Polyalphaolefin phenol with high para-position selectivity

Abstract

This invention provides a detergent additive and method for preparing alkyl sulfide phenate products from polyalphaolefins. [Solution] Provided is an alkyl sulfide phenate comprising a polyalphaolefin-substituted crosslinked hydroxyaromatic compound or a salt thereof, wherein the polyalphaolefin is derived from C6-C14 monomers that form dimers, trimers, tetramers, pentamers, copolymers thereof, copolymer variants thereof, or combinations thereof.

Description

[Technical Field]

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

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

[0003] However, current methods have one or more drawbacks when attempting to minimize the level of unsulfurized alkylphenate / phenol variants when the additive is also overbasicated. While altering the alkyl substitution could be one possible option, alternative alkyl substitutions on the phenol moiety are also problematic in relation to overbasic lubricant detergents. Desired lubricant additives prefer alkyl substitutions at the para position of the aromatic ring, primarily because such substitutions enable efficient sulfidation and overbasic detergent functionality. However, many suitable alkyl substituents from other olefins preferentially alkylate at the ortho position, which is undesirable in relation to lubricant additives. [Overview of the project]

[0004] According to one embodiment, an alkylphenate sulfide comprising a polyalphaolefin-substituted crosslinked hydroxyaromatic compound or a salt thereof is described herein. In the method, 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 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 carbon atoms 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, most preferably 1 carbon atom; and / or the carbon atoms configured to form a tertiary carbocation are arranged to react with a hydroxyaromatic compound at the para position; and / or the polyalphaolefin is obtained from C6-C12 monomers, preferably C8-C10 monomers, that form dimers, trimers, tetramers, pentamers, or combinations thereof; and / or about 50 mole percent of the polyalphaolefin 100% or more, preferably about 60 mol% or more, more preferably about 75 mol% or more, more preferably about 85 mol% or more, most preferably about 90 mol% or more, comprises carbon atoms configured to form a tertiary carbocation; and / or the polyalphaolefin comprises vinylidene olefin, trisubstituted olefin, or a mixture thereof; and / or the polyalphaolefin comprises more than about 40 mol%, more than about 50 mol%, more than about 75 mol%, or more than about 90 mol% vinylidene olefin; and / or the polyalphaolefin is a trisubstituted olefin comprising about 40 wt% or more, preferably about 50 wt% or more, more preferably about 70 wt% or more dimers;and / or, the polyalphaolefin contains about 40% by weight or less of trimers, and / or about 20% by weight or less of tetramers, and / or about 5% by weight or less of pentamers, and / or, the polyalphaolefin mainly contains vinylidene olefins, trisubstituted olefins, or mixtures thereof, and contains about 40% by weight or more, preferably about 50% by weight or more, more preferably about 75% by weight or more, alkyl groups of C3 or less adjacent to the tertiary carbocation; and / or, the polyalphaolefin contains double bonds having a vinylidene structure and / or a trisubstituted structure; and / or, the polyalphaolefin contains 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, of vinylidene olefins, trisubstituted olefins, or combinations thereof.

[0006] In yet another embodiment, a detergent composition comprising an alkyl phenate sulfide having the structure of formula IX is provided herein. In the method, formula IX is,

[0007] [ka] The formula includes, and in the formula, each R 24 R is a polyalphaolefin derived from C6-C14 monomers that independently form dimers, trimers, tetramers, pentamers, copolymers, copolymer variants, or combinations thereof, including tertiary carbocation residues that form a bond to an aromatic ring. 24 At least 50 mole percent of are bonded to the aromatic ring at the para position, x is an integer of 1 or 4, and M 2+ It is a divalent metal ion.

[0008] In other embodiments, the detergent compositions described in the preceding paragraph 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: where each R 24independently has at least one alkyl group adjacent to a tertiary carbocation having 1, 2, or 3 carbon atoms, preferably 2 carbon atoms, more preferably 1 carbon atom; and / or each R 24 is independently formed from C8 - C12 monomers that form dimers, trimers, tetramers, pentamers, or combinations thereof, preferably from C8 - C10 monomers that form dimers, trimers, tetramers, pentamers, or combinations thereof; and / or R 24 is derived from vinylidene olefins, trisubstituted olefins, or mixtures thereof; and / or R 24 contains at least about 40 mole percent, at least about 50 mole percent, at least about 75 mole percent, or at least about 90 mole percent of vinylidene olefins; and / or R 24 is a trisubstituted olefin, at least about 40 weight percent of R 24 is a dimer, at least about 50 weight percent of R 24 is a dimer, or at least about 70 weight percent of R 24 is a dimer; and / or at most about 40 weight percent of R 24 is a trimer, at most about 20 weight percent of R 24 is a tetramer; and / or at most about 5 weight percent of R 24 is a pentamer; and / or at least about 40 weight percent, preferably at least about 50 weight percent, more preferably at least about 75 weight percent of the alkyl groups adjacent to the tertiary carbocation are C3 or lower alkyl groups; and / or R 24 groups are derived from a mixture of oligomers, and most of the oligomers in the mixture have the structure of the following formula VI and / or formula VII.

[0009]

Chemical formula

[0010] In further embodiments, lubricating oil compositions comprising an alkyl phenate sulfide or detergent composition of any embodiment of the outline of the present invention are provided herein in combination with one or more base oils of lubricating viscosity.

[0011] In a further embodiment, alkylphenols suitable for forming alkylphenate detergent compositions are described herein. In the method, the alkylphenol comprises a 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 alkylphenols in the preceding paragraph, the alkylphenols may be combined with any optional embodiment or any feature in any combination. The optional feature or embodiment may include one or more of the following: the polyalphaolefin oligomer is derived from a C8-C12 dimer, trimer, tetramer, pentamer, or combination thereof, preferably a C8-C10 dimer, trimer, tetramer, pentamer, or combination thereof; and / or about 40 mole percent or more of the polyalphaolefin oligomer contains carbon atoms configured to form a tertiary carbocation, and at least one of the alkyl groups adjacent to the tertiary carbocation has 1, 2, or 3 carbon atoms, preferably 2 carbon atoms, more preferably 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 R is an alkyl group; 12 , R 13 , R 14 , R 15 , and / or R 16 Each of these is either identical or different in each occurrence, and independently represents hydrogen or a substituted or unsubstituted hydrocarbyl group; R 17 , R 18 and R 19 Only one of them is hydrogen, R 17 , R 18 and R 19 One of the remaining two is a substituted or unsubstituted hydrocarbyl group having 1, 2, or 3 carbon atoms, R 17 , R 18 and R 19 Of the remaining two, the other one is a substituted or unsubstituted hydrocarbyl group; R 20 , R 21 , R 22 , and / or R 23Each of these is either identical or different with each occurrence and independently represents hydrogen or a substituted or unsubstituted hydrocarbyl group; each n is independently an integer from 0 to 3; and / or here, about 50 mol percent or more, preferably about 60 mol percent or more, preferably about 75 mol percent or more, preferably 85 mol percent or more, and most preferably about 90 mol percent or more of alkyl substitutions are at the para position of the aromatic ring; and / or here, the polyalphaolefin oligomer comprises vinylidene olefin, trisubstituted olefin, or a mixture thereof; and / or here, the polyalphaolefin oligomer comprises about 40 mol percent or more, about 50 mol percent or more, about 75 mol percent or more, or about 90 mol percent or more of vinylidene olefin; and / or Here, the polyalphaolefin oligomer is a trisubstituted olefin, wherein about 40% by weight or more of the polyalphaolefin oligomer is a dimer, about 50% by weight or more of the polyalphaolefin oligomer is a dimer, or about 70% by weight or more of the polyalphaolefin oligomer is a dimer; and / or about 40% by weight or less of the polyalphaolefin oligomer is a trimer, and about 20% by weight or less of the polyalphaolefin oligomer is a tetramer; and / or about 5% by weight or less of the polyalphaolefin oligomer is a pentamer; and / or about 40% by weight or more of the alkyl group adjacent to the tertiary carbocation is C3 or less, preferably about 50% by weight or more, and more preferably about 75% by weight or more of the alkyl group.

[0014] Further embodiments provide the use of polyalphaolefins described in any embodiment of the outline of the present invention for forming detergent compositions and / or substituted crosslinked hydroxyaromatic compounds or salts thereof for use in detergent compositions.

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

[0016] The terms “oil composition,” “lubricating composition,” “lubricating oil composition,” “lubricating oil,” “lubricating oil composition,” “lubricating composition,” “completely formulated lubricating oil composition,” and “lubricant” are considered synonymous and fully interchangeable terms, and refer to a finished lubricating product comprising a primary amount of base oil and a small amount of additive composition.

[0017] As used herein, the terms “additive package,” “additive concentrate,” and “additive composition” are considered to be synonymous and fully interchangeable terms referring to a portion of a lubricating oil composition excluding the main amount of base oil stock mixture.

