Polyalphaolefin phenols with high para-selectivity

Abstract

The present disclosure provides a detergent additive and a process for preparing a sulfurized alkylphenate product from a poly-alpha-olefin.

Description

Technical Field

[0001] The present disclosure generally relates to lubricating oil compositions and sulfurized additives therefor provided by polyalphaolefin substituted phenols and salts thereof having high para-selectivity and / or reactivity on the aromatic ring. Background Art

[0002] The metal salts of sulfurized alkylphenols (also referred to as alkylphenol salts) are often useful lubricant additives. When used in lubricants in automotive applications, these additives can act as, for example, detergents, friction modifiers and / or dispersants, while providing an alkaline base to help neutralize the acids produced during automotive operation. Unsulfurized variants of some alkylphenol salts or phenols (e.g., tetrapropylene phenol or tetrapropylene phenol salts with C12 alkyl substitutions) have reduced effectiveness and are often less desirable in lubricants for many reasons. Therefore, additive manufacturers seek to minimize the level of such unsulfurized alkylphenol salts and / or alkylphenols in their additives.

[0003] However, existing solutions have one or more disadvantages when trying to minimize the level of unsulfurized alkyl phenate / phenol variants when the additive is also overbased. Changing the alkyl substitution can be a potential option, but alternative alkyl substitution on the phenolic moiety is also problematic in the context of overbased lubricant detergents. Desired lubricant additives are preferably alkyl substituted in the para position of the aromatic ring because, among other reasons, such substitution enables efficient sulfurization and functionality as an overbased detergent. However, many suitable alkyl substituents from other olefins are preferentially alkylated in the ortho position, which is undesirable in the context of lubricant additives.

[0004] Summary of the invention and terminology

[0005] According to one embodiment, a sulfurized alkylphenol salt comprising a polyalphaolefin-substituted bridged hydroxyaromatic compound or a salt thereof is described herein. In the method, the polyalphaolefin is derived from a C6 to C14 monomer that forms a dimer, trimer, tetramer, pentamer, copolymer thereof, copolymer variant thereof, or a combination thereof.

[0006] In other embodiments, the sulfurized alkylphenol salt of the previous paragraph may be combined with one or more optional features or embodiments in any combination. These optional features or embodiments may include one or more of the following: wherein about 40 mol% or more of the polyalphaolefin contains carbon atoms configured to form a tertiary carbocation; and / or wherein at least one alkyl group adjacent to the tertiary carbocation is an alkyl group having 1, 2 or 3 carbon atoms, preferably 2 carbon atoms, and most preferably 1 carbon atom; and / or wherein the carbon atom configured to form a tertiary carbocation is positioned to react with the hydroxyaromatic compound in the para position; and / or wherein the polyalphaolefin is formed from dimers, trimers, tetramers, pentamers, or a combination thereof, preferably obtained from C8 to C10 monomers forming dimers, trimers, tetramers, pentamers or a combination thereof; and / or wherein about 50 mol% or more, preferably about 60 mol% or more, more preferably about 75 mol% or more, more preferably about 85 mol% or more, and most preferably about 90 mol% or more of the polyalphaolefin comprises carbon atoms configured to form a tertiary carbocation; and / or wherein the polyalphaolefin contains vinylidene olefins, trisubstituted olefins or mixtures thereof; and / or wherein the polyalphaolefin contains greater than about 40 mol%, greater than about 50 mol%, greater than about 75 mol% or greater than about 90 mol% of vinylidene olefins; and / or wherein the poly alpha-olefin is a trisubstituted olefin and comprises about 40 wt% or more, preferably about 50 wt% or more, and more preferably about 70 wt% or more of the dimer; and / or wherein the poly alpha-olefin comprises about 40 wt% or less of the trimer; and / or about 20 wt% or less of the tetramer; and / or about 5 wt% or less of the pentamer; and / or wherein the poly alpha-olefin comprises mainly vinylidene olefins, trisubstituted olefins or a combination thereof and contains about 40 wt % or more, preferably about 50 wt % or more, and more preferably about 75 wt % or more of the C3 or shorter alkyl group adjacent to the tertiary carbenium ion; and / or wherein the poly-alpha-olefin contains a double bond having a vinylidene structure and / or a trisubstituted structure; and / or wherein the poly-alpha-olefin contains about 40 mol % or more, preferably about 60 mol % or more, more preferably about 75 mol % or more, even more preferably about 85 mol % or more, and most preferably about 90 mol % or more of vinylidene olefins, trisubstituted olefins or combinations thereof.

[0007] In yet other embodiments, provided herein is a detergent composition comprising a sulfurized alkyl phenol salt having the structure of Formula IX. In the method, Formula IX comprises

[0008]

[0009] Each R 24 is independently a polyalphaolefin derived from C6 to C14 monomers forming a dimer, trimer, tetramer, pentamer, copolymer, copolymer variant, or a combination thereof, comprising the residue of a tertiary carbocation forming the bond to the aromatic ring, wherein at least 50 mol % of R 24 is bonded to the aromatic ring at the para position; x is an integer from 1 to 4; and M 2+ It is a divalent metal ion.

[0010] In other embodiments, the detergent composition of the previous paragraph can be combined with one or more optional features or embodiments in any combination. These optional features or embodiments may include one or more of the following: wherein each R 24 independently having at least one alkyl group adjacent to the tertiary carbenium ion, the alkyl group having 1, 2 or 3 carbon atoms, preferably 2 carbon atoms, and more preferably 1 carbon atom; and / or wherein each R 24 is independently formed from C8 to C12 monomers that form dimers, trimers, tetramers, pentamers or combinations thereof, and preferably is formed from C8 to C10 monomers that form dimers, trimers, tetramers, pentamers or combinations thereof; and / or wherein R 24 derived from a vinylidene olefin, a trisubstituted olefin or a mixture thereof; and / or wherein R 24 Contains about 40 mol% or more, about 50 mol% or more, about 75 mol% or more, or about 90 mol% or more of vinylidene olefins; and / or wherein the R 24 is a trisubstituted olefin, and about 40% by weight or more of R 24 is a dimer, about 50 wt% or more of R 24 is a dimer, or about 70 wt % or more of R 24 is a dimer; and / or about 40 wt % or less of R 24 is a trimer, about 20 wt% or less of R 24 is a tetramer, and / or about 5 wt % or less of R 24 is a pentamer; and / or wherein about 40 wt % or more, preferably about 50 wt % or more, and more preferably about 75 wt % or more of the alkyl groups adjacent to the tertiary carbenium ion are the C3 or shorter alkyl groups; and / or wherein the R 24 The group is derived from a mixture of oligomers, and the majority of the oligomers in the mixture have the following structures of Formula VI and / or Formula VII:

[0011]

[0012] Where R 11 is an alkyl group; R 12 , R 13 , R 14 , R 15 and / or R 16 Each of which is the same or different at each occurrence and independently represents hydrogen or a substituted hydrocarbyl group or an unsubstituted hydrocarbyl group; R 17 , R 18 and R 19 Only one of them is hydrogen, R 17 , R 18 and R 19 One of the remaining two is a substituted hydrocarbon group or an unsubstituted hydrocarbon group having 1, 2 or 3 carbon atoms, R 17 , R 18 and R 19 The other of the remaining two is a substituted hydrocarbon group or an unsubstituted hydrocarbon group; R 20 , R 21 , R 22 and / or R 23 Each of is the same or different at each occurrence and independently represents hydrogen or a substituted hydrocarbyl group or an unsubstituted hydrocarbyl group; each n is independently an integer from 0 to 3.

[0013] In further embodiments, provided herein are lubricating oil compositions comprising the sulfurized alkyl phenate or detergent composition of any embodiment of the present disclosure in combination with one or more base oils of lubricating viscosity.

[0014] In other embodiments, alkylphenols suitable for forming sulfurized alkylphenate detergent compositions are described herein. In the method, the alkylphenol comprises the reaction product of a hydroxyaromatic compound and a polyalphaolefin oligomer derived from a C6 to C14 dimer, trimer, tetramer, pentamer, copolymer, copolymer variant, or a combination thereof.

