Polyalphaolefinphenol with high para-selectivity

Abstract

The present disclosure provides detergent additives and methods for preparing sulfurized alkylphenate products from polyalphaolefins.

Description

[Technical field]

[0001] The present disclosure relates generally to lubricating oil compositions and sulfurized additives therefor that are provided from polyalphaolefin-substituted phenols and salts thereof that have high para-position selectivity and / or reactivity on the aromatic ring. [Background technology]

[0002] Metal salts of sulfurized alkylphenols, also known as alkylphenates, tend to be useful lubricating oil additives. These additives can function, for example, as detergents, friction modifiers, and / or dispersants, while when used in lubricants in automotive applications, they provide an alkaline base to aid in neutralizing acids generated during vehicle operation. Unsulfurized variants of some alkylphenates or phenols (e.g., tetrapropylene phenol or phenates with C12 alkyl substitution) tend to be less useful and less desirable in lubricating oils for a number of reasons. As such, additive manufacturers seek to minimize the levels of such unsulfurized alkylphenates and / or alkylphenols in their additives.

[0003] However, current methods have one or more drawbacks when trying to minimize the level of unsulfurized alkylphenate / phenol variants when the additive is also overbased. Varying the alkyl substitution may be one possible option, but alternative alkyl substitution on the phenol moiety is also problematic in the context of overbased lubricant detergents. Desirable lubricant additives prefer alkyl substitution at the para position of the aromatic ring because, among other reasons, such substitution allows for efficient sulfurization and functionality as an overbased detergent. However, many suitable alkyl substituents from other olefins preferentially alkylate at the ortho position, which is undesirable in the context of lubricant additives. Summary of the Invention

[0004] According to one embodiment, described herein is a sulfurized alkylphenate containing polyalphaolefin-substituted bridged hydroxyaromatic compound or salt thereof, in which the polyalphaolefin is derived from C6-C14 monomers that form dimers, trimers, tetramers, pentamers, copolymers thereof, copolymer variants thereof, or combinations thereof.

[0005] In other embodiments, the sulfurized alkylphenates of the preceding paragraph may be combined in any combination with one or more optional features or embodiments. These optional features or embodiments may include one or more of the following: about 40 mole percent or more of the polyalphaolefin comprises a carbon atom configured to form a tertiary carbocation; and / or 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 the carbon atom configured to form the tertiary carbocation is positioned to react with the hydroxy aromatic compound at the para position; and / or the polyalphaolefin is derived from C6-C12 monomers that form dimers, trimers, tetramers, pentamers, or combinations thereof, preferably C8-C10 monomers that form dimers, trimers, tetramers, pentamers, or combinations thereof; and / or about 50 mole percent of the polyalphaolefin is a tertiary carbocation; and / or 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 the carbon atom configured to form the tertiary carbocation is positioned to react with the hydroxy aromatic compound at the para position; and / or the polyalphaolefin is derived from C6-C12 monomers that form dimers, trimers, tetramers, pentamers, or combinations thereof, preferably C8-C10 monomers that form dimers, trimers, tetramers, pentamers, or combinations thereof; and / or at least about 50 mole percent of the polyalphaolefin is a tertiary carbocation; at least about 60 mole percent, more preferably at least about 75 mole percent, more preferably at least about 85 mole percent, and most preferably at least about 90 mole percent, comprise carbon atoms configured to form tertiary carbocations; and / or the polyalphaolefin comprises a vinylidene olefin, a tri-substituted olefin, or a mixture thereof; and / or the polyalphaolefin comprises greater than about 40 mole percent, greater than about 50 mole percent, greater than about 75 mole percent, or greater than about 90 mole percent vinylidene olefin; and / or the polyalphaolefin is a tri-substituted olefin and comprises greater than about 40 weight percent dimer, preferably greater than about 50 weight percent dimer, and more preferably greater than about 70 weight percent dimer;and / or the polyalphaolefin comprises about 40 weight percent or less of trimers, and / or about 20 weight percent or less of tetramers, and / or about 5 weight percent or less of pentamers, and / or the polyalphaolefin comprises primarily vinylidene olefins, tri-substituted olefins, or mixtures thereof, and comprises about 40 weight percent or more, preferably about 50 weight percent or more, and more preferably about 75 weight percent or more of C3 or less alkyl groups adjacent to tertiary carbocations; and / or the polyalphaolefin comprises double bonds having vinylidene and / or tri-substituted structures; and / or the polyalphaolefin comprises about 40 mole percent or more of vinylidene olefins, tri-substituted olefins, or combinations thereof, preferably about 60 mole percent or more, more preferably about 75 mole percent or more, even more preferably about 85 mole percent or more, and most preferably about 90 mole percent or more;

[0006] In yet another embodiment, provided herein is a detergent composition comprising a sulfurized alkylphenate having the structure of formula IX, wherein formula IX is:

[0007] [ka] wherein each R 24 is a polyalphaolefin derived from C6-C14 monomers that independently form dimers, trimers, tetramers, pentamers, copolymers, copolymer variants, or combinations thereof, including residues of tertiary carbocations that form bonds to aromatic rings; R 24 at least 50 mole percent of are attached to the aromatic ring at the para position, x is an integer of 1 or 4, M 2+ is a divalent metal ion.

[0008] In other embodiments, the detergent compositions of the preceding paragraphs can be combined in any combination with one or more optional features or embodiments. These optional features or embodiments may include one or more of the following: 24has at least one alkyl group adjacent to a tertiary carbocation, independently having 1, 2, or 3 carbon atoms, preferably 2 carbon atoms, more preferably 1 carbon atom; and / or each R 24 is formed independently from C8 to C12 monomers that form dimers, trimers, tetramers, pentamers, or combinations thereof, preferably from C8 to C10 monomers that form dimers, trimers, tetramers, pentamers, or combinations thereof; and / or R 24 is derived from a vinylidene olefin, a trisubstituted olefin, or a mixture thereof; and / or R 24 contains about 40 mole percent or more, about 50 mole percent or more, about 75 mole percent or more, or about 90 mole percent or more vinylidene olefins; and / or R 24 is a trisubstituted olefin, and about 40 weight percent or more of R 24 is a dimer and about 50 weight percent or more of R 24 is a dimer, or about 70% by weight or more of R 24 is a dimer; and / or about 40% by weight or less of R 24 is a trimer and has about 20 weight percent or less of R 24 is a tetramer; and / or has about 5 wt. % or less of R 24 is a pentamer; and / or about 40% by weight or more, preferably about 50% by weight or more, more preferably about 75% by weight or more of the alkyl groups adjacent to the tertiary carbocation are C3 or lower alkyl groups; and / or R 24 The group is derived from a mixture of oligomers, where a majority of the oligomers in the mixture have the structure of Formula VI and / or Formula VII below.

[0009] [ka] R 11 is an alkyl group, R 12 , R 13 , R 14 , R 15 , and / or R 16each occurrence is the same or different and independently represents hydrogen or a substituted or unsubstituted hydrocarbyl group; R 17 , R 18 and R 19 is hydrogen and R 17 , R 18 and R 19 one of the remaining two is a substituted or unsubstituted hydrocarbyl group having 1, 2 or 3 carbons; R 17 , R 18 and R 19 the other of the remaining two is a substituted or unsubstituted hydrocarbyl group; R 20 , R 21 , R 22 , and / or R 23 each occurrence is the same or different and independently represents hydrogen or a substituted or unsubstituted hydrocarbyl group; and each n is independently an integer from 0 to 3.

[0010] In still further embodiments, provided herein is a lubricating oil composition comprising the sulfurized alkylphenate or detergent composition of any embodiment of the inventive summary in combination with one or more base oils of lubricating viscosity.

[0011] In a further aspect, described herein are alkyl phenols suitable for forming sulfurized alkyl phenate detergent compositions, in which the alkyl phenol comprises the reaction product of a hydroxyaromatic compound with a polyalphaolefin oligomer derived from a C6-C14 dimer, trimer, tetramer, pentamer, copolymer, copolymer variant, or combination thereof.

[0012] In other embodiments of the alkylphenol of the preceding paragraph, the alkylphenol may be combined with any of the optional embodiments or features in any combination. The optional features or embodiments may include one or more of the following: the polyalphaolefin oligomer is derived from a C8 to C12 dimer, trimer, tetramer, pentamer, or combination thereof, preferably a C8 to C10 dimer, trimer, tetramer, pentamer, or combination thereof; and / or about 40 mole percent or more of the polyalphaolefin oligomer comprises 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 has 2 carbon atoms, and more preferably has 1 carbon atom; and / or the reaction product has the structure of formula VIIIa, VIIIb, and / or VIIIc,

[0013] [ka] In the formula, R 11 is an alkyl group; R 12 , R 13 , R 14 , R 15 , and / or R 16 each occurrence is the same or different and independently represents hydrogen or a substituted or unsubstituted hydrocarbyl group; R 17 , R 18 and R 19 is hydrogen and R 17 , R 18 and R 19 one of the remaining two is a substituted or unsubstituted hydrocarbyl group having 1, 2 or 3 carbons; R 17 , R 18 and R 19 the other of the remaining two is a substituted or unsubstituted hydrocarbyl group; R 20 , R 21 , R 22 , and / or R 23are the same or different at each occurrence and independently represent hydrogen or a substituted or unsubstituted hydrocarbyl group; each n is independently an integer from 0 to 3; and / or wherein about 50 mole percent or more, preferably about 60 mole percent or more, preferably about 75 mole percent or more, preferably 85 mole percent or more, and most preferably about 90 mole percent or more of the alkyl substitution is in the para position of the aromatic ring; and / or wherein the polyalphaolefin oligomer comprises a vinylidene olefin, a trisubstituted olefin, or a mixture thereof; and / or wherein the polyalphaolefin oligomer comprises about 40 mole percent or more, about 50 mole percent or more, about 75 mole percent or more, or about 90 mole percent or more vinylidene olefin; and / or wherein the polyalphaolefin oligomer is a trisubstituted olefin, wherein greater than or equal to about 40 weight percent of the polyalphaolefin oligomer is a dimer, greater than or equal to about 50 weight percent of the polyalphaolefin oligomer is a dimer, or greater than or equal to about 70 weight percent of the polyalphaolefin oligomer is a dimer; and / or less than or equal to about 40 weight percent of the polyalphaolefin oligomer is a trimer, less than or equal to about 20 weight percent of the polyalphaolefin oligomer is a tetramer; and / or less than or equal to about 5 weight percent of the polyalphaolefin oligomer is a pentamers; and / or greater than or equal to about 40 weight percent of the alkyl groups adjacent to the tertiary carbocation are C3 or lower, preferably greater than or equal to about 50 weight percent, more preferably greater than or equal to about 75 weight percent.

[0014] In yet another embodiment, there is provided the use of a polyalphaolefin as described in any of the embodiments of the present summary to form a detergent composition and / or a substituted bridged hydroxyaromatic compound or salt thereof for use in a detergent composition.

[0015] The following definitions are provided to clarify the meaning of certain terms used herein.

[0016] The terms "oil composition," "lubricant composition," "lubricating oil composition," "lubricant," "lubricating oil composition," "lubricating composition," "fully formulated lubricating oil composition," and "lubricant" are considered to be synonymous and fully interchangeable terms and refer to a finished lubricating product that contains a major amount of a base oil and a minor amount of an additive composition.

[0017] As used herein, the terms "additive package," "additive concentrate," and "additive composition" are considered to be synonymous and fully interchangeable terms that refer to that portion of a lubricating oil composition that excludes a major amount of a base oil stock blend.

[0018] The term "overbased", unless otherwise specified, refers to metal salts such as metal salts of sulfonates, carboxylates, salicylates, and / or phenates, in which the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level of more than 100% (i.e., such salts may contain more than 100% of the theoretical amount of metal required to convert the acid to its "standard salt", "neutral salt"). The expression "metal ratio", often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of the metal in an overbased salt to the chemical equivalents of the metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the metal ratio is 1, while in overbased salts the MR is greater than 1. These are generally referred to as overbased, highly based, or superbased salts and may be salts of organic sulfur acids, carboxylic acids, salicylates, sulfonates, and / or phenols.

[0019] The term "alkaline earth metals" refers to calcium, barium, magnesium, and strontium, while the term "alkali metals" refers to lithium, sodium, potassium, rubidium, and cesium.

[0020] As used herein, unless otherwise specified, the term "hydrocarbyl" or "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense, well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having a predominantly hydrocarbon character. Each hydrocarbyl group is independently selected from hydrocarbon substituents, the substituted hydrocarbon substituents containing one or more of halo, hydroxyl, alkoxy, mercapto, nitro, nitroso, amino, pyridyl, furyl, imidazolyl, oxygen, and nitrogen, and no more than two non-hydrocarbon substituents are present for every 10 carbon atoms in the hydrocarbyl group. In some embodiments, hydrocarbyl includes the term "alkyl". As used herein, the term "alkyl" refers to linear, branched, cyclic, and / or substituted saturated chain moieties of about 1 to about 100 carbon atoms, unless otherwise specified. The term "alkenyl" as used herein refers to straight, branched, cyclic, and / or substituted unsaturated chain moieties of about 3 to about 10 carbon atoms. The term "aryl" as used herein refers to monocyclic and polycyclic aromatic compounds containing, but not limited to, alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and / or heteroatoms including nitrogen, oxygen, and sulfur.

