Sulfurized additives containing low levels of alkylphenols

Abstract

The present disclosure provides detergent additives and methods for preparing sulfurized alkylphenate products to achieve high sulfurization ratios and low levels of unsulfurized alkylphenols.

Description

[Technical field]

[0001] The present disclosure relates generally to lubricating oil compositions and sulfurized additives therefor that contain low levels of unsulfurized alkylphenols. [Background technology]

[0002] Metal salts of sulfurized alkylphenols, otherwise known as alkylphenates, tend to be useful lubricating oil additives. These additives can function, for example, as detergents, friction modifiers, and / or dispersants, while when used in lubricants in automotive applications, they provide an alkaline base to assist in neutralizing acids generated during vehicle operation. Unsulfurized variants of alkylphenates or phenols 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, described herein is a sulfurized metal phenate detergent comprising a compound of formula I and a compound of formula II. In the approach, the compounds of formula I and II have a structure comprising:

[0004] [ka] wherein each R1 is independently one of an alkyl group, an aryl group, an alkylaryl group, or an arylalkyl group; R2 is one of a hydrogen, an alkyl group, an alkylamino group, or a hydroxyalkyl group; x is an integer from 1 to 4; n is an integer from 1 to 3; m is an integer from 0 to 1; and M 2+ is a divalent metal ion.

[0005] In other embodiments or approaches, the sulfurized metal phenate detergent described in the preceding paragraph includes optional features or embodiments, which may include, in any combination, the following, where R1 is a C8-C20 alkyl group, and / or R2 is methyl, and / or R2 has the structure -R4N(R5)(R5), where R4 is a C1-C10 hydrocarbyl group and each R5 is independently a C1-C4 alkyl group, and / or the detergent comprises from about 0.01 to about 0.5 weight percent of a compound of formula II, and / or further comprises up to about 0.5 weight percent of an unsulfurized alkylphenol, and / or the detergent comprises from 0 to 300 mg of a sulphurized alkylphenol as measured by the method of ASTM D-2896. KOH, and / or each of the compound of formula I, the compound of formula II, or both, has less than about 15 weight percent R1 substitution in the ortho position, and / or the detergent contains up to about 100,000 ppm of metal provided by an alkali or alkaline metal and up to about 65,000 ppm of sulfur, and / or the alkali or alkaline metal is one of lithium, potassium, sodium, magnesium, calcium, barium, aluminum, or a combination thereof.

[0006] In another embodiment, a lubricating oil composition comprises the metal phenate detergent of any of the embodiments of the previous two paragraphs and one or more base oils of lubricating viscosity.

[0007] In yet another embodiment, a process for preparing a sulfurized alkylphenate product is described. In the approach, the process includes, in any order, sulfurizing an alkylphenol with a sulfur source to provide a sulfurized alkylphenol, where the alkylphenol is derived from the alkylation of a phenol, neutralizing and optionally overbasing the sulfurized alkylphenol in the presence of a solvent to provide a sulfurized alkylphenate composition comprising a mixture of sulfurized alkylphenate and residual unsulfurized alkylphenol, where the sulfurizing, neutralizing, and optional overbasing can be performed in any order, and post-treating the sulfurized alkylphenate composition to obtain a sulfurized alkylphenate product, where the post-treating includes reacting the sulfurized alkylphenate composition with a triazine compound.

[0008] In yet other embodiments or approaches, the process of the preceding paragraph may include optional features or embodiments, which may include one or more of the following embodiments, in any combination, where 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 0.1 to about 3.5, and / or the neutralization and / or optional overbasing comprises contacting the sulfurized alkylphenol with an alkali metal or alkaline earth metal salt, 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 triazine compound has the structure of formula III:

[0009] [ka] wherein each R3 is independently hydrogen, a hydrocarbyl group, an alkyl group, an amino group, a polyamino group, an alkylamino group, a dialkylaminoalkyl group, a C1-C10 hydrocarbyl group, or a -R4N(R5)(R5) group, and each of R4 and R5 is independently a C1-C10 hydrocarbyl group, and / or further comprising about 0.5 weight percent or less of an unsulfurized alkylphenol, and / or the sulfurized alkylphenate product comprises a compound of formula I and a compound of formula II;

[0010] [ka] In the formula, each R1 is independently an alkyl group, an aryl group, an alkylaryl group, or an arylalkyl group; R2 is an alkyl group, an aminoalkyl group, or a hydroxyalkyl group; x is an integer of 1 to 4; n is an integer of 1 to 3; m is an integer of 0 or 1; and M 2+ is a divalent metal ion, and / or R 1 is a C8 to C20 alkyl group, and / or R2 is methyl or has the structure -R4N(R5)(R5), where R4 is a C1 to C10 hydrocarbyl group and each R5 is independently a C1 to C4 alkyl group.

[0011] In yet another embodiment, described herein is a sulfurized metal phenate detergent prepared by the process of any embodiment of the previous two paragraphs.

[0012] In still further embodiments, the use of the sulfurized metal phenate compositions described herein as detergents, the sulfurized metal phenate compositions being any of the embodiments as described in this Summary.

[0013] The following definitions are provided to clarify the meaning of certain terms used herein.