[0015] In other embodiments of the alkylphenol of the previous paragraph, the alkylphenol may be combined with optional embodiments or features in any combination. Optional features or embodiments may include one or more of the following: wherein the polyalphaolefin oligomer is derived from a C8 to C12 dimer, trimer, tetramer, pentamer or a combination thereof, and preferably a C8 to C10 dimer, trimer, tetramer, pentamer or a combination thereof; and / or wherein about 40 mol% or more of the polyalphaolefin oligomer contains carbon atoms configured to form a tertiary carbocation, and at least one of the alkyl groups adjacent to the tertiary carbocation has 1, 2 or 3 carbon atoms, preferably 2 carbon atoms, and more preferably 1 carbon atom; and / or wherein the reaction product has a structure of Formula VIIIa, VIIIb and / or VIIIc

[0016]

[0017] Where R 11 is an alkyl group; R 12 , R 13 , R 14 , R 15 and / or R 16 Each of which is the same or different at each occurrence and independently represents hydrogen or a substituted hydrocarbyl group or an unsubstituted hydrocarbyl group; R 17 , R 18 and R 19 Only one of them is hydrogen, R 17 , R 18 and R 19 One of the remaining two is a substituted hydrocarbon group or an unsubstituted hydrocarbon group having 1, 2 or 3 carbon atoms, R 17 , R 18 and R 19 The other of the remaining two is a substituted hydrocarbon group or an unsubstituted hydrocarbon group; R 20 , R 21 , R 22 and / or R 23wherein each of the above is the same or different at each occurrence and independently represents hydrogen or a substituted hydrocarbyl group or an unsubstituted hydrocarbyl group; and each n is independently an integer from 0 to 3; and / or wherein about 50 mol% or more, preferably about 60 mol% or more, preferably about 75 mol% or more, preferably 85 mol% or more, and most preferably about 90 mol% or more of the alkyl substitution at the para position of the aromatic ring; and / or wherein the poly-alpha-olefin oligomer contains a vinylidene olefin, a trisubstituted olefin, or a mixture thereof; and / or wherein the poly-alpha-olefin oligomer contains about 40 mol% or more, about 50 mol% or more, about 75 mol% or more, or about 90 mol% or more of a vinylidene olefin; and / or wherein the poly-alpha-olefin oligomer is a trisubstituted olefin, and about 40 wt % or more of the poly-alpha-olefin oligomer is a dimer, about 50 wt % or more of the poly-alpha-olefin oligomer is a dimer, or about 70 wt % or more of the poly-alpha-olefin oligomer is a dimer; and / or wherein about 40 wt % or less of the poly-alpha-olefin oligomer is a trimer, about 20 wt % or less of the poly-alpha-olefin oligomer is a tetramer, and / or about 5 wt % or less of the poly-alpha-olefin oligomer is a pentamer; and / or wherein about 40 wt % or more, preferably about 50 wt % or more, and more preferably about 75 wt % or more of the alkyl groups adjacent to the tertiary carbenium ion are the C3 or shorter alkyl groups.

[0018] In yet other embodiments, a poly-alpha-olefin as described in any embodiment of the present disclosure is provided for use in forming a detergent composition and / or a substituted bridged hydroxy aromatic compound or salt thereof for use in a detergent composition.

[0019] The following definitions of terms are provided to clarify the meaning of certain terms as used herein.

[0020] The terms "oil composition," "lubrication composition," "lubricating oil composition," "lubricating oil," "lubricating composition," "lubricating 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.

[0021] 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.

[0022] Unless otherwise indicated, the term "overbased" refers to metal salts, such as metal salts of sulfonic acids, carboxylic acids, salicylic acids and / or phenols, 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" salt, "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.

[0023] 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.

[0024] As used herein, and unless otherwise specified, the term "hydrocarbyl" or "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense, which is known to those skilled in the art. Specifically, it refers to a group having carbon atoms directly connected to the rest of the molecule and having mainly hydrocarbon characteristics. Each hydrocarbyl group is independently selected from a hydrocarbon substituent and a hydrocarbon substituent containing one or more of a halogen group, a hydroxyl group, an alkoxy group, a sulfhydryl group, a nitro group, a nitroso group, an amino group, a pyridyl group, a furanyl group, an imidazolyl group, oxygen and nitrogen, and wherein the non-hydrocarbon substituents present in the hydrocarbyl group for every ten carbon atoms do not exceed two. In some embodiments, the hydrocarbyl includes the term "alkyl". As used herein and unless otherwise specified, the term "alkyl" refers to a straight chain, branched chain, cyclic and / or substituted saturated chain portion having about 1 to about 100 carbon atoms. The term "alkenyl" as used herein refers to a straight chain, branched chain, cyclic and / or substituted unsaturated chain portion having about 3 to about 10 carbon atoms. As used herein, the term "aryl" refers to monocyclic and polycyclic aromatic compounds which may include alkyl, alkenyl, alkaryl, amino, hydroxy, alkoxy, halogen substituents and / or heteroatoms including, but not limited to, nitrogen, oxygen, and sulfur.

[0025] As used herein, and unless otherwise indicated, the term "alkylene substituent" or "alkylene group" is used in its ordinary sense, which is 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 character. Each alkylene group is independently selected from divalent hydrocarbon substituents, and substituted divalent hydrocarbon substituents containing the following: halo groups, alkyl groups, aryl groups, alkaryl groups, aralkyl groups, hydroxyl groups, alkoxy groups, mercapto groups, nitro groups, nitroso groups, amino groups, pyridyl groups, furanyl groups, imidazolyl groups, oxygen and nitrogen, and wherein there are no more than two non-hydrocarbon substituents per ten carbon atoms in the alkylene group.

[0026] Unless otherwise specifically stated, as used herein, the term "weight %" refers to the percentage of the component by weight of the entire composition.

[0027] As used herein, the terms "soluble," "oil-soluble," or "dispersible" may, but do not necessarily, mean that a 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 degree to exert their intended effect in the environment in which the oil is employed. Furthermore, the additional incorporation of other additives may also allow for the incorporation of higher levels of a particular additive, if desired.

[0028] As employed herein, the term "TBN" is used to denote Total Base Number in mg KOH / g as measured by the method of ASTM D2896.

[0029] As used herein, the term "lime" refers to compounds such as calcium hydroxide, calcium oxide, etc., also known as slaked lime or hydrated lime.

[0030] 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 may include a guard column, 4 Agilent PLgel columns (length is 300×7.5 mm; particle size is 5 μ, and pore size range is ), the column temperature is about 40°C. Unstabilized HPLC grade tetrahydrofuran (THF) can be used as a solvent, and the flow rate is 1.0 mL / min. The GPC instrument can be calibrated with commercially available polystyrene (PS) standards having 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.

[0031] Additional details and advantages of the present disclosure will be partially described in the following description, and / or can be learned by practicing the present disclosure. The details and advantages of the present disclosure can be realized and obtained by the elements and combinations specifically pointed out in the attached 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

[0032] The present disclosure provides phenols alkylated with polyalphaolefin oligomers having high para-substitution on the aromatic rings of the phenol detergents, phenate detergents and / or sulfurized phenate detergents thereof, lubricating compositions comprising a base oil of lubricating viscosity and such phenate detergents, and processes for preparing alkylphenol detergents and phenate detergents in the context of neutral to high base 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 from about 100 to about 500 as further discussed below.