[0021] As used herein, unless otherwise specified, the term "hydrocarbylene substituent" or "hydrocarbylene group" is used in its ordinary sense, as is well known to those skilled in the art. Specifically, it refers to a group that is directly attached to the remainder of the molecule by carbon atoms at two locations in the molecule and has a predominantly hydrocarbon character. Each hydrocarbylene group is independently selected from divalent hydrocarbon substituents, where the substituted divalent hydrocarbon substituents include halo, alkyl, aryl, alkylaryl, arylalkyl, hydroxyl, alkoxy, mercapto, nitro, nitroso, amino, pyridyl, furyl, imidazolyl, oxygen, and nitrogen, and no more than two non-hydrocarbon substituents are present for every 10 carbon atoms in the hydrocarbylene group.

[0022] As used herein, unless expressly stated otherwise, the term "weight percent" means the percentage that the recited component represents relative to the weight of the entire composition.

[0023] The terms "soluble", "oil-soluble" or "dispersible" used herein may, but do not necessarily, indicate that a compound or additive is soluble, dissolvable, miscible, or can be suspended in oil in any proportion. However, the terms mean that they are, for example, soluble, suspendable, soluble, or stably dispersible in oil to a sufficient degree to exert their intended effect in the environment in which the oil is used. Furthermore, if desired, the incorporation of other additives may also allow the incorporation of higher levels of the specific additive.

[0024] As used herein, the term "TBN" is used to indicate the total base number in mg KOH / g, as measured by the method of ASTM D2896.

[0025] The term "lime" as used herein refers to, for example, calcium hydroxide, calcium oxide, also known as slaked lime or hydrated lime, and similar compounds.

[0026] The molecular weight of any embodiment herein may be determined using a gel permeation chromatography (GPC) instrument obtained from Waters or similar instrument, and data processed with Waters Empower Software or similar software. The GPC instrument may be provided with a Waters separation module and a Waters refractive index detector (or similar optional instrument). GPC operating conditions may include a guard column, four Agilent PLgel columns (length 300×7.5 mm, particle size 5μ, and pore size ranging from 100 to 10000 Å), and a column temperature of about 40° C. Non-stabilized HPLC grade tetrahydrofuran (THF) may be used as the solvent at a flow rate of 1.0 mL / min. The GPC instrument may be calibrated with commercially available polystyrene (PS) standards with narrow molecular weight distributions ranging from 500 to 380,000 g / mol. The calibration curve may be extrapolated for samples having masses less than 500 g / mol. Samples and PS standards are dissolved in THF and prepared at a concentration of 0.1-0.5 wt.% and can be used without filtration. GPC measurements are also described in U.S. Pat. No. 5,266,223, which is incorporated herein by reference. The GPC method additionally provides molecular weight distribution information. See, for example, W.W. Yau, J.J. Kirkland and D.D. Ly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979, which is incorporated herein by reference.

[0027] Additional details and advantages of the disclosure will be set forth in part in the following description and / or may be learned by practice of the disclosure. The details and advantages of the disclosure may be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure as claimed. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0028] The present disclosure provides methods for preparing alkylphenol and phenate detergents in conjunction with phenols alkylated with polyalphaolefin oligomers configured with high para-substitution on the aromatic ring of the phenol, the phenate detergents and / or sulfurized phenate detergents thereof, base oils of lubricating viscosity and lubricating compositions comprising such phenate detergents, and neutral to overbased additives, such as detergents having a TBN of at least about 0, at least about 20, at least about 50, at least about 100, and otherwise from about 100 to about 500, as discussed further below.

[0029] In one approach or embodiment, the present disclosure relates to polyalphaolefin-substituted alkylphenols having high para-selectivity and / or reactivity suitable for forming phenate detergents or sulfurized phenate detergents. The alkyl substitution is from polyalphaolefin oligomers derived from C6-C14 alpha-olefin monomers, the oligomers being in the form of dimers, trimers, tetramers, pentamers, or combinations thereof. The polyalphaolefin oligomers suitable for the alkylphenols herein have a number of polymeric properties that define their uniqueness in achieving high para-selectivity and / or reactivity in forming alkylphenols and / or their phenate derivatives. For example, in some aspects, the polyalphaolefin oligomers have about 40 mole percent or more, about 50 mole percent or more, about 60 mole percent or more, about 75 mole percent or more, about 85 weight percent or more, or even about 90 mole percent or more of at least one carbon atom configured to form a tertiary carbocation when protonated in the presence of a cationic acid catalyst. In other embodiments, the polyalphaolefin oligomer may also have at least one alkyl group adjacent to the tertiary carbocation, which is an alkyl group having 1, 2, or 3 carbon atoms. Alkylation of phenol with such oligomers is effective to preferentially form alkylphenols and / or salts thereof having high levels of para-alkylation from the polyalphaolefin oligomer. The alkylphenols herein derived from the polyalphaolefin oligomer have at least about 50 mole percent alkylation at the para position, or at least about 60 mole percent alkylation at the para position, or at least about 75 mole percent alkylation at the para position, or at least about 85 mole percent alkylation at the para position, or at least about 90 mole percent alkylation at the para position and up to about 100 mole percent alkylation at the para position (or any range between such points).

[0030] The oligomers herein include one or more C6-C14 alpha olefin monomer moieties, in other terms C8-C14 alpha olefin monomer moieties, in other terms C8-C12 alpha olefin monomer moieties, and in yet other terms C8-C10 alpha olefin monomer moieties. Thus, the alpha olefin monomer moieties have carbon numbers from 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, isomers thereof, or combinations thereof. As used herein, the term "olefin" is given its ordinary meaning in the art and generally refers to an olefin having the chemical formula C x H 2x where x is the number of carbon atoms and has a double bond in its structure. The term "alpha-olefin" is also given its ordinary meaning in the art and refers to an olefin having a double bond in the primary or alpha position in its structure. The oligomers herein can be formed from monomers, combinations of monomers or copolymers thereof, or variants of monomers or copolymers thereof that can be combined to form the various oligomer structures herein.

[0031] Polyalphaolefin Oligomer When alpha olefins are used for the alkylation of phenols, whether linear (i.e. normal) or isomerized, most are preferentially alkylated at the ortho position, which is generally undesirable for alkylphenols used as detergent additives. It is most desirable to leave the ortho position open for sulfurization and / or other phenol cross-linking reactions. As noted above, the novel polyalphaolefin oligomers herein have many oligomeric properties that define their uniqueness with respect to the phenol alkyl substituents having high para-position selectivity and reactivity in relation to the alkylation of phenols. For example, the polyalphaolefin oligomers herein have one or more of: (i) a high content of carbon atoms configured to form a tertiary carbocation when protonated in the presence of an acid catalyst; (2) at least one alkyl group, preferably having 1, 2, or 3 carbon atoms, adjacent to a tertiary carbocation; (3) a high weight percent of dimeric structures and a lower weight percent of trimer, tetramer, and / or pentameric structures; and / or (4) a relatively high mole percent of terminal unsaturation that is vinylidene configuration, and / or in some instances, a relatively high mole percent of trisubstituted configurations, and / or in other instances, a relatively high mole percent of both vinylidene and trisubstituted configurations.

[0032] Tertiary carbocations: In some embodiments, the polyalphaolefin oligomers herein have a high percentage of carbon atoms configured to form tertiary carbocations when protonated in the presence of a catalyst. A carbocation or carbonium ion is a carbon atom configured to carry a positive charge (such as when an unsaturated carbon is protonated with a cationic acid catalyst). The polyalphaolefin oligomers herein may have a high weight percentage of tertiary carbocations upon protonation with a catalyst, having the general structure of formula I below, where R1, R2, and R3 are alkyl or hydrocarbyl groups of the same or different alphaolefin oligomers.

[0033] [ka]

[0034] Carbon atoms configured to form tertiary carbocations may result from the specific configuration of alpha olefin oligomers (discussed further below) when protonated in the presence of a cationic acid catalyst. In one embodiment or approach, the polyalphaolefin oligomers herein have a structure with carbon atoms configured to form a relatively high percentage of oligomers with such tertiary carbocations. For example, the polyalphaolefin oligomers herein have a structure in which about 40 mole percent or more, preferably about 50 mole percent or more, more preferably about 60 mole percent or more, more preferably about 75 mole percent or more, even more preferably about 85 mole percent or more, most preferably about 90 mole percent or more, and in some embodiments about 100 mole percent or less, about 90 mole percent or less, or about 80 mole percent or less (and any range between such points) of the polyalphaolefins include carbon atoms 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 a high preference for para-alkylation of the hydroxyaromatic compound.

[0035] Short chain alkyl groups: In other embodiments, the polyalphaolefin oligomers herein may also have at least one alkyl group adjacent to the tertiary carbocation that is an alkyl group having 1, 2, or 3 carbon atoms. For example, at least one of R1, R2, or R3 in the general oligomer structure of formula I above is a C3 or lower alkyl group (preferably a C2 alkyl group, most preferably a C1 alkyl group). Without wishing to be limited by theory, it is believed that having such short chain alkyl groups adjacent to the tertiary carbocation improves the reactivity of the oligomer to para-substitution on the aromatic ring. In some embodiments, again without wishing to be limited by theory, the polyalphaolefin oligomers herein can contain about 40% by weight or more of C3 or lower alkyl groups adjacent to tertiary carbocations, about 50% by weight or more, about 60% by weight or more, or about 75% by weight or more of C3 or lower alkyl groups, and in other embodiments can contain about 100% by weight or less, about 90% by weight or less, about 80% by weight or less, or about 70% by weight or less of C3 or lower alkyl groups adjacent to tertiary carbocations (as well as any ranges between such points).

[0036] Dimer Structure: In yet further embodiments, the polyalphaolefin oligomers herein are mixtures of oligomeric compounds, and may have a high weight percent of dimer structure in the mixture, as well as lower weight percent of trimer, tetramer, and / or pentamer structures. For example, in some approaches, the polyalphaolefin oligomer may comprise about 40 weight percent or more of dimer, about 50 weight percent or more of dimer, about 60 weight percent or more of dimer, or about 75 weight percent or more of dimer, and in some approaches, about 100 weight percent or less of dimer, about 90 weight percent or less of dimer, about 80 weight percent or less of dimer, about 70 weight percent or less of dimer, or about 60 weight percent or less of dimer (as well as any range between such weight percent amounts). At the same time, the polyalphaolefin oligomers may comprise about 40 weight percent or less of trimers (in other approaches, about 30 weight percent or less) and / or about 20 weight percent or less of tetramers (in other approaches, about 18 weight percent or less or even about 12 weight percent or less), and / or about 5 weight percent or less of pentamers (in other approaches, about 4 weight percent or less or even about 3 weight percent or less), as well as any range between such weight percent amounts for each oligomer type. In other embodiments, the trimers may be from about 0 weight percent to about 40 weight percent, from about 1 weight percent to about 30 weight percent, from about 2 weight percent to about 30 weight percent, or from about 5 weight percent to about 30 weight percent. In other embodiments, the tetramers may be from about 0 weight percent to about 20 weight percent, from about 1 weight percent to about 18 weight percent, from about 2 weight percent to about 18 weight percent, or from about 5 weight percent to about 18 weight percent. In other embodiments, the pentamers can be from about 0 weight percent to about 5 weight percent, from about 1 weight percent to about 4 weight percent, or from about 2 weight percent to about 4 weight percent.

[0037] As used herein, dimer, trimer, tetramer, and pentamer are given their ordinary meaning in the art and generally refer to oligomers having two, three, four, and five monomer units, respectively. Thus, a dimer derived from a C10 alpha olefin monomer is a C20 oligomer, a trimer derived from a C10 alpha olefin monomer is a C30 oligomer, and so on for each monomer and oligomer configuration. Those skilled in the art will understand the respective molecular weights of each oligomer type. Preferably, the oligomers herein have a high weight percent of dimeric structures, but also one or more other oligomeric properties including simultaneously a high percentage of tertiary carbocations, a high percentage of short alkyl chains adjacent to tertiary carbocations, and a high percentage of vinylidene and / or trisubstituted configurations.