[0014] The terms "oil composition," "lubricant composition," "lubricating oil composition," "lubricating oil," "lubricant composition," "lubricant composition," "fully formulated lubricant composition," and "lubricant" are considered to be synonymous, fully interchangeable terms, and refer to a finished lubricant product comprising a major amount of a base oil and a minor amount of an additive composition.

[0015] 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.

[0016] Unless otherwise specified, 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, highly based, or superbased salts, and may be salts of organic sulfur acids, carboxylic acids, salicylates, sulfonates, and / or phenols.

[0017] The term "alkaline earth metals" refers to calcium, barium, magnesium, and strontium, and the term "alkali metals" refers to lithium, sodium, potassium, rubidium, and cesium.

[0018] As used herein, unless otherwise specified, 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.

[0019] As used herein, unless otherwise specified, the term "hydrocarbylene substituent" or "hydrocarbylene group" is used in its ordinary sense, as is well known to those skilled in the art. Specifically, it refers to a group that is directly attached to the remainder of 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.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] The term "alkyl" as used herein, unless otherwise specified, refers to linear, branched, cyclic, and / or substituted saturated chain moieties of about 1 to about 100 carbon atoms. The term "alkenyl" as used herein, unless otherwise specified, refers to linear, branched, cyclic, and / or substituted unsaturated chain moieties of about 3 to about 10 carbon atoms. The term "aryl" as used herein, unless otherwise specified, refers to monocyclic and polycyclic aromatic compounds that can contain alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and / or heteroatoms including, but not limited to, nitrogen, oxygen, and sulfur.

[0025] 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% by weight 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.

[0026] 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. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] The present disclosure provides detergent additives in the form of compositions or mixtures comprising at least a sulfurized alkylphenate containing low levels of residual or unsulfurized alkylphenol, lubricating oil compositions comprising such detergent additives, and methods for preparing detergent additives in the context of neutral to overbased additives, such as detergents having a TBN of at least about 0, at least about 20, at least about 50, at least about 100, and otherwise from about 100 to about 500, as discussed further below.

[0028] In one approach or embodiment, the present disclosure generally relates to a detergent additive or detergent composition comprising at least a sulfurized metal phenate detergent comprising a compound of formula Ia, optionally a compound of formula Ib, and a compound of formula II:

[0029] [ka] wherein each R1 is independently an alkyl group, an aryl group, an alkylaryl group, or an arylalkyl group (preferably, R1 is a C8 to C20 alkyl or hydrocarbyl group, most preferably a C12 linear or branched alkyl or hydrocarbyl group), R2 is one of a hydrogen, an alkyl group, an alkylamino group, or a hydroxyalkyl group, x is an integer from 1 to 4, n is an integer from 1 to 3, each m is independently an integer from 0 or 1, and M 2+is a divalent metal ion. Preferably, the R group is located primarily at the para position on the aromatic ring, as discussed in more detail below. The Mannich reaction to form the post-reactant amine (discussed below) to produce the compounds of formula Ia, formula Ib, and / or formula II may be through any open ortho, meta, or para position on the aromatic ring, but the reacting amine is preferably located at the ortho position shown in the structure above. As also shown above, the sulfur bridge in formula Ia or Ib is primarily at the ortho position, but may be at other positions on the aromatic ring depending on the application and / or reaction conditions. The Mannich reaction to form the post-reactant amine may also produce a diaddition to the aromatic ring (e.g., ortho and para, ortho and meta, or meta and para), depending on the application.

[0030] The overbased sulfurized alkylphenate is made by sulfurization, neutralization, and / or carbonation. These reactions can be carried out in any order, simultaneously, or in a specific order, depending on the application. The sulfurization and neutralization are, for example, completed in any order or simultaneously, usually before carbonation. In general, the detergent additive or composition herein is obtained by first neutralizing an alkylphenol, and then the neutralized alkylphenol is sulfurized with a sulfur source to provide a sulfurized and neutralized alkylphenol. The sulfurized and neutralized alkylphenol is then optionally overbased in the presence of a solvent to provide a neutral to optionally overbased and sulfurized alkylphenate additive or composition. The post-treatment of this additive / composition is then carried out in the presence of an amount of triazine compound effective to reduce the level of unsulfurized or residual alkylphenol / phenate variants to low or ultra-low levels of about 0.5 weight percent or less (in some approaches, about 0.2 weight percent or less, in other approaches, about 0.1 weight percent or less). The triazine compound reacts with the phenate and / or unsulfurized alkylphenol via the Mannich reaction, or alternatively, through in situ generation via an amine and a formaldehyde or paraformaldehyde post-reactant. Further details of the additives and methods of generating such additives are discussed below.

[0031] Alkylation of phenol The sulfurized alkylphenates of the detergent composition herein 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.

[0032] 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 one or more olefins or oligomers can be from about 10:1 to about 0.5:1, and in other approaches, from about 5:1 to about 2:1. The oligomeric alkyl group is generally attached to the phenol or hydroxyaromatic compound at the ortho and / or para positions, preferably the para position, although other substituents may be present depending on the application. For example, the oligomeric alkyl group (i.e., the R1 substituent in the formulas herein) can be about 85 to about 100 percent disubstitution at the para positions on the aromatic ring, about 0 to about 15 percent disubstitution at the ortho positions on the aromatic ring, and in some approaches, about 0 to about 5 percent disubstitution.