[0033] In one method or embodiment, the present disclosure relates to a poly-alpha-olefin substituted alkylphenol with high para-selectivity and / or reactivity, wherein the alkylphenol is suitable for forming a phenate detergent or a sulphurized phenate detergent. The alkyl substitution comes from a poly-alpha-olefin oligomer derived from a C6 to C14 alpha-olefin monomer, wherein the poly-alpha-olefin oligomer is in the form of a dimer, trimer, tetramer, pentamer or a combination thereof. The poly-alpha-olefin oligomer suitable for the alkylphenol herein has many polymer characteristics that define the uniqueness of obtaining high para-selectivity and / or reactivity when forming alkylphenol and / or its phenate derivatives. For example and in some aspects, the poly-alpha-olefin oligomer has about 40 mol% or more, about 50 mol% or more, about 60 mol% or more, about 75 mol% or more, about 85 wt% or more, and even about 90 mol% or more of at least one carbon atom, which is configured to form a tertiary carbocation when protonated in the presence of a cationic acid catalyst. In other aspects, the polyalpha-olefin oligomer may also have at least one alkyl group adjacent to the tertiary carbenium ion, which alkyl group is an alkyl group with 1, 2 or 3 carbon atoms. Alkylation of phenol with such oligomers is effective for preferentially forming alkylphenols and / or salts thereof with high levels of para-alkylation from polyalpha-olefin oligomers. The alkylphenols herein derived from polyalpha-olefin oligomers have at least about 50 mol% alkylation in the para position, or at least about 60 mol% alkylation in the para position, or at least about 75 mol% alkylation in the para position, or at least about 85 mol% alkylation in the para position, or at least about 90 mol% alkylation in the para position and up to about 100 mol% alkylation in the para position (or any range between these endpoints).

[0034] The oligomers herein contain one or more C6 to C14 alpha-olefin monomer moieties, in other methods, contain C8 to C14 alpha-olefin monomer moieties, in other methods, contain C8 to C12 alpha-olefin monomer moieties, and in other methods, contain C8 to C10 alpha-olefin monomer moieties. Thus, the alpha-olefin monomer moieties have carbon numbers of 6 to 14, 8 to 14, 8 to 12, or 8 to 10. For example, the alpha-olefin moieties may be derived from 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, and isomers thereof or combinations thereof. As used herein, the term "olefin" has its ordinary meaning in the art and generally refers to an olefin having the formula C x H 2xThe term "alpha-olefin" refers to an organic compound family of olefinic hydrocarbons, wherein x is the carbon number and has double bonds in its structure. The term "alpha-olefin" also has its ordinary meaning in the art and refers to an olefin having double bonds in the primary or alpha position in its structure. The oligomer herein can be formed by a combination of monomers, monomers or their copolymers, or a variant of a monomer or its copolymer, which can be combined to form various oligomer structures herein.

[0035] Polyalphaolefin oligomers

[0036] When phenol is alkylated with linear (i.e., normal) or isomerized alpha-olefins, alkylation will in most cases preferentially proceed in the ortho position, which is generally undesirable in the context of alkylphenols used as detergent additives. It is most desirable to have the ortho position open for sulfidation and / or other phenol bridging reactions. As described above, the novel polyalphaolefin oligomers herein have a number of oligomer characteristics that define their uniqueness in terms of phenol alkyl substituents having high para-selectivity and reactivity in the context of phenol alkylation. For example, the polyalphaolefin oligomers herein have one or more of the following: (i) a high content of carbon atoms that are configured to form a tertiary carbenium ion when protonated in the presence of an acid catalyst; (2) at least one alkyl group adjacent to the tertiary carbenium ion, the alkyl group being preferably an alkyl group having 1, 2 or 3 carbon atoms; (3) a high weight percentage of dimer structure and a lower weight percentage of trimer structure, tetramer structure and / or pentamer structure; and / or (4) a relatively high mole percentage of terminal unsaturation in the form of a vinylidene configuration, and / or in some cases a relatively high mole percentage of a trisubstituted configuration, and / or in other cases a relatively high mole percentage of both a vinylidene configuration and a trisubstituted configuration.

[0037] Tertiary carbocation :In some embodiments, the poly alpha-olefin oligomers herein have a high percentage of carbon atoms that are configured to form tertiary carbocations when protonated in the presence of a catalyst. A carbocation or carbocation is a carbon atom that is configured to carry a positive charge (such as when an unsaturated carbon is protonated using a cationic acid catalyst). The poly alpha-olefin oligomers herein may have a high weight percentage of tertiary carbocations after protonation using a catalyst, and the tertiary carbocations have the general structure of Formula I below, wherein R1, R2, and R3 are the same or different alkyl groups or hydrocarbyl groups of the alpha-olefin oligomer:

[0038]

[0039] When protonated in the presence of a cationic acid catalyst, certain configurations of alpha-olefin oligomers (discussed more below) can produce carbon atoms that are configured to form tertiary carbocations. In one embodiment or method, the polyalpha-olefin oligomers herein have a structure having carbon atoms that are configured to form a relatively high percentage of oligomers with such tertiary carbocations. For example, the polyalpha-olefin oligomers herein have a structure in which about 40 mol% or more, preferably about 50 mol% or more, more preferably about 60 mol% or more, more preferably about 75 mol% or more, even more preferably about 85 mol% or more, and most preferably about 90 mol% or more of the polyalpha-olefins, and in some embodiments about 100 mol% or less, about 90 mol% or less, or about 80 mol% or less (and any ranges between these endpoints) of the polyalpha-olefins contain carbon atoms that are configured to form tertiary carbocations. Such carbon atoms are configured and / or positioned to react with the hydroxyaromatic compound during alkylation of the hydroxyaromatic compound, with para-alkylation of the hydroxyaromatic compound being highly preferred.

[0040] Short alkyl group :In other embodiments, the polyalphaolefin oligomers herein may also have at least one alkyl group adjacent to the tertiary carbenium ion, which alkyl group is an alkyl group having 1, 2 or 3 carbon atoms. For example, at least one of R1, R2 or R3 of the general oligomer structure of Formula I above is a C3 or shorter alkyl group (preferably a C2 alkyl group, and most preferably a C1 alkyl group). Without wishing to be bound by theory, it is believed that having such a short chain alkyl group adjacent to the tertiary carbenium ion improves the reactivity of the oligomer towards para-substitution on the aromatic ring. In some embodiments, and again without wishing to be bound by theory, the polyalphaolefin oligomers herein may contain about 40 wt% or more of C3 or shorter alkyl groups adjacent to a tertiary carbenium ion, about 50 wt% or more, about 60 wt% or more, or about 75 wt% or more of C3 or shorter alkyl groups, and in other embodiments, may also contain about 100 wt% or less, about 90 wt% or less, about 80 wt% or less, or about 70 wt% or less (and any ranges between these endpoints) of C3 or shorter alkyl groups adjacent to a tertiary carbenium ion.

[0041] Dimer structureIn other embodiments, the poly-alpha-olefin oligomer herein is a mixture of oligomer compounds, and may also have a high weight percent dimer structure and a lower weight percent trimer structure, tetramer structure and / or pentamer structure in the mixture. For example and in some methods, the poly-alpha-olefin oligomer may include about 40 weight % or more dimer, about 50 weight % or more dimer, about 60 weight % or more dimer, or about 75 weight % or more dimer, and in some methods, include about 100 weight % or less dimer, about 90 weight % or less dimer, about 80 weight % or less dimer, about 70 weight % or less dimer, or about 60 weight % or less dimer (and any range between such weight percent amounts). Meanwhile, the poly-alpha-olefin oligomer may include about 40 wt % or less trimer (in other methods, about 30 wt % or less) and / or about 20 wt % or less tetramer (in other methods, about 18 wt % or less or even about 12 wt % or less); and / or about 5 wt % or less (in other methods, about 4 wt % or less or even about 3 wt % or less) and any range of pentamers between such weight % amounts of each oligomer type. In other embodiments, trimer may be about 0 wt % to about 40 wt %, about 1 wt % to about 30 wt %, about 2 wt % to about 30 wt %, or about 5 wt % to about 30 wt %. In other embodiments, tetramer may be about 0 wt % to about 20 wt %, about 1 wt % to about 18 wt %, about 2 wt % to about 18 wt %, or about 5 wt % to about 18 wt %. In other embodiments, the pentamer may be from about 0 wt % to about 5 wt %, from about 1 wt % to about 4 wt %, or from about 2 wt % to about 4 wt %.

