lubricant. In one approach, the molar ratio of sulfur source to alkylphenol or alkylhydroxyaromatic reactant in the sulfurization reaction may be about 0.66 or greater, and in other approaches or embodiments, may be from about 0.66 to about 3.5, from about 0.67 to about 3.5, from about 0.68 to about 3.5, or in yet other approaches or embodiments, from about 0.7 to about 3.5, or from about 0.7 to about 2.0, or from about 0.7 to about 1.4, or even from about 0.7 to about 1.0, depending on the needs 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 range from 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 about 1.0. Such molar ratios of sulfur source to alkylphenol reactant aid in achieving the high sulfurization ratios of the present disclosure of about 500:1 or greater in the sulfurization reaction (in other embodiments, from about 500:1 to about 5000:1, or from about 500:1 to about 4000:1, or from about 500:1 to about 3500:1, or from about 500:1 to about 2000:1), and in some approaches, subsequent processing steps, as described below, maintain or increase the sulfurization ratio, such that the final sulfurized and overbased alkylphenate product maintains a high sulfurization ratio of sulfurized phenate to unsulfurized phenate.In other approaches or embodiments, such molar ratios of sulfur source to alkylphenol herein may aid in achieving sulfurization 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 sulfurization ratios herein may also include any other ranges within the endpoints indicated, as needed for a particular application. In yet other approaches, the molar ratio of the sulfur source to the alkylphenol can help achieve about 0.2 weight percent or less, about 0.1 weight percent or less, about 0.08 weight percent or less, about 0.06 weight percent or less, about 0.04 weight percent or less, or about 0.03 weight percent or less, or in some approaches, an undetectable amount of residual unsulfurized alkylphenate and / or unsulfurized alkylphenol.

[0034] Due to the high sulfurization ratio, the process herein is such that there is no need to remove residual unsulfurized alkylphenols after sulfurization and / or after any of the subsequent process steps such as neutralization, overbasing, and / or workup. Rather, the process herein minimizes the production and / or regeneration of any unsulfurized variants, thus avoiding the need to remove such undesirable components.

[0035] Neutralization After sulfurization, the sulfurized alkylphenol or sulfurized alkyl hydroxyaromatic compound with a high sulfurization rate already achieved is then neutralized to provide a phenate or salt of the sulfurized alkylphenol or sulfurized alkyl hydroxyaromatic compound. In one approach, the neutralization is carried out by contacting the sulfurized alkylphenol with a metal base under reactive conditions, in some approaches in a liquid hydrocarbon diluent containing a promoter, to provide a phenate or salt of the sulfurized alkyl hydroxyaromatic compound. In some cases, the reaction can be carried out under an inert gas such as nitrogen. The metal base may be added at various times during the reaction, either in a single addition or multiple additions, if necessary for a particular application. The neutralization can occur via the exemplary reaction scheme II shown below, although other reactions can proceed as needed depending on the application, materials, and conditions.

[0036] [ka]

[0037] Exemplary metal base reactants include metal hydroxides, oxides, or alkoxides, such as, but 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. 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 a preferred example, the alkaline earth metal base is lime or calcium hydroxide. The additive may be borated as needed depending on the application and use.

[0038] The neutralization (and subsequent overbasing, 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 other approaches, compounds having a boiling point below about 100° C. at a pressure of about 1000 to about 40 mbar (and in other approaches, about 1000 to about 300 mbar). Suitable examples include xylene, toluene, octane, butanol, heptane, methanol, pentanol, acetone, benzene, cyclohexane, cyclopentane, ethanol, hexane, pentane, propanol, water, or combinations thereof. In one approach, the solvent comprises one or more of heptane, methanol, water, and combinations thereof, and in one 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, which in some embodiments may include 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 premix of the metal base and solvent) and then reacted with the sulfurized alkylphenol compound.

[0039] In one approach, the neutralizing solvent is devoid of materials having a higher boiling point, e.g., solvents having a boiling point of about 100° C. or higher at the pressures described, such as ethylene glycol, propylene glycol, and / or decanol, and similar solvents. Devoid or free of such compounds, as used herein in an optional manner, means that the solvent has less than about 10 weight percent, less than about 5 weight percent, less than about 2 weight percent, less than 1 weight percent, less than 0.5 weight percent, or none of the high boiling solvents described.

[0040] The neutralization reaction between the metal base and the sulfurized alkylphenol is carried out under conditions effective to maintain the high sulfurization ratio achieved during the sulfurization reaction. To maintain the high sulfurization ratio achieved during the conventional sulfurization reaction, in one approach, the neutralization occurs at a low temperature, such as a temperature of about 140° C. or less, in some approaches, a temperature of about 120° C. or less, in other approaches, a temperature of about 100° C. or less, and in a more preferred approach, a temperature of about 80° C. or less. Carrying out the neutralization at a higher temperature tends to result in increased levels and / or regeneration of unsulfurized alkylphenol or alkylphenate, which reduces the sulfurization ratio, which is undesirable. Rather, the method herein selects conditions to maintain a high sulfurization level and ratio throughout the process. In other approaches, neutralization is carried out at a temperature ranging from at least about 20° C., at least about 30° C., at least about 40° C., at least about 50° C., at least about 60° C. to less than about 140° C., less than about 130° C., less than about 120° C., less than about 110° C., less than about 100° C., less than about 90° C., or less than about 80° C. The neutralization reaction should occur in about 5 to about 60 minutes.

[0041] Overbasing Overbasing is then optionally, but in some embodiments is preferred, carried out either during or instead thereafter during neutralization. In one approach, the sulfurized alkylphenol / alkylphenate is overbased by reacting with an excess of a metal base and / or by reacting with an acidic overbasing compound, such as carbon dioxide or boric acid. In one approach, overbasing is via carbonation (reaction with carbon dioxide) in the presence of a solvent, such as any 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 overbasing reaction can be removed as needed by distillation either during or after the reaction, as discussed further below.

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

[0043] In other approaches, overbasing is also carried out at temperatures ranging from at least about 20°C, at least about 30°C, at least about 40°C, at least about 50°C, at least about 60°C to less than about 140°C, less than about 130°C, less than about 120°C, less than about 110°C, less than about 100°C, less than about 90°C, or less than about 80°C. The degree of overbasing can be controlled by the amount of alkali metal or alkaline earth metal, the amount of carbon dioxide and other reactants (if any) added to the reaction mixture, and the reaction conditions used during the carbonation process. In the approach, overbasing or overbasing via carbonation occurs for a sufficient time to achieve the desired degree of overbasing or TBN, which in some approaches can be from about 30 minutes to about 180 minutes at the temperatures described.

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

[0045] Post-processing After optional overbasing, compositions containing sulfurized alkylphenates are often subjected to a number of steps to prepare the final sulfurized alkylphenate product. However, such post-treatment steps should also be carried out using conditions effective to maintain a high sulfurization ratio. In an approach, all post-treatments are carried out at low temperatures to maintain a high level of sulfurization relative to the unsulfurized alkylphenate and not regenerate unsulfurized alkylphenol or phenate.

[0046] Examples of post-treatments carried out at low temperatures include one or more of 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 post-treatments carried out individually and / or in combination at conditions effective to maintain high sulfurization levels, such as low temperatures not exceeding about 140° C. As with neutralization and overbasing, any post-treatments are also carried out at temperatures ranging from at least about 20° C., at least about 30° C., at least about 40° C., at least about 50° C., at least about 60° C. to less than about 140° C., less than about 130° C., less than about 120° C., less than about 110° C., less than about 100° C., less than about 90° C., or less than about 80° C.

[0047] The process steps herein produce overbased and sulfurized alkylphenate products having high levels of sulfurization, or high sulfurization ratios of sulfurized alkylphenate / alkylphenol to unsulfurized alkylphenate / alkylphenol of at least about 500:1, in other approaches from about 500:1 to about 5000:1, and in still other approaches from about 1000:1 to about 5000:1, from about 1000:1 to about 3500:1, or even from about 1000:1 to about 2000:1, which demonstrates a high level of sulfurized alkylphenate relative to unsulfurized alkylphenate or unsulfurized alkylphenol when in neutral to overbased form. In other approaches, the additives and methods herein have 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 unsulfurized alkylphenate / alkylphenol, or from about 0.01 to about 0.2 weight percent, or any range therein.