[0038] Oligomeric Unsaturation: In yet other embodiments, the polyalphaolefin oligomers herein may also have a relatively high percentage of unsaturation that is vinylidene configuration, a relatively high percentage of unsaturation that is trisubstituted configuration, and / or in some cases both vinylidene and trisubstituted configurations. In some approaches, the unsaturation is considered to be terminal unsaturation as discussed below. For example, in some embodiments, the polyalphaolefin oligomers herein comprise about 40 mole percent or more, in other approaches about 50 mole percent or more, in still other approaches about 60 mole percent or more, in still other approaches about 75 mole percent or more, in still other approaches about 85 mole percent or more, in still other approaches about 90 mole percent or more, and in still other approaches 100 mole percent or less, 95 mole percent or less, 90 mole percent or less (or any other range between such mole percent amounts) of vinylidene groups. In other embodiments, the polyalphaolefin oligomers herein comprise about 40 mole percent or more, in other ways about 50 mole percent or more, in still other ways about 60 mole percent or more, in still other ways about 75 mole percent or more, in still other ways about 85 mole percent or more, in still other ways about 90 mole percent or more, and in still other ways about 100 mole percent or less, 95 mole percent or less, 90 mole percent or less (or any other range between such mole percent amounts). In still other embodiments, the polyalphaolefin oligomers herein comprise about 40 mole percent or more, in other ways about 50 mole percent or more, in still other ways about 60 mole percent or more, in still other ways about 75 mole percent or more, in still other ways about 85 mole percent or more, in still other ways about 90 mole percent or more, and in still other ways about 100 mole percent or less, 95 mole percent or less, 90 mole percent or less (or any other range between such mole percent amounts).

[0039] Without wishing to be limited by theory, it is believed that the oligomers herein contain primarily terminal unsaturation. As understood by those skilled in the art, oligomer unsaturation refers to a carbon-carbon double bond with at least one of the carbons in the carbon-carbon double bond derived from a terminal monomer group or terminal monomer moiety in the oligomer structure as shown in the following formulas II-V, which reflect vinyl, disubstituted, vinylidene, and trisubstituted terminal unsaturation, as shown in the following formulas II-V, where ~ represents a bond to the remainder of the oligomer. In some approaches, the oligomers herein may have more than 75 mol% terminal unsaturation, more than 80 mol% terminal unsaturation, more than 85 mol% terminal unsaturation, more than 90 mol% terminal unsaturation, more than 95 mol% terminal unsaturation, or even more than 97 mol% terminal unsaturation. The molar percentage of unsaturation or terminal unsaturation can be expressed as: 13 C NMR (see, for example, U.S. Pat. No. 5,128,056, incorporated herein by reference).

[0040] [ka] In the formula, R4~R 10 is a linear or branched alkyl or hydrocarbyl group consistent with the monomeric and / or oligomeric structures discussed further herein. As shown herein, the cis and / or trans isomers of the various structures are intended to be interchangeable, and both cis 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 are included in any structure herein, for example. 1 It can be detected by, but not limited to, H-NMR. As discussed in US Patent Application Publication No. 2016 / 0257862, which is incorporated herein by reference, the amount of each unsaturated bond can be determined from the integrated intensity of each signal.

[0041] Oligomeric Structure: The polyalphaolefin oligomers herein, configured to have high reactivity and high preference for para-alkylation of phenol, may have one or more of the above oligomeric properties, and in some embodiments, may also have the oligomeric structure of formula VI (having a high percentage of vinylidene configuration) and / or formula VII (having a high percentage of tri-substituted configuration), and / or a combination of both formula VI and formula VII structures. For example, in some approaches, the polyalphaolefin compounds herein are polymeric molecules, preferably oligomeric molecules, produced from the oligomerization reaction of alphaolefin monomers in the presence of a catalyst system. The unsaturated polyalphaolefin oligomers herein are understood to include carbon-carbon double bonds therein, where such double bonds are primarily in terminal monomer groups or moieties as described above.

[0042] Each polyalphaolefin oligomer herein has a carbon chain having a maximum number of carbon atoms, which may be referred to as the main carbon chain or carbon backbone of the oligomer. The main chain or backbone typically includes carbon atoms derived from carbon-carbon double bonds in the monomer molecules involved in the oligomerization reaction, and / or any additional carbon atoms from the monomer molecules and / or molecules in the catalyst system that form the two ends of the backbone.

[0043] In some approaches or embodiments, suitable polyalphaolefin oligomers herein may include a mixture of oligomers (such as, but not limited to, those derived from the C6 to C14 monomers listed above), where a majority of the oligomers in the mixture have the structure of Formula VI and / or Formula VII below.

[0044] [ka]

[0045] In some embodiments of Formula VI, R 11 is an alkyl group, and R 12 , R13 , R 14 , R 15 , and / or R 16 Each occurrence is the same or different and independently represents hydrogen or a substituted or unsubstituted hydrocarbyl group (preferably a substituted or unsubstituted alkyl group). In some embodiments of Formula VII, R 17 , R 18 and R 19 is hydrogen and R 17 , R 18 and R 19 one of the remaining two is a substituted or unsubstituted hydrocarbyl group (preferably a substituted or unsubstituted alkyl group) having 1, 2 or 3 carbons; R 17 , R 18 and R 19 The other of the remaining two is a substituted or unsubstituted hydrocarbyl group (preferably a substituted or unsubstituted alkyl group). In yet another embodiment of Formula VII, R 20 , R 21 , R 22 , and R 23 Each of n is the same or different at each occurrence and independently represents hydrogen or a substituted or unsubstituted hydrocarbyl group (preferably a substituted or unsubstituted alkyl group). In either Formula VI and / or Formula VII, each n is independently an integer from 0 to 3 (wherein integer 0 represents a dimer, integer 1 represents a trimer, integer 2 represents a tetramer, and / or integer 3 represents a pentamer).

[0046] Without wishing to be limited by theory, in yet another embodiment or approach of the oligomer of Formula VI, R 11 may be a C4 to C12 alkyl group, R 12 may be hydrogen or a C1-C12 alkyl group, R 13 may be hydrogen or a C1-C12 alkyl group, R 14 may be hydrogen or a C1-C12 alkyl group, R 15 may be hydrogen or a C1-C12 alkyl group, and / or R 16may be hydrogen or an alkyl group (preferably from the catalyst system). One of skill in the art will appreciate that the structure of formula VI may also depend on the polymerization conditions, the catalyst selected, and / or the starting monomer mixture, among other features.

[0047] Without wishing to be limited by theory, in another embodiment or approach of the oligomer of Formula VII, R 19 If is hydrogen, R 17 or R 18 one of R is a C1-C3 alkyl group and the other is a C2-C12 alkyl group; 20 is a C4 to C12 alkyl group. 17 If is hydrogen, R 19 is a C1-C3 alkyl group, and R 18 is a C5 to C13 alkyl group, R 20 is C1 to C11. Similarly, R 18 If is hydrogen, R 19 is a C1-C3 alkyl group, and R 17 is a C5 to C13 alkyl group, R 20 is C1 to C11. Further, in this embodiment of Formula VII, R 21 is hydrogen or a C1-C12 alkyl group, R 22 is hydrogen or a C1-C12 alkyl group, and R 23 is hydrogen or an alkyl group (preferably from the catalyst system). One of skill in the art will appreciate that the structure of formula VII may also depend on the polymerization conditions, the selected catalyst, and / or the starting monomer mixture, among other features.

[0048] The oligomers herein may be prepared using polymerization catalysts and conditions known to those skilled in the art. The oligomerization reaction conditions may be controlled as necessary to provide the desired oligomers herein. Parameters such as reaction temperature, pressure, mixing, reactor heat management, feed rate of one or more reactants, type, ratio, and concentration of catalyst and / or cocatalyst and / or scavenger, and phase of the feed components may be controlled to affect the structure of the copolymer resulting from the reaction. Thus, a combination of several different reaction conditions known to those skilled in the art may be controlled to produce the desired oligomers herein. In some approaches, polyalphaolefin oligomers suitable for alkylating phenols herein may be made using the process described in U.S. Patent Application Publication No. 2021 / 0347921, which is incorporated herein by reference in its entirety.

[0049] 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.

[0050] The oligomers herein can be formed by polymerizing C6-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 skilled in the art, a metallocene comprises a cyclopentadienyl anion ("Cp") bonded to a metal center. The coordination metallocene may comprise zirconium, and in some approaches, the coordination metallocene may comprise Cp2ZrCl2. The coordination polymerization catalyst may further comprise a cocatalyst. The cocatalyst may comprise, for example, methylaluminoxane.

[0051] The oligomers herein may be produced in a reactor, and the parameters that may be controlled during the process are known to those skilled in the art and may include suitable pressure and temperature management as described above. The reaction may be operated continuously, semi-continuously, or batchwise. The catalyst and cocatalyst, if used, may be provided to the reactor in solution. The weight percent of either the catalyst or cocatalyst in the solution may be less than about 20 weight percent, and according to different embodiments, may be less than about 15 weight percent, less than about 10 weight percent, less than about 8 weight percent, less than about 6 weight percent, less than about 5 weight percent, less than about 4 weight percent, less than about 3 weight percent, less than about 2 weight percent, or less than about 1 weight percent, as necessary to achieve the desired oligomers herein. The components may then be mixed in the reactor. Suitable catalysts and conditions therefor are known to those skilled in the art and may be described, for example, at least in U.S. Pat. Nos. 9,441,063 or 8,614,277, both of which are incorporated herein by reference.

[0052] In some approaches, free radical initiators may be used in the oligomerization process herein, if desired. The free radical initiator, if used, may be a peroxide, hydroperoxide, and / or azo compound having a boiling point above 100° C. and thermally decomposing within the reaction temperature range to provide free radicals. Exemplary free radical initiators may be azobutyronitrile, 2,5-dimethyl-hex-3-yn-2,5-bis-tert-butylperoxide; or hexene analogs thereof. The initiator may be provided at low levels of about 0.005 weight percent to about 1 weight percent, based on the total weight of the oligomer solution.

[0053] Alkylation of phenol Phenols or hydroxyaromatic compounds suitable for alkylation with oligomers herein include monohydroxy and / or polyhydroxyaromatic hydrocarbons having 1 to 4, and in some procedures 1 to 3, hydroxyl groups for alkylation with polyalphaolefin oligomers. Suitable compounds include, but are not limited to, phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, and the like, and mixtures thereof. Preferred starting compounds include phenol.

[0054] The alkylating agent includes one or more oligomers derived from the polyalphaolefin oligomers described above. The alkylation of the polyalphaolefin oligomer to the hydroxyaromatic compound may be carried out in the presence of a catalyst, such as Lewis acid catalysts, solid acid catalysts, trifluoromethanesulfonic acid, and other acidic molecular sieve catalysts. Exemplary Lewis acid catalysts are known to those skilled in the art and may include aluminum trichloride, aluminum tribromide, aluminum triiodide, boron trifluoride, boron tribromide, boron triiodide, and the like. In some approaches, the alkylation may use a sulfonated polystyrene solid catalyst, and the like. In some approaches, the molar ratio of the phenol or hydroxyaromatic compound to the polyalphaolefin oligomer may be from about 10:1 to about 0.5:1, and in other approaches, from about 5:1 to about 2:1 (or other ranges within such ratios).

[0055] The oligomeric polyalphaolefins having the above oligomeric characteristics are particularly suitable for alkylation to phenols or hydroxyaromatic compounds in the para position, although other substitutions may be present depending on the application. For example, the oligomeric alkyl groups (i.e., R 24The substituents, when used herein, may be at least about 40 mole percent (and in some approaches at least about 50, at least about 60, at least 75, at least about 85, or at least about 90 mole percent and up to about 100 mole percent (or any mole percent range between such amounts)) at the para positions on the aromatic rings, and from about 0 to about 15 mole percent, and in some approaches from about 0 to about 5 mole percent, disubstituted at the ortho positions on the aromatic rings. Additionally, the alkylated phenol may have the structure of formula VIII, VIIIa, VIIIb, or VIIIc below, and may have a high content of vinylidene and a group R as defined in any of the above embodiments. 11 ~R 23 and the above tri-substituted oligomer having an integer n. Formula VIIIb has R 17 or R 18 is hydrogen and R 19 is an alkyl group having 1, 2 or 3 carbon atoms, preferably R 19 is a C2 group, most preferably R 19 is formed when R is a C group. 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, most preferably R 17 or R 18 is a C1 group.

[0056] [ka] In embodiments, the alkylated phenols herein may include a bond to an aromatic ring of any structure of formula VIII, VIIIa, VIIIb, or VIIIc, or mixtures thereof, with structure VIIIc being most preferred.

[0057] Neutralization Neutralization is carried out by the alkylphenol herein reacting with a metal base. In one approach, neutralization is carried out by contacting the alkylphenol with a metal base under reactive conditions, in some approaches in a liquid hydrocarbon diluent containing a promoter, to provide a phenate or salt of the alkyl hydroxyaromatic compound. In some cases, the reaction can be carried out under an inert gas such as nitrogen. The metal base may be added at various times during the reaction, either in a single addition or multiple additions, if necessary for a particular application. Neutralization can occur via the exemplary reaction scheme I shown below, although other reactions can proceed as needed depending on the selected order of sulfurization, neutralization, and / or overbasing, as well as various applications, materials, and conditions.