[0042] As used herein, dimer, trimer, tetramer and pentamer have their common meaning in the art, and generally refer to oligomers having two monomer units, three monomer units, four monomer units and five monomer units, respectively. Thus, for each monomer and oligomer configuration, a dimer derived from a C10 alpha-olefin monomer will be a C20 oligomer, a trimer derived from a C10 alpha-olefin monomer will be a C30 oligomer, and so on. One of ordinary skill in the art will understand the corresponding molecular weight of each oligomer type. Preferably, the oligomer herein not only has a high weight percentage of a dimer structure, but also has one or more of the other oligomer characteristics, and simultaneously includes a high percentage of tertiary carbocations, a high percentage of short alkyl chains adjacent to the tertiary carbocations, and a high percentage of vinylidene and / or trisubstituted configurations.

[0043] Oligomeric unsaturatedIn other embodiments, the poly alpha-olefin oligomer herein may also have a relatively high percentage of unsaturation for vinylidene configuration, a relatively high percentage of unsaturation for trisubstituted configuration, and / or in some cases both vinylidene configuration and trisubstituted configuration. In some methods, unsaturation is considered as terminal unsaturation as discussed below. For example and in some embodiments, the poly alpha-olefin oligomer herein comprises about 40mol% or more, about 50mol% or more in other methods, about 60mol% or more in other methods, about 75mol% or more in other methods, about 85mol% or more in other methods, and about 90mol% or more in other methods, and 100mol% or less, 95mol% or less, 90mol% or less (or any other scope between such mol% amounts) vinylidene groups in other methods. In other embodiments, the polyalphaolefin oligomers herein contain about 40 mol% or more, about 50 mol% or more in other methods, about 60 mol% or more in yet other methods, about 75 mol% or more in yet other methods, about 85 mol% or more in yet other methods, and about 90 mol% or more in yet other methods, and 100 mol% or less, 95 mol% or less, 90 mol% or less (or any other range between such mol% amounts) of trisubstituted groups in yet other methods. In yet other embodiments, the polyalphaolefin oligomers herein contain about 40 mol% or more, about 50 mol% or more in other methods, about 60 mol% or more in yet other methods, about 75 mol% or more in yet other methods, about 85 mol% or more in yet other methods, and about 90 mol% or more in yet other methods, and 100 mol% or less, 95 mol% or less, 90 mol% or less (or any other range between such mol% amounts) of vinylidene groups and trisubstituted groups.

[0044] Without wishing to be bound by theory, it is believed that the oligomers herein include primarily terminal group unsaturation. As will be appreciated by those skilled in the art, oligomer unsaturation refers to an oligomer having a carbon-carbon double bond, or in the case of an oligomer having terminal unsaturation, the carbon-carbon double bond has at least one carbon in the carbon-carbon double bond, the carbon-carbon double bond being derived from a terminal monomer group or terminal monomer portion in an oligomer structure as shown in Formulae II to V below, wherein Formulae II to V reflect vinyl terminal unsaturation, disubstituted terminal unsaturation, vinylidene terminal unsaturation, and trisubstituted terminal unsaturation (wherein ~ represents a bond to the remainder of the oligomer). In some methods, the oligomers herein may have greater than 75 mol% terminal unsaturation, greater than 80 mol% terminal unsaturation, greater than 85 mol% terminal unsaturation, greater than 90 mol% terminal unsaturation, greater than 95 mol% terminal unsaturation, or even greater than 97 mol% terminal unsaturation. The molar percentage of unsaturation or terminal unsaturation may be determined by 13 C NMR measurement. (See, e.g., U.S. Pat. No. 5,128,056, which is incorporated herein by reference.)

[0045]

[0046] Where R4 to R 10 is a linear or branched alkyl or hydrocarbyl group consistent with the monomer structures and / or oligomer structures discussed more herein. As shown herein, the cis isomers and / or trans isomers of the various structures are intended to be interchangeable, and both cis isomers and trans isomers are included in any structure herein, whether or not shown in the various structures. Terminal vinylidene, trisubstituted isomers of terminal vinylidene, and other types of terminal unsaturated bonds can be obtained, for example, but not limited to 1 H-NMR is used for detection. Based on the integrated intensity of each signal, the amount of each unsaturated bond can be determined, for example, as discussed in U.S. Patent Publication No. 2016 / 0257862, which is incorporated herein by reference.

[0047] Oligomer structure:Poly alpha-olefin oligomers configured herein to have high reactivity and high preference for alkylation of phenol in the para position have one or more of the above-mentioned oligomer characteristics, and in some embodiments, may also have an oligomer structure of formula VI (having a high percentage of vinylidene configuration) and / or formula VII (having a high percentage of trisubstituted configuration) and / or a combination of both formula VI and formula VII structures. For example and in some methods, the poly alpha-olefin compound herein is a polymerized, preferably oligomeric molecule produced by the oligomerization reaction of alpha-olefin monomers in the presence of a catalyst system. Unsaturated poly alpha-olefin oligomers herein are understood to contain carbon-carbon double bonds therein, wherein such double bonds are primarily in the terminal monomer groups or terminal monomer moieties as described above.

[0048] Each polyalphaolefin oligomer herein has a carbon chain with the largest number of carbon atoms, which can be designated as the main carbon chain or carbon backbone of the oligomer. The main chain or backbone generally comprises carbon atoms derived from carbon-carbon double bonds in the monomer molecules participating in the oligomerization reaction, and / or any additional carbon atoms from monomer molecules and / or molecules in the catalyst system that form both ends of the backbone.

[0049] In some methods or embodiments, suitable poly-alpha-olefin oligomers herein may comprise a mixture of oligomers (such as, but not limited to, those derived from C6-C14 monomers as described above), wherein a majority of the oligomers in the mixture have the structure of Formula VI below and / or Formula VII below:

[0050]

[0051] In some embodiments of Formula VI, R 11 is an alkyl group, R 12 , R 13 , R 14 , R 15 and / or R 16 Each of is the same or different at each occurrence and independently represents hydrogen or a substituted hydrocarbyl group or an unsubstituted hydrocarbyl group (preferably, a substituted alkyl group or an unsubstituted alkyl group). In some embodiments of Formula VII, R 17 , R 18 and R 19 Only one of them is hydrogen, and R 17 , R 18 and R 19 One of the remaining two in is a substituted hydrocarbyl group or an unsubstituted hydrocarbyl group (preferably, a substituted alkyl group or an unsubstituted alkyl group) having 1, 2 or 3 carbon atoms, and R 17 , R 18 and R 19The other of the remaining two in is a substituted hydrocarbyl group or an unsubstituted hydrocarbyl group (preferably, a substituted alkyl group or an unsubstituted alkyl group). In yet other embodiments of Formula VII, R 20 , R 21 , R 22 and R 23 Each of the above is the same or different at each occurrence and independently represents hydrogen or a substituted hydrocarbyl group or an unsubstituted hydrocarbyl group (preferably, a substituted alkyl group or an unsubstituted alkyl group). In Formula VI and / or Formula VII, each n is independently an integer from 0 to 3 (wherein an integer of 0 represents a dimer, an integer of 1 represents a trimer, an integer of 2 represents a tetramer, and / or an integer of 3 represents a pentamer).

[0052] Without wishing to be bound by theory, and in yet other embodiments or methods of the oligomer of Formula VI, R 11 It can be a C4 to C12 alkyl group; R 12 It can be hydrogen or a C1 to C12 alkyl group; R 13 It can be hydrogen or a C1 to C12 alkyl group; R 14 It can be hydrogen or a C1 to C12 alkyl group; R 15 may be hydrogen or a C1 to C12 alkyl group; and / or R 16 It may be hydrogen or an alkyl group (preferably from the catalyst system). One of ordinary skill in the art will appreciate that the structure of Formula VI may depend, among other features, on the polymerization process, the catalyst selected, and / or the starting monomer mixture.