[0048] What is unique to the methods of the present invention is that there is generally no need to remove unsulfurized alkylphenates or alkylphenols (such as after sulfurization or any intermediate step) since the method steps do not generate and / or regenerate unsulfurized alkylphenates or alkylphenols at any of the various process steps, but rather maintain high levels of sulfurization throughout the process. As such, the methods herein therefore avoid the expense and complexity of prior methods that required removal of residual and / or unsulfurized alkylphenates / phenols either during intermediate or downstream process steps.

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

[0050] In one approach, the lubricating oil compositions herein may comprise from about 0.02 to about 5 weight percent, in another approach from about 0.2 to about 3 weight percent, and in yet another approach from about 0.2 to about 2 weight percent of the optionally overbased and sulfurized alkylphenate product in the base oil or base oil blend.

[0051] In some approaches, the additives 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 ingredients, dispersant inhibitor packages, and / or individual components 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, wet brake fluids, and the like.

[0053] Suitable engine types may include, but are not limited to, heavy duty diesel, passenger car, light duty diesel, medium speed diesel, or marine engines. The internal combustion engine may be a diesel fueled engine, a gasoline fueled engine, a natural gas fueled engine, a biofuel engine, a diesel / bio-fuel blended fuel-fuel engine, a gasoline / bio-fuel blended fuel-fuel engine, an alcohol fueled engine, a gasoline / alcohol fuel blended engine, a compressed natural gas (CNG) fueled engine, or mixtures thereof. The diesel engine may be a compression ignition engine. The gasoline engine may be a spark ignition engine. The internal combustion engine may also be used in combination with electric or battery power sources. Engines so configured are generally known as hybrid engines. The internal combustion engine may be a two-stroke, four-stroke, or rotary engine. Suitable internal combustion engines include marine diesel engines (such as inland marine), aviation piston engines, light duty diesel engines, as well as motorcycle, automobile, locomotive, and truck engines. The engine may be coupled with a turbocharger.

[0054] The lubricating oil composition 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 wt.% or less, or about 0.8 wt.% or less, or about 0.5 wt.% or less, or about 0.3 wt.% or less, or about 0.2 wt.% or less. In one embodiment, the sulfur content may range from about 0.001 wt.% to about 0.5 wt.%, or about 0.01 wt.% to about 0.3 wt.%. The phosphorus content may be about 0.2 wt.% or less, or about 0.1 wt.% or less, or about 0.085 wt.% or less, or about 0.08 wt.% or less, or even about 0.06 wt.% or less, about 0.055 wt.% or less, or about 0.05 wt.% 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 is 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] Additionally, the lubricants herein may 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™, Dexos2™, MB-Approval™, Dexos3™, Dexos4™, Dexos5™, Dexos6™, Dexos7™, Dexos8™, Dexos9™, Dexos10™, Dexos11™, Dexos12™, Dexos13™, Dexos14™, Dexos15™, Dexos16™, Dexos17™, Dexos18™, Dexos19™, Dexos21™, Dexos22™, Dexos23™, Dexos24™, Dexos25™, Dexos26™, Dexos27™, Dexos28™, Dexos29 ... 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.The compositions may be suitable to meet original equipment manufacturer specifications such as STJLR.5005, STJLR.03.5006, STJLR.03.5007, STJLR.51.5122, or past or future PCMO or HDD specifications not listed 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-V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five base oil groups are generally set forth in Table 1 below.

[0057] [Table 1]

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

[0059] The base oil blends used in the disclosed lubricating oil compositions can be mineral oils, animal oils, vegetable oils, synthetic oils, synthetic oil blends, or mixtures thereof. Suitable oils can be derived from hydrocracked, hydrogenated, hydrofinished, unrefined, refined, and rerefined oils, and mixtures thereof.

[0060] Unrefined oils are derived from natural, mineral, or synthetic sources with little or no further purification treatment. Refined oils are similar to unrefined oils, except that they have been treated with one or more purification steps that may result in the improvement of one or more properties. Examples of suitable purification techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Oils refined to edible quality may or may not be useful. Edible oils may also be called white oils. In some embodiments, the lubricating oil composition does not include edible oils or white oils.

[0061] Rerefined oils are also known as reclaimed or reprocessed oils. These oils are obtained similarly to refined oils using the same or similar processes. Often, these oils are additionally processed by techniques directed to the removal of spent additives and oil breakdown 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 oil, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricating oils, such as liquid petroleum oils, and solvent- or acid-treated mineral lubricating oils of the paraffinic, naphthenic, or mixed paraffinic-naphthenic types. Such oils may be partially or fully hydrogenated, if desired. Oils derived from coal or shale may also be useful.

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

[0064] Other synthetic lubricating oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans. Synthetic oils may be produced by Fischer-Tropsch reactions and are typically hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oils may be prepared by Fischer-Tropsch gas-liquid synthesis procedures, as well as other gas-liquid oils.

[0065] A major amount of base oil included in the lubricating composition may be selected from the group consisting of Group I, Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, but the major amount of base oil is other than the base oil resulting from the provision of an additive component or viscosity index improver in the composition. In another embodiment, a major amount of base oil included in the lubricating composition may be selected from the group consisting of Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, but the major amount of base oil is other than the base oil resulting from the provision of an additive component or viscosity index improver in the composition.

[0066] The amount of oil of lubricating viscosity present can be the difference remaining after subtracting the sum of the amounts of performance additives, including viscosity index improvers and / or pour point depressants and / or other top treat additives, from 100% by weight. For example, the oil of lubricating viscosity may be present in the final fluid in a major amount, such as greater than about 50% by weight, greater than about 60% by weight, greater than about 70% by weight, greater than about 80% by weight, greater than about 85% by weight, or greater than about 90% by weight.

[0067] Optional Additives: The lubricating oil compositions herein may also contain a number of optional additives in combination with the optional overbased and sulfurized alkylphenate products as needed to meet performance criteria, which optional additives are described in the following paragraphs.

[0068] Dispersants: The lubricating oil composition may optionally contain one or more dispersants or mixtures thereof. Dispersants are often known as ashless dispersants because they do not contain ash-forming metals prior to mixing into the lubricating oil composition and do not normally contribute to ash when added to the lubricant. Ashless dispersants are characterized by having polar groups attached to relatively high molecular weight hydrocarbon chains. Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimides in which the number average molecular weight of the polyisobutylene substituent ranges from about 350 to about 50,000, or from about 5,000, or from about 3,000, as measured by GPC. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Pat. No. 7,897,696 or U.S. Pat. No. 4,234,435. The alkenyl substituent may be prepared from polymerizable monomers containing from about 2 to about 16, or from about 2 to about 8, or from about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines, typically poly(ethyleneamines).

[0069] Preferred amines are selected from polyamines and hydroxyamines. Examples of polyamines that may be used include, but are not limited to, diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), and higher homologs such as pentaethylamine hexamine (PEHA).

[0070] Suitable heavy polyamines are mixtures of polyalkylene-polyamines containing small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine), but primarily oligomers with 6 or more nitrogen atoms, 2 or more primary amines per molecule, and more extensive branching than conventional polyamine mixtures. Heavy polyamines preferably include polyamine oligomers containing 7 or more nitrogen atoms per molecule and having 2 or more primary amines per molecule. Heavy polyamines contain greater than 28% by weight (e.g., greater than 32% by weight) total nitrogen and an equivalent weight of 120 to 160 grams of primary amine groups per equivalent.

[0071] In some approaches, suitable polyamines, commonly known as PAM, contain a mixture of ethyleneamines, with TEPA and pentaethylenehexamine (PEHA) being the major portion of the polyamine, usually less than about 80%.