[0033] Neutralization Neutralization is accomplished by an alkylphenol reacting with a metal base. In one approach, neutralization is accomplished by contacting an 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 alkyl hydroxyaromatic compound. In some cases, the reaction can be carried out under an inert gas, such as nitrogen. The metal base can be added at various times during the reaction, either in a single addition or in multiple additions, if necessary for a particular application. Neutralization can occur via the exemplary reaction scheme I shown below, although other reactions can proceed as desired depending on the selected order of sulfurization, neutralization, and / or overbasing, as well as various applications, materials, and conditions.

[0034] [ka]

[0035] 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, ammonium hydroxide, and / or 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.

[0036] In an optional approach, the neutralizing solvent is a higher boiling point, such as a solvent having a boiling point of about 100° C. or higher at the stated pressure, such as ethylene glycol, propylene glycol, and / or decanol, and similar solvents. As used herein, in such optional approach, devoid or free of such compounds means that the solvent has less than about 15 weight percent, less than about 5 weight percent, less than about 2 weight percent.

[0037] The neutralization reaction between the metal base and the alkylphenol is carried out under conditions effective to maintain an elevated temperature. In one approach, the neutralization occurs at a temperature of at least 100° C., in some approaches at least about 120° C., in other approaches at least about 150° C., and in more preferred approaches up to about 180° C. The neutralization reaction can occur for about 1 hour to about 5 hours.

[0038] sulfide The neutralized alkylphenol or alkylhydroxyaromatic compound may be sulfurized by contacting it with a sulfur source in a manner effective to achieve a high degree of sulfurization. In some approaches, the sulfurization generally introduces a sulfur bridging group between the alkylphenol or alkylhydroxyaromatic moieties. In some approaches, the sulfur bridge is -S y -or-S x - group (shown in the exemplary structure below), where y or x is independently an integer from 1 to 4, in other approaches from 1 to 3, in some approaches from 1 to 2, and / or has a total sulfur level provided by the additive of up to about 5 percent. The sulfur source can be any suitable sulfur, such as elemental sulfur or its halides, such as sulfur monochloride or dichloride, hydrogen sulfide, sulfur dioxide, and sodium sulfide hydrate. 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. An exemplary reaction scheme for sulfurization is shown in Reaction Scheme II below, although other reactions can proceed as desired depending on the application, materials, and conditions.

[0039] [ka]

[0040] Sulfiding can occur, for example, at a temperature of about 200° C. to about 250° C., or in other approaches, about 225° C. to about 245° C., for a time effective to achieve the desired level of sulfidation, which can be from about 1 to about 8 hours, from about 2 to about 7 hours, or from about 4 to about 7 hours.

[0041] Overbasing Overbasing is then optionally, but in some embodiments is preferred, either during the neutralization and / or sulfurization described above, or alternatively thereafter. 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 further discussed below.

[0042] In one embodiment, an exemplary overbasing reaction may be reacting a sulfurized alkylphenol or a 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. In one approach, overbasing occurs at a temperature of at least about 50°C, in some approaches at least about 100°C, in other approaches at least about 165°C, and in more preferred approaches up to about 185°C. The degree of overbasing may 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 may be from about 30 minutes to about 180 minutes at the temperatures described.

[0043] After optional overbasing, the overbased sulfurized alkyl phenate, for example the detergent composition herein, may have a TBN of at least about 0, at least about 20, at least about 50, at least about 100, or in other approaches, from about 100 to about 500, from about 100 to about 400, or from about 150 to about 400, in yet other approaches, from about 200 to about 300, and in yet further approaches, from about 220 to about 275. Preferably, the TBN of the composition herein may be from about 100 to about 300 mg KOH as measured by ASTM D-2896. The resulting product may also have a level of residual or unsulfurized alkyl phenol, after optional overbasing, neutralization, and sulfurization, of about 1.0 weight percent or more, in other approaches, about 1.5 weight percent or more, and in yet other approaches, about 0.5 weight percent or more. As discussed further below, the post-treatment herein is effective to reduce such levels of residual or unsulfurized alkylphenol content in the detergents herein.

[0044] Post-processing After optional overbasing, the composition is often subjected to a number of steps to prepare the final sulfurized alkylphenate product. Examples of post-treatments can 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.

[0045] As noted above, the additives and compositions after sulfurization, neutralization, and optional overbasing may contain undesirably large amounts of unsulfurized or residual alkylphenols or phenates. One preferred post-treatment step herein is to further react or post-treat the sulfurized alkylphenate composition, in any of the embodiments previously discussed, as well as after sulfurization, neutralization, and optional overbasing, with a triazine post-treatment reactant to minimize and further reduce either the residual or unsulfurized alkylphenol / phenate in the composition.