[0053] Without wishing to be bound by theory and in other embodiments or methods of the oligomer of formula VII, when R 19 When it is hydrogen, R 17 or R 18 One of them is a C1 to C3 alkyl group and the other is a C2 to C12 alkyl group, and R 20 is a C4 to C12 alkyl group; similarly when R 17 When it is hydrogen, R 19 is a C1 to C3 alkyl group, R 18 is a C5 to C13 alkyl group, and R 20 is C1 to C11; and similarly when R 18 When it is hydrogen, R 19 is a C1 to C3 alkyl group, R 17 is a C5 to C13 alkyl group, and R 20 is C1 to C11. In addition, in this embodiment of Formula VII, R 21 is hydrogen or a C1 to C12 alkyl group; R 22 is hydrogen or a C1 to C12 alkyl group; R23 is hydrogen or an alkyl group (preferably from the catalyst system). One of ordinary skill in the art will appreciate that the structure of Formula VII may depend, among other features, on the polymerization process, the selected catalyst, and / or the starting monomer mixture.

[0054] The oligomers herein can be prepared using polymerization catalysts under conditions known to those of ordinary skill in the art. If necessary, the oligomerization reaction conditions can be controlled to provide the desired oligomers herein. Parameters (such as reaction temperature, pressure, mixing, reactor heat management, feed rate of one or more reactants in various reactants, type, ratio and concentration of catalyst and / or co-catalyst and / or scavenger, and phase of feed components) can be controlled to affect the structure of the copolymer obtained by the reaction. Therefore, the combination of several different reaction conditions known to those of ordinary skill in the art can be controlled to produce the desired oligomers herein. In some methods, the poly-alpha-olefin oligomers suitable for alkylation of phenol herein can be prepared using methods as described in US2021 / 0347921, which is incorporated herein by reference in its entirety.

[0055] In some embodiments, reaction temperatures of about 60°C to about 135°C may be used for the oligomerization reaction, or in other approaches, reaction temperatures of about 62°C to about 130°C, about 65°C to about 125°C, about 68°C to about 120°C, or about 70°C to about 90°C may be used for the polymerization reaction to form the oligomers herein.

[0056] The oligomers herein can be formed by polymerizing C6 to C14 monomers in the presence of a suitable catalyst, such as a solid acid catalyst and / or a single-site coordination polymerization catalyst, such as a coordination metallocene. As known to those of ordinary skill in the art, a metallocene comprises a cyclopentadienyl anion ("Cp") bound to a metal center. The coordination metallocene may comprise zirconium, and in some methods, the coordination metallocene may comprise Cp2ZrCl2. The coordination polymerization catalyst may additionally comprise a cocatalyst. The cocatalyst may comprise, for example, methylaluminoxane.

[0057] The oligomers herein can be produced in a reactor, and the parameters that can be controlled during the process are known to those of ordinary skill in the art, and may include the management of suitable pressure and temperature as described above. The reaction can be operated continuously, semi-continuously or in batches. Catalysts and co-catalysts (if used) can be provided to the reactor in solution form. According to different embodiments and as required, the weight percentage of the catalyst or co-catalyst in the solution may be less than about 20 weight %; less than about 15 weight %, less than about 10 weight %, less than about 8 weight %, less than about 6 weight %, less than about 5 weight %, less than about 4 weight %, less than about 3 weight %, less than about 2 weight % or less than about 1 weight % to obtain the desired oligomers herein. The components can then be mixed in the reactor. Suitable catalysts and conditions thereof are known to those of ordinary skill in the art, and may be described in, for example, at least U.S. Pat. No. 9,441,063 or No. 8,614,277, both of which are incorporated herein by reference.

[0058] In some methods and if desired, a free radical initiator can be used in the oligomerization process herein. The free radical initiator, if used, can be a peroxide, hydroperoxide and / or azo compound that has a boiling point greater than 100° C. and thermally decomposes within the reaction temperature range to provide free radicals. Representative free radical initiators can be azobutyronitrile; 2,5-dimethyl-hex-3-yn-2,5-bis-tert-butyl peroxide; or its hexene analog. The initiator can be provided at a low level of about 0.005 wt % to about 1 wt % based on the total weight of the oligomer solution.

[0059] Alkylation of phenol

[0060] Suitable phenols or hydroxy aromatic compounds for alkylation with the oligomers herein include monohydroxy aromatic hydrocarbons and / or polyhydroxy aromatic hydrocarbons having 1 to 4 and in some methods 1 to 3 hydroxyl groups for alkylation with polyalphaolefin oligomers. Suitable compounds include, but are not limited to, phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, etc. and mixtures thereof. Preferred starting compounds include phenol.

[0061] Alkylating agent comprises one or more oligomers derived from the above-mentioned poly-alpha-olefin oligomer. The poly-alpha-olefin oligomer alkylation to hydroxy aromatic compound can be carried out in the presence of catalyst (such as Lewis acid catalyst, solid acid catalyst, trifluoromethanesulfonic acid and other acidic molecular sieve catalyst). Exemplary Lewis acid catalyst is known to those skilled in the art, and can include aluminum chloride, aluminum tribromide, aluminum triiodide, boron trifluoride, boron tribromide, boron triiodide, etc. In the method, alkylation can use sulfonated polystyrene solid catalyst etc. In some methods, the molar ratio of phenol or hydroxy aromatic compound to poly-alpha-olefin oligomer can be about 10: 1 to about 0.5: 1, and in other methods, it is about 5: 1 to about 2: 1 (or other ranges within these ratios).

[0062] Oligomer polyalphaolefins having the above oligomer characteristics are particularly suitable for alkylation to phenols or hydroxyaromatic compounds in the para position, but other substitutions may also be present depending on the application. For example, when using the oligomers herein, the oligomer alkyl group (i.e., R in Formula VIII below) 24 Substituents) may be at least about 40 mol% (and in some methods, at least about 50 mol%, at least about 60 mol%, at least 75 mol%, at least about 85 mol% or at least about 90 mol% and up to about 100 mol% (or any mol% range between these amounts)) in the para position on the aromatic ring and about 0 mol% to about 15 mol%, and in some methods, about 0 mol% to about 5 mol% disubstituted in the ortho position of the aromatic ring. In addition, the alkylated phenol may have the structure of the following Formula VIII, Formula VIIIa, Formula VIIIb or Formula VIIIc, with a high content of a group R as described above 11 To R 23 and integer n vinylene and trisubstituted oligomers, as defined in any of the above embodiments. 17 or R 18 is hydrogen and R 19 is an alkyl group having 1, 2 or 3 carbon atoms, and preferably R 19 is a C2 group, and most preferably R 19 When R is a C1 group, Formula VIIIb is formed. 19 is hydrogen and R 17 or R 18 is an alkyl group having 1, 2 or 3 carbon atoms, preferably R 17 or R 18 is a C2 group, and most preferably R 17 or R 18 When is a C1 group, Formula VIIIc is formed.

[0063]

[0064] In embodiments, the alkylated phenols herein may include an aromatic ring bonded to any structure of Formula VIII, Formula VIIIa, Formula VIIIb, or Formula VIIIc, or mixtures thereof, with Structure VIIIc being most preferred.

[0065] Neutralization

[0066] Neutralization is carried out by reacting the alkylphenols herein with a metal base. In one approach, neutralization is carried out by contacting the alkylphenols described above with a metal base under reaction conditions, and in some approaches with a promoter in a liquid hydrocarbon diluent to provide a phenolate or salt of an 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 carried out via the exemplary reaction scheme I shown below, but other reactions can be carried out as desired, depending on the selected order of sulfurization, neutralization, and / or overbasing, and various applications, materials, and conditions:

[0067]

[0068] 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 base compounds include lithium oxide, magnesium oxide, calcium oxide and barium oxide. In preferred examples, the alkaline earth metal base is lime or calcium hydroxide. The additive can be borated as needed depending on the application and use.

