Sulfurized additives with low levels of alkylphenols

Abstract

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

Description

Technical Field

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

[0002] Metal salts of sulfurized alkylphenols, also referred to as alkylphenols, are often useful lubricant additives. When used in lubricants in automotive applications, these additives can act as, for example, detergents (dispersant), friction modifiers and / or dispersants, while providing an alkaline base to help neutralize the acids produced during automotive operation. Unsulfurized variants of alkylphenols or phenols have reduced utility and are often less desirable in lubricants for many reasons. Therefore, additive manufacturers seek to minimize the level of unsulfurized alkylphenols and / or alkylphenols in their additives. However, when the additive is also highly alkaline, current methods have one or more disadvantages when seeking to minimize the level of unsulfurized alkylphenol / phenol variants. 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 method, the compounds of Formula I and Formula II have a structure comprising:

[0004]

[0005] Each R 1 R is independently one of an alkyl group, an aryl group, an alkaryl group or an aralkyl group: 2 is one of 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+ It is a divalent metal ion.

[0006] In other embodiments or methods, the sulphurized metal phenate detergent described in the preceding paragraphs includes optional features or embodiments. These optional features or embodiments may include, in any combination: wherein R 1 is a C8 to C20 alkyl group: and / or wherein R 2 is methyl: and / or wherein R 2 With -R 4 N(R 5 )(R 5 ) structure, where R 4 is a C1 to C10 hydrocarbon group, and each R 5is independently a C1 to C4 alkyl group: and / or wherein the detergent comprises from about 0.01 wt % to about 0.5 wt % of a compound of formula II; and / or further comprises about 0.5 wt % or less of an unsulfurized alkylphenol; and / or wherein the detergent has a TBN of 0 mg to 300 mg KOH as measured by the method of ASTM D-2896; and / or wherein the compound of formula I, the compound of formula II, or both each have less than about 15 wt % of R in the ortho position 1 and / or wherein the detergent comprises up to about 100,000 ppm of a metal provided by an alkali metal or alkaline earth metal and up to about 65,000 ppm of sulfur: and / or wherein the alkali metal or alkaline earth metal is one of lithium, potassium, sodium, magnesium, calcium, barium, aluminum or a combination thereof.

[0007] In another embodiment, a lubricating oil composition comprises the metal phenate detergent of any embodiment of the two preceding paragraphs and one or more base oils of lubricating viscosity.

[0008] In yet another embodiment, a process for preparing a sulfurized alkylphenate product is described. In the process, the process comprises, in any order, sulfurizing an alkylphenol with a sulfur source to provide a sulfurized alkylphenol, wherein 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, wherein the sulfurization, neutralization, and optional overbasing may be performed in any order; and post-processing the sulfurized alkylphenate composition to obtain a sulfurized alkylphenate product, wherein the post-processing comprises reacting the sulfurized alkylphenate composition with a triazine compound.

[0009] In yet other embodiments or methods, the method of the preceding paragraph may include optional features or embodiments. These optional features may include one or more of the following embodiments, in any combination: wherein the sulfur source comprises elemental sulfur, sulfur monochloride, sulfur dichloride, hydrogen sulfide, sulfur dioxide, sulfide hydrate, or a combination thereof; and / or wherein the molar ratio of the sulfur source to the alkylphenol is from about 0.1 to about 3.5; and / or wherein the neutralization, and / or optional overbasing comprises contacting the sulfurized alkylphenol with an alkali metal salt or an alkaline earth metal salt; and / or wherein 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 wherein the triazine compound has a structure of formula III

[0010]

[0011] Each R 3are independently hydrogen, a hydrocarbon group, an alkyl group, an amino group, a polyamino group, an alkylamino group, a dialkylaminoalkyl group, a C1 to C10 hydrocarbon group, or -R 4 N(R 5 )(R 5 ) group, wherein R 4 and R 5 Each independently is a C1 to C10 hydrocarbyl group: and / or further comprises about 0.5 wt% or less of unsulfurized alkylphenol; and / or wherein the sulfurized alkylphenol salt product comprises a compound of formula I and a compound of formula II:

[0012]

[0013] Each R 1 are independently an alkyl group, an aryl group, an alkaryl group or an aralkyl 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 from 0 or 1; and M 2+ is a divalent metal ion; and / or wherein R 1 is a C8 to C20 alkyl group. And / or wherein R 2 is methyl or has the structure -R 4 N(R 5 )(R 5 ), where R 4 is a C1 to C10 hydrocarbon group and each R 5 are independently C1 to C4 alkyl groups.

[0014] In yet other embodiments, described herein are sulphurized metal phenate detergents prepared by the method of any of the embodiments of the previous two paragraphs.

[0015] In yet further embodiments, described herein is the use of a sulfurized metal phenate composition as a detergent, wherein the sulfurized metal phenate composition is any embodiment as described in this disclosure.

[0016] The following definitions of terms are provided to clarify the meaning of certain terms as used herein.

[0017] The terms "oil composition," "lubricating composition," "lubricating oil composition," "lubricating oil," "lubricating oil," "lubricant composition," "fully formulated lubricant composition," and "lubricant" are considered synonymous and fully interchangeable terms to refer to a finished lubricating product comprising a major amount of base oil plus a minor amount of an additive composition.

[0018] As used herein, the terms "additive package," "additive concentrate," and "additive composition" are considered synonymous, fully interchangeable terms referring to that portion of a lubricating oil composition that does not include a major amount of a base oil stock blend.

[0019] Unless otherwise indicated, the term "overbased" refers to metal salts, such as metal salts of sulfonates, carboxylates, salicylates and / or phenolates, in which the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level exceeding 100% (i.e., they may contain 100% of the theoretical amount of metal required to convert the acid into its "normal", "neutral" salt). The expression "metal ratio" is usually abbreviated as MR, which is used to represent the ratio of the total chemical equivalents of the metal in the overbased salt to the chemical equivalents of the metal in the neutral salt, based on known chemical reactivity and stoichiometry. In normal or neutral salts, the metal ratio is one, while in overbased salts, MR is greater than one. They are often referred to as overbased, superbased or superbasic salts, and may be salts of organic sulfuric acid, carboxylic acid, salicylic acid, sulfonic acid and / or phenol.

[0020] 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.

[0021] As used herein, unless otherwise indicated, the term "hydrocarbyl" or "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense, which is well 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 predominantly hydrocarbon character. Each hydrocarbyl group is independently selected from a hydrocarbon substituent and a hydrocarbon substituent containing one or more halogen groups, hydroxyl groups, alkoxy groups, mercapto groups, nitro groups, nitroso groups, amino groups, pyridyl groups, furanyl groups, imidazolyl groups, oxygen and nitrogen substitutions, and wherein there are no more than two non-hydrocarbon substituents for every ten carbon atoms in the hydrocarbyl group.

[0022] As used herein, unless otherwise indicated, the term "alkylene substituent" or "alkylene group" is used in its ordinary sense, which is well known to those skilled in the art. Specifically, it refers to a group that is directly attached to the remainder of the molecule at two positions in the molecule through carbon atoms and has predominantly hydrocarbon characteristics. Each alkylene group is independently selected from a divalent hydrocarbon substituent, and a substituted divalent hydrocarbon substituent containing the following: a halo group, an alkyl group, an aryl group, an alkaryl group, an aralkyl group, a hydroxyl group, an alkoxy group, a thiol group, a nitro group, a nitroso group, an amino group, a pyridyl group, a furyl group, an imidazolyl group, oxygen and nitrogen, and wherein there are no more than two non-hydrocarbon substituents for every ten carbon atoms in the alkylene group.

[0023] Unless otherwise specifically stated, as used herein, the term "weight %" refers to the percentage of the component by weight of the entire composition.

[0024] The terms "soluble", "oil-soluble" or "dispersible" as used herein may, but do not necessarily, mean that the compound or additive is soluble, dissolvable, miscible or capable of being suspended in oil in all proportions. However, the aforementioned terms do mean that they are, for example, soluble, suspendable, dissolvable or stably dispersible in oil to a sufficient extent to exert their intended effect in the environment in which the oil is employed. In addition, the additional incorporation of other additives may also allow for the incorporation of higher levels of a particular additive, if desired.

[0025] As used herein, the term "TBN" is used to denote Total Base Number in mg KOH / g as measured by the method of ASTM D2896.

[0026] The term "lime" as used herein refers to compounds such as calcium hydroxide, calcium oxide, etc., also known as slaked lime or hydrated lime.

[0027] Unless otherwise stated, the term "alkyl" as used herein refers to a straight chain, branched chain, cyclic and / or substituted saturated chain portion having from about 1 to about 100 carbon atoms. Unless otherwise stated, the term "alkenyl" as used herein refers to a straight chain, branched chain, cyclic and / or substituted unsaturated chain portion having from about 3 to about 10 carbon atoms. Unless otherwise stated, the term "aryl" as used herein refers to monocyclic and polycyclic aromatic compounds, which may include alkyl, alkenyl, alkaryl, amino, hydroxyl, alkoxy, halogen substituents and / or heteroatoms, including but not limited to nitrogen, oxygen, and sulfur.

[0028] The molecular weight of any embodiment herein can be measured using an instrument such as a gel permeation chromatography (GPC) instrument obtained from Waters, and the data can be processed using software such as Waters Empower software. The GPC instrument can be equipped with a Waters separation module and a Waters refractive index detector (or similar optional equipment). GPC operating conditions can include a guard column, 4 Agilent PLgel columns (length 300×7.5 mm; particle size 5μ, and pore size range ), the column temperature is about 40 ° C. Unstabilized HPLC grade tetrahydrofuran (THF) can be used as a solvent with a flow rate of 1.0 mL / min. The GPC instrument can be calibrated with commercially available polystyrene (PS) standards with a narrow molecular weight distribution ranging from 500 g / mol to 380,000 g / mol. For samples with a mass of less than 500 g / mol, the calibration curve can be extrapolated. Samples and PS standards can be dissolved in THF and prepared at a concentration of 0.1 wt % to 0.5 wt % and used without filtering. GPC measurements are also described in US 5,266,223, which is incorporated herein by reference. The GPC method also provides molecular weight distribution information; see, for example, WW Yau, JJ Kirkland and DD Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979, which is also incorporated herein by reference.