[0046] In this approach, suitable triazine reactants for post-treatment may include any triazine or substituted triazine (or mixtures thereof) capable of reacting with a phenolic compound, in particular triazines of formula III below capable of reacting with a phenolic compound:

[0047] [ka] wherein each R3 is independently hydrogen, a hydrocarbyl group, an alkyl group, an amino group, a polyamino group, an alkylamino group, a dialkylaminoalkyl group, a hydroxyalkyl group, and may be a C1-C20 hydrocarbyl group (optionally a C1-C10 or C1-C4 group) or a -R4N(R5)(R5) group, and each of R4 and R5 is independently a C1-C10 hydrocarbyl group (preferably R4 is a C1-C3 group and each R5 is a C1-C3 group, more preferably a methyl group). The triazine of formula III may be added as a post-reactant, but the triazine may optionally be formed in situ, or the above reaction product may be formed in situ from the amine and formaldehyde or paraformaldehyde added as a post-reactant. Alternatively, trioxane may be used as a formaldehyde equivalent.

[0048] Without wishing to be limited by theory, it is believed that the triazine reacts with the unsulfurized alkylphenol (or sulfurized phenate) in the composition to form an alkylphenol derivative having, for example, amino, polyamino, and / or alkylamino substitution. For example, the following simplified reaction scheme III shows an exemplary post-processing that may occur with the additives herein, in which a triazine compound of formula III reacts with the unsulfurized / residual alkylphenol of the sulfurized phenate detergent / composition to form an alkylphenol derivative of formula II:

[0049] [ka] wherein each R1 is independently an alkyl group, an aryl group, an alkylaryl group, or an arylalkyl group (preferably a C8-C20 linear or branched hydrocarbyl or alkyl group, or a C12 linear or branched alkyl or hydrocarbyl group); R2 is hydrogen, an alkyl group (preferably a C1-C4 group, most preferably a C1 group), an alkylamino group, a dialkylaminoalkyl group, or -R4N(R5)(R5); R4 is a C1-C10 alkyl or hydrocarbyl group; each R5 is independently a C1-C4 alkyl group; R3 is as discussed above; and m is an integer of 0 or 1. In some approaches, suitable triazines include trimethyltriazine, (tris)dimethylaminopropyltriazine, (tris)monoethyltriazine, or mixtures thereof. In general, suitable triazines can be derived from any primary amine and formaldehyde or a formaldehyde equivalent, such as, for example, trioxane. The triazine post-reactant may also be reacted with a phenate in a similar reaction scheme to form residual amounts of the compound of formula Ib above.

[0050] In one approach, the post-treatment with triazine may involve adding up to about 10 weight percent of triazine, or about 0.5 to about 10 weight percent of triazine (in other approaches, about 1 to about 8 weight percent, or about 2 to about 6 weight percent of the desired triazine) to the sulfurized, neutralized, and optionally overbased phenate composition and reacting at a temperature of about 100° C. to about 230° C. (in other approaches, about 130° C. to about 150° C.) for about 1 to about 5 hours, or for a time effective to achieve the desired level of unsulfurized phenol / phenate. In yet another approach, the post-reaction may be at a weight ratio of phenate reactant mass to triazine of about 10:1 to about 20:1, and in other approaches, about 15:1 to about 18:1. However, the amount of triazine may vary depending on the residual unsulfurized phenol content of the reaction mixture. Excess triazine may be removed, if necessary, by heating to above about 230° C. under vacuum and / or through other suitable procedures.

[0051] In some approaches, after post-treatment, the compositions herein may contain about 75 weight percent or more of the compound of formula I discussed above (e.g., about 80 weight percent or more, about 90 weight percent or more, and in some approaches, about 80 to about 95 weight percent) and about 5 weight percent or less of the compound of formula II (e.g., about 0.01 to about 5 weight percent, about 0.1 to about 4 weight percent, or about 0.5 to about 3 weight percent), however, such amounts may vary depending on the circumstances, reactants, and starting materials. The methods, detergent compositions, and lubricating oil compositions containing such detergents herein have low to very low levels of unsulfurized or residual alkylphenols / phenates. In an approach, the detergent compositions and methods herein have less than about 0.5 weight percent, less than about 0.2 weight percent, less than about 0.1 weight percent, less than about 0.08 weight percent, or less than about 0.05 weight percent of unsulfurized alkylphenate / alkylphenol, or from about 0.01 to about 0.5 weight percent or any range therein. For example, the post-treatment is effective such that the detergent compositions herein contain an amount of unsulfurized alkylphenate / alkylphenol ranging from at least about 0.01 weight percent, at least about 0.02 weight percent, at least about 0.04 weight percent, at least about 0.05 weight percent, or at least about 0.08 weight percent to about 0.5 weight percent or less, about 0.2 weight percent or less, about 0.16 weight percent or less, about 0.12 weight percent or less, about 0.1 weight percent or less, about 0.08 weight percent or less, or even 0.05 weight percent or less of unsulfurized alkylphenol or phenate. Together, the cleaning compositions herein contain from about 75 to about 95 weight percent of the sulfurized alkylphenate of formula I and from about 0.01 to about 5 weight percent of the compound of formula II (or other ranges within such endpoints), however, the amounts of the various compounds can vary depending on the application and / or circumstances.

