N-phenyl-1-naphthylamine-based polyether amines and related dispersants

Abstract

A lubricating composition including a combination of a base oil and a dispersant. The dispersant may be a derivative of a N-phenyl-1-naphthylamine-based polyether amine. Such lubricating compositions may have improved soot dispersing capabilities, provide antioxidant functionality, and / or be compatible with seals without further modification. The lubricating compositions may be used in engines, pumps, compressors, and the like.

Description

N-PHENYL-1 -NAPHTHYLAMINE-BASED POLYETHER AMINES AND RELATED DISPERSANTSCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Patent Application Serial Number 63 / 750,075 filed January 27, 2025. The noted application is incorporated herein by reference.FIELD

[0002] The present disclosure generally relates to polyether amines and, more specifically, to N-phenyl-1 -naphthylamine-based polyether amines and dispersants synthesized therewith. The disclosure further relates to lubricating compositions containing said compounds.BACKGROUND

[0003] Many chemical additives are added to the base oil of a lubricant to impart desired properties. Examples of such additives include dispersants, detergents, antioxidants, viscosity modifiers, and corrosion inhibitors. Dispersants may aid in keeping vital engine parts clean, prolonging the life of the engine, maintaining proper emissions, and improving fuel economy.

[0004] A class of widely used dispersants are based on succinimides. A succinimide dispersant typically has a polar head and a long hydrocarbon tail. The polar head can attach to the insoluble material such as soot, sludge, and other impurities while the long hydrocarbon tail keeps the dispersant suspended in lubricating oil. Once several dispersant polar heads have attached themselves to a solid particle, it can no longer combine with other impurities to form large particles that can deposit onto engine surfaces but is rather removed from the engine when the oil is changed. Low performing dispersants may result in one or more of flocculation, filter plugging, oil thickening, wear, and the like. Higher dispersancy dispersants may help mitigate the foregoing.SUMMARY

[0005] The present disclosure includes compositions comprising:Compound (I) wherein A is H, methyl, ethyl, or any combination thereof; and n is 3-10.

[0006] The present disclosure includes compositions comprising:Compound (II) wherein A is H, methyl, ethyl, or any combination thereof; n is 3-10; and R is polyisobutyl.

[0007] The present disclosure includes compositions comprising:Compound (III) wherein A is H, methyl, ethyl, or any combination thereof; n is 3-10; R1 is a C1-C6 alkyl; and R is polyisobutyl.

[0008] The present disclosure includes compositions comprising:Compound (IV) wherein A is H, methyl, ethyl, or any combination thereof; n is 3-10; m is 3-10; R1 is a C1-C6 alkyl; and R is polyisobutyl.

[0009] The present disclosure includes methods of producing Compounds (I)-(IV).

[0010] The present disclosure includes lubricating compositions produced with one or more of Compounds (I)-(IV).

[0011] The present disclosure includes methods for using Compounds (I)-(IV) comprising: supplying to an engine the foregoing lubricating compositions.DETAILED DESCRIPTION

[0012] The present disclosure generally relates to N-phenyl-1 -naphthylamine-based polyether amines and dispersants synthesized therewith. Further, the present disclosure includes lubricating compositions (e g., concentrates and lubricating oils) containing said dispersants.

[0013] Advantageously, dispersants derived from the N-phenyl-1 -naphthylamine-based polyether amines may have a hydrophilic-lipophilic balance that improves detergency and facilitates suspension of the soot and other contaminants in engines.

[0014] Additionally, dispersants derived from the N-phenyl-1 -naphthylamine-based polyether amines therefrom advantageously contain at least three aromatic rings. The high number of aromatic rings provides antioxidant properties.

[0015] Further, dispersants derived from the N-phenyl-1 -naphthylamine-based polyether amines do not have a primary or secondary amine, which is anticipated to mitigate the need to modify the dispersants for compatibility with seals in engines or other equipment in which the lubricating composition is used.

[0016] Before explaining aspects of the present disclosure in detail, it is to be understood that the present disclosure is not limited in its application to the details of construction and the arrangement of components or steps, or methodologies set forth in the following description. The present disclosure is capable of other embodiments or of being practiced or carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein is for the purpose of description and should not be regarded as limiting.