[0029] Additional details and advantages of the present disclosure will be partially set forth in the following description, and / or may be learned by practicing the present disclosure. The details and advantages of the present disclosure may be realized and obtained by the elements and combinations specifically pointed out in the appended claims. It should be understood that the above general description and the following detailed description are only exemplary and explanatory, and do not limit the present disclosure as claimed. DETAILED DESCRIPTION

[0030] The present disclosure provides detergent additives in the form of compositions or mixtures comprising at least one sulfurized alkyl phenol salt having low levels of residual or unsulfurized alkyl phenols; lubricating oil compositions comprising such detergent additives, and methods for preparing detergent additives in the context of neutral to high based 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 additionally about 100 to about 500, as discussed further below.

[0031] In one method or embodiment, the present disclosure is generally directed to a detergent additive or detergent composition comprising at least one sulfurized metal phenate detergent comprising a compound of Formula Ia, optionally a compound of Formula Ib, and a compound of Formula II:

[0032]

[0033] Each R 1 are independently an alkyl group, an aryl group, an alkaryl group or an aralkyl group (preferably, R 1is a C8 to C20 alkyl or hydrocarbyl group, and most preferably a C12 straight or branched alkyl or hydrocarbyl group); R 2 is one of 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 of 0 or 1; and M 2+ is a divalent metal ion. Preferably, R 1 The group is primarily located in the para position on the aromatic ring, as discussed in more detail below. The Mannich reaction to form the post-reactant amine (discussed in detail below) to generate the compound of Formula Ia, Formula Ib and / or Formula II can be carried out through any open ortho, meta or para position on the aromatic ring, but the amine reaction is preferably located in the ortho position as shown in the above structure. As also shown above, the sulfur bridge in Formula Ia or Formula Ib is primarily in the ortho position, but can be at other positions on the aromatic ring depending on the application and / or reaction conditions. Depending on the application, the Mannich reaction to form the post-reactant amine can also produce a diaddition to the aromatic ring (e.g., ortho and para, ortho and meta, or meta and para).

[0034] High alkalinity sulfurized alkylphenol salt is prepared by sulfurization, neutralization and / or carbonation. These reactions can be carried out in any order, simultaneously or according to application in a specific order. Sulfurization and neutralization, for example and in any order or simultaneously, are usually completed before carbonation. Generally speaking, the detergent additive or composition of this article is obtained by: first neutralizing alkylphenol, then sulfurizing the neutralized alkylphenol with a sulfur source to provide sulfurized and neutralized alkylphenol. Then the sulfurized and neutralized alkylphenol is optionally overbased in the presence of a solvent to provide a neutral to optionally overbased and sulfurized alkylphenol salt additive or composition. Then the post-processing of the additive / composition is carried out in the presence of a triazine compound, and the amount of the triazine compound effectively reduces the level of unsulfurized or residual alkylphenol / phenate variant to a low or ultra-low level of about 0.5 weight % or lower (in some methods, about 0.2 weight % or lower, and in other methods, about 0.1 weight % or lower). The triazine compound reacts with the phenoxide and / or unsulfurized alkylphenol via a Mannich reaction and alternatively can also be generated in situ via an amine and formaldehyde or paraformaldehyde post-reactant. Further details of the additives and methods of producing such additives are discussed below.

[0035] Alkylation of phenol

[0036] The sulfurized alkylphenol salts of the detergent compositions herein are first obtained by alkylation of a suitable phenolic (or hydroxyaromatic) compound with one or more olefins and / or oligomers derived from olefins. Suitable phenolic or hydroxyaromatic compounds include monohydroxy and / or polyhydroxy aromatic hydrocarbons having 1 to 4, and in some methods 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.

[0037] Alkylating agent comprises one or more olefins and / or oligomers derived from olefins selected from ethylene, propylene, butylene, isobutylene or their mixture. Suitable olefins include isobutylene, propylene trimer and / or tetramer, butene trimer and / or tetramer, just to name a few examples, but other olefins may be present in oligomers or alkyl groups, such as straight chain olefins, cycloolefins, branched olefins other than propylene oligomers, such as butene or isobutylene oligomers, aryl alkylenes, etc. and their mixtures. Alkylation can be carried out in the presence of catalysts such as Lewis acid catalysts, solid acid catalysts, trifluoromethanesulfonic acid and other acidic molecular sieve catalysts. Exemplary Lewis acid catalysts are known to those skilled in the art, and may include aluminum chloride, aluminum tribromide, aluminum triiodide, boron trifluoride, boron tribromide, boron triiodide, etc. In some methods, the molar ratio of phenol or hydroxy aromatic compound to one or more olefins or oligomers can be about 10:1 to about 0.5:1, and in other methods, about 5:1 to about 2:1. The oligomer alkyl group is usually attached to the phenol or hydroxy aromatic compound in the ortho and / or para position, preferably in the para position, but other substitutions may also be present depending on the application. For example, the oligomer alkyl group (i.e., R in the formula herein) 1 The substituents) may be from about 85% to about 100% in the para position on the aromatic ring and from about 0% to about 15% in the ortho position on the aromatic ring, and in some methods from about 0% to about 5% are disubstituted.

[0038] Neutralization

[0039] Neutralization is performed by reacting the alkylphenol with a metal base. In one method, neutralization is performed by contacting the alkylphenol with a metal base under reaction conditions, and in some methods with a promoter in a liquid hydrocarbon diluent to provide a phenolate or salt of the alkylhydroxyaromatic compound. In some cases, the reaction can be carried out under an inert gas such as nitrogen. If required for certain applications, the metal base can be added at different times during the reaction in a single addition or multiple additions. Neutralization can be performed via the exemplary reaction scheme I shown below, but other reactions can be performed as needed depending on the selected order of sulfurization, neutralization, and / or overbasing and various applications, materials and conditions:

[0040]

[0041] Exemplary metal base reactants include hydroxides, oxides or alkoxides of metals, such as but not limited to alkali metal salts derived from metal bases selected from alkali metal hydroxides, alkali metal oxides or alkali metal alkoxides, or alkaline earth metal salts derived from metal bases selected from alkaline earth metal hydroxides, alkaline earth metal oxides or alkaline earth metal alkoxides. Suitable metal 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 alkaline compounds include lithium oxide, magnesium oxide, calcium oxide and barium oxide. In preferred examples, the alkaline earth metal base is lime or calcium hydroxide. Additives can be borated as needed according to application and use.

[0042] In an optional method, the neutralizing solvent is a higher boiling point, such as a solvent having a boiling point of about 100° C. or higher at the pressure, such as solvents such as ethylene glycol, propylene glycol, and / or decanol. In such optional methods and as used herein, lacking or being free of such compounds means that the solvent has less than about 15 wt%, less than about 5 wt%, less than about 2 wt%.

[0043] The neutralization reaction between the metal base and the alkylphenol is carried out under conditions effective to maintain an elevated temperature. In one method, the neutralization is carried out at a temperature of at least 100° C., in some methods, at a temperature of at least about 120° C., in other methods, at a temperature of at least about 150° C., and in still preferred methods, at a temperature of no greater than about 180° C. The neutralization reaction can be carried out for a duration of about 1 hour to about 5 hours.

[0044] vulcanization

[0045] The neutralized alkylphenol or alkylhydroxyaromatic compound can be sulfurized by contacting it with a sulfur source in a manner effective to achieve a high degree of sulfurization. In the process, sulfurization generally introduces sulfur bridging groups between the alkylphenol or alkylhydroxyaromatic moieties. In some processes, the sulfur bridge is -S y -or-S x -group (shown in the following exemplary structure), wherein y or x is independently an integer from 1 to 4, and in other methods is an integer from 1 to 3, and in some methods is an integer from 1 to 2, and / or wherein the total sulfur level provided by the additive is up to about 5%. The sulfur source can be any suitable sulfur, for example elemental sulfur or its halides such as sulfur monochloride or sulfur dichloride, hydrogen sulfide, sulfur dioxide and sodium sulfide hydrate. Sulfur can be used as molten sulfur or as a solid (powder or granules) or as a solid suspension in a hydrocarbon liquid. An exemplary reaction scheme for sulfurization is shown in the following reaction scheme II, but other reactions can be performed as needed depending on the application, materials and conditions.

[0046]

[0047] Vulcanization can be carried out, for example, at a temperature of about 200° C. to about 250° C., in other methods, at a temperature of about 225° C. to about 245° C. for a time effective to achieve the desired level of vulcanization, which can be about 1 hour to about 8 hours, about 2 hours to about 7 hours, or about 4 hours to about 7 hours.

[0048] Over-alkalization

[0049] Then, overbasing is optional, but is preferred in some embodiments, and during the above-mentioned neutralization, and / or sulfurization or alternatively after the above-mentioned neutralization, and / or sulfurization, carry out. In one method, by reacting with excessive metal base and / or with acidic overbasing compounds such as for example carbon dioxide or boric acid, the alkylphenol / alkylphenol salt of sulfurization is overbased. In one method, overbasing is in the presence of a solvent via carbonation (reaction with carbon dioxide) and neutralization, and this solvent is such as any solvent from the above-mentioned solvent system. A 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 by distillation as required during the reaction or after the reaction, as discussed further below.

[0050] In one embodiment, exemplary overbasing reaction can be to react sulfided alkylphenol or its salt with alkali metal or alkaline earth metal such as lime in the presence of carbon dioxide and solvent system as discussed above. Conveniently, reaction can be carried out by bubbling gaseous carbon dioxide through reaction and solvent system mixture. In one method, overbasing is carried out at a temperature of at least about 50 ℃, in some methods, at a temperature of at least about 100 ℃, in other methods, at a temperature of at least about 165 ℃, and in still preferred methods, at a temperature of not more than about 185 ℃. The degree of overbasing can be controlled by the amount of alkali metal or alkaline earth metal added to the reaction mixture, the amount of carbon dioxide and other reactants (if any) and the reaction conditions used during the carbonation process. In the method, at the temperature, overbasing or overbasing via carbonation is carried out for a time sufficient to achieve the desired degree of overbasing or TBN, and in some methods can be about 30 minutes to about 180 minutes.