[0018] The term “overbasic” relates to metal salts, such as metal salts of sulfonates, carboxylates, salicylates, and / or phenates, where the amount of metal present exceeds the stoichiometric amount, unless otherwise specified. Such salts may have a conversion level greater than 100% (i.e., such salts may contain more than 100% of the theoretical amount of metal required to convert an acid to its “standard salt,” “neutral salt”). The expression “metallic ratio,” often abbreviated as MR, is used to indicate the ratio of the total stoichiometric equivalents of metal in an overbasic salt to the stoichiometric equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the metallic ratio is 1, but in overbasic salts, the MR is greater than 1. These are generally referred to as overbasic, highly basic, or ultrabasic 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] Where used herein, unless otherwise specified, the terms “hydrocarbyl,” “hydrocarbyl substituent,” or “hydrocarbyl group” are used in their ordinary sense as is well known to those skilled in the art. Specifically, it refers to a group having carbon atoms directly bonded to the rest of the molecule and having primarily hydrocarbon characteristics. Each hydrocarbyl group is independently selected from the hydrocarbon substituents, the substituted hydrocarbon substituents comprising one or more of the following: halo, hydroxyl, alkoxy, mercapto, nitro, nitroso, amino, pyridyl, furyl, imidazolyl, oxygen, and nitrogen, and two or fewer non-hydrocarbon substituents present for every 10 carbon atoms in the hydrocarbyl group. In some embodiments, hydrocarbyl includes the term “alkyl.” Where used herein, unless otherwise specified, the term “alkyl” refers to a linear, branched, cyclic, and / or substituted saturated chain portion of about 1 to about 100 carbon atoms. As used herein, the term “alkenyl” refers to a linear, branched, cyclic, and / or substituted unsaturated chain portion comprising approximately 3 to 10 carbon atoms. As used herein, the term “aryl” 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] Where used herein, unless otherwise specified, the terms “hydrocarbilene substituent” or “hydrocarbilene group” are used in their ordinary sense as is well known to those skilled in the art. Specifically, they refer to groups that are directly bonded to the rest of the molecule by carbon atoms at two locations on the molecule and have primarily hydrocarbon characteristics. Each hydrocarbilene group is independently selected from divalent hydrocarbon substituents, the substituted divalent hydrocarbon substituents include halo groups, alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, hydroxyl groups, alkoxy groups, mercapto groups, nitro groups, nitroso groups, amino groups, pyridyl groups, furyl groups, imidazolyl groups, oxygen, and nitrogen, and two or fewer non-hydrocarbon substituents are present for every 10 carbon atoms in the hydrocarbilene group.

[0022] As used herein, the term “weight percentage” means the percentage of the listed ingredient relative to the total weight of the composition, unless otherwise explicitly stated.

[0023] As used herein, the terms “soluble,” “oil-soluble,” and “dispersible” may indicate, but do not necessarily, that a compound or additive is soluble, soluble, miscible, or suspendable in oil in any proportion. However, the aforementioned terms mean that they are soluble, suspendable, soluble, or stably dispersible in oil to a degree sufficient to exert their intended effect, for example, in an environment where oil is used. Furthermore, if desired, it may be possible to incorporate other additives to incorporate a higher level of specific additive properties.

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

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

[0026] The molecular weight of any embodiment described herein may be determined using a gel permeation chromatography (GPC) instrument or similar instrument available from Waters, 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 (300 × 7.5 mm length, 5 μm particle size, and pore size in the range of 100–10000 Å), and a column temperature of approximately 40°C. Unstabilized 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 having a narrow molecular weight distribution in the range of 500–380,000 g / mol. Calibration curves can be extrapolated for samples with a mass of less than 500 g / mol. The sample and PS standard can be dissolved in THF and prepared at a concentration of 0.1–0.5% by weight, and can be used without filtration. GPC measurement is also described in U.S. Patent No. 5,266,223, which is incorporated herein by reference. The GPC method provides additional molecular weight distribution information. See, for example, WWYau, JJKirkland and DDBly, "Modern Size Exclusion Liquid Chromatography," John Wiley and Sons, New York, 1979, which is incorporated herein by reference.

[0027] Additional details and benefits of this disclosure are partially described below and / or may be acquired through the practice of this disclosure. These details and benefits may be realized and achieved through the elements and combinations specifically indicated in the attached claims. It should be understood that both the above general description and the following detailed description are illustrative and descriptive only and do not limit the claimed disclosure. [Modes for carrying out the invention]

[0028] This disclosure provides methods for preparing alkylphenols and phenate detergents in relation to neutral to overbasic additives, such as phenols alkylated with a polyalphaolefin oligomer configured with high para substitution on the aromatic ring of phenol, phenate detergents thereof and / or sulfide phenate detergents, lubricating viscosity base oils and lubricating compositions comprising such phenate detergents, and detergents having a TBN of at least about 0, at least about 20, at least about 50, at least about 100, and otherwise about 100 to about 500, as will be further discussed below.

[0029] In one method or embodiment, the disclosure relates to polyalphaolefin-substituted alkylphenols having high para-selectivity and / or reactivity, which are suitable for forming phenate detergents or sulfide 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 alkylphenols herein have many polymeric properties that define their uniqueness in achieving high para-selectivity and / or reactivity when forming alkylphenols and / or their phenate derivatives. For example, in some embodiments, the polyalphaolefin oligomers have about 40 mol percent or more, about 50 mol percent or more, about 60 mol percent or more, about 75 mol percent or more, about 85 wt percent or more, and even about 90 mol 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 phenols by such oligomers is effective in preferentially forming alkylphenols and / or salts thereof having high levels of para-alkylation from the polyalphaolefin oligomer. The alkylphenols herein derived from polyalphaolefin oligomers have at least about 50 mol percent alkylation at the para position, or at least about 60 mol percent alkylation at the para position, or at least about 75 mol percent alkylation at the para position, or at least about 85 mol percent alkylation at the para position, or at least about 90 mol percent alkylation at the para position and up to about 100 mol percent alkylation at the para position (or any range between such points).

[0030] The oligomers herein comprise one or more C6-C14 alpha-olefin monomer moieties, in other methods, a C8-C14 alpha-olefin monomer moiety, in other methods, a C8-C12 alpha-olefin monomer moiety, and in yet another method, a C8-C10 alpha-olefin monomer moiety. Thus, the alpha-olefin monomer moieties have 6-14, 8-14, 8-12, or 8-10 carbon atoms. For example, the alpha-olefin moieties may be derived from 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, their isomers, or combinations thereof. The term “olefin” as used herein has its given common sense in the art and generally refers to a compound of C10. x H 2x This refers to a family of organic compounds that are alkenes having (wherein x is the number of carbon atoms and has a double bond in its structure). The term "alpha-olefin" also refers to an olefin having a double bond at a primary or alpha position in its structure, in its given common sense in the art. The oligomers herein may 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 oligomers When alphaolefins are used for phenol alkylation, whether linear (i.e., normal) or isomerized, most alkylation occurs preferentially 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 sulfidation and / or other phenol crosslinking reactions. As described above, the novel polyalphaolefin oligomers herein possess many oligomeric properties that define their uniqueness with respect to phenol alkyl substituents that have high para-selectivity and reactivity in relation to phenol alkylation. For example, the polyalphaolefin oligomers herein have (i) a high content of carbon atoms configured to form a tertiary carbocation when protonated in the presence of an acid catalyst, (2) an alkyl group preferably having 1, 2, or 3 carbon atoms, with at least one alkyl group adjacent to the tertiary carbocation, (3) a high weight percent dimer structure, and a lower weight percent trimer, tetramer, and / or pentamer structure, and / or (4) a relatively high molar percent of terminal unsaturation which is a vinylidene configuration, and / or in some examples a relatively high molar percent of trisubstituted configuration, and / or in other examples one or more of both a relatively high molar percent vinylidene configuration and a trisubstituted configuration.

[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 have a positive charge (for example, when an unsaturated carbon is protonated with a cationic acid catalyst). The polyalphaolefin oligomers herein may have a high weight percentage of tertiary carbocations having the general structure of the following formula I upon catalytic protonation, 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 arise from certain configurations of alpha-olefin oligomers (further discussed below) when protonated in the presence of a cationic acid catalyst. In one embodiment or method, the polyalphaolefin oligomers of this specification have a structure having carbon atoms configured to form oligomers having such tertiary carbocations in a relatively high percentage. For example, the polyalphaolefin oligomers of this specification have a structure in which about 40 mol percent or more, preferably about 50 mol percent or more, more preferably about 60 mol percent or more, more preferably about 75 mol percent or more, even more preferably about 85 mol percent or more, most preferably about 90 mol percent or more, and in some embodiments, about 100 mol percent or less, about 90 mol percent or less, or about 80 mol percent or less (and any range between such points) of the polyalphaolefin contain carbon atoms configured to form tertiary carbocations. Such carbon atoms are configured and / or arranged to react with the hydroxyaromatic compound during the alkylation of the hydroxyaromatic compound, with para-alkylation of the hydroxyaromatic compound being highly preferred.

[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, which 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 an alkyl group of C3 or less (preferably a C2 alkyl group, most preferably a C1 alkyl group). Although we do not wish to be limited by theory, having such a short-chain alkyl group adjacent to the tertiary carbocation is thought to improve the reactivity of the oligomer to para substitution on the aromatic ring. In some embodiments, although we do not wish to be limited by theory, the polyalphaolefin oligomers herein may contain about 40% by weight or more of C3 or less alkyl groups adjacent to the tertiary carbocation, about 50% by weight or more, about 60% by weight or more, or about 75% by weight or more of C3 or less alkyl groups, and in other embodiments, they may 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 (and any range between such points) of C3 or less alkyl groups adjacent to the tertiary carbocation.