[0069] 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%.

[0070] 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 may be carried out for a duration of about 1 hour to about 5 hours.

[0071] vulcanization

[0072] The neutralized alkylphenol or neutralized alkylhydroxyaromatic compound can be sulfurized by contacting 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 x -group (shown in the following exemplary structure), wherein x is independently an integer from 1 to 4, and in other methods an integer from 1 to 3, and in some methods 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 desired depending on the application, materials and conditions.

[0073]

[0074] Vulcanization can be carried out, for example, at a temperature of about 160° C. to about 250° C., in other methods, at a temperature of about 180° 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.

[0075] Over-alkalization

[0076] Then, overbasing is optional, but preferred in some embodiments, and is carried out during or alternatively after the above-mentioned neutralization and / or sulfidation. In one method, the alkylphenol / alkylphenol salt of sulfidation is overbased by reacting with excessive metal base and / or with acidic overbasing compounds such as, for example, carbon dioxide or boric acid. In one method, overbasing is in the presence of a solvent via carbonation (reaction with carbon dioxide) and neutralization, and the 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 during the reaction or after the reaction as required, as discussed further below.

[0077] In one embodiment, exemplary overbasing reaction can be to make sulfurized alkylphenol or its salt react 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 250 minutes.

[0078] After optional overbasing, overbased and sulfurized alkyl phenol salts, such as the detergent compositions herein, may have a TBN of at least about 0, at least about 20, at least about 50, at least about 100, or in other approaches, from about 100 to about 500, from about 100 to about 400, or from about 150 to about 400, and in still 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 may be from about 100 mg KOH to about 300 mg KOH as measured by ASTM D-2896.

[0079] In embodiments, exemplary overbased and sulfurized alkylphenate additives herein may have the structure of Formula IX below, wherein R 24 Derived from a poly alpha-olefin oligomer as described above.

[0080]

[0081] Each R 24 A polyalphaolefin independently as described above and which may be derived from a C6 to C14 monomer (as described above) and forming a dimer, trimer, tetramer, pentamer, copolymer, copolymer variant, or a combination thereof, the polyalphaolefin comprising a residue of a tertiary carbocation forming a bond to an aromatic ring as described above. In the method, at least about 50 mol% of R in Formula IX 24 bonded to the aromatic ring in the para position (at least about 60 mol%, at least about 75 mol%, at least about 85 mol%, at least about 90 mol%, or in other approaches, up to about 100 mol% (and any ranges between these endpoints)); x is an integer from 1 to 4 as described above; and M 2+ The number of divalent metal ions is as described above.

[0082] Post-processing

[0083] 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.

[0084] In embodiments, the sulphurized alkylphenol salt is prepared by sulphurization, neutralization and / or carbonation as described above. These reactions can be carried out in any order, simultaneously or in a specific order according to the application. Sulphurization and neutralization, for example and in any order or simultaneously, are usually completed before carbonation. Generally speaking, the detergent additive or composition herein is obtained by: first alkylating phenol with an oligomer as described herein, neutralizing the alkylphenol, and then sulphurizing the neutralized alkylphenol with a sulphur source to provide sulphurized and neutralized alkylphenol. Then the sulphurized and neutralized alkylphenol is optionally overbased in the presence of a solvent to provide a neutral to optionally high alkalinity and sulphurized alkylphenol salt additive or composition.

[0085] Lubricating oil composition

[0086] 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.

[0087] In methods, the lubricating oil compositions herein may comprise from about 0.02 wt. % to about 5 wt. %, in other methods, from about 0.2 wt. % to about 3 wt. %, and in still other methods, 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] Regardless of the 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 is about 1 wt % or less. In yet another embodiment, the sulfur content can be about 0.3 wt % or less, the phosphorus content is about 0.05 wt % or less, and the sulfated ash can be about 0.8 wt % or less.

[0092] 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, SN PLUS, ACEA A1 / B1, A2 / B2, A3 / B3, A3 / B4, A5 / B5, A7 / B7 C1, C2, C3, C4, C5, C6, E4 / E6 / E7 / E9, Euro 5 / 6, JASO DL-1, Low SAPS, Mid SAPS, or original equipment manufacturer specifications, such as Dexos1TM, Dexos2TM, 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 B712290, B71 2294, B71 2295, B71 2296, B71 2297, B71 2300, B71 2302, B71 2312, B71 2007, B71 2008, Renault RN0700, RN0710, RN0720, Ford WSS-M2C153-H, WSS-M2C930-A, WSS-M2C945-A, WSS-M2C913A, WSS-M2C913-B, WSS-M2C913-C, WSS-M2C913-D, WSS-M2C948-B, WSS-M2C948-A, GM 6094-M, Chrysler MS-6395, Fiat 9.55535G1, 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.

[0093] Base oil or base oil blend : The base oil used in the lubricating oil composition herein can 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. Five base oil groups are generally listed in the following Table 1:

[0094] Table 1

[0095]

[0096]

[0097] 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 ethers 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.

[0098] 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.

[0099] 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. Oils refined to edible quality 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.

[0100] 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.

[0101] 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.

[0102] 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); polyphenylenes (e.g., biphenyl, terphenyl, alkylated polyphenylenes); 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.

[0103] Other synthetic lubricating oils include polyol esters, diesters, liquid esters (e.g., toluene phosphate, trioctyl phosphate, and diethyl ester of decanephosphonic acid) or polytetrahydrofuran containing phosphoric acid. Synthetic oils can be produced by Fischer-Tropsch reaction and can typically be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil can be prepared by Fischer-Tropsch gas-liquid synthesis procedures and other gas-liquid oils.

[0104] The major amount of the 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 the 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.

[0105] The oil of lubricating viscosity may be present in an amount that is the remainder remaining after the total amount of performance additives (including viscosity index improvers and / or pour point depressants and / or other top treatment additives) is subtracted from 100 wt %. For example, the oil of lubricating viscosity that may be present in the finished fluid may 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 %.

[0106] Optional additives :

[0107] 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.

[0108] Dispersants: The lubricating oil composition may optionally contain one or more dispersants or mixtures thereof. Dispersants are often referred to as ashless dispersants because they do not contain ash-forming metals prior to 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, for example, in U.S. Pat. No. 7,897,696 or U.S. Pat. No. 4,234,435. The alkenyl substituent can be prepared from polymerizable monomers containing from about 2 to about 16, or from about 2 to about 8, or from about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines, typically poly(ethylene amine).

[0109] 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.

[0110] 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.

[0111] 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%.

[0112] Typically, PAM has 8.7 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.

[0113] 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.

[0114] In some embodiments, polyisobutylene (when included) may have a terminal double bond content of greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol%. Such PIBs are also referred to as highly reactive PIBs ("HR-PIBs"). HR-PIBs having a number average molecular weight in the range of about 800 to about 5000 as determined by GPC are suitable for use in embodiments of the present disclosure. Conventional PIBs typically have a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0115] 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 due to enhanced reactivity, as well as reduce the amount of sediment formation. Suitable methods are described in U.S. Pat. No. 7,897,696.

[0116] 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.

[0117] Chromatographic techniques may be used to determine the % activity of the alkenyl or alkyl succinic anhydride. This method is described in columns 5 and 6 of US Patent No. 5,334,321.

[0118] 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.

[0119] 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.

[0120] In one embodiment, the dispersant may be derived from 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 polyPIBSA. In an embodiment, the dispersant may be derived from an anhydride grafted to an ethylene-propylene copolymer.

[0121] A suitable class 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 is commercially available.

[0122] A suitable class of dispersants is also 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.

[0123] 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.