[0051] After optional overbasing, overbased and sulfurized alkylphenol salts, such as the detergent compositions herein, can 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, and in yet other approaches, from about 200 to about 300, and in yet other approaches, from about 220 to about 275. Preferably, the TBN of the compositions herein can be from about 100 mg to about 300 mg KOH, as measured by ASTM D-2896. After optional overbasing, neutralization, and sulfurization, the resulting product can also have a residual or unsulfurized alkylphenol level of about 1.0 wt % or more, in other approaches about 1.5 wt % or more, and in yet other approaches about 0.5 wt % or more. As discussed further below, post-processing herein is effective to reduce such levels of residual or unsulfurized alkylphenol content in the detergents herein.

[0052] Post-processing

[0053] After optional overbasing, the composition is typically subjected to a number of steps to produce the final sulfurized alkylphenate product. Examples of post-processing may 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.

[0054] As discussed above, additives and compositions after sulfurization, neutralization, and optional overbasing may include undesirably large amounts of unsulfurized or residual alkylphenols or phenates. A preferred post-processing step herein is to further react or post-treat the sulfurized alkylphenol composition with a triazine post-treatment reactant in any of the embodiments discussed previously and after sulfurization, neutralization, and optional overbasing to minimize and further reduce any residual or unsulfurized alkylphenol / phenate within the composition.

[0055] In the process, suitable triazine reactants for post-processing may include any triazine or substituted triazine (or mixtures thereof) that can react with a phenolic compound, and in particular a triazine of the following formula III that can react with a phenolic compound:

[0056]

[0057] Each R 3 independently hydrogen, a hydrocarbon group, an alkyl group, an amino group, a polyamino group, an alkylamino group, a dialkylaminoalkyl group, a hydroxyalkyl group, and may be a C1 to C20 hydrocarbon group (optionally, a C1 to C10 or C1 to C4 group) or -R4 N(R 5 )(R 5 ) group, wherein R 4 and R 5 Each independently is a C1 to C10 hydrocarbon group (preferably, R 4 is a C1 to C3 group, and each R 5 is a C1 to C3 group, and more preferably a methyl group). Although the triazine of formula III can be added as a post-reactant, the triazine can optionally be formed in situ, or the above reaction product can be formed in situ from the amine and formaldehyde or paraformaldehyde added as a post-reactant. Alternatively, trioxane can be used as the formaldehyde equivalent.

[0058] Without being bound 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 substitutions. For example, the following simplified reaction scheme III shows an exemplary post-processing that is believed to occur with the additives herein, wherein 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:

[0059]

[0060] Each R 1 R is independently an alkyl group, an aryl group, an alkaryl group or an aralkyl group (preferably, a C8 to C20 straight chain or branched chain hydrocarbon group or alkyl group, or a C12 straight chain or branched chain alkyl group or hydrocarbon group): 2 is hydrogen, an alkyl group (preferably a C1 to C4 group, and most preferably a C1 group), an alkylamino group, a dialkylaminoalkyl group or -R 4 N(R 5 )(R 5 ), where R 4 is a C1 to C10 alkyl or hydrocarbon group, and each R 5 R is independently a C1 to C4 alkyl group: 3 As discussed above, and m is an integer of 0 or 1. In some methods, suitable triazines include trimethyltriazine, (tri) dimethylaminopropyl triazine, (tri) monoethyl triazine or mixtures thereof. In general, suitable triazines can be obtained from any primary amine and formaldehyde or formaldehyde equivalents (e.g., trioxane, etc.). The triazine post-reactant can also be reacted with a phenolate in a similar reaction scheme to form a residual amount of the compound of formula Ib above.

[0061] In some methods, post-processing with triazine may include adding up to about 10 wt % triazine, or about 0.5 wt % to about 10 wt % triazine (in other methods, about 1 wt % to about 8 wt %, or about 2 wt % to about 6 wt % 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 methods, about 130° C. to about 150° C.) for about 1 hour to about 5 hours or for a time effective to obtain the desired level of unsulfurized phenol / phenate. In still other methods, the post-reaction may be a weight ratio of phenate reaction materials to triazine of about 10:1 to about 20:1, and in other methods, about 15:1 to about 18:1. However, the amount of triazine may vary depending on the residual unsulfurized phenol content in the reaction mixture. If desired, excess triazine may be removed by heating to about 230° C. or higher under vacuum and / or by other suitable procedures.

[0062] In the method and after post-processing, the composition of the present invention may contain about 75% by weight or more of the compound of formula I discussed above (such as about 80% by weight or more, about 90% by weight or more, and in some methods, about 80% by weight to about 95% by weight) and about 5% by weight or less of the compound of formula II (such as about 0.01% by weight to about 5% by weight, about 0.1% by weight to about 4% by weight or about 0.5% by weight to about 3% by weight); however, such amounts may vary depending on the circumstances, reactants and starting materials. The method, detergent composition and lubricating oil composition with such detergent herein have low to ultra-low levels of unsulfurized or residual alkylphenol / phenolate. In the method, the detergent composition and method herein have less than about 0.5% by weight, less than about 0.2% by weight, less than about 0.1% by weight, less than about 0.08% by weight or less than about 0.05% by weight of unsulfurized alkylphenol / alkylphenol or about 0.01 to about 0.5% by weight or any range thereof of unsulfurized alkylphenol / alkylphenol. For example, post-processing is effective so that the detergent composition herein includes an amount of unsulfurized alkylphenol / alkylphenol ranging from at least about 0.01 wt%, at least about 0.02 wt%, at least about 0.04 wt%, at least about 0.05 wt%, or at least about 0.08 wt% to no more than about 0.5 wt%, no more than about 0.2 wt%, no more than about 0.16 wt%, no more than about 0.12 wt%, no more than about 0.1 wt%, no more than about 0.08 wt%, or even no more than 0.05 wt% of unsulfurized alkylphenol or phenate. At the same time, the detergent composition herein contains about 75 wt% to about 95 wt% of the sulfurized alkylphenol of Formula I and about 0.01 wt% to about 5 wt% of the compound of Formula II (or other ranges within such endpoints); however, the amount of each compound can vary depending on the application and / or circumstances.

[0063] The detergent compositions and methods herein are unique in that unsulfurized alkylphenol salts or alkylphenols generally do not need to be removed (such as after sulfurization or after any intermediate steps) because the method steps herein consume and / or minimize any unsulfurized alkylphenol, do not regenerate unsulfurized alkylphenol salts or alkylphenols within any various process steps, and / or more specifically, post-treat any remaining unsulfurized alkylphenol with triazines to allow any remaining alkylphenol to bind or bond with the various reaction products of the phenate process herein. Thus, the methods herein avoid the expense and complexity of prior methods, which require the removal of residual and / or unsulfurized alkylphenol salts / phenols in the middle of the process or during post-processing steps. In addition, the detergent compositions herein of sulfurized alkylphenol salts and one or more compounds of Formula I, Formula II and / or residual amounts of Formula III may also contain up to about 100,000 ppm of metal provided by an alkali metal and up to about 65,000 ppm of sulfur and low levels of unsulfurized alkylphenol / phenol salts of about 0.5 wt % or less as discussed above.

[0064] Lubricating oil composition

[0065] The optionally overbased and sulfurized alkylphenol products described herein may be combined with one or more additional optional additives, 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 the methods, the lubricating oil composition comprises from about 50 wt % or more of a base oil blend, from about 60 wt % or more, from about 70 wt % or more, or from about 80 wt % or more to about 95 wt % or less, from about 90 wt % or less, from about 85 wt % or less of a base oil blend, the blends being discussed further below.

[0066] In some approaches, the lubricating oil compositions herein may comprise from about 0.02 wt. % to about 5 wt. %, in other approaches, from about 0.2 wt. % to about 3 wt. %, and in still other approaches, from about 0.2 wt. % to about 2 wt. % of the optionally overbased and sulfurized alkyl phenate product in the base oil or base oil blend.

[0067] In some methods, the additives herein can be used as detergents in lubricating oils to neutralize acids and / or help control rust, corrosion and deposits. In addition, the detergents described herein can also be used in fuels, including but not limited to gasoline, diesel, biodiesel, for spark, compression and hybrid engines.

[0068] The lubricants, combinations of components, dispersant inhibitor packages and / or individual components described herein may be suitable for use in various types of lubricants, such as automotive lubricants and / or greases, internal combustion engine oils, blended engine oils, hybrid engine oils, electric engine lubricants, driveline 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 breaking fluids, and the like.

[0069] Suitable engine types may include, but are not limited to, heavy-duty diesel engines, passenger cars, light diesel engines, medium-speed diesel engines or marine engines. The internal combustion engine may be a diesel fuel engine, a gasoline fuel engine, a natural gas fuel engine, a biofuel engine, a mixed diesel / biofuel fuel engine, a mixed gasoline / biofuel fuel engine, an alcohol fuel engine, a mixed gasoline / alcohol fuel engine, a compressed natural gas (CNG) fuel engine or a mixture 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 a power source or a battery power source. Such a constructed engine is generally referred to as a hybrid engine. The internal combustion engine may be a 2-stroke, 4-stroke or rotary engine. Suitable internal combustion engines include marine diesel engines (such as inland marine), aviation piston engines, low-load diesel engines and motorcycles, automobiles, locomotives and truck engines. The engine may be coupled to a turbocharger.