[0052] What is unique to the detergent compositions and methods herein is that unsulfurized alkylphenates or alkylphenols generally do not need to be removed (e.g., after sulfurization or after any intermediate steps) because the method steps herein consume and / or minimize any unsulfurized alkylphenols, do not regenerate unsulfurized alkylphenates or alkylphenols within any of the various process steps, and / or rather, post-treat any residual unsulfurized alkylphenols with triazines to tie up or combine any residual alkylphenols with the various reaction products of the phenate process herein. As such, the methods herein thus avoid the expense and complexity of prior methods that required removal of residual and / or unsulfurized alkylphenates / phenols either during intermediate or post-treatment steps of the process. Additionally, the sulfurized alkylphenates and detergent compositions herein of one or more of the compounds of Formula I, Formula II, and / or residual amounts of Formula III may also contain up to about 100,000 ppm of alkali metal or metal provided by alkaline metal and up to about 65,000 ppm of sulfur, as well as low levels of unsulfurized alkylphenols / phenates of up to about 0.5 weight percent as discussed above.

[0053] 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 or 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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 mixed diesel / biofuel-fueled engine, a mixed gasoline / biofuel-fueled engine, an alcohol fueled engine, a mixed gasoline / alcohol fueled 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.

[0058] 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 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 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 is about 0.8% by weight or less.

[0059] 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, A7 / B7, C1, C2, C3, C4, C5, C6, 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.The compositions may be suitable to meet original equipment manufacturer specifications such as STJLR.03.5004, STJLR.03.5005, 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.

[0060] 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.

[0061] [Table 1]

[0062] 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 should be 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.

[0063] 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.

[0064] 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, which 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.

[0065] 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.

[0066] 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.

[0067] 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, and derivatives, analogs, and homologs thereof, or mixtures thereof. The polyalphaolefins are typically hydrogenated materials.

[0068] 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 the Fischer-Tropsch reaction and typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oils may be prepared by the Fischer-Tropsch gas-liquid synthesis procedure, as well as other gas-liquid oils.

[0069] 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.

[0070] The amount of oil of lubricating viscosity present may be the remaining amount after subtracting the sum of the amounts of performance additives, including viscosity index improvers and / or pour point depressants and / or other top treatment additives, from 100% by weight. For example, the oil of lubricating viscosity 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.

[0071] 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.

[0072] Dispersants: The lubricating oil composition may optionally contain one or more dispersants or mixtures thereof. Dispersants are often referred to as ashless dispersants because they do not contain ash-forming metals prior to mixing into the lubricating oil composition and do not normally contribute 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).

[0073] 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).

[0074] 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 more than 28% by weight (e.g., >32% by weight) of total nitrogen and primary amine groups with an equivalent weight of 120 to 160 grams per gram equivalent.

[0075] 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%.

[0076] 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.

[0077] In some embodiments, the present disclosure further comprises at least one polyisobutylene succinimide dispersant derived from a polyisobutylene having a number average molecular weight in the range of 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.

[0078] 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%.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] Percent polyolefin conversion is calculated from the % actives using the formula in columns 5 and 6 of US Pat. No. 5,334,321.

[0083] 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.

[0084] 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.

[0085] A suitable class of nitrogen-containing dispersants may be derived from olefin copolymers (OCPs), more specifically ethylene-propylene dispersants that may be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that 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.

[0086] 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.

[0087] 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.

[0088] 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); Nos. 4,614,603 and 4,666,460; cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132, 4,647,390, 4,646,860, and 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent No. 2,440,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiocarbonates, etc. olactams, thiolactones, or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460); cyclic carbamates, cyclic thiocarbamates, or cyclic dithiocarbamates (e.g., U.S. Pat. Nos. 4,663,062 and 4,666,459); hydroxyaliphatic carboxylic acids (e.g., U.S. Pat. Nos. 4,482,464; 4,521,318; and 4,713,189); oxidizing agents (e.g., U.S. Pat. No. 4,379,064); combinations of phosphorus pentasulfide and polyalkylene polyamines (e.g., U.S. Pat. Nos. 4,379,064); , U.S. Pat. No. 3,185,647; combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chlorides (e.g., U.S. Pat. Nos. 3,390,086, 3,470,098); combinations of hydrazine and carbon disulfide (e.g., U.S. Pat. No. 3,519,564); combinations of aldehydes and phenols (e.g., U.S. Pat. Nos. 3,649,229, 5,030,249, 5,039,307); combinations of aldehydes and O-diesters of dithiophosphoric acids (e.g., U.S. Pat. No. 3,865,740);Combinations of hydroxyaliphatic carboxylic acids and boric acid (e.g., U.S. Pat. No. 4,554,086); combinations of hydroxyaliphatic carboxylic acids followed by formaldehyde and 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). The above-mentioned patents are hereby incorporated in their entirety;

[0089] The TBN of suitable dispersants may be from about 10 to about 65 mg KOH / g on an oil-free basis, which equates to about 5 to about 30 TBN when measured on a dispersant sample containing about 50% diluent oil. TBN is measured by the method of ASTM D2896.

[0090] 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 measured by GPC using polystyrene as the calibration standard.