[0058] [ka]

[0059] Exemplary metal base reactants include metal hydroxides, oxides, or alkoxides, such as, but not limited to, alkali metal salts derived from metal bases selected from alkali hydroxides, alkali oxides, or alkali alkoxides, or alkaline earth metal salts derived from metal bases selected from alkaline earth hydroxides, alkaline earth oxides, or alkaline earth alkoxides. Suitable metal base compounds include lithium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, ammonium hydroxide, and / or aluminum hydroxide. Other examples of metal base compounds include lithium oxide, magnesium oxide, calcium oxide, and barium oxide. In a preferred example, the alkaline earth metal base is lime or calcium hydroxide. The additive may be borated as needed depending on the application and use.

[0060] In an optional approach, the neutralizing solvent is a higher boiling point solvent, such as a solvent having a boiling point of about 100° C. or higher at the stated pressure, such as solvents such as ethylene glycol, propylene glycol, and / or decanol. As used herein, in such optional approaches, devoid of or free of such compounds means that the solvent has less than about 15 weight percent, less than about 5 weight percent, less than about 2 weight percent.

[0061] The neutralization reaction between the metal base and the alkylphenol is carried out under conditions effective to maintain an elevated temperature. In one approach, the neutralization occurs at a temperature of at least 100° C., in some approaches at least about 120° C., in other approaches at least about 150° C., and in more preferred approaches up to about 180° C. The neutralization reaction can occur for about 1 hour to about 5 hours.

[0062] sulfide The neutralized alkylphenol or alkylhydroxyaromatic compound may be sulfurized by contacting it with a sulfur source in a manner effective to achieve a high degree of sulfurization. In a process, the sulfurization generally introduces a sulfur bridging group between the alkylphenol or alkylhydroxyaromatic moieties. In some processes, the sulfur bridge is -S y - or -Sx- group (shown in the exemplary structure below), where x is independently an integer from 1 to 4, in other ways from 1 to 3, in some ways from 1 to 2, and / or has a total sulfur level provided by the additive of up to about 5 percent. The sulfur source can be any suitable sulfur, such as sulfur monochloride or dichloride, hydrogen sulfide, sulfur dioxide, and sodium sulfide hydrate, for example, elemental sulfur or its halides. The sulfur can be used either as molten sulfur, or as a solid (powder or particulate), or as a solid suspension in a hydrocarbon liquid. An exemplary reaction scheme for sulfurization is shown in Reaction Scheme II below, although other reactions can proceed as needed depending on the application, materials, and conditions.

[0063] [ka] Sulfiding can occur at a temperature of, for example, about 160° C. to about 250° C., or in other procedures, about 180° C. to about 245° C., for a time effective to achieve the desired level of sulfidation, which can be from about 1 to about 8 hours, from about 2 to about 7 hours, or from about 4 to about 7 hours.

[0064] Overbasing Overbasing is then optionally, but in some embodiments is preferred, either during the neutralization and / or sulfurization described above, or alternatively thereafter. In one approach, the sulfurized alkylphenol / alkylphenate is overbased by reacting with an excess of a metal base and / or by reacting with an acidic overbasing compound, such as carbon dioxide or boric acid. In one approach, overbasing is via carbonation (reaction with carbon dioxide) in the presence of a solvent, such as any of the solvents from the solvent system described above with neutralization. One convenient carbonation reaction is to pass gaseous carbon dioxide through the reaction mixture. Excess solvent and any water formed during the overbasing reaction can be removed as needed by distillation either during or after the reaction, as further discussed below.

[0065] In one embodiment, an exemplary overbasing reaction may be reacting a sulfurized alkylphenol or a salt thereof with an alkali metal or alkaline earth metal, such as lime, in the presence of carbon dioxide and a solvent system already discussed above. Conveniently, the reaction may be carried out by bubbling gaseous carbon dioxide through the reaction and solvent system mixture. In one approach, overbasing occurs at a temperature of at least about 50° C., in some approaches at least about 100° C., in other approaches at least about 165° C., and in more preferred approaches up to about 185° C. The degree of overbasing may be controlled by the amount of alkali metal or alkaline earth metal, the amount of carbon dioxide and other reactants (if any) added to the reaction mixture, and the reaction conditions used during the carbonation process. In the approach, overbasing or overbasing via carbonation occurs for a sufficient time to achieve the desired degree of overbasing or TBN, which in some approaches may be from about 30 minutes to about 250 minutes at the temperatures described.

[0066] After optional overbasing, the overbased sulfurized alkylphenates, for example, 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 ways from about 100 to about 500, from about 100 to about 400, or from about 150 to about 400, in yet other ways from about 200 to about 300, and in a further way from about 220 to about 275. Preferably, the TBN of the compositions herein may be from about 100 to about 300 mg KOH as measured by ASTM D-2896.

[0067] In embodiments, the exemplary overbased and sulfurized alkylphenate additives herein are R 24 The compound may have a structure of the following formula IX:

[0068] [ka] In the formula, each R 24 are independently as described above and may be polyalphaolefins derived from C6-C14 monomers (as described above) to form dimers, trimers, tetramers, pentamers, copolymers, copolymer variants, or combinations thereof that contain residues of tertiary carbocations that form bonds to aromatic rings as described herein above. 24 At least about 50 mole percent of are attached to the aromatic ring at the para position (in other approaches, at least about 60 mole percent, at least about 75 mole percent, at least about 85 mole percent, at least about 90 mole percent, or in other approaches, up to about 100 mole percent (as well as any ranges between such endpoints)). x is an integer from 1 to 4, as defined above, and M 2+ is a divalent metal ion as described above.

[0069] Post-processing After optional overbasing, the composition is often subjected to a number of steps to prepare the final sulfurized alkylphenate product. Examples of post-treatments can include one or more of vacuum stripping, distillation, sparging, filtration, degassing, evaporation, wiped film evaporation, centrifugation, dilution, liquid-liquid extraction, membrane separation, chromatography, absorption, supercritical extraction, and / or combinations thereof.

[0070] In embodiments, the sulfurized alkylphenate is made by sulfurization, neutralization, and / or carbonation. These reactions can be carried out in any order, simultaneously, or in a specific order, depending on the application. The sulfurization and neutralization are, for example, completed in any order or simultaneously, usually before carbonation. In general, the detergent additive or composition herein is obtained by first alkylating a phenol with an oligomer as described herein, neutralizing the alkylphenol, and then sulfurizing the neutralized alkylphenol with a sulfur source to provide a sulfurized and neutralized alkylphenol. The sulfurized and neutralized alkylphenol is then optionally overbased in the presence of a solvent to provide a neutral to optionally overbased and sulfurized alkylphenate additive or composition.

[0071] lubricating oil composition The optionally overbased and sulfurized alkylphenate products described herein, in combination with one or more further optional additives, may be combined with a major amount of a base oil or base oil blend of lubricating viscosity (as described below) to produce a lubricating oil composition comprising at least about 50 weight percent of a base oil, at least about 60 weight percent, at least about 70 weight percent, or at least about 80 weight percent to at most about 95 weight percent, at most about 90 weight percent, at most about 85 weight percent of a base oil as further discussed below.

[0072] In some approaches, the lubricating oil compositions herein may contain from about 0.02 to about 5 weight percent, in other approaches from about 0.2 to about 3 weight percent, and in yet other approaches from about 0.2 to about 2 weight percent of the optionally overbased and sulfurized alkylphenate product in the base oil or base oil blend.

[0073] In some approaches, the additives herein can be used as detergents in lubricating oils to neutralize acids and / or to help control rust, corrosion, and deposits. In addition, the detergents described herein may also be used in fuels, including, but not limited to, gasoline, diesel, and biodiesel, for spark, compression, and hybrid engines.

[0074] The lubricants, combinations of ingredients, dispersant inhibitor packages, and / or individual components herein may be suitable for use in various types of lubricants, such as automotive lubricants and / or greases, internal combustion engine oils, hybrid engine oils, electric engine lubricants, drivetrain lubricants, transmission lubricants, gear oils, hydraulic lubricants, tractor hydraulic fluids, metal working fluids, turbine engine lubricants, stationary engine lubricants, tractor lubricants, motorcycle lubricants, power steering fluids, clutch fluids, axle fluids, wet brake fluids, and the like.

[0075] Suitable engine types may include, but are not limited to, heavy duty diesel, passenger car, light duty diesel, medium speed diesel, or marine engines. The internal combustion engine may be a diesel fueled engine, a gasoline fueled engine, a natural gas fueled engine, a biofuel engine, a diesel / bio-fuel blended fuel-fuel engine, a gasoline / bio-fuel blended fuel-fuel engine, an alcohol fueled engine, a gasoline / alcohol fuel blended engine, a compressed natural gas (CNG) fueled engine, or 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 an electric or battery power source. Engines so configured are generally known as hybrid engines. The internal combustion engine may be a two-stroke, four-stroke, or rotary engine. Suitable internal combustion engines include marine diesel engines (such as inland marine), aviation piston engines, light duty diesel engines, as well as motorcycle, automobile, locomotive, and truck engines. The engine may be coupled with a turbocharger.

[0076] The lubricating oil composition for internal combustion engines may be suitable for any engine lubricant, regardless of sulfur, phosphorus, or sulfated ash (ASTM D-874) content. The sulfur content of the engine oil lubricant may be about 1 wt.% or less, or about 0.8 wt.% or less, or about 0.5 wt.% or less, or about 0.3 wt.% or less, or about 0.2 wt.% or less. In one embodiment, the sulfur content may range from about 0.001 wt.% to about 0.5 wt.%, or about 0.01 wt.% to about 0.3 wt.%. The phosphorus content may be about 0.2 wt.% or less, or about 0.1 wt.% or less, or about 0.085 wt.% or less, or about 0.08 wt.% or less, or even about 0.06 wt.% or less, about 0.055 wt.% or less, or about 0.05 wt.% or less. In one embodiment, the phosphorus content may be about 50 ppm to about 1000 ppm, or about 325 ppm to about 850 ppm. The total sulfated ash content may be about 2% by weight or less, or about 1.5% by weight or less, or about 1.1% by weight or less, or about 1% by weight or less, or about 0.8% by weight or less, or about 0.5% by weight or less. In one embodiment, the sulfated ash content may be about 0.05% by weight to about 0.9% by weight, or about 0.1% by weight or about 0.2% by weight to about 0.45% by weight. In another embodiment, the sulfur content may be about 0.4% by weight or less, the phosphorus content may be about 0.08% by weight or less, and the sulfated ash content is about 1% by weight or less. In yet another embodiment, the sulfur content may be about 0.3% by weight or less, the phosphorus content may be about 0.05% by weight or less, and the sulfated ash content may be about 0.8% by weight or less.

[0077] Additionally, the lubricants herein may meet one or more industry specification requirements, such as ILSAC GF-3, GF-4, GF-5, GF-6, PC-11, CF, CF-4, CH-4, CK-4, FA-4, CJ-4, CI-4 Plus, CI-4, API SG, SJ, SL, SM, SN, SN PLUS, ACEA A1 / B1, A2 / B2, A3 / B3, A3 / B4, A5 / B5, A7 / B7, C1, C2, C3, C4, C5, C6, E4 / E6 / E7 / E9, Euro 5 / 6, JASO DL-1, Low SAPS, Mid SAPS, or Dexos1™, Dexos2™, MB-Approval™, Dexos3™, Dexos4™, Dexos5™, Dexos6™, Dexos7™, Dexos8™, Dexos9™, Dexos10™, Dexos11™, Dexos12™, Dexos13™, Dexos14™, Dexos15™, Dexos16™, Dexos17™, Dexos18™, Dexos19™, Dexos21™, Dexos22™, Dexos23™, Dexos24™, Dexos25™, Dexos26™, Dexos27™, Dexos28™, Dexos29 ... 229.1, 229.3, 229.5, 229.51 / 229.31, 229.52, 229.6, 229.71, 226.5, 226.51, 228.0 / .1, 228.2 / .3, 228.31, 228.5, 228.51, 228.61, VW 501.01, 502.00, 503.00 / 503.01, 504.00, 505.00, 505.01, 506.00 / 506.01, 507.00, 508.00, 509.00, 508.88, 509.99, BMW Longlife-01, Longlife-01 FE, Longlife-04, Longlife-12 FE, Longlife-14 FE+, Longlife-17 FE+, Porsche A40, C30, Peugeot Citroen Automobiles B71 2290, B71 2294, B71 2295, B71 2296, B71 2297, B71 2300, B71 2302, B71 2312, B71 2007, B71 2008, Renault RN0700, RN0710, RN0720, Ford WSS-M2C153-H, WSS-M2C930-A, WSS-M2C945-A, WSS-M2C913A, WSS-M2C913-B, WSS-M2C913-C, WSS-M2C913-D, WSS-M2C948-B, WSS-M2C948-A, GM 6094-M, Chrysler MS-6395, Fiat 9.55535 G1, G2, M2, N1, N2, Z2, S1, S2, S3, S4, T2, DS1, DSX, GH2, GS1, GSX, CR1, Jaguar Land Rover STJLR.03.5003, STJLR.03.The phosphorus content of the final fluid may be suitable to meet the original equipment manufacturer's specifications, such as STJLR.03.5004, STJLR.03.5005, STJLR.03.5006, STJLR.03.5007, STJLR.51.5122, or past or future PCMO or HDD specifications not listed herein. In some embodiments for passenger car motor oil (PCMO) applications, the amount of phosphorus in the final fluid is 1000 ppm or less, or 900 ppm or less, or 800 ppm or less.