[0124] 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. Pat. No. 5,241,003, incorporated herein by reference. Such treatments include treatment with: inorganic phosphorous acid or anhydrates (e.g., U.S. Pat. Nos. 3,403,102 and 4,648,980); organophosphorus compounds (e.g., U.S. Pat. No. 3,502,677); phosphorus pentasulfide; boron compounds as described above (e.g., U.S. Pat. Nos. 3,178,663 and 4,652,387); carboxylic acids, polycarboxylic acids, anhydrides and / or acid halides (e.g., U.S. Pat. Nos. 3,708,522 and 4,948,980); , 386); 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 British Patent No. GB ​​1,065,595); organic sulfonic acids (e.g., U.S. Pat. No. 3,189,544 and British Patent No. 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. Nos. 4,971,598 and GB Patent No. 4,971,598); 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); oxidizing agents (e.g., U.S. Pat. No. 4,379,064); combinations of phosphorus pentasulfide and polyalkylene polyamines (e.g., U.S. Pat. No. 3,185,647); combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (e.g., U.S. Pat. Nos. 3,390,086; 3,470,098); combinations of hydrazine and carbon disulfide (e.g., U.S. Pat. No. 3,519,564); combinations of aldehydes and phenols (e.g., U.S. Pat. Nos. 3,649,229; 5,030,249; 5,039,307); combinations of aldehydes and O-diesters of dithiophosphoric acids (e.g., U.S. Pat. Nos. 3,8 65,740); 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 Combinations of part or all of the sulfur analogs 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 above-mentioned patents are incorporated herein in their entirety. ;

[0125] The TBN of a suitable dispersant may be from 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.

[0126] 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 chain hydrocarbyl group or a branched chain 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.

[0127] In some methods, the polyalkylene polyamine used to form the dispersant has the formula

[0128]

[0129] wherein each R and R' is independently a divalent C1 to C6 alkylene linking group, each R1 and R2 is independently hydrogen, a C1 to C6 alkyl group, or together with the nitrogen atom to which they are attached, forms a 5-membered 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.

[0130] Dispersants, if present, can be used in an amount sufficient to provide up to about 20 wt % based on the final weight of the lubricating oil composition. Another amount of dispersant that can be used can be about 0.1 wt % to about 15 wt %, or about 0.1 wt % to about 10 wt %, or about 0.1 wt % to about 8 wt %, or about 1 wt % to about 10 wt %, or about 1 wt % to about 8 wt %, or 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 can be used in any desired ratio.

[0131] AntioxidantsThe 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.

[0132] The hindered phenol antioxidant may contain a sec-butyl and / or tert-butyl group as a sterically hindered group. The phenolic 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, BASF commercially available 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 the esters available from SI Group. 4716.

[0133] 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.

[0134] Examples of suitable olefins that can be sulfurized to form sulfurized olefins include propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecaene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecaene, or mixtures thereof, and dimers, trimers, and tetramers thereof are particularly suitable olefins. Alternatively, the olefin can be a Diels-Alder adduct of a diene (such as 1,3-butadiene) and an unsaturated ester (such as butyl acrylate).

[0135] 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 mixtures thereof. Usually, fatty acids are obtained from lard, pine oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil or mixtures thereof. Fatty acids and / or esters can be mixed with olefins such as alpha-olefins.

[0136] 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).

[0137] The 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.

[0138] Antiwear Agents :The lubricating oil composition herein may also optionally contain one or more anti-wear agents. Examples of suitable anti-wear agents include, but are not limited to, metal thiophosphates; metal 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.

[0139] 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-alkyldithiocarbamoyl) disulfides). 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.

[0140] 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.

[0141] 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.

[0142] 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.

[0143] The detergent matrix can be salified with alkali metals or alkaline earth metals such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium or mixtures thereof. In some embodiments, the detergent does not contain barium. In some embodiments, the detergent may 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 may include alkali metal or alkaline earth metal salts of petroleum sulfonic acid and long-chain mono- or dialkyl aryl sulfonic acids, wherein the aryl groups are 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, sodium salixarates, 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.

[0144] 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.

[0145] The term "overbased" relates 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 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" salt, "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, or phenol.

[0146] 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.

[0147] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenates, overbased calcium sulfonates, overbased calcium calixarates, overbased calcium salicylates, overbased calcium carboxylates, overbased calcium phosphates, overbased calcium monothiophosphates and / or dithiophosphates, overbased calcium alkylphenates, overbased sulfur-coupled alkylphenate calcium compounds, overbased methylene-bridged calcium phenates, overbased magnesium phenates, overbased magnesium sulfonates, overbased magnesium calixarates, overbased magnesium salicylates, overbased magnesium carboxylates, overbased magnesium phosphates, overbased magnesium monothiophosphates and / or dithiophosphates, overbased magnesium alkylphenates, overbased sulfur-coupled alkylphenate magnesium compounds, or overbased methylene-bridged magnesium phenates.

[0148] 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.).

[0149] 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 a transmission 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 %.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] 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 terminal 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.

[0154] Amine friction modifiers may include amines or polyamines. Such compounds may have linear chains, saturated or unsaturated hydrocarbon groups, or mixtures thereof, and may contain from about 12 to about 25 carbon atoms. Other examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds may have linear chains, saturated or unsaturated hydrocarbon groups, or mixtures thereof. They may contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

[0155] 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.

[0156] Friction modifiers 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 %.

[0157] 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.

[0158] Suitable examples of molybdenum compounds that may be used include commercial materials sold under the following trade names such as RT Vanderbilt Co., Ltd. 822, A. 2000 and 855, and commercially available from Adeka Corporation S-165, S-200, S-300, S-310G, S-525, S-600, S-700 and S-710, and mixtures thereof. Suitable molybdenum components are described in US 5,650,381; US ​​RE 37,363 E1; US ​​RE 38,929 E1; and US RE 40,595 E1, the entireties of which are incorporated herein by reference.

[0159] 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 text of which is incorporated herein by reference.

[0160] 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, which is incorporated herein by reference in its entirety.

[0161] The oil-soluble molybdenum compound may be present in an amount sufficient to provide from about 0.5 ppm to about 2000 ppm, from about 1 ppm to about 700 ppm, from about 1 ppm to about 550 ppm, from about 5 ppm to about 300 ppm, or from about 20 ppm to about 250 ppm of molybdenum.

[0162] Compounds containing transition metalsIn another embodiment, the oil-soluble compound may be a transition metal-containing compound or metalloid. Transition metals may include, but are not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten, etc. Suitable metalloids include, but are not limited to, boron, silicon, antimony, tellurium, etc.

[0163] In one embodiment, the oil-soluble transition metal-containing compound may 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 may be an oil-soluble titanium compound, such as a titanium (IV) alkoxide. Among the titanium-containing compounds that may be used in the disclosed technology or may 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) alkoxides, 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 carboxylates, 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 that are 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.

[0164] 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 free, condensable-NH functional groups; (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.

[0165] Another titanium-containing compound can be a titanium alkoxide with a C6 to C 25 The reaction product of carboxylic acid. The reaction product can be represented by the following formula:

[0166]

[0167] 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:

[0168]

[0169] wherein m+n=4 and n is in the range of 1 to 3, R4 is an alkyl moiety having a carbon atom range of 1 to 8, R1 is selected from a hydrocarbon group containing about 6 to 25 carbon atoms, and R2 and R3 are the same or different and are selected from a hydrocarbon group containing about 1 to 6 carbon atoms, or the titanium compound can be represented by the following formula:

[0170]

[0171] wherein x is in the range of 0 to 3, R1 is selected from a hydrocarbon group containing about 6 to 25 carbon atoms, R2 and R3 are the same or different and are selected from a hydrocarbon group containing about 1 to 6 carbon atoms, and R4 is selected from H, or C6 to C 25A group consisting of carboxylic acid moieties.

[0172] 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.

[0173] 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.

[0174] Viscosity Index Improver :The lubricating oil composition herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutylene, hydrogenated styrene-isoprene polymers, styrene / maleic acid ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, α-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.

[0175] 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.

[0176] Viscosity Index Improvers and / or Dispersants The total amount of viscosity index improvers can be 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.

[0177] Other optional additives Other 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.

[0178] 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 swelling agents and mixtures thereof. Typically, a fully formulated lubricating oil will contain one or more of these performance additives.