[0091] In some approaches, the polyalkylene polyamine used to form the dispersant has the following formula:

[0092] [ka] where each R and R' is independently a divalent C1-C6 alkylene linker, and each R1 and R2 is independently hydrogen, a C1-C6 alkyl group, or together with the nitrogen atom to which they are attached form a 5- or 6-membered ring optionally fused to one or more aromatic or non-aromatic rings, and n is an integer from 0 to 8. In another approach, the polyalkylene polyamine is selected from the group consisting of a mixture of polyethylene polyamines having an average of 5 to 7 nitrogen atoms, triethylenetetramine, tetraethylenepentamine, and combinations thereof.

[0093] Dispersants, when present, may be used in an amount sufficient to provide up to about 20% by weight, based on the final weight of the lubricating oil composition. Alternative amounts of dispersant that may be used may be from about 0.1% to about 15% by weight, or from about 0.1% to about 10% by weight, or from about 0.1 to 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.

[0094] 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.

[0095] 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.

[0096] Useful antioxidants may include diarylamines and high molecular weight phenols. In an embodiment, the lubricating oil composition may contain a mixture of diarylamines and high molecular weight phenols, such that each antioxidant may be present in an amount sufficient to provide up to about 5 wt. %, based on the final weight of the lubricating oil composition. In an embodiment, the antioxidant may be a mixture of about 0.3 to about 1.5 wt. % diarylamines and about 0.4 to about 2.5 wt. % high molecular weight phenols, based on the final weight of the lubricating oil composition.

[0097] 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.

[0098] 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.

[0099] 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).

[0100] 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.

[0101] 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.

[0102] Further examples of suitable antiwear agents include titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (e.g., dibutyl phosphite), phosphonates, thiocarbamate-containing compounds such as thiocarbamate esters, thiocarbamate amides, thiocarbamic acid ethers, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides. The tartrates or tartrimides may contain alkyl-ester groups, but the total of carbon atoms on the alkyl group may be at least 8. The antiwear agent may, in one embodiment, include citrates.

[0103] 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.

[0104] 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. %, about 0.01 wt. % to about 7 wt. %, about 0.05 wt. % to about 5 wt. %, or about 0.1 wt. % to about 3 wt. % of the lubricating oil composition.

[0105] Additional detergents: The lubricating oil composition may optionally further comprise one or more neutral detergents, low-based detergents, 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-bound alkylphenol compounds, or methylene-bridged phenols. Suitable detergents and their preparation methods are described in more detail in numerous patent publications, including U.S. Pat. No. 7,732,390 and references cited therein.

[0106] 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 does not contain barium. In some embodiments, the detergent may contain trace amounts of other metals, such as magnesium or calcium, in amounts such as 50 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less, or 10 ppm or less. Suitable detergents 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.

[0107] 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.

[0108] 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.

[0109] 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.

[0110] 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.

[0111] The overbased calcium phenate detergents have a total base number of at least about 150 mg KOH / g, at least about 225 mg KOH / g, at least about 225 to about 400 mg KOH / g, at least about 225 to about 350 mg KOH / g, or about 230 to about 350 mg KOH / g, all measured by the method of ASTM D-2896. When such detergent compositions are formed in an inert diluent, such as a process oil, often 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.).

[0112] 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 from about 0 wt.% to about 10 wt.%, or from about 0.1 wt.% to about 8 wt.%, or from about 1 wt.% to about 4 wt.%, or from greater than about 4 wt.% to about 8 wt.%.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free mechanical friction modifiers. Such friction modifiers may include esters formed by reacting carboxylic acids and anhydrides with alkanols, and generally may include polar end groups (e.g., carboxyl or hydroxyl) covalently bonded to an oleophilic hydrocarbon chain. An example of an organic ashless nitrogen-free friction modifier is 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.

[0117] 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.

[0118] 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-alkyl borates. Other suitable friction modifiers are described in U.S. Patent No. 6,300,291, which is incorporated herein by reference in its entirety.

[0119] Friction modifiers may optionally be present in ranges such as from about 0% to about 10% by weight, or from about 0.01% to about 8% by weight, or from about 0.1% to about 4% by weight.

[0120] 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.

[0121] Suitable examples of molybdenum compounds that can be used include commercially available materials sold under trade names such as Molyvan 822™, Molyvan™ A, Molyvan 2000™, and Molyvan 855™ from R.T. Vanderbilt Co., Ltd., and Sakura-Lube™ S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 available from Adeka Corporation, and mixtures thereof. Suitable molybdenum components are described in U.S. Pat. No. 5,650,381, U.S. Reissue Pat. Nos. 37,363 (E1), 38,929 (E1), and 40,595 (E1), the entireties of which are incorporated herein by reference.

[0122] Additionally, the molybdenum compound can be an acidic molybdenum compound, including molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates, and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide, or similar acidic molybdenum compounds. 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] In some embodiments, the oil-soluble transition metal-containing compound may function as an antiwear agent, a friction modifier, an antioxidant, an adhesion control additive, or two or more of these functions. In some embodiments, the oil-soluble transition metal-containing compound may be an oil-soluble titanium compound, such as titanium (IV) alkoxide. Among the titanium-containing compounds that may be used in or for the preparation of oil-soluble materials in the technology of the present disclosure are various Ti (IV) compounds, such as titanium (IV) oxide; titanium (IV) sulfide; titanium (IV) nitrate; titanium (IV) alkoxides, such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide; and other titanium compounds or complexes, such as, but not limited to, titanium phenate; titanium carboxylates, such as titanium (IV) 2-ethyl-1,3-hexanedioate or titanium citrate or titanium oleate; and titanium (IV) (triethanolamino) 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.