[0078] Base Oil or Base Oil Blend: The base oil used in the lubricating oil compositions herein may be an oil of lubricating viscosity and is selected from any of the base oils in Groups I-V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five base oil groups are generally set forth in Table 1 below.

[0079] [Table 1]

[0080] Group I, Group II, and Group III are mineral oil process feedstocks. Group IV base oils contain true synthetic molecular species produced by polymerization of olefinically unsaturated hydrocarbons. Many Group V base oils are also true synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers, and / or polyphenyl ethers, etc., but may also be natural oils, such as vegetable oils. It is noted that Group III base oils are derived from mineral oils, but the rigorous processing these fluids undergo makes their physical properties very similar to some true synthetic oils, such as PAOs. Thus, oils derived from Group III base oils may be referred to as synthetic fluids in the industry. Group II+ may include high viscosity index Group II.

[0081] The base oil blends used in the disclosed lubricating oil compositions can be mineral oils, animal oils, vegetable oils, synthetic oils, synthetic oil blends, or mixtures thereof. Suitable oils can be derived from hydrocracked, hydrogenated, hydrofinished, unrefined, refined, and rerefined oils, and mixtures thereof.

[0082] Unrefined oils are derived from natural, mineral, or synthetic sources with little or no further purification treatment. Refined oils are similar to unrefined oils, except that they have been treated with one or more purification steps that may result in the improvement of one or more properties. Examples of suitable purification techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Oils refined to edible quality may or may not be useful. Edible oils may also be called white oils. In some embodiments, the lubricating oil composition does not include edible oils or white oils.

[0083] Rerefined oils are also known as reclaimed or reprocessed oils. These oils are obtained similarly to refined oils using the same or similar processes. Often, these oils are additionally processed by techniques directed to the removal of spent additives and oil breakdown products.

[0084] Mineral oils may include oils obtained by drilling or from plants and animals, or any mixture thereof. For example, such oils may include, but are not limited to, castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricating oils, such as liquid petroleum oils, and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic, or mixed paraffinic-naphthenic types. Such oils may be partially or fully hydrogenated, if desired. Oils derived from coal or shale may also be useful.

[0085] Useful synthetic lubricating oils may include hydrocarbon oils such as polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylene, polypropylene, propylene isobutylene copolymers); poly(1-hexene), poly(1-octene), trimers or oligomers of 1-decene, such as poly(1-decene) (such materials are often referred to as alpha-olefins), and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers, and alkylated diphenyl sulfides, as well as derivatives, analogs, and homologs thereof, or mixtures thereof. The polyalphaolefins are typically hydrogenated materials.

[0086] Other synthetic lubricating oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans. Synthetic oils may be produced by Fischer-Tropsch reactions and are typically hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oils may be prepared by Fischer-Tropsch gas-liquid synthesis procedures, as well as other gas-liquid oils.

[0087] A major amount of base oil included in the lubricating composition may be selected from the group consisting of Group I, Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, but the major amount of base oil is other than the base oil resulting from the provision of an additive component or viscosity index improver in the composition. In another embodiment, a major amount of base oil included in the lubricating composition may be selected from the group consisting of Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, but the major amount of base oil is other than the base oil resulting from the provision of an additive component or viscosity index improver in the composition.

[0088] The amount of oil of lubricating viscosity present can be the difference remaining after subtracting the sum of the amounts of performance additives, including viscosity index improver(s) and / or pour point depressant(s) and / or other top treat additives, from 100% by weight. For example, the oil of lubricating viscosity may be present in the final fluid in a major amount, such as greater than about 50% by weight, greater than about 60% by weight, greater than about 70% by weight, greater than about 80% by weight, greater than about 85% by weight, or greater than about 90% by weight.

[0089] Optional Additives: The lubricating oil compositions herein may also contain a number of optional additives in combination with the optional overbased and sulfurized alkylphenate products as needed to meet performance criteria, which optional additives are described in the following paragraphs.

[0090] Dispersants: The lubricating oil composition may optionally contain one or more dispersants or mixtures thereof. Dispersants are often known as ashless dispersants because they do not contain ash-forming metals prior to mixing into the lubricating oil composition and do not normally contribute to ash when added to the lubricant. Ashless dispersants are characterized by having polar groups attached to relatively high molecular weight hydrocarbon chains. Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimides in which the number average molecular weight of the polyisobutylene substituent ranges from about 350 to about 50,000, or from about 5,000, or from about 3,000, as measured by GPC. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Pat. No. 7,897,696 or U.S. Pat. No. 4,234,435. The alkenyl substituent may be prepared from polymerizable monomers containing from about 2 to about 16, or from about 2 to about 8, or from about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines, typically poly(ethyleneamines).

[0091] Preferred amines are selected from polyamines and hydroxyamines. Examples of polyamines that can be used include, but are not limited to, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and higher homologs such as pentaethylaminehexamine (PEHA).

[0092] Suitable heavy polyamines are mixtures of polyalkylene-polyamines containing small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine), but primarily oligomers with 6 or more nitrogen atoms, 2 or more primary amines per molecule, and more extensive branching than conventional polyamine mixtures. Heavy polyamines preferably include polyamine oligomers containing 7 or more nitrogens per molecule and having 2 or more primary amines per molecule. Heavy polyamines contain more than 28% by weight (e.g., >32% by weight) of total nitrogen and primary amine groups with an equivalent weight of 120 to 160 grams per gram equivalent.

[0093] In some approaches, suitable polyamines are commonly known as PAM and contain a mixture of ethyleneamines, with TEPA and pentaethylenehexamine (PEHA) being the majority of the polyamine, usually less than about 80%.

[0094] Typically, PAM has 8.7-8.9 milliequivalents of primary amine per gram (115-112 grams equivalent per equivalent of primary amine) and a total nitrogen content of about 33-34% by weight. Heavier cuts of PAM oligomers that are substantially free of TEPA and contain only small amounts of PEHA, but contain primarily oligomers with more than 6 nitrogens and more extensive branching, may produce dispersants with improved dispersancy.

[0095] In embodiments, the present disclosure further comprises at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight in the range of from about 350 to about 50,000, or to about 5,000, or to about 3,000, as determined by GPC. The polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0096] In some embodiments, when polyisobutylene is included, the polyisobutylene may have a terminal double bond content of more than 50 mol%, more than 60 mol%, more than 70 mol%, more than 80 mol%, or more than 90 mol%. Such PIB is also referred to as highly reactive PIB ("HR-PIB"). HR-PIB having a number average molecular weight in the range of about 800 to about 5000 as determined by GPC is suitable for use in embodiments of the present disclosure. Conventional PIB typically has a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0097] HR-PIB having a number average molecular weight in the range of about 900 to about 3000 as determined by GPC may be suitable. Such HR-PIB is commercially available or can be synthesized by polymerization of isobutene in the presence of a non-chlorinated catalyst such as boron trifluoride, as described in U.S. Patent No. 4,152,499 to Boerzel, et al. and U.S. Patent No. 5,739,355 to Gateau, et al. When HR-PIB is used in the thermal ene reaction, it may result in higher conversion during the reaction and less precipitate formation due to increased reactivity. A suitable method is described in U.S. Patent No. 7,897,696.

[0098] In one embodiment, the present disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"), which may have an average of about 1.0 to about 2.0 succinic moieties per polymer.

[0099] The percent actives of the alkenyl or alkyl succinic anhydride can be determined using chromatographic techniques, which are described in U.S. Patent No. 5,334,321, columns 5 and 6.

[0100] Percent polyolefin conversion is calculated from the % actives using the formula in columns 5 and 6 of US Pat. No. 5,334,321.

[0101] Unless otherwise stated, all percentages are weight percent and all molecular weights are number average molecular weights as determined by gel permeation chromatography (GPC) using commercially available polystyrene standards (having number average molecular weights of 180 to about 18,000) as calibration standards.

[0102] In one embodiment, the dispersant may be derived from a polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant may be derived from an olefin maleic anhydride copolymer. As an example, the dispersant may be described as poly-PIBSA. In an embodiment, the dispersant may be derived from an anhydride grafted to an ethylene-propylene copolymer.

[0103] A suitable class of nitrogen-containing dispersants may be derived from olefin copolymers (OCPs), more specifically ethylene-propylene dispersants that may be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that may be reacted with the functionalized OCPs is described in U.S. Patent Nos. 7,485,603, 7,786,057, 7,253,231, 6,107,257, and 5,075,383, and / or is commercially available.

[0104] One class of suitable dispersants may also be Mannich bases. Mannich bases are materials formed by condensation of higher molecular weight alkyl-substituted phenols, polyalkylene polyamines, and aldehydes such as formaldehyde. Mannich bases are described in more detail in U.S. Pat. No. 3,634,515.

[0105] A suitable class of dispersants may also be high molecular weight esters or half ester amides. Suitable dispersants may also be post-treated by reaction with any of a variety of agents by conventional methods. Among these are boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydrides, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds. U.S. Patent No. 7,645,726, U.S. Patent No. 7,214,649, and U.S. Patent No. 8,048,831 are incorporated herein by reference in their entirety.

[0106] In addition to the carbonate and boric acid post-treatments, any of the compounds may be post-treated or further post-treated with a variety of post-treatments designed to improve or impart different properties. Such post-treatments include those summarized in columns 27-29 of U.S. Pat. No. 5,241,003, which is incorporated herein by reference. Such treatments include treatment with inorganic phosphoric acids or anhydrides (e.g., U.S. Pat. Nos. 3,403,102 and 4,648,980); organic phosphorus compounds (e.g., U.S. Pat. No. 3,502,677); phosphorus pentasulfide; boron compounds as already mentioned above (e.g., U.S. Pat. Nos. 3,178,663 and 4,652,387); carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Pat. Nos. 3,708,522 and 4,912,522); and / or carboxylic acids such as carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Pat. Nos. 3,708,522 and 4,912,522). 48,386; epoxides, polyepoxyates or thioepoxides (e.g., U.S. Pat. Nos. 3,859,318 and 5,026,495); aldehydes or ketones (e.g., U.S. Pat. No. 3,458,530); carbon disulfide (e.g., U.S. Pat. No. 3,256,185); glycidol (e.g., U.S. Pat. No. 4,617,137); urea, thiourea, or guanidine (e.g., U.S. Pat. No. 3,312,61 9, 3,865,813, and British Patent No. 1,065,595; organic sulfonic acids (e.g., U.S. Pat. No. 3,189,544 and British Patent No. 2,140,811); alkenyl cyanides (e.g., U.S. Pat. Nos. 3,278,550 and 3,366,569); diketenes (e.g., U.S. Pat. No. 3,546,243); diisocyanates (e.g., U.S. Pat. No. 3,573,205); alkanesuls t (e.g., U.S. Pat. No. 3,749,695); 1,3-dicarbonyl compounds (e.g., U.S. Pat. No. 4,579,675); sulfates of alkoxylated alcohols or phenols (e.g., U.S. Pat. No. 3,954,639); cyclic lactones (e.g., U.S. Pat. Nos. 4,617,138; 4,645,515; 4,668,246; 4,963,275; and 4,971,711);Cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132, 4,647,390, 4,648,886, 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent No. 2,140,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Pat. No. 4,612,132, U.S. Pat. No. 4,647,390, U.S. Pat. No. 4,648,886, U.S. Pat. No. 4,670,170); Nos. 4,614,603 and 4,666,460; cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132, 4,647,390, 4,646,860, and 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent No. 2,440,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiocarbonates, etc. olactams, thiolactones, or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460); cyclic carbamates, cyclic thiocarbamates, or cyclic dithiocarbamates (e.g., U.S. Pat. Nos. 4,663,062 and 4,666,459); hydroxyaliphatic carboxylic acids (e.g., U.S. Pat. Nos. 4,482,464; 4,521,318; and 4,713,189); oxidizing agents (e.g., U.S. Pat. No. 4,379,064); combinations of phosphorus pentasulfide and polyalkylene polyamines (e.g., U.S. Pat. Nos. 4,379,064); , U.S. Pat. No. 3,185,647; combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chlorides (e.g., U.S. Pat. Nos. 3,390,086, 3,470,098); combinations of hydrazine and carbon disulfide (e.g., U.S. Pat. No. 3,519,564); combinations of aldehydes and phenols (e.g., U.S. Pat. Nos. 3,649,229, 5,030,249, 5,039,307); combinations of aldehydes and O-diesters of dithiophosphoric acids (e.g., U.S. Pat. No. 3,865,740);Combinations of hydroxyaliphatic carboxylic acids and boric acid (e.g., U.S. Pat. No. 4,554,086); combinations of hydroxyaliphatic carboxylic acids followed by formaldehyde and phenols (e.g., U.S. Pat. No. 4,636,322); combinations of hydroxyaliphatic carboxylic acids and then aliphatic dicarboxylic acids (e.g., U.S. Pat. No. 4,663,064); combinations of formaldehyde and phenols and then glycolic acid (e.g., U.S. Pat. No. 4,699,724); combinations of hydroxyaliphatic carboxylic acids or oxalic acid followed by a diisocyanate (e.g., U.S. Pat. No. 4,713,191); inorganic acids or anhydrides of phosphorus. or a combination of its partial or total sulfur analogue and a boron compound (e.g., U.S. Pat. No. 4,857,214); a combination of an organic diacid, followed by an unsaturated fatty acid, followed by a nitrosoaromatic amine, optionally followed by a boron compound, and then a glycosylation agent (e.g., U.S. Pat. No. 4,973,412); a combination of an aldehyde and a triazole (e.g., U.S. Pat. No. 4,963,278); a combination of an aldehyde and a triazole, followed by a boron compound (e.g., U.S. Pat. No. 4,981,492); a combination of a cyclic lactone and a boron compound (e.g., U.S. Pat. Nos. 4,963,275 and 4,971,711), wherein the above-mentioned patents are incorporated herein in their entirety;