[0036] Dimer Structure: In further embodiments, the polyalphaolefin oligomers herein are mixtures of oligomer compounds, the mixture may also have high weight percent dimer structures, as well as lower weight percent trimer, tetramer, and / or pentamer structures. For example, in some methods, the polyalphaolefin oligomer may contain about 40 weight percent or more dimers, about 50 weight percent or more dimers, about 60 weight percent or more dimers, or about 75 weight percent or more dimers, and in some methods, dimers of about 100 weight percent or less, about 90 weight percent or less dimers, about 80 weight percent or less dimers, about 70 weight percent or less dimers, or about 60 weight percent or less dimers (and any range between such weight percent amounts). Simultaneously, the polyalphaolefin oligomer may include trimers of about 40 weight percent or less (or about 30 weight percent or less in other methods) and / or tetramers of about 20 weight percent or less (or about 18 weight percent or less in other methods, or even about 12 weight percent or less), and / or pentamers of about 5 weight percent or less (or about 4 weight percent or less in other methods, or even about 3 weight percent or less), as well as any range between such weight percentages for each oligomer type. In other embodiments, the trimers may be about 0 to about 40 weight percent, about 1 to about 30 weight percent, about 2 to about 30 weight percent, or about 5 to about 30 weight percent. In other embodiments, the tetramers may be about 0 to about 20 weight percent, about 1 to about 18 weight percent, about 2 to about 18 weight percent, or about 5 to about 18 weight percent. In other embodiments, the pentamer may be present in an amount of about 0 to about 5 weight percent, about 1 to about 4 weight percent, or about 2 to about 4 weight percent.

[0037] As used herein, dimers, trimers, tetramers, and pentamers are given their usual meanings in the art and generally refer to oligomers having two monomer units, three monomer units, four monomer units, 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 not only have a high weight percent dimer structure but also one or more other oligomer properties, including a high percentage of tertiary carbocation, a high percentage of a short alkyl chain adjacent to the tertiary carbocation, and a high percentage of vinylidene and / or a trisubstituted configuration.

[0038] Oligomer Unsaturation: In yet another embodiment, the polyalphaolefin oligomers herein may also have a relatively high percentage of unsaturation with a vinylidene configuration, a relatively high percentage of unsaturation with a trisubstituted configuration, and / or optionally both with a vinylidene configuration and a trisubstituted configuration. In some methods, unsaturation is considered to be terminal unsaturation as discussed below. For example, in some embodiments, the polyalphaolefin oligomers herein contain vinylidene groups in an amount of about 40 mol percent or more, in another method about 50 mol percent or more, in yet another method about 60 mol percent or more, in yet another method about 75 mol percent or more, in yet another method about 85 mol percent or more, in yet another method about 90 mol percent or more, and in yet another method 100 mol percent or less, 95 mol percent or less, 90 mol percent or less (or any other range between such mol percent amounts). In other embodiments, the polyalphaolefin oligomers according to this specification include three substituents in amounts of about 40 mol percent or more, in other methods about 50 mol percent or more, in yet other methods about 60 mol percent or more, in yet other methods about 75 mol percent or more, in yet other methods about 85 mol percent or more, in yet other methods about 90 mol percent or more, and in yet other methods 100 mol percent or less, 95 mol percent or less, 90 mol percent or less (or any other range between such mol percent amounts). In yet another embodiment, the polyalphaolefin oligomers according to this specification include about 40 mol percent or more, in other methods about 50 mol percent or more, in yet other methods about 60 mol percent or more, in yet other methods about 75 mol percent or more, in yet other methods about 85 mol percent or more, in yet other methods about 90 mol percent or more, and in yet other methods 100 mol percent or less, 95 mol percent or less, 90 mol percent or less (or any other range between such mol percent amounts).

[0039] While we do not wish to limit ourselves to theory, the oligomers used herein are considered to primarily include end-unsaturated groups. As will be understood by those skilled in the art, oligomeric unsaturation refers to a carbon-carbon double bond having at least one carbon 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, reflecting vinyl, disubstituted, vinylidene, and trisubstituted end-unsaturation (wherein ~ represents a bond to the rest of the oligomer). In some ways, the oligomers used herein may have more than 75 mol% end-unsaturation, more than 80 mol% end-unsaturation, more than 85 mol% end-unsaturation, more than 90 mol% end-unsaturation, more than 95 mol% end-unsaturation, or even more than 97 mol% end-unsaturation. The molar percentages of unsaturation or end-unsaturation are: 13 This can be determined by 13C NMR. (See, for example, U.S. Patent No. 5,128,056 incorporated herein by reference.)

[0040] [ka] In the formula, R4~R 10 This is a linear or branched alkyl or hydrocarbyl group that matches the monomer and / or oligomer structure further discussed herein. As shown herein, the cis and / or trans isomers of various structures are intended to be interchangeable, and both cis and trans isomers are included in any structure herein, whether or not they are shown in various structures. Terminal vinylidenes, trisubstituted isomers of terminal vinylidenes, and other types of terminal unsaturated bonds are, for example, 1 The amounts of each unsaturated bond can be determined from the integrated intensity of each signal, as discussed in U.S. Patent Application Publication No. 2016 / 0257862, incorporated herein by reference.

[0041] Oligomer Structure: Polyalphaolefin oligomers herein, configured to have high reactivity and preference for para-alkylation of phenols, possess one or more of the above-described oligomeric properties, and in some embodiments, may have oligomeric structures of formula VI (having a high percentage vinylidene configuration) and / or formula VII (having a high percentage trisubstituted configuration), and / or combinations of both formula VI and formula VII structures. For example, in some methods, the polyalphaolefin compounds herein are polymer molecules, preferably oligomeric molecules, produced from the oligomerization reaction of alphaolefin monomers in the presence of a catalytic system. Unsaturated polyalphaolefin oligomers herein are understood to contain a carbon-carbon double bond, where such a double bond is mainly located at the terminal monomer group or moiety as described above.

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

[0043] In some methods or embodiments, the preferred polyalphaolefin oligomers herein may comprise a mixture of oligomers (e.g., derived from, but not limited to, the above C6-C14 monomers), the majority of which 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 R is an alkyl group, 12 , R13 , R 14 , R 15 , and / or R 16 Each of these is either the same or different in each occurrence 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 Only one of them is hydrogen, R 17 , R 18 and R 19 One of the remaining two is a substituted or unsubstituted hydrocarbyl group having one, two, or three carbon atoms (preferably a substituted or unsubstituted alkyl group), R 17 , R 18 and R 19 Of the remaining two, the other one 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 these is either the same or different in 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 between 0 and 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] While we do not wish to be limited by theory, in yet other embodiments or methods of the oligomer of formula VI, R 11 R may be a C4-C12 alkyl group, 12 R may be hydrogen or a C1-C12 alkyl group, 13 R may be hydrogen or a C1-C12 alkyl group, 14 R may be hydrogen or a C1-C12 alkyl group, 15 R may be hydrogen or a C1-C12 alkyl group, and / or R 16may be hydrogen or an alkyl group (preferably from the catalyst system). Those skilled in the art will understand that the structure of Formula VI may also depend on, among other features, the polymerization conditions, the selected catalyst, and / or the starting monomer mixture.

[0047] Without wishing to be bound by theory, in other embodiments or approaches of the oligomers of Formula VII, R 19 when it is hydrogen, one of R 17 or R 18 is a C1-C3 alkyl group and the other is a C2-C12 alkyl group, and R 20 is a C4-C12 alkyl group. Similarly, when R 17 is hydrogen, R 19 is a C1-C3 alkyl group, R 18 is a C5-C13 alkyl group, and R 20 is C1-C11. Similarly, when R 18 is hydrogen, R 19 is a C1-C3 alkyl group, R 17 is a C5-C13 alkyl group, and R 20 is C1-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). Those skilled in the art will understand that the structure of Formula VII may also depend on, among other features, the polymerization conditions, the selected catalyst, and / or the starting monomer mixture.

[0048] The oligomers described herein may be prepared using polymerization catalysts and conditions known to those skilled in the art. The oligomerization reaction conditions can be controlled as needed to provide the desired oligomers described herein. Parameters such as reaction temperature, pressure, mixing, reactor heat control, feed rate of one or more reactants, type, ratio, and concentration of catalyst and / or co-catalyst and / or scavenger, and phase of feed components can be controlled to affect the structure of the copolymer obtained from the reaction. Thus, the desired oligomers described herein can be produced by controlling several different combinations of reaction conditions known to those skilled in the art. In some methods, polyalphaolefin oligomers suitable for alkylation of phenols described herein may be prepared using the process described in U.S. Patent Application Publication 2021 / 0347921 (which is incorporated herein in its entirety by reference).

[0049] In some embodiments, reaction temperatures of about 60°C to about 135°C may be used for the oligomerization reaction, or in other methods, 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 specified herein.