[0017] If appearing herein, the term “comprising” and derivatives thereof are not intended to exclude the presence of any additional component, step, or procedure, whether or not the same is disclosed herein. In order to avoid any doubt, all compositions claimed herein through use of the term “comprising” may include any additional additive, adjuvant, or compound, unless stated to the contrary. In contrast, the term, “consisting essentially of’ if appearing herein, excludes from the scope of any succeeding recitation any other component, step, or procedure, except those that are not essential to operability and the term “consisting of’, if used, excludes any component, step or procedure not specifically delineated or listed. The terms “or” and “and / or”, unless stated otherwise, refer to the listed members individually as well as in any combination. For example, the expressions A or B and A and / or B refer to A alone, B alone, or to both A and B.

[0018] The articles “a” and “an” are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical objects of the article. By way of example, “a solvent” means one solvent or more than one solvent. The phrases “in one embodiment”, “according to one embodiment” and the like generally mean the feature, structure, or characteristic following the phrase is included in at least one embodiment of the present disclosure and may be included in more than one embodiment of the present disclosure. Importantly, such phrases do not necessarily refer to the same embodiment. If the specification states a component or feature “may”, “can”,“could”, or “might” be included or have a characteristic, that component or feature is not required to be included or have the characteristic.

[0019] The terms “preferred” and “preferably” refer to embodiments that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful and is not intended to exclude other embodiments from the scope of the present disclosure.

[0020] The term “about” as used herein can allow for a degree of variability in a value or range, for example, it may be within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range.

[0021] The use of ordinal number terminology (i.e., “first”, “second”, “third”, “fourth”, etc.) is solely for the purpose of differentiating between two or more items and, unless otherwise stated, is not meant to imply any sequence or order or importance to one item over another or any order of addition.

[0022] Values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but to also include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range such as from 1 to 6, should be considered to have specifically disclosed sub-ranges, such as, from 1 to 3, from 2 to 4, from 3 to 6, etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.

[0023] In the methods described herein, the acts can be carried out in any order without departing from the principles of the invention, except when a temporal or operational sequence is explicitly recited. Furthermore, specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.

[0024] The term “optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0025] The polyether amines of the present disclosure have a structure according to Compound (I):Compound (I) where A is H, methyl, ethyl, or any combination thereof; and n is 3-10.

[0026] It is noted that Compound (I) is not a salt and that the compositions described herein do not include a salt derivative of Compound (I).

[0027] Compound (I) may generally be prepared by reaction of N-phenyl-1 -naphthylamine with one or more of ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO). This reaction is followed by conversion of the resulting terminal hydroxyl group to an amine, thereby providing a polyether backbone (comprising EO, PO, BO, or any mixture thereof) and a terminal primary amino group.

[0028] When using two or more of EO, PO, and BO, any mole ratio between the components may be used and, consequently, be present in the poly ether amine product at the [O-CH2-CHR’]nunits in a similar ratio. One skilled in the art will recognize that referring to EO, PO, and BO in a polyether amine product refers to the corresponding reacted monomeric unit in the polyether amine.

[0029] Where the polyether amine includes EO and PO units, a mole ratio of EO:PO in the polyether amines may range from about 9:1 to about 1:9 (e.g., about 9:1 to about 1:1, about 5:1 to about 1:5, about 3:1 to about 1:3, or about 1:1 to about 1:9). Where the polyether amine includes EO and BO units, a mole ratio of EO:BO in the polyether amines may range from about 9:1 to about 1:9 (e.g., about 9:1 to about 1:1, about 5:1 to about 1:5, about 3:1 to about 1:3, or about 1:1 to about 1 :9). Where the polyether amine includes PO and BO units, a mole ratio of PO:BO in the polyether amines may range from about 9:1 to about 1:9 (e.g., about 9:1 to about 1:1, about 5:1 to about 1:5, about 3:1 to about 1:3, or about 1:1 to about 1:9). Where all three of EO, PO, and BOunits are included in the polyether amine, a mole ratio of EO:PO may range from about 8:1 to about 1 :8 (e.g., about 8: 1 to about 1:1, about 5: 1 to about 1:5, about 3 : 1 to about 1 :3, or about 1 : 1 to about 1:8), and a mole ratio of EO:BO may range from about 8:1 to about 1:8 (e.g., about 8:1 to about 1:1, about 5:1 to about 1:5, about 3:1 to about 1:3, or about 1:1 to about 1:8).