[0107] The TBN of suitable dispersants may be from about 10 to about 65 mg KOH / g dispersant on an oil-free basis, which equates to about 5 to about 30 TBN when measured on a dispersant sample containing about 50% diluent oil. TBN is measured by the method of ASTM D2896.

[0108] In yet another embodiment, the optional dispersant additive may be a hydrocarbyl-substituted succinamide or succinimide dispersant. In some approaches, the hydrocarbyl-substituted succinamide or succinimide dispersant may be derived from a hydrocarbyl-substituted acylating agent reacted with a polyalkylene polyamine, where the hydrocarbyl substituent of the succinamide or succinimide dispersant is a linear or branched hydrocarbyl group having a number average molecular weight of about 250 to about 5,000 as determined by GPC using polystyrene as the calibration standard.

[0109] In some approaches, the polyalkylene polyamine used to form the dispersant has the following formula:

[0110] [ka] where each R and R' is independently a divalent C1-C6 alkylene linker, and each R1 and R2 is independently hydrogen, a C1-C6 alkyl group, or together with the nitrogen atom to which they are attached form a 5- or 6-membered ring optionally fused to one or more aromatic or non-aromatic rings, and n is an integer from 0 to 8. In another approach, the polyalkylene polyamine is selected from the group consisting of a mixture of polyethylene polyamines having an average of 5 to 7 nitrogen atoms, triethylenetetramine, tetraethylenepentamine, and combinations thereof.

[0111] Dispersants, when present, may be used in an amount sufficient to provide up to about 20% by weight, based on the final weight of the lubricating oil composition. Alternative amounts of dispersants that may be used may be from about 0.1 to about 15% by weight, or from about 0.1 to about 10% by weight, or from about 0.1 to about 8% by weight, or from about 1 to about 10% by weight, or from about 1 to about 8% by weight, or from about 1 to about 6% by weight, based on the final weight of the lubricating oil composition. In some embodiments, the lubricating oil composition utilizes a mixed dispersant system. A single type or a mixture of two or more types of dispersants in any desired ratio may be used.

[0112] Antioxidants: The lubricating oil compositions herein may also optionally contain one or more antioxidants. Antioxidant compounds are known and include, for example, phenates, phenate sulfides, sulfurized olefins, phosphosulfurized terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, di-nonyldiphenylamine, octyldiphenylamine, di-octyldiphenylamine), phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, polymeric antioxidants, or mixtures thereof. The antioxidant compounds may be used alone or in combination.

[0113] The hindered phenol antioxidant may contain secondary butyl and / or tertiary butyl groups as steric hindrance groups. The phenol group may be further substituted with a hydrocarbyl group and / or a bridging group that connects to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester and may include, for example, Irganox® L-135 available from BASF or an addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, where the alkyl group may contain from about 1 to about 18, or from about 2 to about 12, or from about 2 to about 8, or from about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant may be an ester and may include Ethanox® 4716 available from SI Group.

[0114] Useful antioxidants may include diarylamines and high molecular weight phenols. In embodiments, the lubricating oil composition may contain a mixture of diarylamines and high molecular weight phenols, such that each antioxidant may be present in an amount sufficient to provide up to about 5 weight percent, based on the final weight of the lubricating oil composition. In embodiments, the antioxidant may be a mixture of about 0.3 to about 1.5 weight percent diarylamines and about 0.4 to about 2.5 weight percent high molecular weight phenols, based on the final weight of the lubricating oil composition.

[0115] Examples of suitable olefins that can be sulfurized to form sulfurized olefins include propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof, as well as their dimers, trimers, and tetramers, are particularly useful olefins. Alternatively, the olefins can be Diels-Alder adducts of dienes such as 1,3-butadiene and unsaturated esters such as butyl acrylate.

[0116] Another class of sulfurized olefins includes sulfurized fatty acids and their esters. The fatty acids are often derived from vegetable or animal oils and typically contain from about 4 to about 22 carbon atoms. Examples of suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof. Often, the fatty acids are derived from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or mixtures thereof. The fatty acids and / or esters may be mixed with olefins, such as α-olefins.

[0117] In another alternative embodiment, the antioxidant composition contains a molybdenum-containing antioxidant in addition to the phenolic and / or aminic antioxidants discussed above. When a combination of these three antioxidants is used, preferably the ratio of phenolic to amine to molybdenum-containing is (0-2):(0-2):(0-1).

[0118] The one or more antioxidants may be present in the range of from about 0% to about 20%, or from about 0.1% to about 10%, or from about 1% to about 5% by weight of the lubricating oil composition.

[0119] Antiwear agents: The lubricating oil compositions herein may also optionally contain one or more antiwear agents. Examples of suitable antiwear agents include, but are not limited to, metal thiophosphates; metal dialkyldithiophosphates; phosphoric acid esters or salts thereof; phosphoric acid ester(s); phosphites; phosphorus-containing carboxylic acid esters, ethers, or amides; sulfurized olefins; thiocarbamate-containing compounds, such as thiocarbamate esters, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides; and mixtures thereof. A suitable antiwear agent may be molybdenum dithiocarbamate. Phosphorus-containing antiwear agents are more fully described in EP 612839. The metal in the dialkyldithiophosphate salt may be an alkali metal, an alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful antiwear agent may be zinc dialkyldithiophosphate.

[0120] Further examples of suitable antiwear agents include titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (e.g., dibutyl phosphite), phosphonates, thiocarbamate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamic acid ethers, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides. Tartrates or tartrimides may contain alkyl-ester groups, but the total number of carbon atoms on the alkyl group may be at least 8. Antiwear agents may include citrates in one embodiment.

[0121] The antiwear agent may be present in ranges including from about 0 to about 15 weight percent, or from about 0.01 to about 10 weight percent, or from about 0.05 to about 5 weight percent, or from about 0.1 to about 3 weight percent of the lubricating oil composition.

[0122] Boron-containing compounds: The lubricating oil compositions herein may optionally contain one or more boron-containing compounds. Examples of boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, and borated dispersants, such as borated succinimide dispersants, as disclosed in U.S. Pat. No. 5,883,057. The boron-containing compounds, when present, may be used in an amount sufficient to provide up to about 8% by weight, about 0.01 to about 7% by weight, about 0.05 to about 5% by weight, or about 0.1 to about 3% by weight of the lubricating oil composition.

[0123] Additional detergents: The lubricating oil composition may optionally further comprise one or more neutral, underbased, or overbased detergents, and mixtures thereof. Suitable detergent substrates include phenates, sulfur-containing phenates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, phosphoric acids, mono- and / or di-thiophosphoric acids, alkylphenols, sulfur-linked alkylphenol compounds, or methylene bridged phenols. Suitable detergents and methods for their preparation are described in more detail in numerous patent publications, including U.S. Pat. No. 7,732,390 and references cited therein.

[0124] The detergent substrate may be salified with an alkali or alkaline earth metal, such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent is barium-free. In some embodiments, the detergent may contain trace amounts of other metals, such as magnesium or calcium, in amounts such as 50 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less, or 10 ppm or less. Suitable detergents may include alkali or alkaline earth metal salts of petroleum sulfonic acids and long chain mono- or di-alkylaryl sulfonic acids, where the aryl groups are benzyl, tolyl, and xylyl. Examples of suitable detergents include, but are not limited to, calcium phenate, sulfur-containing calcium phenate, calcium sulfonate, calcium calixarate, calcium salixarate, calcium salicylate, calcium carboxylate, calcium phosphate, calcium mono- and / or di-thiophosphate, calcium alkylphenol, calcium sulfur-bound alkylphenol compound, calcium methylene bridged phenol, magnesium phenate, sulfur-containing magnesium phenate, magnesium sulfonate, magnesium calixarate, magnesium salixarate, magnesium salicylate, magnesium carboxylate, magnesium phosphate, magnesium mono- and / or di-thiophosphate, magnesium alkylphenol, magnesium sulfur-bound alkylphenol compound, magnesium methylene bridged phenol, sodium phenate, sulfur-containing sodium phenate, sodium sulfonate, sodium calixarate, sodium salixarate, sodium salicylate, sodium carboxylate, sodium phosphate, sodium mono- and / or di-thiophosphate, sodium alkylphenol, sodium sulfur-bound alkylphenol compound, or sodium methylene bridged phenol.

[0125] Overbased detergent additives are well known in the art and may be alkali or alkaline earth metal overbased detergent additives. Such detergent additives may be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas. The substrate is typically an acid, such as an aliphatic substituted sulfonic acid, an aliphatic substituted carboxylic acid, or an aliphatic substituted phenol.

[0126] The term "overbased" refers to metal salts, such as metal salts of sulfonic acids, carboxylic acids, and phenols, in which the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level of more than 100% (i.e., such salts may contain more than 100% of the theoretical amount of metal required to convert the acid to its "standard" or "neutral" salt). The expression "metal ratio", often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of the metal in an overbased salt to the chemical equivalents of the metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the metal ratio is 1, while in overbased salts the MR is greater than 1. They are generally referred to as overbased, hyperbased, or superbased salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.

[0127] The overbased detergent of the lubricating oil composition may have a Total Base Number (TBN) of about 200 mg KOH / gram or greater, or, as a further example, about 250 mg KOH / gram or greater, or about 350 mg KOH / gram or greater, or about 375 mg KOH / gram or greater, or about 400 mg KOH / gram or greater, as measured by the method of ASTM D-2896.

[0128] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenates, overbased calcium sulfur-containing phenates, overbased calcium sulfonates, overbased calcium calixarates, overbased calcium salixarates, overbased calcium salicylates, overbased calcium carboxylic acids, overbased calcium phosphates, overbased calcium mono- and / or di-thiophosphates, overbased calcium alkylphenols, overbased calcium sulfur-bound alkylphenol compounds, overbased calcium methylene bridged phenols, overbased magnesium phenates, overbased magnesium sulfur-containing phenates, overbased magnesium sulfonates, overbased magnesium calixarates, overbased magnesium salixarates, overbased magnesium salicylates, overbased magnesium carboxylic acids, overbased magnesium phosphates, overbased magnesium mono- and / or di-thiophosphates, overbased magnesium alkylphenols, overbased magnesium sulfur-bound alkylphenol compounds, or overbased magnesium methylene bridged phenols.

[0129] Overbased calcium phenate detergents have a total base number of at least about 150 mg KOH / g, at least about 225 mg KOH / g, at least about 225 to about 400 mg KOH / g, at least about 225 to about 350 mg KOH / g, or about 230 to about 350 mg KOH / g, all measured by the method of ASTM D-2896. When such detergent compositions are formed in an inert diluent, such as a process oil, often a mineral oil, the total base number reflects the basicity of the entire composition, including the diluent and any other materials that may be included in the detergent composition (e.g., accelerators, etc.).