[0072] Typically, PAM has 8.7-8.9 milliequivalents of primary amine per gram (115-112 grams equivalent per equivalent of primary amine) and a total nitrogen content of about 33-34% by weight. Heavier cuts of PAM oligomers that are substantially free of TEPA and contain only small amounts of PEHA, but contain primarily oligomers with more than 6 nitrogens and more extensive branching, may produce dispersants with improved dispersancy.

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

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

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

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

[0077] The percent actives of the alkenyl or alkyl succinic anhydride can be determined using chromatographic techniques, which are described in U.S. Patent No. 5,334,321, columns 5 and 6.

[0078] Percent polyolefin conversion is calculated from the % actives using the formula in columns 5 and 6 of US Pat. No. 5,334,321.

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

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

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

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

[0083] A suitable class of dispersants may also be high molecular weight esters or half ester amides. Suitable dispersants may also be post-treated by reaction with any of a variety of agents by conventional methods. Among these are boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydrides, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds. U.S. Patent No. 7,645,726, U.S. Patent No. 7,214,649, and U.S. Patent No. 8,048,831 are incorporated herein by reference in their entirety.

[0084] In addition to the carbonate and boric acid post-treatments, any of the compounds may be post-treated or further post-treated with a variety of post-treatments designed to improve or impart different properties. Such post-treatments include those summarized in columns 27-29 of U.S. Pat. No. 5,241,003, which is incorporated herein by reference. Such treatments include treatment with inorganic phosphoric acids or anhydrides (e.g., U.S. Pat. Nos. 3,403,102 and 4,648,980); organic phosphorus compounds (e.g., U.S. Pat. No. 3,502,677); phosphorus pentasulfide; boron compounds as already mentioned above (e.g., U.S. Pat. Nos. 3,178,663 and 4,652,387); carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Pat. Nos. 3,708,522 and 4,912,522); and / or carboxylic acids such as carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Pat. Nos. 3,708,522 and 4,912,522). 48,386; epoxides, polyepoxyates or thioepoxides (e.g., U.S. Pat. Nos. 3,859,318 and 5,026,495); aldehydes or ketones (e.g., U.S. Pat. No. 3,458,530); carbon disulfide (e.g., U.S. Pat. No. 3,256,185); glycidol (e.g., U.S. Pat. No. 4,617,137); urea, thiourea, or guanidine (e.g., U.S. Pat. No. 3,312,61 9, 3,865,813, and British Patent No. 1,065,595; organic sulfonic acids (e.g., U.S. Pat. No. 3,189,544 and British Patent No. 2,140,811); alkenyl cyanides (e.g., U.S. Pat. Nos. 3,278,550 and 3,366,569); diketenes (e.g., U.S. Pat. No. 3,546,243); diisocyanates (e.g., U.S. Pat. No. 3,573,205); alkanesuls t (e.g., U.S. Pat. No. 3,749,695); 1,3-dicarbonyl compounds (e.g., U.S. Pat. No. 4,579,675); sulfates of alkoxylated alcohols or phenols (e.g., U.S. Pat. No. 3,954,639); cyclic lactones (e.g., U.S. Pat. Nos. 4,617,138; 4,645,515; 4,668,246; 4,963,275; and 4,971,711);Cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132, 4,647,390, 4,648,886, 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent No. 2,140,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Pat. No. 4,612,132, U.S. Pat. No. 4,647,390, U.S. Pat. No. 4,648,886, U.S. Pat. No. 4,670,170); US Patent Nos. 4,614,603 and 4,666,460; cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., US Patent Nos. 4,612,132, 4,647,390, 4,646,860, and 4,670,170); nitrogen-containing carboxylic acids (e.g., US Patent No. 4,971,598 and British Patent No. 2,440,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., US Patent No. 4,614,522); lactams. , thiolactams, thiolactones, or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460); cyclic carbamates, cyclic thiocarbamates, or cyclic dithiocarbamates (e.g., U.S. Pat. Nos. 4,663,062 and 4,666,459); hydroxyaliphatic carboxylic acids (e.g., U.S. Pat. Nos. 4,482,464; 4,521,318; and 4,713,189); oxidizing agents (e.g., U.S. Pat. No. 4,379,064); combinations of phosphorus pentasulfide and polyalkylene polyamines (e.g., For example, U.S. Pat. No. 3,185,647; combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (e.g., U.S. Pat. Nos. 3,390,086 and 3,470,098); combinations of hydrazine and carbon disulfide (e.g., U.S. Pat. No. 3,519,564); combinations of aldehydes and phenols (e.g., U.S. Pat. Nos. 3,649,229, 5,030,249 and 5,039,307); combinations of aldehydes and O-diesters of dithiophosphoric acids (e.g., U.S. Pat. No. 3,865,740);Combinations of hydroxyaliphatic carboxylic acids and boric acid (e.g., U.S. Pat. No. 4,554,086); combinations of hydroxyaliphatic carboxylic acids followed by formaldehyde and phenols (e.g., U.S. Pat. No. 4,636,322); combinations of hydroxyaliphatic carboxylic acids and then aliphatic dicarboxylic acids (e.g., U.S. Pat. No. 4,663,064); combinations of formaldehyde and phenols and then glycolic acid (e.g., U.S. Pat. No. 4,699,724); combinations of hydroxyaliphatic carboxylic acids or oxalic acid followed by a diisocyanate (e.g., U.S. Pat. No. 4,713,191); inorganic acids or anhydrides of phosphorus. or a combination of its partial or total sulfur analogue and a boron compound (e.g., U.S. Pat. No. 4,857,214); a combination of an organic diacid, followed by an unsaturated fatty acid, followed by a nitrosoaromatic amine, optionally followed by a boron compound, and then a glycosylation agent (e.g., U.S. Pat. No. 4,973,412); a combination of an aldehyde and a triazole (e.g., U.S. Pat. No. 4,963,278); a combination of an aldehyde and a triazole, followed by a boron compound (e.g., U.S. Pat. No. 4,981,492); a combination of a cyclic lactone and a boron compound (e.g., U.S. Pat. Nos. 4,963,275 and 4,971,711), wherein the above-mentioned patents are incorporated herein in their entirety;

[0085] The TBN of suitable dispersants may be from about 10 to about 65 mg KOH / g dispersant on an oil-free basis, which equates to about 5 to about 30 TBN when measured on a dispersant sample containing about 50% diluent oil. TBN is measured by the method of ASTM D2896.

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

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

[0088] [ka] (wherein each R and R' is independently a divalent C1-C6 alkylene linker; each R 1 and R 2 are independently hydrogen, a C1-C6 alkyl group, or together with the nitrogen atom to which they are attached form a 5- or 6-membered ring optionally fused to one or more aromatic or non-aromatic rings, and n is an integer from 0 to 8. In another approach, the polyalkylene polyamine is selected from the group consisting of a mixture of polyethylene polyamines having an average of 5 to 7 nitrogen atoms, triethylenetetramine, tetraethylenepentamine, and combinations thereof.

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

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

[0091] The hindered phenol antioxidant may contain secondary butyl and / or tertiary butyl groups as steric hindrance groups. The phenol group may be further substituted with a hydrocarbyl group and / or a bridging group that connects 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 from about 1 to about 18, or from about 2 to about 12, or from about 2 to about 8, or from about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant 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, such that each antioxidant may be present in an amount sufficient to provide up to about 5 weight percent, 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 weight percent diarylamines and about 0.4 to about 2.5 weight percent high molecular weight phenols, based on the final weight of the lubricating oil composition.

[0093] Examples of suitable olefins that can be sulfurized to form sulfurized olefins include propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof, as well as their dimers, trimers, and tetramers, are particularly useful olefins. Alternatively, the olefins can 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. The fatty acids are often derived from vegetable or animal oils and typically contain from about 4 to about 22 carbon atoms. Examples of suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof. Often, the fatty acids are derived from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or mixtures thereof. The fatty acids and / or esters may be mixed with olefins, such as α-olefins.

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

[0096] The one or more antioxidants may be present in the range of from about 0% to about 20%, or from about 0.1% to about 10%, or from about 1% to about 5% by weight of the lubricating oil composition.