[0050] The oligomers described 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 is known to those skilled in the art, metallocenes contain a cyclopentadienyl anion ("Cp") bonded to a metal center. The coordination metallocene may contain zirconium, and in some methods, the coordination metallocene may contain Cp2ZrCl2. The coordination polymerization catalyst may further contain a co-catalyst, which may contain, for example, methylaluminoxane.

[0051] The oligomers described herein may be generated in a reactor, and parameters that can be controlled during the process are known to those skilled in the art and may include suitable pressure and temperature control as described above. The reaction can be operated continuously, semi-continuously, or batchwise. Catalysts and co-catalysts, if used, may be supplied to the reactor in solution. The weight percent of either the catalyst or co-catalyst in solution may be less than about 20% by weight, and depending on different embodiments, may be less than about 15% by weight, less than about 10% by weight, less than about 8% by weight, less than about 6% by weight, less than about 5% by weight, less than about 4% by weight, less than about 3% by weight, less than 2% by weight, or less than 1% by weight, as necessary to achieve the desired oligomers described herein. The components may then be mixed in the reactor. Suitable catalysts and conditions for this are known to those skilled in the art and may be described, for example, at least U.S. Patent No. 9,441,063 or No. 8,614,277, both of which are incorporated herein by reference.

[0052] In some methods, a free radical initiator may be used in the oligomerization process herein, if necessary. The free radical initiator, if used, may be a peroxide, hydroperoxide, and / or azo compound having a boiling point above 100°C and providing free radicals through thermal decomposition within the reaction temperature range. Typical free radical initiators may be azobutyronitrile, 2,5-dimethyl-hexa-3-in-2,5-bis-tert-butylperoxide, or their hexene analogs. The initiator may be supplied at a low level, approximately 0.005% to approximately 1% by weight, based on the total weight of the oligomer solution.

[0053] Alkylation of phenols Suitable phenols or hydroxyaromatic compounds for alkylation by oligomers as used herein include monohydroxy and / or polyhydroxyaromatic hydrocarbons having 1 to 4 hydroxyl groups, and in some methods, 1 to 3 hydroxyl groups, for alkylation by polyalphaolefin oligomers. Suitable compounds include, but are not limited to, phenols, catechols, resorcinols, hydroquinones, pyrogallols, cresols, and mixtures thereof. Phenols are among the preferred starting compounds.

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

[0055] Oligomer polyalphaolefins having the above oligomeric properties are particularly suitable for alkylation to phenols or hydroxyaromatic compounds at the para position, but other substitutions may be present depending on the application. For example, oligomeric alkyl groups (i.e., R in formula VIII below) 24The substituents) may be at least about 40 mol percent at the para position of the aromatic ring (in some methods, at least about 50, at least about 60, at least 75, at least about 85, or at least about 90 mol percent and up to about 100 mol percent (or any range of mol percent between such amounts)) when using the oligomers herein, and may be disubstituted at the ortho position of the aromatic ring by about 0 to about 15 mol percent, in some methods, by about 0 to about 5 mol percent. Furthermore, the alkylated phenol may have the structure of the following formulas VIII, VIIIa, VIIIb, or VIIIc, and consist of a high content of vinylidene and the group R as defined in any of the embodiments above. 11 ~R 23 and the above trisubstituted oligomer having an integer n. Equation VIIIb is R 17 or R 18 is hydrogen, R 19 is an alkyl group having 1, 2, or 3 carbon atoms, preferably R 19 It is a C2 group, and most preferably R 19 It is formed when it is a C1 group. Formula VIIIc is R 19 is hydrogen, R 17 or R 18 is an alkyl group having 1, 2, or 3 carbon atoms, preferably R 17 or R 18 It is a C2 group, and most preferably R 17 or R 18 It is formed when it is a C1 group.

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

[0057] Neutralization Neutralization is carried out by alkylphenols as defined herein, which react with a metal base. In one method, neutralization is carried out by contacting the alkylphenols described above with a metal base under reactive conditions, and in several methods, by contacting them in a liquid hydrocarbon diluent containing an accelerator, to provide phenates or salts of alkylhydroxyaromatic compounds. In some cases, the reaction can be carried out under an inert gas such as nitrogen. The metal base may be added at various points in the reaction, either as a single addition or in multiple additions, if required for a particular application. Neutralization may occur via the exemplary reaction scheme I shown below, but other reactions may proceed as needed, depending on the selected order of sulfidation, neutralization, and / or overbasification, as well as the various applications, materials, and conditions.

[0058] [ka]

[0059] Examples of metal-base reactants include, but are 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, as well as metal hydroxides, oxides, or alkoxides. Suitable metal-base compounds include lithium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, ammonium hydroxide, and / or aluminum hydroxide. Other examples of metal-base compounds include lithium oxide, magnesium oxide, calcium oxide, and barium oxide. In preferred examples, the alkaline earth metal base is lime or calcium hydroxide. Additives may be borated as needed, depending on the application and use.

[0060] In optional methods, the neutralizing solvent is one with a higher boiling point, such as ethylene glycol, propylene glycol, and / or decanol, or other solvents having a boiling point of about 100°C or higher at the pressure described. In this specification, when such optional methods are used, the absence or lack of such compounds means that the solvent contains less than about 15% by weight, less than about 5% by weight, or less than about 2% by weight.

[0061] The neutralization reaction between a metal base and an alkylphenol is carried out under conditions that are effective for maintaining high temperatures. In one method, neutralization occurs at a temperature of at least 100°C, in some methods at at least about 120°C, in others at at least about 150°C, and in a more preferred method at a temperature of about 180°C or lower. The neutralization reaction can take about 1 to 5 hours.

[0062] sulfide Neutralized alkylphenols or alkylhydroxyaromatic compounds can be sulfurized by contacting them with a sulfur source in a manner effective in achieving a high degree of sulfurization. In these methods, sulfurization generally involves introducing sulfur crosslinking groups between the alkylphenol or alkylhydroxyaromatic moieties. In some methods, the sulfur crosslinking is -S y The group is - or -Sx- (as shown in the exemplary structure below), where x is an integer from 1 to 4, in other methods from 1 to 3, and in some methods from 1 to 2, and / or has a total sulfur level provided by an additive of up to approximately 5 percent. The sulfur source may be any suitable sulfur, e.g., sulfur monochloride or dichloride, hydrogen sulfide, sulfur dioxide, and sodium sulfide hydrate, e.g., elemental sulfur or its halides. The sulfur can be used either as molten sulfur, as a solid (powder or fine particles), or as a solid suspension in a hydrocarbon liquid. An exemplary reaction scheme for sulfidation is shown in Reaction Scheme II below, but other reactions may proceed as needed, depending on the application, materials, and conditions.

[0063] [ka] Sulfidation can occur over a period of time effective in achieving the desired level of sulfidation, for example, at a temperature of about 160°C to 250°C, or by other methods, about 180°C to 245°C, for about 1 to 8 hours, about 2 to 7 hours, or about 4 to 7 hours.

[0064] Overbasication Next, overbasification is optional, but preferred in some embodiments, and is carried out either during or after the neutralization and / or sulfidation described above. In one method, the alkylphenol / alkylphenate sulfide is overbasified by reacting it with an excess metal base and / or with an acidic overbasification compound, such as carbon dioxide or boric acid. In another method, overbasification is carried out via carbonation (reaction with carbon dioxide) in the presence of a solvent, for example, one 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 overbasification reaction can be removed as needed by distillation either during or after the reaction, as will be further discussed below.

[0065] In one embodiment, an exemplary overbasication reaction may be carried out by reacting an alkylphenol sulfide or a salt thereof with an alkali metal or alkaline earth metal, such as lime, in the presence of carbon dioxide and the 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 method, overbasication occurs at a temperature of at least about 50°C, at least about 100°C in some methods, at least about 165°C in other methods, and at least about 185°C or lower in more preferred methods. The degree of overbasication can be controlled by the amount of alkali metal or alkaline earth metal, the amount of carbon dioxide and other reactants (if present) added to the reaction mixture, and the reaction conditions used during the carbonation process. In the method, overbasication or overbasication via carbonation occurs for a time sufficient to achieve the desired degree of overbasication or TBN, which in some methods may be about 30 minutes to about 250 minutes at the temperatures described.

[0066] Following optional overbasication, the overbasicated alkyl phenate sulfide, for example, the detergent composition herein, may have a TBN of at least about 0, at least about 20, at least about 50, at least about 100, or by other means, about 100 to about 500, about 100 to about 400, or about 150 to about 400, by yet another method, about 200 to about 300, and by yet another method, about 220 to about 275. Preferably, the TBN of the composition herein may be about 100 to about 300 mg KOH as measured by ASTM D-2896.

[0067] In embodiments, the exemplary overbasic and alkyl sulfide phenate additives described herein are derived from the above-mentioned polyalphaolefin oligomers. 24 It may have the following structure of formula IX, which includes [the specified element].

[0068] [ka] In the formula, each R 24 The following are independently derived from C6-C14 monomers (as described above) and may be polyalphaolefins forming dimers, trimers, tetramers, pentamers, copolymers, copolymer variants, or combinations thereof containing tertiary carbocation residues that form a bond to an aromatic ring as described herein. In the method, R in formula IX 24 At least about 50 mole percent of are bonded to the aromatic ring at the para position (in other methods, 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 methods, up to about 100 mole percent (and any range between such endpoints)). x is an integer from 1 to 4 as described above, and M 2+ As mentioned above, it is a divalent metal ion.