[0130] The overbased detergent may have a metal to substrate ratio of 1.1:1 or greater, or 2:1 or greater, or 4:1 or greater, or 5:1 or greater, or 7:1 or greater, or 10:1 or greater. In some embodiments, the detergent is effective in reducing or preventing rust in engines or other automotive components such as transmissions or gears. The detergent may be present in the lubricating composition at about 0 to about 10 wt%, or about 0.1 to about 8 wt%, or about 1 to about 4 wt%, or greater than about 4 wt% to about 8 wt%.

[0131] Extreme Pressure Agents: The lubricating oil compositions herein may also optionally contain one or more extreme pressure agents. Extreme pressure (EP) agents that are soluble in oil include sulfur and chlorosulfur containing EP agents, chlorinated hydrocarbon EP agents, and phosphorus EP agents. Examples of such EP agents include chlorinated waxes; organic sulfides and polysulfides such as dibenzyl disulfide, bis(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenols, sulfurized dipentenes, sulfurized terpenes, and sulfurized Diels-Alder adducts; phosphorus sulfurized hydrocarbons such as the reaction products of phosphorus sulfide with turpentine or methyl oleate; dihydrocarbyl and trihydrocarbyl phosphites, for example, phosphate esters such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl phenyl phosphite; dipentyl phenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene substituted phenyl phosphites; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol diacid; amine salts of alkyl and dialkyl phosphates, including, for example, the amine salt of the reaction product of a dialkyl dithiophosphoric acid with propylene oxide; and mixtures thereof.

[0132] Friction modifiers: The lubricating oil compositions herein may also optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing and metal-free friction modifiers, but may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerol esters, sulfurized fatty compounds and olefins, sunflower oil, other naturally occurring vegetable or animal oils, dicarboxylic acid esters, esters or partial esters of polyols with one or more aliphatic or aromatic carboxylic acids, and the like.

[0133] Suitable friction modifiers may contain hydrocarbyl groups selected from linear, branched, or aromatic hydrocarbyl groups, or mixtures thereof, and may be saturated or unsaturated. The hydrocarbyl groups may be composed of carbon and hydrogen or heteroatoms such as sulfur or oxygen. The hydrocarbyl groups may range from about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long chain fatty acid ester. In other embodiments, the long chain fatty acid ester may be a mono-ester, or a di-ester, or a (tri)glyceride. The friction modifier may be a long chain fatty amide, a long chain fatty ester, a long chain fatty epoxide derivative, or a long chain imidazoline.

[0134] Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free mechanical friction modifiers. Such friction modifiers may include esters formed by reacting carboxylic acids and anhydrides with alkanols, and generally may include a polar end group (e.g., carboxyl or hydroxyl) covalently bonded to an oleophilic hydrocarbon chain. An example of an organic ashless nitrogen-free friction modifier is generally known as glycerol monooleate (GMO), which may include mono-, di-, and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Patent No. 6,723,685, the entirety of which is incorporated herein by reference.

[0135] Aminic friction modifiers may include amines or polyamines. Such compounds may have hydrocarbyl groups that are linear, either saturated or unsaturated, or a mixture thereof, and may contain from about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds may have hydrocarbyl groups that are linear, either saturated or unsaturated, or a mixture thereof. They may contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

[0136] The amines and amides may be used by themselves or in the form of adducts or reaction products with boron compounds such as boron oxides, boron halides, metaborates, boric acid or mono-, di-, or tri-alkylborates. Other suitable friction modifiers are described in U.S. Patent No. 6,300,291, the entirety of which is incorporated herein by reference.

[0137] Friction modifiers may optionally be present in a range such as from about 0 to about 10 weight percent, or from about 0.01 to about 8 weight percent, or from about 0.1 to about 4 weight percent.

[0138] Molybdenum-containing components: The lubricating oil compositions herein may also optionally contain one or more molybdenum-containing compounds. The oil-soluble molybdenum compounds may have the functional properties of antiwear agents, antioxidants, friction modifiers, or mixtures thereof. The oil-soluble molybdenum compounds may include molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dithiophosphinates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organomolybdenum compounds, and / or mixtures thereof. Molybdenum sulfides include molybdenum disulfide. The molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compounds may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil soluble molybdenum compound can be a molybdenum dithiocarbamate.

[0139] Suitable examples of molybdenum compounds that may be used include commercially available materials sold under trade names such as Molyvan® 822, Molyvan® A, Molyvan® 2000, and Molyvan® 855 from R.T. Vanderbilt Co., Ltd., and Sakura-Lube® S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 available from Adeka Corporation, and mixtures thereof. Suitable molybdenum components are described in U.S. Patent No. 5,650,381, U.S. Reissue Patent Nos. 37,363 (E1), 38,929 (E1), and 40,595 (E1), the entireties of which are incorporated herein by reference.

[0140] Additionally, the molybdenum compound can be an acidic molybdenum compound, including molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates, as well as other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide, or similar acidic molybdenum compounds. Alternatively, the composition can provide the molybdenum via molybdenum / sulfur complexes of basic nitrogen compounds, as described, for example, in U.S. Pat. Nos. 4,263,152, 4,285,822, 4,283,295, 4,272,387, 4,265,773, 4,261,843, 4,259,195, and 4,259,194, and WO 94 / 06897, the foregoing patents being incorporated herein by reference in their entireties.

[0141] Another class of suitable organomolybdenum compounds are trinuclear molybdenum compounds and mixtures thereof, such as compounds of the formula Mo3SkLnQz, where S represents sulfur, L represents an independently selected ligand having a sufficient number of carbon atoms in the organic group to render the compound soluble or dispersible in oil, n is 1-4, k varies from 4-7, Q is selected from the group of neutral electron donor compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0-5, including non-stoichiometric values. There may be at least 21 total carbon atoms in the organic groups of all the ligands, such as at least 25, at least 30, or at least 35 carbon atoms. Additional suitable molybdenum compounds are described in U.S. Pat. No. 6,723,685, which is incorporated herein by reference in its entirety.

[0142] 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.

[0143] Transition metal-containing compounds: In another embodiment, the oil-soluble compound may be a transition metal-containing compound or metalloid. Transition metals may include, but are not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten, etc. Suitable metalloids include, but are not limited to, boron, silicon, antimony, tellurium, etc.

[0144] In embodiments, the oil-soluble transition metal-containing compound may function as an antiwear agent, a friction modifier, an antioxidant, an adhesion control additive, or one or more of these functions.In embodiments, the oil-soluble transition metal-containing compound may be an oil-soluble titanium compound, such as titanium (IV) alkoxide.Some of the titanium-containing compounds that may be used in or for the preparation of oil-soluble materials in the technology of the present disclosure include, but are not limited to, various Ti (IV) compounds, such as titanium (IV) oxide; titanium (IV) sulfide; titanium (IV) nitrate; titanium (IV) alkoxides, such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide; and other titanium compounds or complexes, such as titanium phenate; titanium carboxylates, such as titanium (IV) 2-ethyl-1,3-hexanedioate or titanium citrate or titanium oleate; and titanium (IV) (triethanolaminato) isopropoxide. Other forms of titanium encompassed by the disclosed technology include titanium phosphates, such as titanium dithiophosphates (e.g., dialkyl dithiophosphates) and titanium sulfonates (e.g., alkyl benzene sulfonates), or generally reaction products of titanium compounds with various acid materials to form salts, such as oil-soluble salts. Thus, titanium compounds may be derived from organic acids, alcohols, and glycols, among others. Ti compounds may also exist in dimeric or oligomeric forms containing Ti-O-Ti structures. Such titanium materials are commercially available or can be readily prepared by suitable synthetic techniques that will be apparent to those skilled in the art. They may exist at room temperature as solids or liquids, depending on the particular compound. They may also be provided in solution form in a suitable inert solvent.

[0145] In one embodiment, titanium may be provided as a Ti-modified dispersant, such as a succinimide dispersant. Such materials may be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as an alkenyl-(or alkyl) succinic anhydride. The resulting titanate-succinate intermediate may be used directly or may be reacted with any of a number of materials, such as (a) polyamine-based succinimide / amide dispersants having free condensable -NH functional groups; (b) components of polyamine-based succinimide / amide dispersants, i.e., alkenyl (or alkyl) succinic anhydrides and polyamines; (c) hydroxy-containing polyester dispersants prepared by reaction of substituted succinic anhydrides with polyols, amino alcohols, polyamines, or mixtures thereof. Alternatively, the titanate-succinate intermediate can be reacted with other agents such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product can be used directly to impart Ti to lubricating oils or can be further reacted with succinic dispersants as described above. As an example, one part (mole) of tetraisopropyl titanate can be reacted with about two parts (mole) of polyisobutene-substituted succinic anhydride at 140-150°C for 5-6 hours to provide a titanium modified dispersant or intermediate. The resulting material (30g) can be further reacted with a succinimide dispersant from a polyisobutene-substituted succinic anhydride and polyethylene polyamine mixture (127 grams + diluent oil) at 150°C for 1.5 hours to produce a titanium modified succinimide dispersant.

[0146] Another titanium-containing compound is titanium alkoxide and C6-C 25 It may be a reaction product with a carboxylic acid. The reaction product has the following formula:

[0147] [ka] wherein n is an integer selected from 2, 3, and 4, and R is a hydrocarbyl group containing from about 5 to about 24 carbon atoms, or the following formula:

[0148] [ka] or the titanium compound may be represented by the formula:

[0149] [ka] (wherein x ranges from 0 to 3; R1 is selected from hydrocarbyl groups containing about 6 to 25 carbon atoms; R2 and R3 are the same or different and are selected from hydrocarbyl groups containing about 1 to 6 carbon atoms; R4 is H, C6 to C 25 The carboxylic acid moiety may be selected from the group consisting of

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

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

[0152] Viscosity index improver: The lubricating oil composition herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, hydrogenated styrene-isoprene polymers, styrene / maleic acid ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenylaryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers may include star polymers, suitable examples of which are described in US Patent Application Publication No. 20120101017(A1).

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

[0154] The total amount of viscosity index improver and / or dispersant viscosity index improver can be from about 0 to about 20 weight percent, from about 0.1 to about 15 weight percent, from about 0.1 to about 12 weight percent, or from about 0.5 to about 10 weight percent of the lubricating oil composition.

[0155] Other optional additives: Other additives may be selected to perform one or more functions required in a lubricating fluid. Additionally, one or more of the aforementioned additives may be multifunctional and may provide functions in addition to or other than those described herein.

[0156] The lubricating oil composition according to the present disclosure may optionally contain other performance additives. The other performance additives may be in addition to the specific additives of the present disclosure and / or may include one or more of metal deactivators, viscosity index improvers, detergents, ashless TBN boosters, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam suppressants, demulsifiers, emulsifiers, pour point depressants, seal swell agents, and mixtures thereof. Typically, a fully formulated lubricating oil will contain one or more of these performance additives.

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

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

[0159] Suitable pour point depressants may include polymethyl methacrylate or mixtures thereof. The pour point depressant may be present in an amount sufficient to provide 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.

[0160] A suitable rust inhibitor can be a single compound or a mixture of compounds that have the property of inhibiting corrosion of ferrous metal surfaces. Non-limiting examples of rust inhibitors useful herein include oil-soluble high molecular weight organic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid, as well as oil-soluble polycarboxylic acids including dimer and trimer acids such as those produced from tall oil fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long chain alpha, omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000, and alkenyl succinic acids in which the alkenyl group contains about 10 or more carbon atoms, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Another useful type of acidic corrosion inhibitor is the half ester of an alkenyl succinic acid having about 8 to about 24 carbon atoms in the alkenyl group with an alcohol, such as a polyglycol. The corresponding half amides of such alkenyl succinic acids are also useful.Useful rust inhibitors are high molecular weight organic acids.

[0161] When present, the rust inhibitor may be used in an amount sufficient to provide from about 0 to about 5 wt. %, from about 0.01 to about 3 wt. %, from about 0.1 to about 2 wt. %, based on the final weight of the lubricating oil composition.

[0162] Generally speaking, suitable lubricating oils containing the neutral to overbased sulfurized alkylphenate products herein may contain additive components in the ranges listed in the table below.

[0163] [Table 2]

[0164] The percentages of each component above represent the weight percent of each component based on the weight of the final lubricating oil composition. The remainder of the lubricating oil composition consists of one or more base oils. The additives used in formulating the compositions described herein can be blended into the base oil individually or in various partial combinations. However, it may be preferred to blend all of the components simultaneously using an additive concentrate (i.e., additives plus a diluent such as a hydrocarbon solvent). Fully formulated lubricants conventionally contain an additive package, referred to herein as a dispersant / inhibitor package or DI package, that provides the properties required in the formulation. EXAMPLES

[0165] The following examples illustrate exemplary embodiments of the present disclosure. In these examples, as well as elsewhere in this application, all ratios, parts, and percentages are by weight unless otherwise indicated. It is intended that these examples are presented for illustrative purposes only and are not intended to limit the scope of the invention disclosed herein.