[0070] Regardless of sulfur, phosphorus or sulfated ash (ASTM D-874) content, the lubricating oil composition for internal combustion engines can be suitable for any engine lubricant. The sulfur content of the engine oil lubricant can be about 1 weight % or less, or about 0.8 weight % or less, or about 0.5 weight % or less, or about 0.3 weight % or less, or about 0.2 weight % or less. In one embodiment, the sulfur content can be in the range of about 0.001 weight % to about 0.5 weight %, or about 0.01 weight % to about 0.3 weight %. The phosphorus content can be about 0.2 weight % or less, or about 0.1 weight % or less, or about 0.085 weight % or less, or about 0.08 weight % or less, or even about 0.06 weight % or less, about 0.055 weight % or less, or about 0.05 weight % or less. In one embodiment, the phosphorus content can be about 50ppm to about 1000ppm, or about 325ppm to about 850ppm. The total sulfated ash content can be about 2 wt % or less, or about 1.5 wt % or less, or about 1.1 wt % or less, or about 1 wt % or less, or about 0.8 wt % or less, or about 0.5 wt % or less. In one embodiment, the sulfated ash content can be about 0.05 wt % to about 0.9 wt %, or about 0.1 wt % or about 0.2 wt % to about 0.45 wt %. In another embodiment, the sulfur content can be about 0.4 wt % or less, the phosphorus content can be about 0.08 wt % or less, and the sulfated ash can be about 1 wt % or less. In another embodiment, the sulfur content can be about 0.3 wt % or less, the phosphorus content can be about 0.05 wt % or less, and the sulfated ash can be about 0.8 wt % or less.

[0071] In addition, the lubricants of the present specification may be suitable for meeting 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-4Plus, CI-4, API SG, SJ, SL, SM, SN, 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 original equipment manufacturer specifications, such as DexosTM 1, DexosTM 2, MB-Approval 229.1, 229.3, 229.5, 229.51 / 229.31, 229.52, 229.6, 229.71, 226.5, 226.51, 228.0 / .1, 228.2 / .3, 228.31, 228.5, 228.51, 228.61, VW 501.01、502.00、503.00 / 503.01、504.00、505.00、505.01、506.00 / 506.01、507.00、508.00、509.00、508.88、509.99、BMW Longlife-01, Longlife-01FE, Longlife-04, Longlife-12FE, Longlife-14FE+, Longlife-17FE+, Porsche A40, C30, Peugeot 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, WS S-M2C913-C, WSS-M2C913-D, WSS-M2C948-B, WSS-M2C948-A, GM6094-M, Chrysler MS-6395、Fiat 9.55535G1, G2, M2, N1, N2, Z2, S1, S2, S3, S4, T2, DS1, DSX, GH2, GS1, GSX, CR1, Jaguar Land Rover STJLR.03.5003, STJLR.03.5004, STJLR.03.5005, STJLR.03.5006, STJLR.03.5007, STJLR.51.5122, or any past or future PCMO or HDD specification not mentioned herein. In some embodiments, for passenger car motor oil (PCMO) applications, the amount of phosphorus in the finished fluid is 1000 ppm or less, or 900 ppm or less, or 800 ppm or less.

[0072] Base oil or base oil blend The base oil used in the lubricating oil composition herein may be an oil of lubricating viscosity and is selected from any one of Group I to Group V base oils as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five base oil groups are generally listed in Table 1 below:

[0073] Table 1

[0074]

[0075] Class I, Class II and Class III are mineral oil processing raw materials.Class IV base oil contains real synthetic molecular substances, and these synthetic molecular substances are prepared by the polymerization of olefinically unsaturated hydrocarbons.Many Class V base oils are also real synthetic products, and can include diesters, polyol esters, polyalkylene glycols, alkylated aromatic compounds, polyphosphates, polyvinyl ethers and / or polyphenylene oxides etc., but can also be naturally occurring oils, such as vegetable oils.It should be noted that although Class III base oil is derived from mineral oil, the strict processing of these fluid experiences causes their physical properties to be very similar to some real synthetic oils, such as PAO.Therefore, the oil derived from Class III base oil can be called synthetic fluid in industry.The II+ class can include high viscosity index Class II.

[0076] The base oil blend used in the disclosed lubricating oil composition can be a mineral oil, an animal oil, a vegetable oil, a synthetic oil, a synthetic oil blend, or a mixture thereof. Suitable oils can be derived from hydrocracked, hydrogenated, hydrorefined, unrefined, refined and re-refined oils and mixtures thereof.

[0077] Unrefined oils are those derived from natural, mineral or synthetic sources with little or no further purification. Refined oils are similar to unrefined oils, except that they have been subjected to one or more purification steps, which may result in improvements in one or more properties. Examples of suitable purification techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Refining to edible quality oils may or may not be useful. Edible oils may also be referred to as white oils. In some embodiments, the lubricating oil composition does not contain edible oils or white oils.

[0078] Re-refined oils are also called reclaimed oils or reprocessed oils. Similar to refined oils, these oils are obtained using the same or similar processes. Typically these oils are further processed by techniques directed to the removal of spent additives and oil breakdown products.

[0079] Mineral oil can include oil obtained by drilling or oil from plants and animals or any mixture thereof. For example, such oil can include but is not limited to: castor oil, lard, olive oil, peanut oil, corn oil, soybean oil and linseed oil, and mineral lubricating oil, such as liquid petroleum and paraffins, cycloparaffins or mixed paraffin-cycloparaffins through solvent treatment or acid-treated mineral lubricating oil. If desired, such oil can be partially or completely hydrogenated. Oil derived from coal or shale can also be useful.

[0080] Useful synthetic lubricating oils may include hydrocarbon oils such as polymerized, oligomeric or copolymerized olefins (e.g., polybutene, polypropylene, propylene isobutylene copolymers); poly(1-hexene), poly(1-octene), 1-decene trimers or oligomers, such as poly(1-decene), such materials are generally 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. Polyalpha-olefins are typically hydrogenated materials.

[0081] Other synthetic lubricating oils include polyol esters, diesters, liquid esters (e.g., diethyl esters of toluene phosphate, trioctyl phosphate and decanephosphonic acid) or polytetrahydrofurans containing phosphoric acid. Synthetic oils can be produced by Fischer-Tropsch reaction and can generally be Fischer-Tropsch hydrocarbons or waxes of hydroisomerization. In one embodiment, oil can be prepared by Fischer-Tropsch gas-liquid synthesis procedures and other gas-liquid oils.

[0082] The major amount of base oil included in the lubricating composition may be selected from Group I, Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, and wherein the major amount of the base oil is different from the base oil resulting from providing an additive component or a viscosity index improver in the composition. In another embodiment, the major amount of base oil included in the lubricating composition may be selected from Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, and wherein the major amount of the base oil is different from the base oil resulting from providing an additive component or a viscosity index improver in the composition.

[0083] The amount of oil of lubricating viscosity present can be the balance remaining after subtracting the sum of the amounts of performance additives including viscosity index improvers and / or pour point depressants and / or other pre-treatment additives from 100 wt %. For example, the oil of lubricating viscosity that can be present in the finished fluid can be a major amount, such as greater than about 50 wt %, greater than about 60 wt %, greater than about 70 wt %, greater than about 80 wt %, greater than about 85 wt %, or greater than about 90 wt %.

[0084] Optional additives :

[0085] The lubricating oil compositions herein may also include a number of optional additives in combination with the optionally overbased and sulfurized alkyl phenate product as needed to meet performance criteria. Those optional additives are described in the following paragraphs.

[0086] Dispersants :The lubricating oil composition may optionally contain one or more dispersants or mixtures thereof. Dispersants are generally referred to as ashless dispersants because they do not contain ash-forming metals before being mixed into the lubricating oil composition, and they generally do not provide any ash when added to the lubricant. Ashless dispersants are characterized by polar groups attached to relatively high molecular weight hydrocarbon chains. Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimides, wherein the number average molecular weight of the polyisobutylene substituent is in the range of about 350 to about 50,000 or to about 5,000 or to about 3,000 as measured by GPC. Succinimide dispersants and their preparation are disclosed in, for example, U.S. Patent No. 7,897,696 or U.S. Patent No. 4,234,435. The alkenyl substituent can be prepared from polymerizable monomers containing about 2 to about 16, or about 2 to about 8, or about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines, usually poly(ethylene amines).

[0087] Preferred amines are selected from polyamines and hydroxylamines. Examples of polyamines that may be used include, but are not limited to, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA) and higher homologues such as pentaethylaminehexamine (PEHA) and the like.

[0088] Suitable heavy polyamines are mixtures of polyalkylene-polyamines containing small amounts of low polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine) but predominantly oligomers having 6 or more nitrogen atoms per molecule, 2 or more primary amines, and more extensive branching than conventional polyamine mixtures. Heavy polyamines preferably include polyamine oligomers containing 7 or more nitrogen atoms per molecule and having 2 or more primary amines per molecule. Heavy polyamines contain greater than 28 wt% (e.g., >32 wt%) total nitrogen and an equivalent weight of primary amine groups of 120 g / equivalent to 160 g / equivalent.

[0089] In some processes, suitable polyamines are generally referred to as PAMs and contain a mixture of ethyleneamines, with TEPA and pentaethylenehexamine (PEHA) being the major portion of the polyamine, typically less than about 80%.

[0090] Typically, PAM has 8.7 milliequivalents / gram to 8.9 milliequivalents / gram of primary amine (equivalent weight of primary amine is 115 to 112 grams / equivalent) and a total nitrogen content of about 33 to 34 weight percent. Heavier PAM oligomer cuts have little TEPA, only very small amounts of PEHA, but contain predominantly oligomers with more than 6 nitrogens and more extensive branching, producing dispersants with improved dispersibility.

[0091] In one embodiment, the present disclosure further comprises at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight in the range of about 350 to about 50,000 or to about 5000 or to about 3000 as determined by GPC. The polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0092] In some embodiments, polyisobutylene (when included) can have a terminal double bond content of greater than 50%, greater than 60%, greater than 70%, greater than 80%, or greater than 90% by volume. Such PIBs are also referred to as highly reactive PIBs ("HR-PIBs"). HR-PIBs with a number average molecular weight in the range of about 800 to about 5000 as determined by GPC are suitable for embodiments of the present disclosure. Conventional PIBs typically have a terminal double bond content of less than 50%, less than 40%, less than 30%, less than 20%, or less than 10% by volume.