[0069] Post-processing Following optional overbasification, the composition is often subjected to several steps to prepare the final alkyl phenate sulfide product. Examples of post-treatment include one or more of the following: 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, alkylphenates are produced by sulfidation, neutralization, and / or carbonation. These reactions can be carried out in any order, simultaneously, or in a specific order, depending on the application. Sulfidation and neutralization are typically completed before carbonation, for example, in any order or simultaneously. Generally, detergent additives or compositions herein are obtained by first alkylating a phenol with an oligomer described herein, neutralizing the alkylphenol, and then sulfiding the neutralized alkylphenol with a sulfur source to provide a sulfurized and neutralized alkylphenol. The sulfurized and neutralized alkylphenol is then optionally overbasidized in the presence of a solvent to provide a neutral to optionally overbasidized and alkylphenate additive or composition.

[0071] lubricating oil composition The optionally overbasicated and sulfurized alkylphenate products described herein may be combined with one or more further optionally selected additives to produce lubricating oil compositions with a primary amount of base oil or base oil blend (as described below) of lubricating viscosity. In the method, the lubricating oil composition comprises about 50 weight percent or more of base oil, about 60 weight percent or more, about 70 weight percent or more, or about 80 weight percent to about 95 weight percent or less, about 90 weight percent or less, or about 85 weight percent or less of the base oils further considered below.

[0072] In the method, the lubricating oil composition described herein may contain, in the base oil or base oil blend, about 0.02 to about 5 weight percent, in the other method, about 0.2 to about 3 weight percent, and in yet another method, about 0.2 to about 2 weight percent of optionally over-basidized and sulfurized alkylphenate products in the base oil or base oil blend.

[0073] In some methods, the additives described 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 components, dispersant inhibitor packages, and / or individual components described herein may be suitable for use in various types of lubricants, such as automotive lubricants and / or greases, internal combustion engine oils, 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, and wet brake fluids.

[0075] Suitable engine types may include, but are not limited to, heavy-duty diesels, passenger car engines, light-duty diesels, medium-speed diesels, or marine engines. Internal combustion engines may be diesel-fueled engines, gasoline-fueled engines, natural gas-fueled engines, biofuel-fueled engines, diesel / biofuel-blended engines, gasoline / biofuel-blended engines, alcohol-fueled engines, gasoline / alcohol-fuel-blended engines, compressed natural gas (CNG)-fueled engines, or mixtures thereof. Diesel engines may be compression-ignition engines. Gasoline engines may be spark-ignition engines. Internal combustion engines may also be used in combination with electric or battery power sources. Engines configured in this way are generally known as hybrid engines. Internal combustion engines may be two-stroke, four-stroke, or rotary engines. Suitable internal combustion engines include marine diesel engines (such as those for inland vessels), aircraft piston engines, low-load diesel engines, and engines for motorcycles, automobiles, locomotives, and trucks. Engines may be coupled with turbochargers.

[0076] Lubricant compositions 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% by weight or less, or about 0.8% by weight or less, or about 0.5% by weight or less, or about 0.3% by weight or less, or about 0.2% by weight or less. In one embodiment, the sulfur content may be in the range of about 0.001% by weight to about 0.5% by weight, or about 0.01% by weight to about 0.3% by weight. The phosphorus content may be about 0.2% by weight or less, or about 0.1% by weight or less, or about 0.085% by weight or less, or about 0.08% by weight or less, or even about 0.06% by weight or less, about 0.055% by weight or less, or about 0.05% by weight 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 may be 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] Furthermore, the lubricants described herein 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 (trademark), Dexos2 (trademark), MB-Approval 229.1, 229.3, 229.5, 229.51 / 229.31, 229.52, 229.6, 229.71, 226.5, 226.51, 228.0 / .1, 228.2 / .3, 228.31, 228.5, 228.51, 228.61, VW 501.01, 502.00, 503.00 / 503.01, 504.00, 505.00, 505.01, 506.00 / 506.01, 507.00, 508.00, 509.00, 508.88, 509.99, BMW Longlife-01, Longlife-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.It may be suitable for meeting the original equipment manufacturer's specifications such as 5004, STJLR.03.5005, STJLR.03.5006, STJLR.03.5007, STJLR.51.5122, or past or future PCMO or HDD specifications not described 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 to V as specified in the American Petroleum Institute (API) Base Oil Interoperability Guidelines. The five base oil groups are generally shown in Table 1 below.

[0079] [Table 1]

[0080] Groups I, II, and III are mineral oil process raw materials. Group IV base oils contain true synthetic molecular species produced by the polymerization of olefinic 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, but may also be natural oils such as vegetable oils. It should be noted that Group III base oils are derived from mineral oil, but due to the rigorous processing these fluids undergo, their physical properties become very similar to those of some true synthetic oils such as PAO. Therefore, oils derived from Group III base oils can be referred to as synthetic fluids in industry. Group II+ may include high viscosity index Group II.

[0081] The base oil blends used in the disclosed lubricating oil compositions may be mineral oils, animal oils, vegetable oils, synthetic oils, synthetic oil blends, or mixtures thereof. Suitable oils may be derived from hydrocracking, hydrotapping, hydrofinishing, unrefined oils, refined oils, and re-refined oils, as well as mixtures thereof.

[0082] Unrefined oils are derived from natural, mineral, or synthetic sources that undergo little to no further refining. Refined oils are similar to unrefined oils except that they have been treated with one or more refining steps that may result in an improvement in one or more properties. Examples of preferred refining techniques include solvent extraction, secondary distillation, acid or base extraction, filtration, and osmosis. Oils refined to a quality suitable for consumption may or may not be useful. Edible oils are sometimes called white oils. In some embodiments, lubricating oil compositions do not contain edible oils or white oils.

[0083] Refined oil is also known as recycled oil or reprocessed oil. These oils are obtained in the same way as refined oil using the same or similar processes. Often, these oils are further treated by techniques that target the removal of spent additives and oil degradation 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 lubricants, such as liquid petroleum, and paraffinic, naphthenic, or mixed paraffin-naphthenic type solvent-treated or acid-treated mineral lubricants. Such oils may be partially or completely hydrogenated if desired. Oils derived from coal or shale may also be useful.

[0085] Useful synthetic lubricants include hydrocarbon oils, for example, polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylene, polypropylene, propylene isobutylene copolymer); trimers or oligomers of poly(1-hexene), poly(1-octene), and 1-decene, for example, poly(1-decene) (such materials are often referred to as α-olefins), and mixtures thereof; alkylbenzenes (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 their derivatives, analogs, and homologs, or mixtures thereof. Polyalphaolefins are typically hydrogenated materials.

[0086] Other synthetic lubricants include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl esters of decanephosphonic acid), or polymeric tetrahydrofurans. Synthetic oils may be produced by the Fischer-Tropsch reaction and are typically hydrogenated isomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil may be prepared by the Fischer-Tropsch gas-liquid synthesis procedure and other gas-liquid oils.

[0087] In another embodiment, the main amount of base oil contained in the lubricating composition may be selected from the group consisting of Group I, Group II, Group III, Group IV, Group V, and any combination of two or more of the aforementioned, but the main amount of base oil is other than base oil resulting from the provision of additive components or viscosity index modifiers in the composition.

[0088] The amount of oil with lubricating viscosity present may be the difference remaining after subtracting from 100% by weight the total amount of performance additives, including viscosity index modifiers and / or pour point depressants and / or other top-treatment additives. For example, the amount of oil with lubricating viscosity that may be present in the final fluid may be the main amount, e.g., more than about 50% by weight, more than about 60% by weight, more than about 70% by weight, more than about 80% by weight, more than about 85% by weight, or more than about 90% by weight.

[0089] Optional additives: The lubricating oil compositions described herein may also include several optional additives, which may be combined with optional overbasication and alkyl phenate sulfide products as necessary to meet performance requirements. These optional additives are described in the following paragraphs.

[0090] Dispersants: Lubricating oil compositions may optionally contain one or more dispersants or mixtures thereof. Dispersants are often known as ashless dispersants because they do not contain metals that form ash before being mixed into the lubricating oil composition and do not typically contribute to ash when added to the lubricant. Ashless dispersants are characterized by polar groups being bonded to relatively high molecular weight hydrocarbon chains. Typical ashless dispersants include N-substituted long-chain alkenyl succinimides. An example of an N-substituted long-chain alkenyl succinimide is polyisobutylene succinimide, in which the number-average molecular weight of the polyisobutylene substituent is in the range of about 350 to about 50,000, or about 5,000, or about 3,000, as measured by GPC. Succinimide dispersants and their preparations are disclosed, for example, in U.S. Patent No. 7,897,696 or U.S. Patent No. 4,234,435. Alkenyl substituents can be prepared from polymerizable monomers containing about 2 to about 16 carbon atoms, or about 2 to about 8 carbon atoms, or about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines (typically poly(ethyleneamine)).