[0097] Antiwear agents: The lubricating oil compositions herein may also optionally contain one or more antiwear agents. Examples of suitable antiwear agents include, but are not limited to, metal thiophosphates; metal dialkyldithiophosphates; phosphoric acid esters or salts thereof; phosphoric acid esters; phosphites; phosphorus-containing carboxylic acid esters, ethers, or amides; sulfurized olefins; thiocarbamate-containing compounds, such as thiocarbamate esters, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides; and mixtures thereof. A suitable antiwear agent may be molybdenum dithiocarbamate. Phosphorus-containing antiwear agents are more fully described in EP 612839. The metal in the dialkyldithiophosphate salt may be an alkali metal, an alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful antiwear agent may be zinc dialkyldithiophosphate.

[0098] Further examples of suitable antiwear agents include titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (e.g., dibutyl phosphite), phosphonates, thiocarbamate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamic acid ethers, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides. Tartrates or tartrimides may contain alkyl-ester groups, but the total number of carbon atoms on the alkyl group may be at least 8. Antiwear agents may include citrates in one embodiment.

[0099] The antiwear agent may be present in a range including from about 0% to about 15%, or from about 0.01% to about 10%, or from about 0.05% to about 5%, or from about 0.1% to about 3% by weight of the lubricating oil composition.

[0100] Boron-containing compounds: The lubricating oil compositions herein may optionally contain one or more boron-containing compounds. Examples of boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, and borated dispersants, such as borated succinimide dispersants, as disclosed in U.S. Pat. No. 5,883,057. The boron-containing compounds, when present, may be used in an amount sufficient to provide up to about 8 wt. %, from about 0.01 wt. % to about 7 wt. %, from about 0.05 wt. % to about 5 wt. %, or from about 0.1 wt. % to about 3 wt. % of the lubricating oil composition.

[0101] Additional detergents: The lubricating oil composition may optionally further comprise one or more neutral, underbased, or overbased detergents, and mixtures thereof. Suitable detergent substrates include phenates, sulfur-containing phenates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, phosphoric acids, mono- and / or di-thiophosphoric acids, alkylphenols, sulfur-linked alkylphenol compounds, or methylene bridged phenols. Suitable detergents and methods for their preparation are described in more detail in numerous patent publications, including U.S. Pat. No. 7,732,390 and references cited therein.

[0102] The detergent substrate may be salified with an alkali or alkaline earth metal, such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent is barium-free. In some embodiments, the detergent may contain trace amounts of other metals, such as magnesium or calcium, in amounts such as 50 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less, or 10 ppm or less. Suitable detergents may include alkali or alkaline earth metal salts of petroleum sulfonic acids and long chain mono- or di-alkylaryl sulfonic acids, where the aryl groups are benzyl, tolyl, and xylyl. Examples of suitable detergents include, but are not limited to, calcium phenate, sulfur-containing calcium phenate, calcium sulfonate, calcium calixarate, calcium salixarate, calcium salicylate, calcium carboxylate, calcium phosphate, calcium mono- and / or di-thiophosphate, calcium alkylphenol, calcium sulfur-bound alkylphenol compound, calcium methylene bridged phenol, magnesium phenate, sulfur-containing magnesium phenate, magnesium sulfonate, magnesium calixarate, magnesium salixarate, magnesium salicylate, magnesium carboxylate, magnesium phosphate, magnesium mono- and / or di-thiophosphate, magnesium alkylphenol, magnesium sulfur-bound alkylphenol compound, magnesium methylene bridged phenol, sodium phenate, sulfur-containing sodium phenate, sodium sulfonate, sodium calixarate, sodium salixarate, sodium salicylate, sodium carboxylate, sodium phosphate, sodium mono- and / or di-thiophosphate, sodium alkylphenol, sodium sulfur-bound alkylphenol compound, or sodium methylene bridged phenol.

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

[0104] The term "overbased" refers to metal salts, such as metal salts of sulfonic acids, carboxylic acids, and phenols, in which the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level of more 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" or "neutral" salt). The expression "metal ratio", often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of the metal in an overbased salt to the chemical equivalents of the metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the metal ratio is 1, while in overbased salts the MR is greater than 1. They are generally referred to as overbased, hyperbased, or superbased salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.

[0105] The overbased detergent of the lubricating oil composition may have a Total Base Number (TBN) of about 200 mg KOH / gram or greater, or, as a further example, about 250 mg KOH / gram or greater, or about 350 mg KOH / gram or greater, or about 375 mg KOH / gram or greater, or about 400 mg KOH / gram or greater, as measured by the method of ASTM D-2896.

[0106] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenates, overbased calcium sulfur-containing phenates, overbased calcium sulfonates, overbased calcium calixarates, overbased calcium salixarates, overbased calcium salicylates, overbased calcium carboxylic acids, overbased calcium phosphates, overbased calcium mono- and / or di-thiophosphates, overbased calcium alkylphenols, overbased calcium sulfur-bound alkylphenol compounds, overbased calcium methylene bridged phenols, overbased magnesium phenates, overbased magnesium sulfur-containing phenates, overbased magnesium sulfonates, overbased magnesium calixarates, overbased magnesium salixarates, overbased magnesium salicylates, overbased magnesium carboxylic acids, overbased magnesium phosphates, overbased magnesium mono- and / or di-thiophosphates, overbased magnesium alkylphenols, overbased magnesium sulfur-bound alkylphenol compounds, or overbased magnesium methylene bridged phenols.

[0107] The overbased calcium phenate detergent has 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 from about 230 mg KOH / g to about 350 mg KOH / g, all measured by the method of ASTM D-2896. When such detergent compositions are formed in an inert diluent, such as a process oil, usually a mineral oil, the total base number reflects the basicity of the entire composition, including the diluent and any other materials that may be included in the detergent composition (e.g., accelerators, etc.).

[0108] The overbased detergent may have a metal to substrate ratio of 1.1:1 or greater, or 2:1 or greater, or 4:1 or greater, or 5:1 or greater, or 7:1 or greater, or 10:1 or greater. In some embodiments, the detergent is effective in reducing or preventing rust in engines or other automotive components such as transmissions or gears. The detergent may be present in the lubricating composition at about 0% to about 10% by weight, or about 0.1% to about 8% by weight, or about 1% to about 4% by weight, or greater than about 4% to about 8% by weight.

[0109] Extreme Pressure Agents: The lubricating oil compositions herein may also optionally contain one or more extreme pressure agents. Extreme Pressure (EP) agents that are soluble in oil include sulfur and chlorosulfur containing EP agents, chlorinated hydrocarbon EP agents, and phosphorus EP agents. Examples of such EP agents include chlorinated waxes; organic sulfides and polysulfides such as dibenzyl disulfide, bis(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenols, sulfurized dipentenes, sulfurized terpenes, and sulfurized Diels-Alder adducts; phosphorus sulfurized hydrocarbons such as the reaction products of phosphorus sulfide with turpentine or methyl oleate; dihydrocarbyl and trihydrocarbyl phosphites, for example, phosphate esters such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl phenyl phosphite; dipentyl phenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene substituted phenyl phosphites; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol diacid; amine salts of alkyl and dialkyl phosphates, including, for example, the amine salt of the reaction product of a dialkyl dithiophosphoric acid with propylene oxide; and mixtures thereof.

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

[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. The hydrocarbyl groups may be composed of carbon and hydrogen or heteroatoms such as sulfur or oxygen. The hydrocarbyl groups may range from about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long chain fatty acid ester. In other embodiments, the long chain fatty acid ester may be a mono-ester, or a di-ester, or a (tri)glyceride. The friction modifier may be a long chain fatty amide, a long chain fatty ester, a long chain fatty epoxide derivative, or a long chain imidazoline.

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

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

[0114] The amines and amides may be used by themselves or in the form of adducts or reaction products with boron compounds such as boron oxides, 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, the entirety of which is incorporated herein by reference.