[0093] HR-PIBs with a number average molecular weight in the range of about 900 to about 3000 as determined by GPC may be suitable. Such HR-PIBs are commercially available or may be synthesized by polymerizing isobutylene in the presence of a non-chlorinated catalyst such as boron trifluoride, as described in U.S. Pat. No. 4,152,499 to Boerzel et al. and U.S. Pat. No. 5,739,355 to Gateau et al. When used in the aforementioned thermal olefin reaction, HR-PIBs may increase the conversion rate in the reaction, as well as reduce the amount of sediment formation, due to enhanced reactivity. Suitable methods are described in U.S. Pat. No. 7,897,696.

[0094] In one embodiment, the present disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"). The PIBSA may have an average of between about 1.0 and about 2.0 succinic acid moieties per polymer.

[0095] The % activity of the alkenyl or alkyl succinic anhydride can be determined using chromatographic techniques. This method is described in columns 5 and 6 of US Patent No. 5,334,321.

[0096] The percent conversion of the polyolefin was calculated from the % activity using the equations in columns 5 and 6 of US Patent No. 5,334,321.

[0097] Unless otherwise indicated, all percentages are by weight and all molecular weights are number average molecular weights as determined by gel permeation chromatography (GPC) using commercially available polystyrene standards with number average molecular weights ranging from 180 to about 18,000 as calibration reference.

[0098] 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. For example, the dispersant may be described as a polyPIBSA. In an embodiment, the dispersant may be derived from an anhydride grafted to an ethylene-propylene copolymer.

[0099] Suitable classes of nitrogen-containing dispersants can be derived from olefin copolymers (OCPs), more specifically ethylene-propylene dispersants, which can be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that can react with functionalized OCPs is described in U.S. Pat. Nos. 7,485,603; 7,786,057; 7,253,231; 6,107,257; and 5,075,383; and / or are commercially available.

[0100] A class of suitable dispersants may also be Mannich bases. Mannich bases are materials formed by the condensation of higher molecular weight alkyl-substituted phenols, polyalkylene polyamines, and aldehydes such as formaldehyde. Mannich bases are described in more detail in U.S. Pat. No. 3,634,515.

[0101] A class of suitable dispersants may also be high molecular weight esters or half ester amides. Suitable dispersants may also be post-treated by conventional methods by reaction with any of a variety of reagents. Among these are boron, urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenolic esters, and phosphorus compounds. US 7,645,726; US 7,214,649; and US 8,048,831 are incorporated herein by reference in their entirety.

[0102] In addition to carbonate and boric acid post-treatments, both 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 to 29 of U.S. Patent No. 5,241,003, incorporated herein by reference. Such treatments include treatment with: inorganic phosphorous acid or anhydrates (e.g., U.S. Patent Nos. 3,403,102 and 4,648,980); organic phosphorus compounds (e.g., U.S. Patent No. 3,502,677); phosphorus pentasulfide; boron compounds as described above (e.g., U.S. Patent Nos. 3,178,663 and 4,652,387); carboxylic acids, polycarboxylic acids, anhydrides and / or acid halides (e.g., U.S. Patent Nos. 3,708,522 and 4,948,3 86); epoxides, polyepoxides 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. Nos. 3,312,619; 3,865,813; and GB 1,065,595); organic sulfonic acids (e.g., U.S. Pat. No. 3,189,544 and GB 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); alkane sultones (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. GB 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. 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 GB 2,440,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiolactams, thiolactones or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460); cyclic carbamates, cyclic thiocarbamates or cyclic dithiocarbamates (e.g., U.S. Pat. Nos. 4,663,062 and 4,666,459); hydroxy aliphatic carboxylic acids (e.g., U.S. Pat. Nos. 4,482,464; 4,521,318; 4,713,189); oxidants ( For example, U.S. Pat. No. 4,379,064); phosphorus pentasulfide and polyalkylene polyamines (for example, U.S. Pat. No. 3,185,647); carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (for example, U.S. Pat. Nos. 3,390,086; 3,470,098); hydrazine and carbon disulfide (for example, U.S. Pat. No. 3,519,564); aldehydes and phenols (for example, U.S. Pat. Nos. 3,649,229; 5,030,249; 5,039,307); aldehydes and O-diesters of dithiophosphoric acids (for example, U.S. Pat. Nos. 3,865,000; 3,984,000). ,740); a combination of a hydroxyaliphatic carboxylic acid and boric acid (e.g., U.S. Pat. No. 4,554,086); a combination of a hydroxyaliphatic carboxylic acid, then formaldehyde and phenol (e.g., U.S. Pat. No. 4,636,322); a combination of a hydroxyaliphatic carboxylic acid and then an aliphatic dicarboxylic acid (e.g., U.S. Pat. No. 4,663,064); a combination of formaldehyde and phenol and then glycolic acid (e.g., U.S. Pat. No. 4,699,724); a combination of a hydroxyaliphatic carboxylic acid or oxalic acid, and then a diisocyanate (e.g., U.S. Pat. No. 4,713,191); an inorganic acid or anhydride of phosphorus or a portion thereof Combinations of part or all of the sulfur analogues with boron compounds (e.g., U.S. Pat. No. 4,857,214); combinations of organic diacids, then unsaturated fatty acids, then nitrosoaromatic amines, optionally followed by boron compounds, and then ethanolating agents (e.g., U.S. Pat. No. 4,973,412); combinations of aldehydes and triazoles (e.g., U.S. Pat. No. 4,963,278); combinations of aldehydes and triazoles, then boron compounds (e.g., U.S. Pat. No. 4,981,492); combinations of cyclic lactones and boron compounds (e.g., U.S. Pat. Nos. 4,963,275 and 4,971,711). The patents mentioned above are incorporated herein in their entirety. ;

[0103] Suitable dispersants may have a TBN of about 10 mg KOH / g to about 65 mg KOH / g dispersant on an oil-free basis, which is comparable to about 5 TBN to about 30 TBN if measured on a dispersant sample containing about 50% diluent oil. TBN is measured by the method of ASTM D2896.

[0104] In yet other embodiments, the optional dispersant additive can be a hydrocarbyl-substituted succinamide or succinimide dispersant. In the method, the hydrocarbyl-substituted succinamide or succinimide dispersant is derived from a hydrocarbyl-substituted acylating agent reacted with a polyalkylene polyamine, and wherein 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 a calibration reference.

[0105] In some methods, the polyalkylene polyamine used to form the dispersant has the formula

[0106]

[0107] wherein each R and R' is independently a divalent C1 to C6 alkylene linking group, each R 1 and R 2 are independently hydrogen, C1 to C6 alkyl groups 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 between 0 and 8. In other methods, 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.

[0108] Dispersants, if present, may be used in an amount sufficient to provide up to about 20 wt % based on the final weight of the lubricating oil composition. Other amounts of dispersants that may be used may be from about 0.1 wt % to about 15 wt %, or from about 0.1 wt % to about 10 wt %, from about 0.1 wt % to about 8 wt %, or from about 1 wt % to about 10 wt %, or from about 1 wt % to about 8 wt %, or from about 1 wt % to about 6 wt %, 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 of dispersant or a mixture of two or more types of dispersants may be used in any desired ratio.

[0109] Antioxidants The lubricating oil composition herein may also optionally contain one or more antioxidants. Antioxidant compounds are known and include, for example, phenates, phenate sulfides, sulfurized olefins, phosphorus sulfurized terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, dinonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine), phenyl-α-naphthylamine, alkylated phenyl-α-naphthylamine, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, macromolecular antioxidants, or mixtures thereof. The antioxidant compounds may be used alone or in combination.

[0110] Hindered phenol antioxidants may contain sec-butyl and / or tert-butyl groups as sterically hindered groups. The phenol group may also be substituted with a hydrocarbyl group and / or a bridging group connected 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 and may include, for example, Irganox®, which may be purchased from BASF. TM L-135 or the addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, wherein 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 and may include Ethanox acrylate available from Albemarle Corporation. TM 4716.

[0111] Useful antioxidants may include diarylamines and high molecular weight phenols. In one embodiment, the lubricating oil composition may contain a mixture of diarylamines and high molecular weight phenols such that each antioxidant may be present in an amount sufficient to provide up to about 5 weight percent based on the final weight of the lubricating oil composition. In an embodiment, the antioxidant may be a mixture of about 0.3 weight percent to about 1.5 weight percent diarylamine and about 0.4 weight percent to about 2.5 weight percent high molecular weight phenol based on the final weight of the lubricating oil composition.

[0112] The example of suitable olefin that can be sulfurized to form sulfurized olefin comprises propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nineteendecene, eicosene or their mixture. In one embodiment, hexadecene, heptadecene, octadecene, nineteendecene, eicosene or their mixture, and their dimer, trimer and tetramer are particularly suitable olefins. Alternatively, olefin can be the Diels-Alder adduct of diene (such as 1,3-butadiene) and unsaturated ester (such as butyl acrylate).

[0113] Another class of sulphurized olefins includes sulphurized fatty acids and esters thereof. Fatty acids are usually obtained from vegetable oils or animal oils and usually contain about 4 to about 22 carbon atoms. Examples of suitable fatty acids and esters thereof include triglycerides, oleic acid, linoleic acid, palmitoleic acid or their mixtures. Usually, fatty acids are obtained from lard, pine oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil or their mixtures. Fatty acids and / or esters can be mixed with olefins such as alpha-olefins.

[0114] In another alternative embodiment, the antioxidant composition contains a platinum-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 antioxidant to aminic antioxidant to platinum-containing antioxidant is (0 to 2):(0 to 2):(0 to 1).

[0115] One or more antioxidants may be present in a range from about 0 wt % to about 20 wt %, or from about 0.1 wt % to about 10 wt %, or from about 1 wt % to about 5 wt % of the lubricating oil composition.