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

[0092] A suitable heavy polyamine is a polyalkylene-polyamine mixture containing small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine), but mainly containing six or more nitrogen atoms, two or more primary amines per molecule, and oligomers having a broader branching range than conventional polyamine mixtures. The heavy polyamine preferably contains polyamine oligomers containing seven or more nitrogen atoms per molecule and two or more primary amines per molecule. The heavy polyamine contains more than 28% by weight (e.g., >32% by weight) of total nitrogen and primary amine groups in an equivalent weight of 120 to 160 grams per gram equivalent.

[0093] In some methods, preferred polyamines, commonly known as PAMs, contain a mixture of ethyleneamines, with TEPA and pentaethylenehexamine (PEHA) being the main components of the polyamine, typically making up less than 80%.

[0094] Typically, PAMs contain 8.7–8.9 milliequivalents of primary amine per gram (115–112 gram equivalents per primary amine equivalent) and a total nitrogen content of approximately 33–34% by weight. Heavier cuts of PAM oligomers, which are substantially TEPA-free and contain very small amounts of PEHA, but mainly contain oligomers with more than 6 nitrogen atoms and broader branching, can produce dispersants with improved dispersibility.

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

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

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

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

[0099] The percentage of active ingredients in alkenyl or alkyl succinic anhydride can be determined using chromatographic techniques. This method is described in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0100] The conversion percentage of polyolefins is calculated from the active ingredient percentage using the formulas in columns 5 and 6 of U.S. Patent No. 5,334,321.

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

[0102] In one embodiment, the dispersant may be derived from polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant may be derived from 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 onto an ethylene-propylene copolymer.

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

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

[0105] A suitable class of dispersants may also be high molecular weight esters or semi-esteramides. Suitable dispersants may also be post-treated by conventional methods with any of a variety of agents. These include boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydride, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds. U.S. Patents 7,645,726, 7,214,649, and 8,048,831 are incorporated herein by reference in their entirety.

[0106] In addition to the post-treatment of carbonates and boric acid, each compound may be post-treated or further post-treated by 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. Patent No. 5,241,003, which is incorporated herein by reference. Such treatments include: inorganic phosphoric acid or anhydride (e.g., U.S. Patents No. 3,403,102 and 4,648,980); organophosphorus compounds (e.g., U.S. Patent No. 3,502,677); phosphorus pentasulfide; boron compounds as already described above (e.g., U.S. Patents No. 3,178,663 and 4,652,387); carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Patents No. 3,708,522 and 4,9 48,386); Epoxy polyepoxyates or thioepoxides (e.g., U.S. Patents 3,859,318 and 5,026,495); Aldehydes or ketones (e.g., U.S. Patent 3,458,530); Carbon disulfide (e.g., U.S. Patent 3,256,185); Glycidol (e.g., U.S. Patent 4,617,137); Urea, thiourea, or guanidine (e.g., U.S. Patent 3,312,61 Patent No. 9, No. 3,865,813, and British Patent No. 1,065,595); Organic sulfonic acids (e.g., U.S. Patent No. 3,189,544 and British Patent No. 2,140,811); Alkenyl cyanides (e.g., U.S. Patents No. 3,278,550 and No. 3,366,569); Diketene (e.g., U.S. Patent No. 3,546,243); Diisocyanates (e.g., U.S. Patent No. 3,573,205); Alkansul Tons (e.g., U.S. Patent No. 3,749,695); 1,3-dicarbonyl compounds (e.g., U.S. Patent No. 4,579,675); alkoxylated alcohols or phenolic sulfates (e.g., U.S. Patent No. 3,954,639); cyclic lactones (e.g., U.S. Patents No. 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. Patent Nos. 4,612,132, 4,647,390, 4,648,886, and 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Patent No. 4,971,598 and British Patent No. 2,140,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Patent No. 4,614,522); lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Patents No. 4,614,603 and No. 4,666,460); cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Patents No. 4,612,132, 4,647,390, 4,646,860, and 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Patent No. 4,971,598 and British Patent No. 2,440,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Patent No. 4,614,522); lactams, thiocarbonates Olactams, thiolactones, or dithiolactones (e.g., U.S. Patent Nos. 4,614,603 and 4,666,460); cyclic carbamates, cyclic thiocarbamates, or cyclic dithiocarbamates (e.g., U.S. Patents Nos. 4,663,062 and 4,666,459); hydroxyaliphatic carboxylic acids (e.g., U.S. Patents Nos. 4,482,464, 4,521,318 and 4,713,189); oxidizing agents (e.g., U.S. Patent No. 4,379,064); combinations of phosphorus pentasulfide and polyalkylene polyamines (e.g., (e.g., U.S. Patent No. 3,185,647); combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (e.g., U.S. Patents No. 3,390,086 and 3,470,098); combinations of hydrazine and carbon disulfide (e.g., U.S. Patent No. 3,519,564); combinations of aldehydes and phenols (e.g., U.S. Patents No. 3,649,229, 5,030,249 and 5,039,307); combinations of aldehydes and O-diesters of dithiophosphate (e.g., U.S. Patent No. 3,865,740);Combinations of hydroxyaliphatic carboxylic acids and boric acid (e.g., U.S. Patent No. 4,554,086); combinations of hydroxyaliphatic carboxylic acids followed by formaldehyde and phenol (e.g., U.S. Patent No. 4,636,322); combinations of hydroxyaliphatic carboxylic acids and followed by aliphatic dicarboxylic acids (e.g., U.S. Patent No. 4,663,064); combinations of formaldehyde and phenol, followed by glycolic acid (e.g., U.S. Patent No. 4,699,724); combinations of hydroxyaliphatic carboxylic acids or oxalic acid followed by diisocyanates (e.g., U.S. Patent No. 4,713,191); inorganic acids or anhydrides of phosphorus or combinations of partially or entirely sulfur analogs and boron compounds (e.g., U.S. Patent No. 4,857,214); combinations of organic diacids, followed by unsaturated fatty acids, followed by nitroso aromatic amines, optionally followed by boron compounds, and followed by glycolating agents (e.g., U.S. Patent No. 4,973,412); combinations of aldehydes and triazoles (e.g., U.S. Patent No. 4,963,278); combinations of aldehydes and triazoles followed by boron compounds (e.g., U.S. Patent No. 4,981,492); combinations of cyclic lactones and boron compounds (e.g., U.S. Patents No. 4,963,275 and 4,971,711). Hereinafter, the aforementioned patents are incorporated herein in their entirety.

[0107] A suitable dispersant may have a TBN of approximately 5 to 30 TBN when measured in a dispersant sample containing approximately 50% diluted oil, and may be a dispersant of approximately 10 to 65 mg KOH / g on an oil-free basis. TBN is measured by the method of ASTM D2896.

[0108] In further embodiments, the optional dispersion additive may be a hydrocarbyl-substituted succinamide or succinimide dispersant. In some methods, the hydrocarbyl-substituted succinamide or succinimide dispersant may be derived from a hydrocarbyl-substituted acylating agent reacted with a polyalkylene polyamine, wherein the hydrocarbyl substituent of the succinamide or succinimide dispersant is a linear or branched hydrocarbyl group having a number-average molecular weight of about 250 to about 5,000 when measured by GPC using polystyrene as the calibration standard.

[0109] In some methods, the polyalkylene polyamine used to form the dispersant is given by the following formula:

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

[0111] If present, the dispersant 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. Other amounts of dispersant that may be used may be about 0.1 to about 15% by weight, or about 0.1 to about 10% by weight, about 0.1 to about 8% by weight, or about 1 to about 10% by weight, or about 1 to about 8% by weight, or 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 described herein may optionally contain one or more antioxidants. Known antioxidant compounds include, for example, phenates, phenate sulfides, sulfurized olefins, phosphosulfur terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, di-nonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine), phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, polymeric antioxidants, or mixtures thereof. Antioxidant compounds may be used alone or in combination.

[0113] Hindered phenol antioxidants may contain secondary butyl groups and / or tertiary butyl groups as sterically hindering groups. The phenol group may be further substituted with a hydrocarbyl group and / or a crosslinking group bonded 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 about 1 to about 18 carbon atoms, or about 2 to about 12 carbon atoms, or about 2 to about 8 carbon atoms, or about 2 to about 6 carbon atoms, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant may also be an ester and may include Ethanox® 4716 available from the 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, so that each antioxidant may be present in an amount sufficient to provide up to about 5% by weight, 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% by weight of diarylamine and about 0.4 to about 2.5% by weight of high molecular weight phenol, based on the final weight of the lubricating oil composition.

[0115] 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 may 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. Fatty acids are often obtained from vegetable or animal oils and typically contain about 4 to about 22 carbon atoms. Suitable examples of fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof. Often, fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or mixtures thereof. Fatty acids and / or esters can be mixed with olefins such as α-olefins.

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

[0118] One or more antioxidants may be present in the lubricating oil composition in an amount ranging from about 0% to about 20% by weight, or from about 0.1% to about 10% by weight, or from about 1% to about 5% by weight.

[0119] Anti-wear agents: The lubricating oil compositions described herein may also optionally contain one or more anti-wear agents. Examples of suitable anti-wear agents include, but are not limited to, metal thiophosphates; metal dialkyldithiophosphates; phosphate esters or salts thereof; phosphate esters (plural); phosphates; 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 anti-wear agent may be molybdenum dithiocarbamate. Phosphorus-containing anti-wear agents are fully described in European Patent No. 612839. The metal in the dialkyldithiophosphate salt may be alkali metals, alkaline earth metals, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful anti-wear agent may be zinc dialkyldithiophosphate.