[0179] 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.

[0180] Suitable foam suppressors include silicon-based compounds such as siloxanes.

[0181] Suitable pour point depressants may include polymethyl methacrylate or mixtures thereof. The pour point depressant may be present in an amount sufficient to provide from about 0 wt % to about 1 wt %, from about 0.01 wt % to about 0.5 wt %, or from about 0.02 wt % to about 0.04 wt % based on the final weight of the lubricating oil composition.

[0182] Suitable rust inhibitors can be single compounds or compound mixtures having 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.

[0183] 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.

[0184] Generally speaking, suitable lubricants including the neutral to overbased and sulfurized alkyl phenate products herein may include additive components within the ranges listed in the table below.

[0185] Table 2: Suitable lubricating compositions

[0186]

[0187] 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 oils 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.

[0188] Example

[0189] 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.

[0190] Example 1

[0191] The terminal unsaturation and oligomeric configuration of various polyalphaolefin oligomers were evaluated. The characterization of the oligomers is provided in Table 3 below. Oligomer A is obtained by oligomerization of 1-decene monomer in the presence of a solid acid catalyst. Oligomer B is a C10 dimer. Oligomer C is mainly C20-C26 olefins. Oligomer D is a mixture of C10 oligomers with a high vinylidene content.

[0192] Table 3

[0193]

[0194] Example 2

[0195] The oligomers from Table 3 of Example 1 were used to alkylate phenol in the presence of a solid catalyst. The results of the alkylation are provided in Table 4 below. For each case, the alkylation was conducted in the presence of a solid catalyst at about 110°C and lasted from about 4 hours to about 6 hours.

[0196] Table 4

[0197]

[0198] *Mole percentages reflect alkylphenol content and do not include any unreacted olefins or other by-products.

[0199] Example 3

[0200] Sulfurized phenate lubricant additives were prepared as described in Table 5 below. Samples 1 and 2 are comparative additives prepared using alkylphenols derived from tetrapropylene (C12). Sample 3 is an additive of the present invention obtained from an alkylphenol derived from a polyalphaolefin oligomer having the characteristics of Oligomer D of Tables 3 and 4 above.

[0201] Table 5 Sulfurized phenate additives

[0202]

[0203] **Active detergent % is the non-diluted oil portion of the additive blend.

[0204] As shown in Table 5, the inventive additives with higher active detergent content (i.e., lower diluent oil) exhibit lower viscosity than the comparative additives. Thus, the inventive phenate 3 obtained with the polyalphaolefin oligomers herein can achieve the desired viscosity with a lower active phenate detergent.

[0205] 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. The term "comprising" and its grammatical variations as used herein are intended to be non-limiting, such that recitation of items in a list does not exclude other similar items that can be substituted or added to the listed items.

[0206] 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.

[0207] 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.

[0208] 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.

[0209] 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.

[0210] 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.

[0211] 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 sulfurized alkylphenol salt comprising a polyalphaolefin-substituted bridged hydroxyaromatic compound or a salt thereof, wherein the polyalphaolefin is derived from one or more C6 to C14 monomers that form oligomers in the form of dimers, trimers, tetramers, pentamers, or combinations thereof, or copolymers of the oligomers, copolymer variants of the oligomers, or combinations thereof; and wherein 40 mol% or more of the polyalphaolefin contains carbon atoms configured to form a tertiary carbenium ion that is positioned to react with the hydroxyaromatic compound in the para position.

2. The sulphurized alkylphenate of claim 1 , wherein at least one alkyl group adjacent to the tertiary carbenium ion is an alkyl group having 1, 2 or 3 carbon atoms.

3. The sulphurized alkyl phenate according to claim 1, wherein the poly alpha-olefin is obtained from one or more C8 to C12 monomers that form the oligomers in the form of dimers, trimers, tetramers, pentamers or combinations thereof.

4. The sulfurized alkylphenate according to claim 1, wherein 50 mol% or more of the poly-alpha-olefin contains carbon atoms configured to form tertiary carbenium ions.

5. The sulfurized alkyl phenate of claim 1, wherein the poly-alpha-olefin comprises a vinylidene olefin, a tri-substituted olefin, or a mixture thereof.

6. The sulfurized alkylphenate of claim 5, wherein the polyalphaolefin contains greater than 40 mol% of the vinylidene olefin, the trisubstituted olefin, or a mixture thereof.

7. The sulfurized alkylphenate according to claim 5, wherein the poly-alpha-olefin is a tri-substituted olefin and contains 40 wt% or more of the dimer.

8. The sulfurized alkylphenol salt according to claim 7, wherein the poly-alpha-olefin comprises 40 wt% or less of the trimer; and / or 20 wt% or less of the tetramer; and / or 5 wt% or less of the pentamer.

9. The sulfurized alkyl phenol salt according to claim 1, wherein the poly-alpha-olefin contains a vinylidene olefin, a tri-substituted olefin or a mixture thereof and contains 40 wt% or more of a C3 or C2 or C1 alkyl group adjacent to the tertiary carbenium ion.

10. The sulfurized alkylphenol according to claim 1, wherein the poly-α-olefin contains a double bond having a vinylidene structure and / or a tri-substituted structure.

11. A detergent composition comprising a sulfurized alkyl phenol salt having the structure of Formula IX: (Formula IX) in Each R 24 The polyalphaolefin is independently a polyalphaolefin derived from one or more C6 to C14 monomers that form oligomers in the form of dimers, trimers, tetramers, pentamers, or combinations thereof, or copolymers of said oligomers, copolymer variants of said oligomers, or combinations thereof, comprising residues of tertiary carbocations forming bonds to aromatic rings, wherein at least 50 mol % of R 24 is bonded to the aromatic ring in the para position; wherein each R 24 independently having 40 wt % or more of at least one alkyl group adjacent to a tertiary carbenium ion having 1, 2 or 3 carbon atoms; x is an integer from 1 to 4; and M 2+ It is a divalent metal ion.

12. The detergent composition according to claim 11, wherein each R 24 Independently formed from one or more C8 to C12 monomers, the one or more C8 to C12 monomers form the oligomer in the form of the dimer, the trimer, the tetramer, the pentamer or a combination thereof.

13. The detergent composition according to claim 11, wherein R 24 Derived from vinylidene olefins, trisubstituted olefins or mixtures thereof.

14. The detergent composition according to claim 13, wherein the R 24 Contains 40 mol% or more of the vinylidene olefin, the trisubstituted olefin or a mixture thereof.

15. The detergent composition according to claim 13, wherein the R 24 is a trisubstituted olefin, and 40 wt % or more of R 24 It is a dimer.

16. The detergent composition according to claim 15, wherein 40 wt % or less of R 24 is a trimer, 20 wt% or less of R 24 is a tetramer, and / or 5 wt% or less of R 24 It is a pentamer.

17. The detergent composition according to claim 11, wherein the R 24 The group is derived from a mixture of oligomers, and the oligomers have the following structures of Formula VI and / or Formula VII: in R 11 is an alkyl group; R 12 , R 13 , R 14 , R 15 and / or R 16 Each of which is the same or different at each occurrence and independently represents hydrogen or a substituted hydrocarbyl group or an unsubstituted hydrocarbyl group; R 17 , R 18 and R 19 Only one of them is hydrogen, and R 17 , R 18 and R 19 One of the remaining two in is a substituted hydrocarbyl group or an unsubstituted hydrocarbyl group having 1, 2 or 3 carbon atoms, and R 17 , R 18 and R 19 The other of the remaining two is a substituted hydrocarbyl group or an unsubstituted hydrocarbyl group; R 20 , R 21 , R 22 and / or R 23 Each of which is the same or different at each occurrence and independently represents hydrogen or a substituted hydrocarbyl group or an unsubstituted hydrocarbyl group; Each n is independently an integer from 0 to 3.

18. A lubricating oil composition comprising the sulfurized alkyl phenol according to claim 1 and one or more base oils of lubricating viscosity.

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

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