[0116] Anti-wear agent :The lubricating oil composition of the present invention may also optionally contain one or more anti-wear agents. Examples of suitable anti-wear agents include, but are not limited to, metal thiophosphates; metal dialkyl dithiophosphates; phosphates or their salts; phosphate esters; phosphites; phosphorus-containing carboxylates, ethers or amides; sulfurized olefins; compounds containing thiocarbamates, including thiocarbamates, alkylene coupled thiocarbamates and bis(S-alkyldithiocarbamoyl) disulfides; and mixtures thereof. A suitable anti-wear agent may be molybdenum dithiocarbamates. Phosphorus-containing anti-wear agents are more fully described in European Patent 612 839. The metal in the dialkyl dithiophosphate may be an alkali metal, an alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium or zinc. A suitable anti-wear agent may be zinc dialkyl dithiophosphate.

[0117] Other examples of suitable antiwear agents include titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulphurized olefins, phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds (such as thiocarbamates, thiocarbamate amides, thiocarbamate ethers, alkylene coupled thiocarbamates and bis (S-alkyl dithiocarbamoyl) disulfide). The tartrate or tartrimide may contain an alkyl ester group, wherein the total number of carbon atoms in the alkyl group may be at least 8. In one embodiment, the antiwear agent may include a citrate ester.

[0118] The antiwear agent may be present in a range comprising about 0 wt % to about 15 wt %, or about 0.01 wt % to about 10 wt %, or about 0.05 wt % to about 5 wt %, or about 0.1 wt % to about 3 wt % of the lubricating oil composition.

[0119] Boron compounds :The lubricating oil composition 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 compound, if 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.

[0120] Additional detergent The lubricating oil composition may optionally further comprise one or more neutral, low-alkaline or high-alkaline detergents and mixtures thereof. Suitable detergent bases include benzoates, sulfur-containing benzoates, sulfonates, calixformates, salicylates, salicylates, carboxylic acids, phosphoric acid, monothiophosphoric acid and / or dithiophosphoric acid, alkylphenols, sulfur-coupled alkylphenol compounds or methylene-bridged phenols. Suitable detergents and methods for their preparation are described in more detail in a number of patent publications, including US 7,732,390 and references cited therein.

[0121] The detergent matrix can be salified with alkali metal or alkaline earth metal such as but not limited to calcium, magnesium, potassium, sodium, lithium, barium or their mixture. In some embodiments, the detergent does not contain barium. In some embodiments, the detergent can contain trace amounts of other metals such as magnesium or calcium, such as 50ppm or less, 40ppm or less, 30ppm or less, 20ppm or less or 10ppm or less. Suitable detergents can include alkali metal or alkaline earth metal salts of petroleum sulfonic acid and long-chain mono- or dialkyl aryl sulfonic acid, wherein the aryl group is benzyl, tolyl and xylyl. Examples of suitable detergents include, but are not limited to, calcium phenates, sulfur-containing calcium phenates, calcium sulfonates, calcium calixarates, calcium salixarates, calcium salicylates, calcium carboxylates, calcium phosphates, calcium monothiophosphates and / or dithiophosphates, calcium alkylphenates, sulfur-coupled alkylphenate calcium compounds, methylene-bridged calcium phenates, magnesium phenates, sulfur-containing magnesium phenates, magnesium sulfonates, magnesium calixarates, magnesium salixarates, magnesium salicylates, magnesium carboxylates, magnesium phosphates, magnesium monothiophosphates and / or dithiophosphates, magnesium alkylphenates, sulfur-coupled alkylphenate magnesium compounds, methylene-bridged magnesium phenates, sodium phenates, sulfur-containing sodium phenates, sodium sulfonates, sodium calixarates, calixarates), sodium salixarates, sodium salicylates, sodium carboxylates, sodium phosphates, sodium monothiophosphates and / or sodium dithiophosphates, sodium alkylphenols, sodium sulfur-coupled alkylphenol compounds, or sodium methylene-bridged phenols.

[0122] Overbased detergent additives are well known in the art and can be alkali metal or alkaline earth metal overbased detergent additives. Such detergent additives can be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas. The substrate is typically an acid, such as an acid such as an aliphatic substituted sulfonic acid, an aliphatic substituted carboxylic acid, or an aliphatic substituted phenol.

[0123] The term "overbased" refers to metal salts, such as metal salts with sulfonic acids, carboxylic acids and phenols, in which the amount of metal present exceeds the stoichiometric amount. Such salts can have a conversion level exceeding 100% (i.e., they can contain 100% of the theoretical amount of metal required to convert the acid into its "normal", "neutral" salt). The expression "metal ratio" is usually abbreviated as MR, which is used to represent the ratio of the total chemical equivalents of the metal in the overbased salt to the chemical equivalents of the metal in the neutral salt, based on known chemical reactivity and stoichiometry. In normal or neutral salts, the metal ratio is one, while in overbased salts, MR is greater than one. They are often referred to as overbased, superbased or superbasic salts, and can be salts of organic sulfuric acid, carboxylic acid, or phenol.

[0124] The total base number (TBN) of the overbased detergent of the lubricating oil composition can be about 200 mg KOH / gram or greater, or as other examples, 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. TBN is measured by the method of ASTM D-2896.

[0125] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenate, overbased sulfur-containing calcium phenate, overbased calcium sulfonate, overbased calcium calixarate, overbased calcium salicylate, overbased calcium carboxylate, overbased calcium phosphate, overbased calcium monothiophosphate and / or dithiophosphate, overbased calcium alkyl phenate, overbased sulfur-coupled alkyl phenate calcium compounds, overbased methylene-bridged calcium phenate, overbased magnesium phenate, overbased sulfur-containing magnesium phenate, overbased magnesium sulfonate, overbased magnesium calixarate, overbased magnesium salicylate, overbased magnesium carboxylate, overbased magnesium phosphate, overbased magnesium monothiophosphate and / or dithiophosphate, overbased magnesium alkyl phenate, overbased sulfur-coupled alkyl phenate magnesium compounds, or overbased methylene-bridged magnesium phenate.

[0126] The total base number of the overbased calcium phenate detergent is at least about 150 mg KOH / g, at least about 225 mg KOH / g, at least about 225 mg KOH / g to about 400 mg KOH / g, at least about 225 mg KOH / g to about 350 mg KOH / g, or about 230 mg KOH / g to about 350 mg KOH / g, all as measured by the method of ASTM D-2896. When such detergent compositions are formed in an inert diluent (e.g., process oil, typically mineral oil), the total base number reflects the alkalinity of the overall composition, which includes the diluent and any other materials that may be contained in the detergent composition (e.g., promoters, etc.).

[0127] The metal to matrix ratio of the overbased detergent may be 1.1:1, or 2:1, or 4:1, or 5:1, or 7:1, or 10:1. In some embodiments, the detergent is effective in reducing or preventing rust in the engine or other automotive parts such as transmissions or gears. The detergent may be present in the lubricating composition at about 0 wt % to about 10 wt %, or about 0.1 wt % to about 8 wt %, or about 1 wt % to about 4 wt %, or greater than about 4 wt % to about 8 wt %.

[0128] Extreme Pressure AgentsThe lubricating oil composition herein may also optionally contain one or more extreme pressure agents. Extreme pressure (EP) agents soluble in oil include sulfur-containing and chlorine-containing sulfur-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 bisdibenzyl disulfide, bis(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized methyl oleate, sulfurized alkylphenols, sulfurized dipentenes, sulfurized terpenes, sulfurized Diels-Alder adducts; phosphosulfurized hydrocarbons such as the reaction product of phosphorus sulfide with turpentine or methyl oleate; phosphites such as dialkyl phosphites and trialkyl phosphites, for example, dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, amylphenyl phosphite; diamylphenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene-substituted phenyl phosphites; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol dioate; amine salts of alkyl and dialkyl phosphoric acids, including, for example, amine salts of the reaction product of dialkyldithiophosphoric acids with propylene oxide; and mixtures thereof.

[0129] Friction modifiers The lubricating oil composition herein may also optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing and metal-free friction modifiers and may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerides, sulfurized fatty compounds and olefins, sunflower oil, other naturally occurring plant or animal oils, dicarboxylic acid esters, esters or partial esters of polyols, and one or more aliphatic or aromatic carboxylic acids, and the like.

[0130] Suitable friction modifiers may contain a hydrocarbyl group selected from a linear, branched or aromatic hydrocarbyl group or a mixture thereof, and may be saturated or unsaturated. The hydrocarbyl group may be composed of carbon and hydrogen or heteroatoms, such as sulfur or oxygen. The hydrocarbyl group may be in the range of about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long-chain fatty acid ester. In another embodiment, the long-chain fatty acid ester may be a monoester or a diester 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.

[0131] Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers may include esters formed by reacting carboxylic acids and anhydrides with alkanols, and generally contain polar end groups (e.g., carboxyl or hydroxyl groups) covalently bonded to oleophilic hydrocarbon chains. An example of an organic ashless, nitrogen-free friction modifier is generally known as glyceryl monooleate (GMO), which may contain monoesters, diesters, and triesters of oleic acid. Other suitable friction modifiers are described in U.S. Pat. No. 6,723,685, which is incorporated herein by reference in its entirety.

[0132] Amine friction modifiers can include amines or polyamines. Such compounds can have straight chain, saturated or unsaturated hydrocarbon groups, or mixtures thereof, and can contain from about 12 to about 25 carbon atoms. Other examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds can have straight chain, saturated or unsaturated hydrocarbon groups, or mixtures thereof. They can contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

[0133] The amines and amides can be used as such or in the form of adducts or reaction products with boron compounds such as boron oxide, boron halides, metaborates, boric acid or mono-, di- or tri-alkyl borate esters. Other suitable friction modifiers are described in U.S. Pat. No. 6,300,291, which is incorporated herein by reference in its entirety.