[0127] 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 a lubricant or can be further reacted with a succinic dispersant 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 (30 g) can be further reacted with a succinimide dispersant from a polyisobutene-substituted succinic anhydride and polyethylene polyamine mixture (127 grams + diluent oil) at 150°C for 1.5 hours to produce a titanium modified succinimide dispersant.

[0128] Another titanium-containing compound is titanium alkoxide and C6-C 25 The reaction product may be a reaction product with a carboxylic acid. The reaction product has the following formula:

[0129] [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:

[0130] [ka] or the titanium compound may be represented by the formula:

[0131] [ka] (wherein x ranges from 0 to 3; R1 is selected from hydrocarbyl groups containing about 6 to 25 carbon atoms; R2 and R3 are the same or different and are selected from hydrocarbyl groups containing about 1 to 6 carbon atoms; R4 is H, C6 to C 25 The carboxylic acid moiety may be selected from the group consisting of

[0132] 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.

[0133] In some 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.

[0134] 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).

[0135] 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) with an amine, amine-functionalized polymethacrylates, or esterified maleic anhydride-styrene copolymers reacted with amines.

[0136] The total amount of viscosity index improver and / or dispersant viscosity index improver may be from about 0% to about 20%, from about 0.1% to about 15%, from about 0.1% to about 12%, or from about 0.5% to about 10% by weight of the lubricating oil composition.

[0137] 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.

[0138] 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.

[0139] 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.

[0140] Suitable suds suppressors include silicon-based compounds such as siloxanes.

[0141] 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.

[0142] 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.

[0143] 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.

[0144] Generally speaking, suitable lubricants containing the neutral to overbased sulfurized alkylphenate products herein may contain additive components in the ranges listed in the table below.

[0145] [Table 2]

[0146] 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 may be blended into the base oil individually or in various partial combinations. However, it may be preferred to blend all of the components simultaneously using an additive concentrate (i.e., additives plus a diluent such as a hydrocarbon solvent). Fully formulated lubricants conventionally contain an additive package, referred to herein as a dispersant / inhibitor package or DI package, that supplies the properties required in the formulation. EXAMPLES

[0147] 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.

[0148] For samples having unsulfurized alkylphenol / phenate levels of about 0.3 weight percent or greater, the concentration of unsulfurized alkylphenol / phenate was determined, for example, by reversed-phase High Performance Liquid Chromatography (HPLC). 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 acquisition 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. 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.

[0149] For samples of the present invention having low or very low levels of unsulfurized alkylphenates / alkylphenols (e.g., less than 0.2 weight percent), the above method is generally not sensitive enough to measure such low levels of unsulfurized alkylphenates / alkylphenols. Rather, measurements were modified using samples consistent with the above method but with a target phenate concentration of 5 mg / ml, 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, 100 mm x 2.1 mm ID column, and an Agilent MSD XT or equivalent device, as follows. For the sample measurements of the present invention, the following system settings were used in the analysis: column temperature 45°C, flow rate 0.3 ml / min, injection volume 3 μl, and run time 22 minutes. The MS system settings and conditions were as follows: ion source: ESI negative, mode SIM, gas temperature 300° C., gas flow rate 13 l / min, nebulizer 35 psi, capillary 3000 (v), 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.

[0150] Example 1 A commercially available calcium phenate (Afton Chemical) with a TBN of 250 and a residual level of unsulfurized tetrapropylene phenol (TPP) of about 1.5 weight percent was post-treated with methyltriazine using the following procedure: 500 grams of calcium phenate (starting TPP 1.5%) was placed in a 2 liter reactor and the temperature was then increased to about 120° C. About 125 grams of methyltriazine was then added and the mixture was allowed to react at about 150° C. for about 4 hours. Analytical results did not detect the presence of any residual or unsulfurized TPP.

[0151] Example 2 First, a calcium phenate product was prepared as follows: about 509 grams of tetrapropylene phenol (TPP), about 336 grams of a slurry made of Ca(OH)2 and base oil, about 60 grams of ethylene glycol, and about 85 grams of recycled base oil were placed in a 2-liter reactor. The reactor temperature was then increased to about 135°C and held for about 4 hours. About 125 grams of elemental sulfur was then placed in the reactor, and the temperature was increased to about 230°C and held for about 7 hours. After 7 hours of heating, the reaction was cooled to about 165°C, and then about 27 grams of neutral calcium sulfonate was added (providing a TBN of 150 and about 2.6 weight percent calcium), and about 438 grams of a slurry made of Ca(OH)2 and base oil were added. Finally, the composition was overbased by introducing carbon dioxide at a rate of about 0.5 liters / minute for about 5 hours and 30 minutes. The resulting product has a residual or unsulfurized TPP content of about 1.5%.