[0115] Friction modifiers may optionally be present in a range such as from about 0% to about 10% by weight, or from about 0.01% to about 8% by weight, or from about 0.1% to about 4% by weight.

[0116] Molybdenum-containing components: The lubricating oil compositions herein may also optionally contain one or more molybdenum-containing compounds. The oil-soluble molybdenum compounds may have the functional properties of antiwear agents, antioxidants, friction modifiers, or mixtures thereof. The oil-soluble molybdenum compounds may include molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dithiophosphinates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organomolybdenum compounds, and / or mixtures thereof. Molybdenum sulfides include molybdenum disulfide. The molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compounds may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil soluble molybdenum compound can be a molybdenum dithiocarbamate.

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

[0118] Additionally, the molybdenum compound can be an acidic molybdenum compound, including 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, the composition can provide the molybdenum via molybdenum / sulfur complexes of basic nitrogen compounds, as described, for example, in U.S. Pat. Nos. 4,263,152, 4,285,822, 4,283,295, 4,272,387, 4,265,773, 4,261,843, 4,259,195, and 4,259,194, and WO 94 / 06897, the foregoing patents being incorporated herein by reference in their entireties.

[0119] Another class of suitable 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 in the organic group to render the compound soluble or dispersible in oil, n is 1-4, k varies from 4-7, Q is selected from the group of neutral electron donor compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0-5, including non-stoichiometric values. There may be at least 21 total carbon atoms in the organic groups of all the ligands, such as at least 25, at least 30, or at least 35 carbon atoms. Additional suitable molybdenum compounds are described in U.S. Pat. No. 6,723,685, which is incorporated herein by reference in its entirety.

[0120] The oil soluble molybdenum compound may be present in an amount sufficient to provide from about 0.5 ppm to about 2000 ppm, from about 1 ppm to about 700 ppm, from about 1 ppm to about 550 ppm, from about 5 ppm to about 300 ppm, or from about 20 ppm to about 250 ppm of molybdenum.

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

[0122] In embodiments, the oil-soluble transition metal-containing compound may function as an antiwear agent, a friction modifier, an antioxidant, an adhesion control additive, or one or more of these functions.In embodiments, the oil-soluble transition metal-containing compound may be an oil-soluble titanium compound, such as titanium (IV) alkoxide.Some of the titanium-containing compounds that may be used in or for the preparation of oil-soluble materials in the technology of the present 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, such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide; and other titanium compounds or complexes, such as titanium phenate; titanium carboxylates, such as titanium (IV) 2-ethyl-1,3-hexanedioate or titanium citrate or titanium oleate; and titanium (IV) (triethanolaminato) isopropoxide. Other forms of titanium encompassed by the disclosed technology include titanium phosphates, such as titanium dithiophosphates (e.g., dialkyl dithiophosphates) and titanium sulfonates (e.g., alkyl benzene sulfonates), or generally reaction products of titanium compounds with various acid materials to form salts, such as oil-soluble salts. Thus, titanium compounds may be derived from organic acids, alcohols, and glycols, among others. Ti compounds may also exist in dimeric or oligomeric forms containing Ti-O-Ti structures. Such titanium materials are commercially available or can be readily prepared by suitable synthetic techniques that will be apparent to those skilled in the art. They may exist at room temperature as solids or liquids, depending on the particular compound. They may also be provided in solution form in a suitable inert solvent.

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

[0124] Another titanium-containing compound is titanium alkoxide and C 6 ~C 25 It may be a reaction product with a carboxylic acid. The reaction product has the following formula:

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

[0126] [ka] (wherein m+n=4, n is in the range of 1 to 3, and R 4 is an alkyl moiety having in the range of 1 to 8 carbon atoms, R 1 is selected from hydrocarbyl groups containing from about 6 to 25 carbon atoms; R 2 and R 3 are the same or different and are selected from hydrocarbyl groups containing 1 to 6 carbon atoms), or the titanium compound may be represented by the following formula:

[0127] [ka] (wherein x is in the range of 0 to 3; R 1 is selected from hydrocarbyl groups containing from about 6 to 25 carbon atoms; R 2 , and R 3 are the same or different and are selected from hydrocarbyl groups containing from about 1 to 6 carbon atoms; R 4 , H, C 6 ~C 25 The carboxylic acid moiety may be selected from the group consisting of

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

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

[0130] Viscosity index improver: The lubricating oil composition herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, hydrogenated styrene-isoprene polymers, styrene / maleic acid ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenylaryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers may include star polymers, suitable examples of which are described in US Patent Application Publication No. 20120101017(A1).

[0131] The lubricating oil compositions herein may also optionally contain one or more dispersant viscosity index improvers in addition to or instead of the viscosity index improver. Suitable viscosity index improvers may include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with the reaction product of an acylating agent (such as maleic anhydride) and an amine, amine-functionalized polymethacrylates, or esterified maleic anhydride-styrene copolymers reacted with amines.

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

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

[0134] The lubricating oil composition according to the present disclosure may optionally contain other performance additives. The other performance additives may be in addition to the specific additives of the present disclosure and / or may include one or more of metal deactivators, viscosity index improvers, detergents, ashless TBN boosters, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam suppressants, demulsifiers, emulsifiers, pour point depressants, seal swell agents, and mixtures thereof. Typically, a fully formulated lubricating oil will contain one or more of these performance additives.

[0135] Suitable metal deactivators may include derivatives of benzotriazole (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzothiazole; foam suppressors including copolymers of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates, or polyacrylamides.

[0136] Suitable suds suppressors include silicon-based compounds such as siloxanes.

[0137] Suitable pour point depressants may include polymethyl methacrylate or mixtures thereof. The pour point depressant may be present in an amount sufficient to provide from about 0 wt. % to about 1 wt. %, from about 0.01 wt. % to about 0.5 wt. %, or from about 0.02 wt. % to about 0.04 wt. %, based on the final weight of the lubricating oil composition.

[0138] A suitable rust inhibitor can be a single compound or a mixture of compounds that have the property of inhibiting corrosion of ferrous metal surfaces. Non-limiting examples of rust inhibitors useful herein include oil-soluble high molecular weight organic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid, as well as oil-soluble polycarboxylic acids including dimer and trimer acids such as those produced from tall oil fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long chain alpha, omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000, and alkenyl succinic acids in which the alkenyl group contains about 10 or more carbon atoms, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Another useful type of acidic corrosion inhibitor is the half ester of an alkenyl succinic acid having about 8 to about 24 carbon atoms in the alkenyl group with an alcohol, such as a polyglycol. The corresponding half amides of such alkenyl succinic acids are also useful.Useful rust inhibitors are high molecular weight organic acids.

[0139] When present, the rust inhibitor may be used in an amount sufficient to provide from about 0 wt. % to about 5 wt. %, from about 0.01 wt. % to about 3 wt. %, from about 0.1 wt. % to about 2 wt. %, based on the final weight of the lubricating oil composition.

[0140] Generally speaking, suitable lubricating oils containing the neutral to overbased sulfurized alkylphenate products herein may contain additive components in the ranges listed in the table below.

[0141] [Table 2]

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

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

[0144] For comparative examples with sulfurization ratios less than 500:1, the concentration of unsulfurized alkylphenate was measured by reversed-phase High Performance Liquid Chromatography (HPLC), e.g., as described in U.S. Pat. No. 8,933,022(B2), where the level of unsulfurized alkylphenate was at least about 0.3 weight percent or greater. In an exemplary HPLC method, samples were prepared by weighing about 80-120 mg into a 10 mL volumetric flask, diluting to the level mark with methylene chloride, and mixing until the sample was completely dissolved. The HPLC system used in the HPLC method included an HPLC pump, a thermostated HPLC column compartment, an HPLC fluorescence detector, and a PC-based chromatographic data collection system. An exemplary system is 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 comparative examples, 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 of diluted sample, elution type: gradient, reversed phase, gradient: 0-7 min switching from 85 / 15 methanol / water to 100% methanol linear gradient, run time: 17 min.