[0134] The friction modifier may optionally be present in a range such as from about 0 wt % to about 10 wt %, or from about 0.01 wt % to about 8 wt %, or from about 0.1 wt % to about 4 wt %.

[0135] Molybdenum-containing components :The lubricating oil composition herein may also optionally contain one or more molybdenum-containing compounds. The oil-soluble molybdenum compound may have the functional properties of an antiwear agent, an antioxidant, a friction modifier, or a mixture thereof. The oil-soluble molybdenum compound may include molybdenum dithiocarbamates, molybdenum dialkyl dithiophosphates, molybdenum dithiophosphinates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organic molybdenum compounds, and / or mixtures thereof. Molybdenum sulfides include molybdenum disulfide. Molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyl dithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound may be molybdenum dithiocarbamates.

[0136] Suitable examples of molybdenum compounds that may be used include commercial materials sold under the following trade names: Molyvan 822 from RT Vanderbilt Co., Ltd. TM 、Molyvan TM A. Molyvan 2000 TM and Molyvan 855 TM and Sakura-Lube available from Adeka Corporation TM S-165, S-200, S-300, S-310G, S-525, S-600, S-700 and S-710, and mixtures thereof. Suitable molybdenum components are described in US 5,650,381; US ​​RE 37,363 E1; US ​​RE 38,929 E1; and US RE 40,595 E1, which are incorporated herein by reference in their entirety.

[0137] In addition, the molybdenum compound can be an acidic molybdenum compound. Including molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate and other alkali metal salts of molybdate and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide or similar acidic molybdenum compounds. Alternatively, these compositions can provide molybdenum through molybdenum / sulfur complexes of basic nitrogen compounds, such as, for example, U.S. Patent Nos. 4,263,152; 4,285,822; 4,283,295; 4,272,387; 4,265,773; 4,261,843; 4,259,195 and 4,259,194; and WO 94 / 06897, the entire contents of which are incorporated herein by reference.

[0138] Another class of suitable organomolybdenum compounds are trinuclear molybdenum compounds, such as those having the formula Mo3SkLnQz and mixtures thereof, wherein S represents sulfur, L represents an independently selected ligand having an organic group having a sufficient number of carbon atoms to render the compound soluble or dispersible in oil, n is 1 to 4, k varies in the range of 4 to 7, Q is selected from the group of neutral electron donating compounds, such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. There may be a total of at least 21 carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms, in the organic groups of all ligands. Additional suitable molybdenum compounds are described in U.S. Pat. No. 6,723,685, the entirety of which is incorporated herein by reference.

[0139] The oil-soluble molybdenum compound may be present in an amount sufficient to provide about 0.5 ppm to about 2000 ppm, about 1 ppm to about 700 ppm, about 1 ppm to about 550 ppm, about 5 ppm to about 300 ppm, or about 20 ppm to about 250 ppm of molybdenum.

[0140] Compounds containing transition metals In another embodiment, the oil-soluble compound may be a compound containing a transition metal or a metalloid. The transition metal may include, but is 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.

[0141] In one embodiment, the oil-soluble transition metal-containing compound can function as an antiwear agent, a friction modifier, an antioxidant, a deposit control additive, or more than one of these functions. In one embodiment, the oil-soluble transition metal-containing compound can be an oil-soluble titanium compound, such as titanium (IV) alkoxide. Among the titanium-containing compounds that can be used in the disclosed technology or can be used to prepare the oil-soluble materials of the disclosed technology are various Ti (IV) compounds, such as titanium (IV) oxide; titanium (IV) sulfide; titanium (IV) nitrate; titanium (IV) alkoxide, such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, 2-ethylhexyl titanium; and other titanium compounds or complexes, including but not limited to titanium phenolate; titanium carboxylate, such as 2-ethyl-1-3-adipate titanium (IV) or titanium citrate or titanium oleate; and (triethanolamine) isopropoxide titanium (IV). Other forms of titanium encompassed within the disclosed technology include titanium phosphates, such as titanium dithiophosphates (e.g., titanium dialkyl dithiophosphates), and titanium sulfonates (e.g., titanium alkylbenzene sulfonates), or generally, the reaction products of titanium compounds reacting with various acidic materials to form salts (e.g., oil-soluble salts). Titanium compounds can therefore be derived, in particular, from organic acids, alcohols, and glycols. Ti compounds can also exist in dimerized or oligomeric forms, containing Ti--O--Ti structures. Such titanium materials are commercially available or can be readily prepared by appropriate synthesis techniques readily known to those skilled in the art. They exist at room temperature in solid or liquid form, depending on the specific compound. They can also be provided in the form of solutions in suitable inert solvents.

[0142] In one embodiment, titanium can be supplied as a Ti-modified dispersant, such as a succinimide dispersant. Such materials can be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as an alkenyl (or alkyl) succinic anhydride. The resulting titanate-succinate intermediate can be used directly, or it can be reacted with any of a number of materials, such as (a) a polyamine-based succinimide / amide dispersant having a free, condensable-NH functional group; (b) components of a polyamine-based succinimide / amide dispersant, i.e., alkenyl (or alkyl) succinic anhydride and a polyamine, (c) a hydroxyl-containing polyester dispersant prepared by reacting a substituted succinic anhydride with a polyol, an amino alcohol, a polyamine, or a mixture thereof. Alternatively, the titanate-succinate intermediate can be reacted with other reagents, such as an alcohol, an amino alcohol, an ether alcohol, a polyether alcohol, or a polyol or a fatty acid, and the product thereof can be used directly to impart Ti to the lubricant, or alternatively, reacted with a succinic acid dispersant as described herein. As an example, 1 part (by mole) of tetraisopropyl titanate can be reacted with about 2 parts (by mole) of polyisobutylene-substituted succinic anhydride at 140° C. to 150° C. for 5 to 6 hours to provide a titanium-modified dispersant or intermediate. The resulting material (30 g) can also be reacted with a succinimide dispersant from polyisobutylene-substituted succinic anhydride and a polyethylene polyamine mixture (127 g + diluent oil) at 150° C. for 1.5 hours to produce a titanium-modified succinimide dispersant.

[0143] Another titanium-containing compound can be a titanium alkoxide and a C 6 To C 25 The reaction product of carboxylic acid. The reaction product can be represented by the following formula:

[0144]

[0145] 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 is represented by the formula:

[0146]

[0147] Where m+n=4 and n is in the range of 1 to 3, R 4 is an alkyl moiety having 1 to 8 carbon atoms, R 1 is selected from hydrocarbon groups containing from about 6 to 25 carbon atoms, and R 2 and R 3 The same or different and selected from hydrocarbon groups containing about 1 to 6 carbon atoms, or the titanium compound can be represented by the following formula:

[0148]

[0149] Where x is in the range of 0 to 3, R 1is selected from hydrocarbon groups containing from about 6 to 25 carbon atoms, R 2 and R 3 are the same or different and are selected from hydrocarbon groups containing about 1 to 6 carbon atoms, and R 4 Choose from H, or C 6 to C 25 A group consisting of carboxylic acid moieties.

[0150] Suitable carboxylic acids may include, but are not limited to, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, and the like.

[0151] In embodiments, the oil soluble titanium compound may be present in the lubricating oil composition in an amount providing 0 ppm to 3000 ppm by weight titanium, or 25 ppm to about 1500 ppm by weight titanium, or about 35 ppm to 500 ppm by weight titanium, or about 50 ppm to about 300 ppm by weight.

[0152] Viscosity Index Improver :The lubricating oil composition of the present invention may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutylene, hydrogenated styrene-isoprene polymers, styrene / maleic acid ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenyl aryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers may include star polymers, and suitable examples are described in U.S. Publication No. 20120101017A1.

[0153] The lubricating oil compositions herein may optionally contain one or more dispersant viscosity index improvers in addition to or in place of the viscosity index improvers. Suitable viscosity index improvers may include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with the reaction product of an acylating agent (such as maleic anhydride) and an amine; polymethacrylates functionalized with amines, or esterified maleic anhydride-styrene copolymers reacted with amines.

[0154] Viscosity Index Improvers and / or Dispersants The total amount of viscosity index improvers may range from about 0 wt % to about 20 wt %, from about 0.1 wt % to about 15 wt %, from about 0.1 wt % to about 12 wt %, or from about 0.5 wt % to about 10 wt % of the lubricating oil composition.

[0155] Other optional additivesOther additives may be selected to perform one or more functions required of the lubricating fluid. In addition, one or more of the additives mentioned may be multifunctional and provide functions other than those described herein or different from those specified herein.

[0156] Lubricating oil compositions according to the present disclosure may optionally include other performance additives. Other performance additives may be additives other than the specified additives of the present disclosure and / or may include one or more of the following: metal passivators, viscosity index improvers, detergents, ashless TBN promoters, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam inhibitors, 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.

[0157] Suitable metal deactivators may include derivatives of benzotriazole (typically tolyltriazole), dithiothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole or 2-alkyldithiobenzothiazole; foam inhibitors including copolymers of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycol, polyethylene oxide, polypropylene oxide and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides.

[0158] Suitable foam suppressors include silicon-based compounds such as siloxanes.

[0159] Suitable pour point depressants may include polymethyl methacrylate or mixtures thereof. The pour point depressant may be present in an amount sufficient to provide about 0 wt % to about 1 wt %, about 0.01 wt % to about 0.5 wt %, or about 0.02 wt % to about 0.04 wt % based on the final weight of the lubricating oil composition.

[0160] Suitable rust inhibitors can be single compounds or compound mixtures with properties that inhibit corrosion of ferrous metal surfaces. Non-limiting examples of useful rust inhibitors 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; and oil-soluble polycarboxylic acids including dimer acids and trimer acids, such as those produced by pine oil fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long-chain α, ω-dicarboxylic acids with a molecular weight ranging from about 600 to about 3000, and alkenyl succinic acids in which the alkenyl group contains about 10 or more carbon atoms, such as tetrapropylene succinic acid, tetradecene succinic acid, and hexadecene succinic acid. Another type of acidic corrosion inhibitor available is a half ester of alkenyl succinic acid and an alcohol (such as polyethylene glycol) having about 8 to about 24 carbon atoms in the alkenyl group. The corresponding half amides of such alkenyl succinic acids are also useful. Useful rust inhibitors are high molecular weight organic acids.