[0030] The polyether amines of Compound (I) may be used to produce dispersants. The dispersant may be a polyisobutylene succinimide according to Compound (II):Compound (II) where A is H, methyl, ethyl, or any combination thereof; n is 3-10; and R is polyisobutyl.

[0031] Compound (II) may be produced by reacting Compound (I) and polyisobutylene succinic anhydride.

[0032] The dispersant may also be a Mannich base produced by reacting Compound (I) with a polyisobutyl-substituted phenol and one or more aldehydes in a Mannich condensation reaction.

[0033] The aldehyde may be an aliphatic aldehyde, aromatic aldehyde, or combination thereof. Examples of aliphatic aldehydes may include, but are not limited to, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde, the like, and any combination thereof. Examples of aromatic aldehydes may include, but are not limited to, benzaldehyde, alkylbenzaldehyde (e g., para-tolualdehyde), the like, and any combination thereof. In some instances, formaldehyde producing reagents, such as paraformaldehyde and aqueous formaldehyde solutions (e.g., formalin), may be used in place or in addition to the aldehyde.

[0034] For example, the dispersant may be a Mannich base dispersant according to Compound (III) or Compound (IV):Compound (III) where A is H, methyl, ethyl, or any combination thereof; n is 3-10; R1 is a C1-C6 alkyl; and R is polyisobutyl; orCompound (IV) where A is H, methyl, ethyl, or any combination thereof; n is 3-10; m is 3-10; R1 is a C1-C6 alkyl; and R is polyisobutyl.

[0035] One or more of Compounds (IT)-(TV) may be included as dispersants in lubricating compositions like lubricating oils and concentrates.

[0036] Lubricating compositions may include a base oil, a dispersant (e.g., one or more dispersants of the present disclosure), and optionally other additives. Examples of other additives may include, but are not limited to, dispersants (other than the dispersants of Compounds (II)-(IV)), detergents, antioxidants, viscosity modifiers, corrosion inhibitors, antiwear agents, metal deactivators, foam inhibitors, demulsifiers, pour point depressants, seal compatibility agents, thelike, and any combination thereof. Table 1 provides nonlimiting examples of concentrate formulations. Table 2 provides nonlimiting examples of lubricating oil formulations.Table 1Table 2

[0037] Base Oil

[0038] The base oil in the lubricating compositions of the present disclosure should have a lubricating viscosity. The base oil may have a kinematic viscosity of about 1.5 mm2 / s to about 100 mm2 / s (e.g., about 2.5 mm2 / s to about 50 mm2 / s, or about 2.5 mm2 / s to about 20 mm2 / s) at about 100° C. In at least one example, the kinematic viscosity may be measured according to ASTM D445-21.

[0039] The base oil in the lubricating compositions of the present disclosure may be selected from natural oils, synthetic oils, and any combination thereof, and may be used unrefined, refined, or re-refined (e g., reclaimed or reprocessed oil).

[0040] Examples of natural oils may include, but are not limited to, animal oils (e.g., lard oil); vegetable oils (e.g., castor oil and other vegetable acid esters); liquid petroleum oils; mineral oils; the like; and any combination thereof.

[0041] Examples of synthetic base oils may include, but are not limited to, polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(l -hexenes), poly(l -octenes), poly(l -decenes)); alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenols); alkylated diphenyl ethers; alkylated diphenyl sulfides; esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azclaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol); silicon-based oils (e.g., the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicone oils and silicate oils) (e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2-ethylhexyl)disiloxane, poly(methyl)siloxanes, and poly(methylphenyl)siloxanes); liquid esters of phosphorous-containing acids (e.g., trieresyl phosphate, tri octyl phosphate, and diethyl ester of decylphosphonic acid); polymeric tetrahydrofurans; the like; and any combination thereof.

[0042] The base oil in the lubricating compositions of the present disclosure may correspond to any oil according to Groups I-V as specified by the American Petroleum Institute (API) Publication 1509 Annex E (“API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils,” December 2016). Group I base oils have a viscosity index of between80 to 120 and contain greater than 0.03% sulfur and / or less than 90% saturates. Group II base oils have a viscosity index of between 80 to 120, and contain less than or equal to 0.03% sulfur and greater than or equal to 90% saturates. Group III base oils have a viscosity index greater than 120 and contain less than or equal to 0.03% sulfur and greater than 90% saturates. Group IV base oils include polyalphaolefins (PAD). Group V base oils include base oils not included in Groups I-IV.