[0146] For the comparative samples, the resulting chromatograph typically contains several peaks. The peak due to the unsulfurized alkylphenate typically elutes at an early retention time, while the peak due to the sulfurized alkylphenate elutes at a longer retention time. For quantification purposes, the area of ​​the single largest peak of the unsulfurized alkylphenate was measured and this area was used to determine the concentration of the total unsulfurized alkylphenate. The area of ​​the selected peaks can be compared to a calibration curve to determine the weight percent of the unsulfurized alkylphenate, and from that the amount of sulfurized alkylphenate.

[0147] For the samples of the present invention that had sulfurization ratios of 500:1 or more, the above method is generally not sensitive enough to measure such low levels of unsulfurized alkylphenate / alkylphenol. Rather, the measurement was modified using a sample with a target phenate concentration of 5mg / mL in accordance with the above method, and using liquid chromatography-mass spectrometry (LC-MS) using a single quad or triple quad MS or equivalent via an Agilent MS 6420 QQQ with an Agilent 1260 LC column, such as a Supelco Ascentis Express RP Amide 2.7u, 100mm×2.1mmID column, and an Agilent MSD XT or equivalent device, as follows. For the sample measurement of the present invention, the following system settings were used in the analysis: column temperature 45° C., flow rate 0.3mL / min, injection volume 3μl, 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), fragmentor 135, and peak width 0.07. The percentage of unsulfurized alkylphenols / alkylphenates was determined using MassHunter Quant Program or equivalent to generate a calibration curve and then calculate the percentage of unsulfurized alkylphenols / phenates in the samples.

[0148] Comparative Example 1 As described in U.S. Pat. No. 8,933,002 (B2), Examples 1 and 3 thereof describe the sulfurization, neutralization, and overbasing of tetrapropenylphenol with methanol and xylene, but such a process was only able to 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: A 4 liter round bottom flask was charged with 1620 g of tetrapropenylphenol (available from Chevron Oronite Company LLC) at room temperature. The tetrapropenylphenol was heated to 110° C. in 30 minutes. At 60° C., 14 g of 50 wt. % aqueous potassium hydroxide was added under stirring. Next, 192 g of sulfur flakes (i.e., elemental sulfur) were added at 110° C. and the pressure was reduced to 680 mm Hg. The reaction temperature was then increased to 180° C. in 30 minutes and the pressure was slowly reduced to 260 mm Hg to allow for the sulfurization of H. 2 S release was promoted. H formed 2 The S gas was trapped in a concentrated potassium hydroxide solution located prior to the vacuum pump. The reaction conditions were maintained for 2 hours and 45 minutes. The pressure was reduced to 50 mmHg in an additional 15 minutes and maintained under these conditions for an additional 3 hours. The sulfurized alkylphenol reaction product was allowed to cool. The '002 patent states that the resulting sulfurized alkylphenol had the following analyses: 6.85 percent sulfur, 2646 ppm potassium, a viscosity at 100°C of 65.4 mm2 / s, and 26.5 percent TPP (i.e., unreacted tetrapropenyl phenol and its calcium salts).

[0150] Example 1 of the '002 patent then further describes step 2, which is the distillation of the sulfurized alkylphenol from step 1, as follows: The sulfurized alkylphenol reaction product obtained in step 1 is preheated to about 140° C. and then passed through a continuous 0.0385 m 2 Approximately 400 g / hr was fed to a wiped film evaporator. The evaporator temperature was maintained at about 210° C. and the pressure was maintained at about 1.5 mbar. The '002 patent states that the average distilled product had the following analytical properties: about 10.3% sulfur, about 4293 ppm potassium, viscosity at 100° C. of about 402.8 mm2 / s, and 0.31% TPP.

[0151] Then, 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 hydrated lime was added to a 5 liter double jacketed glass reactor along with 243.2 g of methanol and 876 g of xylene. Next, 713.4 g of sulfurized tetrapropenylphenol 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 in 30 minutes while the reaction temperature was increased from room temperature to 30°C. The reaction mixture was then cooled to 25°C in 20 minutes. To this mixture, 29.6 g of a 90 / 10 molar mixture of acetic acid and formic acid was added in 2 minutes. The temperature of the reaction mixture increased from 25°C to 34°C due to an exothermic reaction. Then, 24.4 g of CO was added while heating from 34°C to 36°C. 2 was added over a period of 30 minutes. Next, 41.6 g of CO was added while heating to 36 to 42°C. 2 A slurry of 60.8 g hydrated lime, 60.8 g methanol, and 334 g xylene was added to the reactor in 1 minute. Then, an additional 51.4 g of CO was added while heating from 41° C. to 46° C. 2 was added over 64 minutes. The temperature of the reaction mixture was raised to 65°C in 26 minutes and methanol distillation was started. The temperature was raised to 93°C in a further 60 minutes. The temperature was raised to 130°C in a further 30 minutes. 550g of 130 neutral lube oil was added to the reaction mixture. Crude sediment was measured to be 2.4% by volume. The crude product was centrifuged and then xylene distillation was carried out at 170°C, 25mBar for 1 hour.

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

[0153] Comparative Example 2 Similar to Comparative Example 1, Example 4 of US Pat. No. 8,933,002 (B2) describes the neutralization and overbasing of tetrapropenylphenol with methanol, but such a process could only achieve a sulfurization ratio of 178:1. In this example, 609.01 g of sulfurized tetrapropenylphenol (Example 1 of US Pat. No. 8,933,002) was charged to a 2 liter round bottom flask. Then, 425.2 g of methanol and 0.2 g of foam suppressor SI200 available from Dow Corning were added to the reactor. The reaction mixture was warmed to 60° C. with stirring. During this process, 78.5 g of hydrated lime was introduced along with 300 g of 100N diluent oil. At 60° C., 4.6 g of a 50 / 50 weight ratio mixture of acetic acid and formic acid was added. The neutralization was held at 60° C. and atmospheric pressure for 210 minutes. The methanol was evaporated by slowly reducing the pressure to 30 mmHg in about 2 hours. 354 g of lubricating oil was added dropwise during this process. The distillation was held at 30 mmHg and 60°C for 1 hour. The crude sediment of neutralized calcium salts of sulfurized alkylhydroxyaromatic was determined to be 0.4% by volume. The product was filtered on a Buchner to remove unreacted lime.

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

[0155] Comparative Example 3 A tetrapropylene calcium phenate composition having a TBN of 118, about 4.26 weight percent calcium, and 1.8 weight percent unsulfurized tetrapropylene phenol / phenate derived from catalyzed sulfur monochloride was overbased at 165° C. for 3 hours and then vacuum distilled at 200° C. for 1 hour. After overbasing and distillation, the product had a TBN of 314 but now had 4.4 weight percent unsulfurized tetrapropylene phenate / phenol.

[0156] Comparative Example 4 As described in U.S. Patent No. 4,973,411, Example 1 describes a sulfurized phenate product, however, such a process achieves only about 0.3 to about 0.5 weight percent residual unsulfurized alkylphenol when tested using the measurement methods of the present application, and therefore only achieves a sulfurization ratio of about 300:1. Example 1 of the '411 patent utilized sulfur dichloride from Sigma Aldrich, with impurities including 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: A charge of about 192 parts by weight of dodecylphenol was added to a 3-liter, four-neck flask along with about 840 parts by weight of isooctane or heptane. Nitrogen gas was then bubbled through the mixture at a rate of about 400 mL / min. Next, about 51 parts of the above sulfur dichloride (80% SCl 2 and 20% S. 2 Cl 2 ) was added via an addition funnel to maintain the reaction temperature near room temperature. The reaction was stirred for about 5 minutes, and then the reaction was heated to about 80° C. for one-half hour. The reaction was then cooled to about 45° C. Next, about 216 parts of 100P pale oil plus about 115 parts methanol, and about 105 parts Ca(OH) 2 The introduction of nitrogen gas was stopped, and the mixture was stirred at about 55°C to about 57°C for 1 hour. The temperature was maintained and CO 2was bubbled at an appropriate rate of about 200 to about 300 mL / min for about 77 minutes. Finally, the crude product was filtered and the solvent was removed under vacuum at about 100° C. The replicated product had about 8.8 weight percent calcium, about 3.4 weight percent sulfur, and a KV100 of about 143 and a TBN of 232, which was consistent with the final product reported in the '411 patent.