[0166] Example 1 Various polyalphaolefin oligomers were evaluated for terminal unsaturation and oligomerization configuration. The characterization of the oligomers is shown in Table 3 below. Oligomer A was obtained from the oligomerization of 1-decenene monomer in the presence of a solid acid catalyst. Oligomer B is a C10 dimer. Oligomer C is primarily a C20-C26 olefin. Oligomer D is a mixture of C10 oligomers with high vinylidene content.

[0167] [Table 3]

[0168] Example 2 The oligomers in Table 3 from Example 1 were used to alkylate phenol in the presence of a solid catalyst. The alkylation results are shown below in Table 4. In each case, the alkylation was carried out in the presence of a solid catalyst at about 110° C. for about 4 to about 6 hours.

[0169] [Table 4] * The mole percentage reflects the alkylphenol content and does not include unreacted olefin or other by-products.

[0170] Example 3 Sulfurized phenate lubricant additives were prepared as shown in Table 5 below. Samples 1 and 2 were comparative additives prepared using an alkylphenol derived from tetrapropylene (C12). Sample 3 was an additive of the present invention obtained from an alkylphenol derived from a polyalphaolefin oligomer having the properties of Oligomer D from Tables 3 and 4 above.

[0171] [Table 5] ** The % Active Detergent is the undiluted oil portion of the additive mixture.

[0172] As shown in Table 5, the additives of the present invention having higher active detergent content (i.e., lower diluent oil) exhibited lower viscosity than the comparative additives. Thus, the inventive phenate 3 obtained with the polyalphaolefin oligomer herein was able to achieve the desired viscosity with a less active phenate detergent.

[0173] It should be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless expressly and unambiguously limited to one referent. Thus, for example, reference to an "antioxidant" includes two or more different antioxidants. As used herein, the term "comprising" and grammatical variations thereof are intended to be open-ended such that the recitation of items in a list excludes other similar items that may be substituted for or added to the items in the list.

[0174] For purposes of this specification and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values ​​used in the specification and claims should be understood in all instances to be modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending on the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0175] It is understood that each component, compound, substituent, or parameter disclosed herein should be construed as disclosed for use alone or in combination with one or more of any and all other components, compounds, substituents, or parameters disclosed herein.

[0176] It is further to be understood that each range disclosed herein should be construed as a disclosure of each specific value within the disclosed range having the same number of significant digits. Thus, for example, a range of 1 to 4 should be construed as an explicit disclosure of not only the values ​​1, 2, 3, and 4, but any range of such values.

[0177] It is further understood that each lower limit of each range disclosed herein should be interpreted as being disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compound, substituent, or parameter. Thus, the present disclosure should be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or each specific value within each range, or by combining each upper limit of each range with each specific value within each range. That is, it is further understood that any range between the endpoint values ​​within the broad range is also contemplated herein. Thus, a range of 1 to 4 also means a range of 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0178] Furthermore, a specific amount / value of a component, compound, substituent, or parameter disclosed in the details or examples should be construed as a disclosure of either a lower or upper limit of a range and therefore can be combined with any other lower or upper limit or specific amount / value in a range for the same component, compound, substituent, or parameter disclosed elsewhere in this application to form a range for that component, compound, substituent, or parameter.

[0179] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents may occur that are not presently anticipated or that cannot be currently anticipated by the applicants or others skilled in the art. It is therefore intended that the appended claims as filed, and the appended claims as they may be amended, cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A sulfurized alkylphenate comprising a polyalphaolefin-substituted bridged hydroxyaromatic compound or salt thereof, wherein the polyalphaolefin is derived from C6 to C14 monomers that form dimers, trimers, tetramers, pentamers, copolymers thereof, copolymer variants thereof, or combinations thereof.

2. 2. The sulfurized alkylphenate of claim 1, wherein greater than or equal to about 40 mole percent of the polyalphaolefin comprises carbon atoms configured to form tertiary carbocations.

3. 3. The sulfurized alkylphenate of claim 2, 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.

4. The sulfurized alkylphenate of any one of claims 2 to 3, wherein the carbon atom configured to form a tertiary carbocation is positioned to react with the hydroxyaromatic compound at the para position.

5. The sulfurized alkylphenate according to any one of claims 2 to 4, wherein the polyalphaolefin is obtained from C8 to C12 monomers that form dimers, trimers, tetramers, pentamers, or combinations thereof, preferably C8 to C10 monomers that form dimers, trimers, tetramers, pentamers, or combinations thereof.

6. The sulfurized alkylphenate of any one of claims 2 to 5, wherein at least about 50 mole percent, preferably at least about 60 mole percent, more preferably at least about 75 mole percent, more preferably at least about 85 mole percent, and most preferably at least about 90 mole percent of the polyalphaolefin comprises carbon atoms configured to form tertiary carbocations.

7. The sulfurized alkylphenate of any one of claims 2 to 6, wherein the polyalphaolefin comprises a vinylidene olefin, a tri-substituted olefin, or a mixture thereof.

8. 8. The sulfurized alkylphenate of claim 7, wherein the polyalphaolefin contains greater than about 40 mole percent, greater than about 50 mole percent, greater than about 75 mole percent, or greater than about 90 mole percent vinylidene olefin.

9. 8. The sulfurized alkylphenate of claim 7, wherein said polyalphaolefin is a trisubstituted olefin and comprises about 40 weight percent or more of said dimer, preferably about 50 weight percent or more of said dimer, and more preferably about 70 weight percent or more of said dimer.

10. 10. The sulfurized alkylphenate of claim 9, wherein said polyalphaolefin comprises about 40 weight percent or less of said trimer; and / or about 20 weight percent or less of said tetramer; and / or about 5 weight percent or less of said pentamers.

11. The sulfurized alkylphenate of any one of claims 1 to 10, wherein the polyalphaolefin comprises primarily vinylidene olefins, tri-substituted olefins, or mixtures thereof, and comprises at least about 40 wt.%, preferably at least about 50 wt.%, and more preferably at least about 75 wt.%, of C3 or lower alkyl groups adjacent to the tertiary carbocation.

12. The sulfurized alkylphenate of any one of claims 1 to 11, wherein the polyalphaolefin comprises a double bond having a vinylidene structure and / or a trisubstituted structure.

13. 13. The sulfurized alkylphenate of any one of claims 1 to 12, wherein the polyalphaolefin comprises about 40 mole percent or more, preferably about 60 mole percent or more, more preferably about 75 mole percent or more, even more preferably about 85 mole percent or more, and most preferably about 90 mole percent or more vinylidene olefins, tri-substituted olefins, or combinations thereof.

14. 1. A detergent composition comprising a sulfurized alkylphenate having a structure of formula IX: 【Chemistry 1】 During the ceremony, Each R ２４ is a polyalphaolefin derived from C6 to C14 monomers that independently form a dimer, trimer, tetramer, pentamer, copolymer, copolymer variant, or combinations thereof that contain the residue of a tertiary carbocation that forms said bond to an aromatic ring, where R ２４ at least 50 mole percent of are attached to the aromatic ring at the para position; x is an integer from 1 to 4; M ２＋ is a divalent metal ion.

15. Each R ２４ has at least one alkyl group adjacent to said tertiary carbocation independently having 1, 2, or 3 carbon atoms, preferably 2 carbon atoms, more preferably 1 carbon atom.

16. Each R ２４ are formed from C8 to C12 monomers that independently form dimers, trimers, tetramers, pentamers, or combinations thereof, preferably formed from C8 to C10 monomers that form dimers, trimers, tetramers, pentamers, or combinations thereof.

17. R ２４ The detergent composition of any one of claims 14 to 16, wherein is derived from a vinylidene olefin, a tri-substituted olefin, or a mixture thereof.

18. The R ２４ 20. The detergent composition of claim 17, wherein the vinylidene olefin comprises greater than or equal to about 40 mole percent, greater than or equal to about 50 mole percent, greater than or equal to about 75 mole percent, or greater than or equal to about 90 mole percent.

19. The R ２４ is a trisubstituted olefin, R ２４ or about 40 weight percent or more of R ２４ or R ２４ 20. The detergent composition of claim 17, wherein about 70 weight percent or more of is dimer.

20. R ２４ is about 40 weight percent or less of a trimer, R ２４ is tetramer, and / or R ２４ 20. The detergent composition of claim 19, wherein no more than about 5 weight percent of is a pentamer.

21. The detergent composition according to any one of claims 14 to 20, wherein about 40% by weight or more, preferably about 50% by weight or more, more preferably about 75% by weight or more of the alkyl groups adjacent to the tertiary carbocations are C3 or lower alkyl groups.

22. The R ２４ 22. A detergent composition according to any one of claims 14 to 21, wherein the group is derived from a mixture of oligomers, a majority of the oligomers in the mixture having the structure of Formula VI and / or Formula VII: 【Chemistry 2】 During the ceremony, R １１ is an alkyl group, R １２ , R １３ , R １４ , R １５ , and / or R １６ each occurrence is the same or different and independently represents hydrogen or a substituted or unsubstituted hydrocarbyl group; R １７ , R １８ and R １９ is hydrogen, and １７ , R １８ and R １９ one of the remaining two is a substituted or unsubstituted hydrocarbyl group having 1, 2 or 3 carbons; R １７ , R １８ and R １９ the other of the remaining two is a substituted or unsubstituted hydrocarbyl group; R ２０ , R ２１ , R ２２ , and / or R ２３ each occurrence is the same or different and independently represents hydrogen or a substituted or unsubstituted hydrocarbyl group; A detergent composition wherein each n is independently an integer from 0 to 3.

23. A lubricating oil composition comprising the sulfurized alkylphenate of any one of claims 1 to 13 and one or more base oils of lubricating viscosity.

24. A lubricating oil composition comprising the detergent composition of any one of claims 14 to 22 and one or more base oils of lubricating viscosity.

25. An alkylphenol suitable for forming a sulfurized alkylphenate detergent composition, said alkylphenol comprising 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 combinations thereof.

26. 26. The alkylphenol of claim 25, wherein the polyalphaolefin oligomer is derived from a C8 to C12 dimer, trimer, tetramer, pentamer, or combination thereof, preferably a C8 to C10 dimer, trimer, tetramer, pentamer, or combination thereof.

27. 27. The alkylphenol of claim 25 or 26, wherein about 40 mole percent or more of the polyalphaolefin oligomer comprises 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.

28. the reaction product has the structure of formula VIIIa, VIIIb, and / or VIIIc; 【Chemistry 3】 During the ceremony, R １１ is an alkyl group, R １２ , R １３ , R １４ , R １５ , and / or R １６ each occurrence is the same or different and independently represents hydrogen or a substituted or unsubstituted hydrocarbyl group; R １７ , R １８ and R １９ is hydrogen, and １７ , R １８ and R １９ one of the remaining two is a substituted or unsubstituted hydrocarbyl group having 1, 2 or 3 carbons; R １７ , R １８ and R １９ the other of the remaining two is a substituted or unsubstituted hydrocarbyl group; R ２０ , R ２１ , R ２２ , and / or R ２３ each occurrence is the same or different and independently represents hydrogen or a substituted or unsubstituted hydrocarbyl group; The detergent composition according to any one of claims 25 to 27, wherein each n is independently an integer from 0 to 3.

29. 29. The alkylphenol of any one of claims 25 to 28, wherein at least about 50 mole percent, preferably at least about 60 mole percent, preferably at least about 75 mole percent, preferably at least 85 mole percent, and most preferably at least about 90 mole percent of the alkyl substitution is in the para position of the aromatic ring.

30. 30. The alkylphenol of any one of claims 25 to 29, wherein the polyalphaolefin oligomer comprises a vinylidene olefin, a tri-substituted olefin, or a mixture thereof.

31. 31. The alkylphenol of claim 30, wherein the polyalphaolefin oligomer contains greater than or equal to about 40 mole percent, greater than or equal to about 50 mole percent, greater than or equal to about 75 mole percent, or greater than or equal to about 90 mole percent vinylidene olefin.

32. 32. The alkylphenol of claim 31 , wherein the polyalphaolefin oligomer is a trisubstituted olefin and about 40 weight percent or more of the polyalphaolefin oligomer is a dimer, about 50 weight percent or more of the polyalphaolefin oligomer is a dimer, or about 70 weight percent or more of the polyalphaolefin oligomer is a dimer.

33. 33. The alkylphenol of claim 32, wherein up to about 40% by weight of the polyalphaolefin oligomers are trimers, up to about 20% by weight of the polyalphaolefin oligomers are tetramers, and / or up to about 5% by weight of the polyalphaolefin oligomers are pentamers.

34. The alkylphenol according to any one of claims 25 to 33, wherein about 40% by weight or more, preferably about 50% by weight or more, more preferably about 75% by weight or more of the alkyl groups adjacent to the tertiary carbocation are C3 or lower alkyl groups.

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