[0161] Rust inhibitors, if present, may be used in amounts 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.

[0162] Generally speaking, suitable lubricants including the neutral to overbased and sulfurized phenol alkyl ester products herein may include additive components within the ranges listed in the table below.

[0163] Table 2: Suitable lubricating compositions

[0164]

[0165]

[0166] The percentages of each component above represent the weight percentage of each component based on the weight of the final lubricating oil composition. The remainder of the lubricating oil composition consists of one or more base oils. The additives used to formulate the compositions described herein can be blended into the base oil individually or in various sub-combinations. However, it may be appropriate to blend all components simultaneously using an additive concentrate (i.e., additives plus diluents, such as hydrocarbon solvents). A fully formulated lubricant typically contains an additive package, referred to herein as a dispersant / inhibitor package or DI package, which will supply the desired features in the formulation.

[0167] Example

[0168] The following examples are illustrations of exemplary embodiments of the present disclosure. In these examples, and elsewhere in this application, unless otherwise stated, all ratios, parts and percentages are by weight. It is intended to present these examples only for illustrative purposes, and is not intended to limit the scope of the invention disclosed herein.

[0169] For samples having an unsulfurized alkylphenol / phenate level of about 0.3 wt % or greater, the concentration of unsulfurized alkylphenol / phenate is determined, for example, by reverse phase high performance liquid chromatography (HPLC). In an exemplary HPLC method, the sample is prepared by weighing about 80 mg to 120 mg into a 10 ml volumetric flask, diluting to the liquid mark with dichloromethane, and mixing until the sample is completely dissolved. The HPLC system used in the HPLC method includes an HPLC pump, a thermostatic HPLC column chamber, an HPLC fluorescence detector, and a PC-based chromatographic data acquisition system. An exemplary system is an Agilent 1200 HPLC with ChemStation software or equivalent. The HPLC column is a Phenomenex Luna C8(2) 150×4.6 mm 5 μm or equivalent. The following system settings were used when performing the analysis: Pump flow = 1.0 ml / min, Maximum pressure = 200 bar, Fluorescence wavelength: 225 excitation 313 emission: Gain = 9, Column thermostat temperature = 25°C, Injection volume = 1 μL diluted sample, Elution type: Gradient, reverse phase, Gradient: 0 to 7 minutes 85 / 15 methanol / water to 100% methanol linear gradient, and Run time: 17 minutes

[0170] For samples of the present invention having low or ultra-low levels of unsulfurized alkylphenates / phenols (those injected at less than 0.2 wt %), the above method is generally not sensitive enough to measure such low levels of unsulfurized alkylphenates / alkylphenols. Instead, measurements were made consistently with the above method, but using samples with a target phenate concentration of 5 mg / ml, and using liquid chromatography-mass spectrometry (LC-MS) as follows, using a single quadruple or triple quadruple MS or equivalent, modified via an Agilent MS 6420QQQ equipped with an Agilent MSD XT equipped with an Agilent 1260 LC column, such as a Supelco Ascentis Express RP Amide 2.7u, 100 mm×2.1 mm ID column or equivalent. For 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 of 300C, gas flow rate of 13 l / min, nebulizer 35 psi, capillary 3000 (v), splitter 135, and peak width of 0.07. The percentage of unsulfurized alkylphenols / phenates was determined by generating a calibration curve using MassHunterQuant Program or equivalent and then calculating the percentage of unsulfurized alkylphenols / phenates in the samples.

[0171] Example 1

[0172] Commercially available calcium phenate (Afton Chemical) having a TBN of 250 and a residual level of unsulfurized tetrapropylene phenol (TPP) of about 1.5 wt% was post-treated with methyltriazine using the following procedure: 500 grams of calcium phenate (starting TPP was 1.5%) were charged to a 2-liter reactor and the temperature was then raised to about 120° C. About 125 grams of methyltriazine were then added and the mixture was reacted at about 150° C. for about 4 hours. The analytical results did not detect the presence of any residual or unsulfurized TPP.

[0173] Example 2

[0174] First, the calcium phenate product was prepared as follows: about 509 grams of tetrapropylene phenol (TPP), about 336 grams of Ca(OH) 2A slurry made of 100 g ... 2 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 had a residual or unsulfurized TPP content of about 1.5%.

[0175] About half of the above calcium phenate product is then charged to a 2 liter reactor, heated to about 150°C, and then about 20 grams of methyl triazine is added. The mixture is then reacted at about 150°C for about 2 hours under a nitrogen purge. Thereafter, the temperature is raised to about 200°C and maintained under maximum vacuum and nitrogen for about 1 to 2 hours, cooled to about 200°C and filtered through vacuum and with a diatomaceous earth Hyflo ultra cell. The resulting product has a residual or unsulfurized TPP content of about 0.23%.

[0176] 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 affirmatively limited to one referent. Thus, for example, reference to "an antioxidant" includes two or more different antioxidants. As used herein, the term "comprising" and its grammatical variations are intended to be non-limiting, such that recitation of items in a list does not exclude other like items that can be substituted or added to the listed items.

[0177] For purposes of this specification and the appended claims, unless otherwise indicated, all numbers and other numerical values ​​used in the specification and claims indicating quantities, percentages or ratios should be understood to be modified in all cases by the term "about". Therefore, unless otherwise indicated, the numerical parameters set forth in the following specification and the appended claims are approximate values ​​that may vary depending on the desired properties attempted to be obtained by the present disclosure. At a minimum, and without attempting to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be interpreted in light of the number of reported significant figures and by applying ordinary rounding techniques.

[0178] It should be understood that each component, compound, substituent or parameter disclosed herein should be interpreted as disclosed for use alone or in combination with one or more of each of the other components, compounds, substituents or parameters disclosed herein.

[0179] It should be further understood that each range disclosed herein should be interpreted as a disclosure of each specific value within the disclosed range with the same number of significant figures. Thus, for example, a range of 1 to 4 should be interpreted as an explicit disclosure of the values ​​1, 2, 3, and 4, as well as any range of such values.

[0180] It should be further understood that each lower limit of each scope disclosed herein should be interpreted as being disclosed in combination with each upper limit of each scope disclosed herein for the same component, compound, substituent or parameter and each specific value in each scope. Therefore, the disclosure should be interpreted as being disclosed by combining each lower limit of each scope with each upper limit of each scope or with each specific value in each scope, or by combining each upper limit of each scope with each specific value in each scope. That is, it should also be further understood that any scope between the endpoint values ​​in a wide range is also discussed herein. Therefore, the scope of 1 to 4 also means the scope of 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0181] In addition, a specific amount / value of a component, compound, substituent or parameter disclosed in this specification or the examples should be interpreted as a disclosure of a lower or upper limit of a range, and therefore can be combined with any other lower or upper limit or specific amount / value of a range for the same component, compound, substituent or parameter disclosed elsewhere in this disclosure to form a range for that component, compound, substituent or parameter.

[0182] Although specific embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are not currently foreseen or may not currently be foreseen may occur to applicants or other persons skilled in the art. Therefore, the appended claims as filed and as they may be amended are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A method for preparing a sulfurized alkylphenate product, the method comprising: sulfurizing an alkylphenol with a sulfur source to provide a sulfurized alkylphenol, wherein 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 alkylphenates and residual unsulfurized alkylphenol, wherein the sulfurizing, the neutralizing, and the optional overbasing can be performed in any order; and post-processing the sulfurized alkylphenate composition to obtain the sulfurized alkylphenate product, wherein the post-processing comprises reacting the sulfurized alkylphenate composition with a triazine compound.

2. The process for preparing a sulfurized alkylphenol product according to claim 1, wherein the sulfur source comprises elemental sulfur, sulfur monochloride, sulfur dichloride, hydrogen sulfide, sulfur dioxide, sulfide hydrates, or combinations thereof.

3. The process for preparing a sulfurized alkylphenate product according to claim 2, wherein the molar ratio of the sulfur source to the alkylphenol is from 0.1 to 3.

5.

4. The process for preparing a sulfurized alkylphenol salt product according to claim 1, wherein the neutralization and / or the optional overbasing comprises contacting the sulfurized alkylphenol with a metal base, wherein the metal base 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.

5. The process for preparing a sulfurized alkylphenol salt product according to claim 1, wherein the triazine compound has a structure of formula III wherein each R3 is independently hydrogen, a hydrocarbyl group, an amino group, a polyamino group, an alkylamino group or a dialkylaminoalkyl group.

6. A process for preparing a sulfurized alkylphenate product according to claim 5, wherein the hydrocarbyl group is an alkyl group or a C1 to C10 hydrocarbyl group, and the alkylamino group is a -R4N(R5)(R5) group, wherein R4 and R5 are each independently a C1 to C10 hydrocarbyl group.

7. The method for preparing a sulfurized alkylphenate product according to claim 1, further comprising 0.5 wt% or less of unsulfurized alkylphenol.

8. The process for preparing a sulfurized alkylphenate product according to claim 1, wherein the sulfurized alkylphenate product comprises a compound of formula I and a compound of formula II: in Each R1 is independently an alkyl group, an aryl group, an alkaryl group or an aralkyl group; R2 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; and M 2+ It is a divalent metal ion.

9. A process for preparing a sulphurised alkylphenate product according to claim 8, wherein R1 is a C8 to C20 alkyl group.

10. A process for preparing a sulphurised alkyl phenate product according to claim 9 wherein R2 is methyl or has the structure -R4N(R5)(R5) wherein R4 is a C1 to C10 hydrocarbyl group and each R5 is independently a C1 to C4 alkyl group.

11. A sulphurised metal phenate detergent prepared by the process according to claim 1.

12. A lubricating oil composition comprising the metal phenate detergent according to claim 11, and one or more base oils of lubricating viscosity.

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