[0120] Further examples of suitable abrasion resistant agents include titanium compounds, tartrates, taltrimids, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, phosphates (e.g., dibutylphosphite), phosphonates, thiocarbamate-containing compounds such as thiocarbamate esters, thiocarbamate amides, thiocarbamate ethers, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides. Tartrates or taltrimids may contain alkyl ester groups, where the total number of carbon atoms on the alkyl group is at least 8. In one embodiment, the abrasion resistant agent may include citrates.

[0121] The anti-wear agent may be present in the lubricating oil composition in amounts ranging from about 0 to about 15% by weight, or about 0.01 to about 10% by weight, or about 0.05 to about 5% by weight, or about 0.1 to about 3% by weight.

[0122] Boron-containing compounds: The lubricating oil compositions described herein may optionally contain one or more boron-containing compounds. Examples of boron-containing compounds include borate esters, borate fatty amines, borate epoxides, borate detergents, and borate dispersants such as succinimide borate dispersants, as disclosed in U.S. Patent No. 5,883,057. If present, the boron-containing compound 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 contain one or more neutral detergents, low-basic detergents, or over-basic detergents, and mixtures thereof. Suitable detergent substrates include phenates, sulfur-containing phenates, sulfonates, calixalates, salixalates, salicylates, carboxylic acids, phosphoric acids, mono- and / or di-thiophosphates, alkylphenols, sulfur-linked alkylphenol compounds, or methylene-crosslinked phenols. Suitable detergents and methods for preparing them are described in detail in numerous patent publications, including U.S. Patent No. 7,732,390 and the references cited therein.

[0124] The detergent substrate may, but is not limited to, alkali metals or alkaline earth metals such as calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent does not contain barium. In some embodiments, the detergent may contain trace amounts of other metals such as magnesium or calcium in amounts such as 50 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less, or 10 ppm or less. Suitable detergents include alkali metal or alkaline earth metal salts of petroleum sulfonic acid and long-chain mono- or di-alkylaryl sulfonic acid whose aryl group is benzyl, tolyl, or xylyl. Suitable detergents include, but are not limited to, calcium carbonate, sulfur-containing calcium carbonate, calcium sulfonate, calcium calixalate, calcium salixalate, calcium salicylate, calcium carboxylate, calcium phosphate, mono- and / or di-thiophosphate calcium, calcium alkylphenol, calcium sulfur-linked alkylphenol compounds, calcium methylene crosslinked phenol, magnesium carbonate, sulfur-containing magnesium carbonate, magnesium sulfonate, magnesium calixalate, magnesium salixalate, magnesium salicylate, magnesium carboxylate, magnesium phosphate, mono- and / or di-thiophosphate magnesium, magnesium alkylphenol, magnesium sulfur-linked alkylphenol compounds, magnesium methylene crosslinked phenol, sodium carbonate, sulfur-containing sodium carbonate, sodium sulfonate, sodium calixalate, sodium salixalate, sodium salicylate, sodium carboxylate, sodium phosphate, mono- and / or di-thiophosphate sodium, sodium alkylphenol, sodium sulfur-linked alkylphenol compounds, or sodium methylene crosslinked phenol.

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

[0126] The term "overbasic" refers to metal salts such as sulfonic acids, carboxylic acids, and phenolic acid metal salts in which the amount of metal present exceeds the stoichiometric amount. Such salts can have a conversion level greater 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" or "neutral salt"). The expression "metallic ratio," often abbreviated as MR, is used to indicate the ratio of the total stoichiometric equivalents of metal in an overbasic salt to the stoichiometric equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the metallic ratio is 1, but in overbasic salts, the MR is greater than 1. They are generally referred to as overbasic, highly basic, or ultrabasic salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.

[0127] The overbasic detergent in the lubricating oil composition may have a total base number (TBN) of approximately 200 mg KOH / gram or more, or, as further examples, approximately 250 mg KOH / gram or more, or approximately 350 mg KOH / gram or more, or approximately 375 mg KOH / gram or more, or approximately 400 mg KOH / gram or more. The TBN is measured by the method of ASTM D-2896.

[0128] Suitable examples of perbasic detergents include, but are not limited to, perbasic calcium phenate, perbasic calcium sulfur-containing phenate, perbasic calcium sulfonate, perbasic calcium calixalate, perbasic calcium salixalate, perbasic calcium salicylate, perbasic calcium carboxylic acid, perbasic calcium phosphate, perbasic calcium mono- and / or di-thiophosphate, perbasic calcium alkylphenol, perbasic calcium sulfur-bonded alkylphenol compound, perbasic calcium methylene crosslinked phenol, perbasic magnesium phenate, perbasic magnesium sulfur-containing phenate, perbasic magnesium sulfonate, perbasic magnesium calixalate, perbasic magnesium salixalate, perbasic magnesium salicylate, perbasic magnesium carboxylic acid, perbasic magnesium phosphate, perbasic magnesium mono- and / or di-thiophosphate, perbasic magnesium alkylphenol, perbasic magnesium sulfur-bonded alkylphenol compound, or perbasic magnesium methylene crosslinked phenol.

[0129] Overbasic phenate calcium detergents, when measured according to the ASTM D-2896 method, 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. When such detergent compositions are formed in an inert diluent, e.g., process oil, often mineral oil, the total base number reflects the basicity of the overall composition, including the diluent and any other materials that may be present in the detergent composition (e.g., accelerators).

[0130] The over-basic 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 the engine or other automotive parts such as the transmission or gears. The detergent may be present in the lubricating composition in an amount of about 0 to about 10% by weight, or about 0.1 to about 8% by weight, or about 1 to about 4% by weight, or more than about 4% by weight to about 8% by weight.

[0131] Extreme pressure agents: The lubricating oil compositions described herein may optionally contain one or more extreme pressure agents. Oil-soluble extreme pressure (EP) agents 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, dibutyltetrasulfide, methyl sulfide esters of oleic acid, alkylphenol sulfides, dipentene sulfides, terpenes sulfides, and Diels-Alder sulfide adducts; phosphorus sulfide hydrocarbons such as reaction products of phosphorus sulfide with terpentine or methyl oleate; phosphate esters such as dihydrocarbyl and trihydrocarbyl phosphite, e.g., dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, and pentylphenyl phosphite; dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene-substituted phenyl phosphite; metal thiocarbamates such as zinc dioctyl dithiocarbamate and barium heptylphenol dioate; amine salts of alkyl and dialkyl phosphates, e.g., amine salts of reaction products of dialkyldithiophosphate and propylene oxide; and mixtures thereof.

[0132] Friction modifiers: The lubricating oil compositions described herein may also optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing and metal-free friction modifiers, but are not limited to imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated etheramines, 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. Hydrocarbyl groups may consist of carbon and a heteroatom such as hydrogen or sulfur or oxygen. 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, di-ester, or (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), and nitrogen-free organic friction modifiers. Such friction modifiers may include esters formed by reacting a carboxylic acid and an anhydride with an alkanol, and generally may include polar end groups (e.g., carboxyl or hydroxyl) covalently bonded to a lipophilic hydrocarbon chain. Examples of organic ashless nitrogen-free friction modifiers are generally known as glycerol monooleate (GMOs), which may contain mono-, di-, and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Patent No. 6,723,685, which is incorporated herein by reference in its entirety.

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

[0136] Amines and amides may be used on their own or as adducts or reaction products with boron compounds such as boron oxide, 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, which is incorporated herein by reference in its entirety.

[0137] The friction modifier may be present in an optional range of approximately 0 to approximately 10% by weight, or approximately 0.01 to approximately 8% by weight, or approximately 0.1 to approximately 4% by weight.

[0138] Molybdenum-containing components: The lubricating oil compositions described herein may also optionally contain one or more molybdenum-containing compounds. Oil-soluble molybdenum compounds may have the functional properties of anti-wear agents, antioxidants, friction modifiers, or mixtures thereof. Oil-soluble molybdenum compounds may include molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum dithiophosphinate, amine salts of molybdenum compounds, molybdenum xanthate, molybdenum thioxanthate, molybdenum sulfide, molybdenum carboxylate, molybdenum alkoxide, trinuclear organic molybdenum compounds, and / or mixtures thereof. Examples of molybdenum sulfide include molybdenum disulfide. Molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound may be a molybdenum dithiocarbamate.

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

[0140] Additionally, the molybdenum compounds may be acidic molybdenum compounds. These include 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, compositions can provide molybdenum by molybdenum / sulfur complexes of basic nitrogen compounds, as described, for example, in U.S. Patents 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 International Publication No. 94 / 06897, the aforementioned patent documents are incorporated herein by reference in their entirety.

[0141] Another class of preferred 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 to make the organic group soluble or dispersible in oil, n is 1 to 4, k varies from 4 to 7, Q is selected from the group of neutral electron-donating compounds such as water, amines, alcohols, phosphines, and ethers, and z is in the range of 0 to 5, including non-stoichiometric values. In all ligand organic groups, there may be at least 21 total carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms. Additional preferred molybdenum compounds are described in U.S. Patent No. 6,723,685, which is incorporated herein by reference in whole.