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

[0159] When evaluated for residual unsulfurized alkylphenols using the test methods of the present application, including either reverse phase high performance liquid chromatography (HPLC) and / or liquid chromatography-mass spectrometry (LC-MS) as described above, the residual unsulfurized alkylphenol level of Example 1 of U.S. Pat. No. 4,973,411 was determined to be 0.39 weight percent.

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

[0161] S1: Tetrapropylene phenol was charged to a kettle and sulfur monochloride was added dropwise at about 100° C., then the temperature was increased to about 180° C. and held for about 1 hour, then increased to about 190° C. and held for about 1 hour, then vacuum stripped at about 200° C. for about 1 hour, then the mixture was cooled to about 150° C. and about 252 grams of process oil was added. After sulfurization, the intermediate sulfurized product had a sulfurization ratio of about 499:1.

[0162] S2: Tetrapropylene phenol was charged to a kettle with about 100 grams of heptane, sulfur monochloride was added dropwise at about 40° C., then the temperature was raised to about 100° C. and full vacuum stripping was performed to distill off the heptane for about 1 hour, then vacuum stripping was performed at about 200° C. for about 1 hour, then cooled to about 150° C. and about 252 grams of process oil was added. After sulfurization, the intermediate sulfurized product had a sulfurization ratio of about 1110:1.

[0163] S3: Tetrapropylene phenol was charged to a kettle with about 100 grams of heptane and sulfur monochloride was added dropwise at about 40° C., then the temperature was increased to about 100° C. and full vacuum stripping was performed to distill off the heptane for about 1 hour, then about 252 grams of process oil was added. After sulfurization, the intermediate sulfurized product had a sulfurization ratio of about 2499:1.

[0164] Each sulfurized tetrapropylene phenol S1, S2, or S3 was then 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 overbased in the solvent system by treatment with about 208 sccm of gaseous carbon dioxide, as shown in Tables 5 and 6. Table 3 provides properties of the neutralized overbased products.

[0165] [Table 3] * Unsulfurized alkylphenol refers to both the unsulfurized alkylphenate and any unsulfurized alkylphenol in the product. ** For example, the sulfurization ratio of Sample A was determined from 99.92% sulfurized alkylphenate in the sample and 0.08% unsulfurized alkylphenate / 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] * 21 g of CaO was added during overbasing.

[0169] After overbasing, the sample was subjected to filtration and vacuum stripping at a temperature not exceeding about 140° C. to produce the sulfurized alkylphenate products summarized in Table 3 above.

[0170] Example 2 Further experiments were carried out to replicate Example 1 of U.S. Patent No. 8,933,002 (B2) for the sulfurization of tetrapropenylphenol. Following the sulfurization in step 1 of Example 1 of the '002 patent, the intermediate product obtained had 6.88 percent sulfur, 56.8 mmHg, and 1.08% sulfur. 2 / s KV100, 1958 ppm potassium, and an unsulfurized tetrapropenylphenol content of 30.4 percent.

[0171] The intermediate product was then subjected to a distillation using a wiped film evaporator consistent with step 2 of Example 1 of the '002 patent to produce a sulfurized tetrapropylene alkylated phenate product having a high sulfurization ratio (i.e., low levels of unreacted or unsulfurized tetrapropylene phenol), except that the vacuum was 1100 mTorr and the feed rate was 360 g / hr. 2 / s, 3133 ppm potassium, and 0.05% unreacted or unsulfurized tetrapropylene phenol or a high sulfurization ratio of 1999:1.

[0172] Example 3 The sulfurized alkylphenol replicated from Example 2 above was then neutralized and overbased in accordance with Example 3 of U.S. Pat. No. 8,933,002 B2, except that the solvents were heptane and methanol, and the neutralization, overbasing, and work-up were carried out at low temperatures not exceeding about 100° C.

[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 the product was then degassed at a temperature not exceeding 100° C. to obtain a product with 4.24% sulfur, 298.8 mm 2 This formed a final sulfurized product having a KV100 of 10.01 ppm / s, 1048 ppm potassium, an unsulfurized alkylphenol content of less than 0.03 percent (i.e., an undetectable amount or a sulfurization ratio of 3333:1 or greater), a TBN of 270.4, and a calcium content of 10.52 percent.

[0174] Comparing the results of this example using a heptane / methanol solvent system to Comparative Example 2 above (using the method of U.S. Pat. No. 8,933,002 as well as a methanol / xylene solvent and high temperature work-up), the impact of solvent selection and low temperature treatment, particularly the low temperature work-up discovered herein, can be seen. In Comparative Example 2, using the methanol / xylene solvent system of the '002 patent and high temperature work-up, the level of unreacted TPP increased after neutralization, overbasing, and work-up, whereas in this example, using a heptane / methanol solvent and low temperature work-up, the level of unreacted TPP was even further reduced 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 of Figure 1, which illustrates the reaction kinetics of regeneration of unsulfurized TPP based on temperature. As shown in Figure 1, if the temperature is maintained below about 100°C (such as about 80°C) during processing, the level of unreacted or unsulfurized TPP is not regenerated.

[0176] Example 4 Further experiments were carried out to produce sulfurized tetrapropylene alkylated phenate products using the methods of the present application having high sulfurization ratios (i.e., low levels of unreacted or unsulfurized tetrapropylene phenol), as shown below in Table 7. In this example, the sulfur source used was about 67 weight percent sulfur dichloride (SCl) with different molar ratios of sulfur source to tetrapropylene phenol (TPP). 2 ) and about 33 weight percent sulfur monochloride (S 2 Cl 2 ) generally using the sulfurization method of Comparative Example 1, with any post-treatment at a temperature of about 100° C. or less.

[0177] Residual levels of unreacted tetrapropylene phenol were measured using LCMS as discussed above to detect unreacted or unsulfurized alkylphenol 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, ratios of sulfur source to alkylphenol of at least 0.7 or greater result in undetectable levels of unreacted or unsulfurized tetrapropylene phenol in the sulfurized product and / or when combined with the low temperature processing disclosed herein.

[0178] [Table 7]

[0179] Any neutralization and / or overbasing consistent with this disclosure may be performed on the compositions of this example.

[0180] It should be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless expressly and unambiguously limited to one referent. Thus, for example, reference to an "antioxidant" includes two or more different antioxidants. As used herein, the term "comprising" and grammatical variations thereof are intended to be open-ended such that the recitation of items in a list excludes other similar items that may be substituted for or added to the items in the list.

[0181] For purposes of this specification and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values ​​used in the specification and claims should be understood in all instances to be modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending on the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

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

[0183] It is further to be understood that each range disclosed herein should be construed as a disclosure of each specific value within the disclosed range having the same number of significant digits. Thus, for example, a range of 1 to 4 should be construed as an explicit disclosure of not only the values ​​1, 2, 3, and 4, but any range of such values.

[0184] It is 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. Thus, the present disclosure should be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or each specific value within each range, or by combining each upper limit of each range with each specific value within each range. That is, it is further understood that any range between the endpoint values ​​within the broad range is also contemplated herein. Thus, a range of 1 to 4 also means a range of 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0185] Furthermore, a specific amount / value of a component, compound, substituent, or parameter disclosed in the details or examples should be construed as a disclosure of either a lower or upper limit of a range and therefore can be combined with any other lower or upper limit or specific amount / value in a 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 particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents may occur that are not presently anticipated or that cannot be currently anticipated by the applicants or others skilled in the art. It is therefore intended that the appended claims as filed, and the appended claims as they may be amended, cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. 1. A process for preparing a sulfurized alkylphenate product to achieve a high sulfurization ratio of sulfurized alkylphenate to unsulfurized alkylphenate, comprising: sulfurizing an alkylphenol with a sulfur source to provide a sulfurized alkylphenol, said alkylphenol being derived from the alkylation of phenol, and wherein the molar ratio of said sulfur source to said alkylphenol is from about 0.66 to about 3.5, from about 0.68 to about 3.5, or from about 0.7 to about 3.5; neutralizing and optionally overbasing said sulfurized alkylphenol in the presence of a solvent to provide a sulfurized alkylphenate composition, said neutralization and optional overbasing being carried out at a temperature not exceeding about 140° C. to achieve a sulfurization ratio of about 500:1 or greater; and post-treating said sulfurized alkylphenate composition to obtain said sulfurized alkylphenate product, said post-treating being conducted at a temperature not exceeding about 140° C. to maintain said sulfurization ratio at or above about 500:

1.