[0152] About half of the calcium phenate product was then placed in a 2 liter reactor and heated to about 150°C, and then about 20 grams of methyl triazine was added. The mixture was then reacted at about 150°C for about 2 hours with a nitrogen sweep. The temperature was then increased to about 200°C and held under full vacuum and nitrogen for about 1-2 hours, cooled to about 200°C, and filtered by vacuum and using Celite Hyflo Supercel. The resulting product has a residual or unsulfurized TPP content of about 0.23%.

[0153] 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 does not exclude other similar items that may be substituted for or added to the items in the list.

[0154] 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.

[0155] 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.

[0156] 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.

[0157] 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.

[0158] Furthermore, a specific amount / value of a component, compound, substituent, or parameter disclosed in the description or examples should be construed as a disclosure of either a lower or upper limit of a range and therefore can be combined with any other lower or upper limit 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.

[0159] 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 sulfurized metal phenate detergent comprising a compound of formula I and a compound of formula II, 【Chemistry 1】 During the ceremony, Each R １ is independently an alkyl group, an aryl group, an alkylaryl group, or an arylalkyl group; R ２ is hydrogen, an alkyl group, an alkylamino group, or a hydroxyalkyl group; x is an integer from 1 to 4; n is an integer from 1 to 3; m is an integer of 0 or 1; M ２＋ is a divalent metal ion.

2. R １ is a C8 to C20 alkyl group, and / or R ２ is methyl or R ２ But, -R ４ N (R ５ ) (R ５ wherein R ４ is a C1 to C10 hydrocarbyl group, and each R ５ The sulfurized metal phenate detergent of claim 1, wherein is independently a C1 to C4 alkyl group.

3. 2. The sulfurized metal phenate detergent of claim 1, wherein said detergent comprises from about 0.01 to about 0.5 weight percent of said compound of formula II.

4. 2. The sulfurized metal phenate detergent of claim 1 further comprising up to about 0.5 weight percent of an unsulfurized alkylphenol.

5. 2. The sulfurized metal phenate detergent of claim 1, wherein said detergent has a TBN of 0 to 300 mg KOH as measured by the method of ASTM D-2896.

6. The compound of formula I, the compound of formula II, or both each have less than about 15 weight percent R １ 2. The sulfurized metal phenate detergent of claim 1 having a substitution.

7. 2. The sulfurized metal phenate detergent of claim 1, wherein the detergent comprises up to about 100,000 ppm of the metal provided by an alkali or alkaline metal and up to about 65,000 ppm of sulfur, and / or the alkali or alkaline metal is one of lithium, potassium, sodium, magnesium, calcium, barium, aluminum, or combinations thereof.

8. 1. A process for preparing a sulfurized alkylphenate product comprising: sulfurizing an alkylphenol with a sulfur source to provide a sulfurized alkylphenol, said alkylphenol being derived from the alkylation of phenol; and neutralizing and optionally overbasing said sulfurized alkylphenol in the presence of a solvent to provide a sulfurized alkylphenate composition comprising a mixture of sulfurized alkylphenate and residual unsulfurized alkylphenol, said sulfurizing, neutralizing, and optional overbasing may be performed in any order; post-treating the sulfurized alkylphenate composition to obtain the sulfurized alkylphenate product, said post-treating comprising reacting the sulfurized alkylphenate composition with a triazine compound.

9. 9. The process for preparing a sulfurized alkylphenate product according to claim 8, wherein 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 0.1 to about 3.

5.

10. 9. The process for preparing a sulfurized alkylphenate product according to claim 8, wherein said neutralizing and / or optional overbasing comprises contacting said sulfurized alkylphenol with an alkali metal salt or an alkaline earth metal salt.

11. 11. The process for preparing a sulfurized alkylphenate product according to claim 10, 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.

12. The triazine compound has the structure of Formula III: 【Chemistry 2】 In the formula, each R ３ are independently hydrogen, a hydrocarbyl group, an alkyl group, an amino group, a polyamino group, an alkylamino group, a dialkylaminoalkyl group, a C1 to C10 hydrocarbyl group, or -R ４ N (R ５ ) (R ５ ) group, R ４ and R ５ 9. The process for preparing a sulfurized alkylphenate product according to claim 8, wherein each of is independently a C1 to C10 hydrocarbyl group.

13. and / or said sulfurized alkylphenate product comprises a compound of formula I and a compound of formula II, 【Chemistry 3】 During the ceremony, Each R １ is independently an alkyl group, an aryl group, an alkylaryl group, or an arylalkyl group; R ２ is an alkyl group, an aminoalkyl group, or a hydroxyalkyl group, x is an integer from 1 to 4; n is an integer from 1 to 3; m is an integer of 0 or 1; M ２＋ 9. The process for preparing the sulfurized alkylphenate product of claim 8, wherein is a divalent metal ion.

14. R １ is a C8 to C20 alkyl group, and / or R ２ is methyl or -R ４ N (R ５ ) (R ５ wherein R ４ is a C1 to C10 hydrocarbyl group, and each R ５ 14. The process for preparing a sulfurized metal phenate product according to claim 13, wherein is independently a C1 to C4 alkyl group.

15. 9. A sulfurized metal phenate detergent prepared by the process of claim 8.

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