[0142] Oil-soluble molybdenum compounds may be present in amounts sufficient to provide molybdenum in concentrations of approximately 0.5 ppm to 2000 ppm, 1 ppm to 700 ppm, 1 ppm to 550 ppm, 5 ppm to 300 ppm, or 20 ppm to 250 ppm.

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

[0144] In embodiments, oil-soluble transition metal-containing compounds may function as a wear inhibitor, friction modifier, antioxidant, adhesion control additive, or one or more of these functions. In embodiments, oil-soluble transition metal-containing compounds may be oil-soluble titanium compounds such as titanium(IV) alkoxides. Titanium-containing compounds that may be used in or for the preparation of oil-soluble materials in the art of this 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, e.g., titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide; and other titanium compounds or complexes, e.g., titanium phenate; titanium carboxylates, e.g., titanium(IV) 2-ethyl-1,3-hexanedioate or titanium citrate or titanium oleate; and titanium(IV) (triethanolamine) isopropoxide. Other forms of titanium included in the disclosed technology include titanium phosphates such as titanium dithiophosphates (e.g., dialkyldithiophosphates) and titanium sulfonates (e.g., alkylbenzene sulfonates), or reaction products of titanium compounds that form salts, such as oil-soluble salts, with various acidic materials. Therefore, titanium compounds can be derived, among other things, from organic acids, alcohols, and glycols. Ti compounds may also exist in dimer or oligomeric forms containing a Ti-O-Ti structure. Such titanium materials are commercially available or can be readily prepared by appropriate synthetic techniques evident to those skilled in the art. Depending on the specific compound, they may exist as solids or liquids at room temperature. They may also be provided in solution form in a suitable inert solvent.

[0145] In one embodiment, titanium may be supplied as a Ti-modified dispersant, such as a succinimide dispersant. Such a material may be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as alkenyl-(or alkyl) succinic anhydride. The resulting titanate-succinate intermediate may be used directly or reacted with any of several materials, such as (a) a polyamine-based succinimide / amide dispersant having a free, condensable -NH functional group; (b) a component of a polyamine-based succinimide / amide dispersant, i.e., alkenyl-(or alkyl) succinic anhydride and a polyamine; or (c) a hydroxy-containing polyester dispersant prepared by the reaction of substituted succinic anhydride with a polyol, amino alcohol, polyamine, or a mixture thereof. Alternatively, the titanate-succinate intermediate may be reacted with other agents such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product may be used directly to impart Ti to the lubricating oil, or it may be further reacted with a succinic acid dispersant as described above. As an example, to provide a titanium-modified dispersant or intermediate, 1 part (mol) of tetraisopropyl titanate may be reacted with about 2 parts (mol) of polyisobutene-substituted succinic anhydride at 140-150°C for 5-6 hours. The resulting material (30 g) may be further reacted at 150°C for 1.5 hours with a succinimide dispersant from a mixture of polyisobutene-substituted succinic anhydride and polyethylene polyamine (127 g + diluent oil) to produce a titanium-modified succinimide dispersant.

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

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

[0148] [ka] (wherein m+n=4, n is in the range of 1 to 3, R4 is an alkyl moiety having 1 to 8 carbon atoms, R1 is selected from hydrocarbyl groups containing approximately 6 to 25 carbon atoms, and R2 and R3 are the same or different and selected from hydrocarbyl groups containing 1 to 6 carbon atoms) or the titanium compound may be represented by the following formula:

[0149] [ka] (In the formula, x is in the range of 0 to 3, R1 is selected from hydrocarbyl groups containing approximately 6 to 25 carbon atoms, R2 and R3 are the same or different and selected from hydrocarbyl groups containing approximately 1 to 6 carbon atoms, and R4 is H, C6 to C) 25 It can be represented by (selected from the group consisting of any of the carboxylic acid moieties).

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

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

[0152] Viscosity Index Modifiers: The lubricating oil compositions described herein may also optionally contain one or more viscosity index modifiers. Suitable viscosity index modifiers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, styrene-isoprene polymers, styrene / maleate copolymers, styrene-butadiene copolymers, styrene-isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrated alkenylaryl conjugated diene copolymers, or mixtures thereof. Viscosity index modifiers may include star polymers, but a preferred example is described in U.S. Patent Application Publication No. 20120101017(A1).

[0153] The lubricating oil compositions described herein may optionally contain, in addition to or instead of viscosity index modifiers, one or more dispersant viscosity index modifiers. Suitable viscosity index modifiers include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with reaction products of acyling agents (such as maleic anhydride) and amines, amine-functionalized polymethacrylates, or esterified maleic anhydride-styrene copolymers reacted with amines.

[0154] The total amount of viscosity index modifiers and / or dispersible viscosity index modifiers may be about 0 to about 20% by weight, about 0.1 to about 15% by weight, about 0.1 to about 12% by weight, or about 0.5 to about 10% by weight of the lubricating oil composition.

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

[0156] The lubricating oil compositions according to this disclosure may optionally include other performance additives. These other performance additives may be additions to the specific additives of this disclosure and / or may include one or more of the following: metal deactivators, viscosity index modifiers, detergents, ashless TBN boosters, friction modifiers, anti-wear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index modifiers, extreme pressure agents, antioxidants, foam inhibitors, deemulsifiers, emulsifiers, pour point depressants, seal swelling agents, and mixtures thereof. Typically, a complete lubricating oil will contain one or more of these performance additives.

[0157] Suitable metal deactivators include derivatives of benzotriazole (typically toltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzothiazole; foam inhibitors comprising copolymers of ethyl acrylate, 2-ethylhexyl acrylate, and optionally vinyl acetate; demulsifiers comprising trialkyl phosphates, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers; and pour point depressants comprising esters of maleate-styrene anhydride, polymethacrylate, polyacrylate, or polyacrylamide.

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

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

[0160] Suitable rust inhibitors may be a single compound or a mixture of compounds having properties that inhibit corrosion of iron metal surfaces. Non-limiting examples of useful rust inhibitors as used 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 dimeric and trimeric acids such as those derived from tall oil fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long-chain alpha- and omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000, and alkenyl succinates containing about 10 or more carbon atoms in the alkenyl group, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Another useful type of acidic corrosion inhibitor is a semi-ester of alkenyl succinic acid having about 8 to about 24 carbon atoms in the alkenyl group with an alcohol such as polyglycol. The corresponding semiamides of such alkenyl succinic acids are also useful. Useful rust inhibitors are high molecular weight organic acids.

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

[0162] Generally speaking, suitable lubricating oils containing neutral to overbasic alkylphenate sulfide products as used herein may contain additive components within the range listed in the table below.

[0163] [Table 2]

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

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

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

[0167] [Table 3]

[0168] Example 2 Phenols were alkylated in the presence of a solid catalyst using the oligomers shown in Table 3 from Example 1. The alkylation results are shown in Table 4 below. In all cases, alkylation was carried out in the presence of a solid catalyst at approximately 110°C for approximately 4 to 6 hours.

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

[0170] Example 3 Sulfide phenate lubricant additives were prepared as shown in Table 5 below. Samples 1 and 2 were comparative additives prepared using alkylphenols derived from tetrapropylene (C12). Sample 3 was the 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] ** % active detergent is the undiluted oil portion of the additive mixture.

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

[0173] As used herein and in the appended claims, the singular forms “a,” “an,” and “the” include multiple references unless explicitly and clearly limited to one. For example, a reference to “antioxidants” includes two or more different antioxidants. Where used herein, the term “includes” and its grammatical variations are intended to be non-limiting so as not to exclude other similar items that may be substituted for or added to the items in the list.

[0174] For the purposes of this specification and the appended claims, unless otherwise indicated, all numbers representing quantities, percentages, or proportions, and other numerical values ​​used herein and in the claims should be understood in all cases as being modified by the term “approximately.” Therefore, unless otherwise indicated, the numerical parameters described in the following specification and the appended claims are approximations that may vary depending on the desired characteristics sought by this disclosure. At a minimum, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be interpreted at least in terms of the number of significant figures reported and by applying common rounding techniques.

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

[0176] It should be further understood that each range disclosed herein should be interpreted as a disclosure of each specific value within the disclosure range having the same number of significant figures. Therefore, for example, the range 1–4 should be interpreted as a clear disclosure of any range of such values, not just the values ​​1, 2, 3, and 4.

[0177] It should be 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. Therefore, this 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 with 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 should also be further understood that any range between endpoint values ​​within a broad range is also considered herein. Therefore, the range 1-4 also means ranges such as 1-3, 1-2, 2-4, 2-3, etc.

[0178] Furthermore, any specific amounts / values ​​of components, compounds, substituents, or parameters disclosed in detail or examples should be interpreted as disclosures of either a lower or upper limit of a range, and can therefore be combined with any other lower or upper limit or specific amounts / values ​​in the 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 specific embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents may emerge that are not currently anticipated or can not be anticipated by the applicants or others skilled in the art. Accordingly, the attached claims filed and any modified attached claims are intended to encompass all such alternatives, modifications, variations, improvements, and substantial equivalents.

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