2. 2. The process for preparing a sulfurized alkylphenate 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. 3. The process for preparing a sulfurized alkylphenate according to claim 1 or 2, wherein the molar ratio of said sulfur source to said alkylphenol is from about 0.68 to about 3.

5.

4. 4. The process for preparing a sulfurized alkylphenate according to any one of claims 1 to 3, wherein the molar ratio of the sulfur source to the alkylphenol is from about 0.7 to about 2.

5. The process for preparing a sulfurized alkylphenate according to any one of claims 1 to 4, wherein the sulfur source is sulfur monochloride and sulfur dichloride.

6. 6. The process for preparing a sulfurized alkylphenate according to any one of claims 1 to 5, wherein the solvent is another solvent having a boiling point of about 100°C or less at about 1000 to about 40 mbar.

7. 7. The process for preparing a sulfurized alkylphenate according to claim 6, wherein the solvent is xylene, toluene, octane, butanol, heptane, methanol, acetone, benzene, cyclohexane, cyclopentane, ethanol, hexane, pentane, propanol, water, or a combination thereof, preferably heptane and methanol, more preferably about 85 to about 95 weight percent heptane and about 5 to about 15 weight percent methanol.

8. 8. The process for preparing a sulfurized alkylphenate according to any one of claims 1 to 7, wherein said neutralization and / or said optional overbasing comprises contacting said sulfurized alkylphenol with an alkali metal or alkaline earth metal salt at a temperature not exceeding about 140°C.

9. 9. The process for preparing a sulfurized alkylphenate according to claim 8, wherein the alkali metal salt or alkaline earth metal salt is lithium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, aluminum hydroxide, lithium oxide, magnesium oxide, calcium oxide, barium oxide, or a combination thereof.

10. 9. The process for preparing a sulfurized alkylphenate according to claim 8, wherein said neutralization and / or said optional overbasing is carried out in the presence of a carbonation agent at a temperature not exceeding about 140°C.

11. 11. The process for preparing a sulfurized alkylphenate according to any one of claims 1 to 10, wherein the work-up treatment comprises one or more of vacuum stripping, sparging, distillation, filtration, degassing, evaporation, wiped film evaporation, centrifugation, dilution, liquid-liquid extraction, membrane separation, chromatography, adsorption, supercritical extraction, or a combination thereof, all work-up treatments being carried out at a temperature not exceeding about 140°C, preferably not exceeding 100°C.

12. 12. The process for preparing a sulfurized alkylphenate according to any one of claims 1 to 11, wherein the process does not remove residual unsulfurized alkylphenate during the sulfurization, the neutralization, and / or the optional overbasing.

13. 13. The process for preparing a sulfurized alkylphenate according to any one of claims 1 to 12, wherein said temperature of said neutralization and said optional overbasing and said temperature of said post-treatment do not exceed about 100°C.

14. 14. The process for preparing a sulfurized alkylphenate according to any one of claims 1 to 13, wherein the sulfurization ratio of the sulfurized alkylphenate product is from about 5000:1 to about 500:

1.

15. 15. The process for preparing a sulfurized alkylphenate according to any one of claims 1 to 14, wherein the sulfurization ratio of the sulfurized alkylphenate product is from about 3500:1 to about 1000:

1.

16. 16. The process for preparing a sulfurized alkylphenate according to any one of claims 1 to 15, wherein the sulfurized alkylphenate product has a total base number of from about 100 to about 400 mg KOH / g as measured by the method of ASTM D-2896.

17. 17. The process for preparing a sulfurized alkylphenate according to any one of claims 1 to 16, wherein the sulfurization is carried out at a temperature of from about 0 to about 250°C.

18. 18. The process for preparing a sulfurized alkylphenate according to any one of claims 1 to 17, wherein the sulfurization is carried out at a temperature of from about 40 to about 120°C.

19. 19. The process for preparing a sulfurized alkylphenate according to any one of claims 1 to 18, wherein the sulfurization is carried out in the absence of a base.

20. 20. The process for preparing a sulfurized alkylphenate according to any one of claims 1 to 19, wherein the sulfurized alkylphenol is neutralized and overbased.

21. 21. The process for preparing a sulfurized alkylphenate according to any one of claims 1 to 20, wherein the alkylation of the phenol is with one or more oligomers derived from an olefin.

22. 22. The process for preparing a sulfurized alkylphenate according to claim 21, wherein the olefin comprises ethylene, propylene, butylene, isobutylene, pentene, or combinations thereof.

23. 23. The process for preparing a sulfurized alkylphenate according to any one of claims 1 to 22, wherein the sulfurized alkylphenate product has less than about 0.2 weight percent unsulfurized alkylphenate and / or unsulfurized alkylphenol, less than about 0.1 weight percent, less than about 0.08 weight percent, less than about 0.06 weight percent, less than about 0.04 weight percent, or less than about 0.03 weight percent unsulfurized alkylphenate and / or unsulfurized alkylphenol.

24. A sulfurized alkylphenate product prepared by the process of any one of claims 1 to 23.

25. 1. A metal phenate detergent having a high sulfurization ratio of sulfurized alkylphenate to unsulfurized alkylphenate or unsulfurized alkylphenol, comprising: a sulfurized alkylphenate derived from a sulfur source and an alkylphenol and having a total base number of from about 50 to about 400 mg KOH / g as measured by the method of ASTM D-2896, wherein the molar ratio of sulfur source to alkylphenol is from about 0.66 to about 3.5, from about 0.68 to about 3.5, or from about 0.7 to about 3.5; up to about 100,000 ppm alkali or alkali metal and up to about 65,000 ppm sulfur; and a sulfurization ratio of about 500:1 to about 5500:1 with about 900 ppm or less of unsulfurized alkylphenate and / or unsulfurized alkylphenol, 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 of unsulfurized alkylphenate and / or unsulfurized alkylphenol.

26. 26. The metal phenate detergent of claim 25, wherein the metal is calcium and the metal phenate detergent has from about 35,000 ppm to about 100,000 ppm calcium.

27. 27. The metal phenate detergent of claim 26, wherein the metal phenate detergent has at least about 25,000 ppm sulfur.

28. 28. The metal phenate detergent of claim 27, wherein the metal phenate detergent has at least about 30,000 ppm sulfur.

29. The metal phenate detergent of any one of claims 25 to 28, wherein the sulfurization ratio is from about 1200:1 to about 5000:

1.

30. The metal phenate detergent according to any one of claims 25 to 29, wherein the alkylphenate is derived from the alkylation of phenol with one or more C6 to C36 alkylene groups.

31. 31. The metal phenate detergent of claim 30, wherein the alkylene group is oligomeric.

32. 32. The metal phenate detergent of claim 31, wherein the oligomers are derived from ethylene, propylene, butylene, isobutylene, pentene, or combinations thereof.

33. The metal phenate detergent of any one of claims 25 to 32, wherein the sulfurized alkylphenate detergent has a total base number of from about 90 to about 250 mg KOH / g as measured by the method of ASTM D-2896.

34. The metal phenate detergent of any one of claims 25 to 33, wherein the sulfurized alkyl phenate has less than about 50 percent alkyl substitution in the ortho position.

35. A lubricating oil composition comprising the metal phenate detergent of any one of claims 25 to 34 and one or more base oils of lubricating viscosity.

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