[0043] Combinations of any of the foregoing oils may be used in the lubricating compositions of the present disclosure.

[0044] A base oil may be present in a lubricating composition of the present disclosure in an amount of at least about 30 wt% (e.g., at least about 40 wt%, at least about 50 wt%, at least about 60 wt%, at least about 70 wt%, at least about 80 wt%, at least about 90 wt%, about 30 wt% to about 99 wt%, about 30 wt% to about 50 wt%, about 40 wt% to about 60 wt%, about 50 wt% to about 70 wt%, about 50 wt% to about 99 wt%, about 60 wt% to about 99 wt%, about 70 wt% to about 99 wt%, or about 80 wt% to about 99 wt%), based on a total weight of the lubricating compositions. For concentrates, the amount of base oil may be lower than in a lubricating oil. For example, a base oil may be present in a concentrate of the present disclosure in an amount of about 30 wt% to about 70 wt% (e.g., about 30 wt% to about 50 wt%, about 40 wt% to about 60 wt%, or about 50 wt% to about 70 wt%), based on a total weight of the concentrate. In another example, a base oil may be present in a lubricating oil of the present disclosure in an amount of at least about 50 wt% (e.g., at least about 60 wt%, at least about 70 wt%, at least about 80 wt%, at least about 90 wt%, about 50 wt% to about 99 wt%, about 60 wt% to about 99 wt%, about 70 wt% to about 99 wt%, or about 80 wt% to about 99 wt%), based on a total weight of the lubricating oil.

[0045] Dispersants

[0046] Dispersants may be included in lubricating compositions to assist with the suspension of contaminants like soot.

[0047] The lubricating compositions of the present disclosure may include one or more dispersants according to Compound (II), one or more dispersants according to Compound (III), one or more dispersants according to Compound (IV), and any combination thereof. Further, lubricating compositions of the present disclosure may optionally include one or more dispersants not having a structure according to any of Compounds (II)-(IV) (also referred to herein as supplementary dispersants).

[0048] Preferably, supplementary dispersants include ashless dispersants, which may be characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long chain alkenyl succinimides (e.g., polyisobutylene succinimide with the number average molecular weight of the polyisobutylene substituent being in the range about 350 g / mol to about 50,000 g / mol, as measured by GPC.) Succinimide dispersants are typically the imide formed from a polyamine, typically a poly (ethyleneamine). Preferred amines are selected from polyamines and hydroxylamines. Examples of polyamines that may be used include, but are not limited to, diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), and higher homologues such as pentaethylamine hexamine (PEHA), and the like.

[0049] Another suitable class of supplementary dispersants may include Mannich bases. Mannich bases are materials that are formed by the condensation of a higher molecular weight, alkyl substituted phenol, a polyalkylene polyamine, and an aldehyde such as formaldehyde.

[0050] Another suitable class of supplementary dispersants may include high molecular weight esters or half ester amides. A suitable dispersant may also be post-treated by conventional methods by a reaction with any of a variety of agents. Among these are boron, urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbonsubstituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenolic esters, and phosphorus compounds. U.S. Pat. Nos. 7,645,726; 7,214,649; and 8,048,831 are incorporated herein by reference in their entireties.

[0051] Yet another suitable class of supplementary dispersants may include a hydrocarbyl substituted succinamide or succinimide dispersants. In approaches, the hydrocarbyl substituted succinamide or succinimide dispersant may be derived from a hydrocarbyl substituted acylating agent reacted with a polyalkylene polyamine and wherein the hydrocarbyl substituent of the succinamide or the succinimide dispersant is a linear or branched hydrocarbyl group having a number average molecular weight of about 250 g / mol to about 5,000 g / mol as measured by GPC.

[0052] Dispersants (all dispersants cumulatively) may be present in a lubricating composition of the present disclosure in an amount of up to about 20 wt% (e.g., up to about 15 wt%, up to about 10 wt%, up to about 5 wt%, about 0.02 wt% to about 20 wt%, about 0.02 wt% to about 15 wt%, about 0.02 wt% to about 10 wt%, about 0.02 wt% to about 5 wt%, about 0.02 wt% to about 2 wt%, about 1 wt% to about 20 wt%, about 1 wt% to about 15 wt%, about 1 wt% to about 10 wt%, about1 wt% to about 5 wt%, about 2 wt% to about 20 wt%, about 2 wt% to about 15 wt%, about 2 wt% to about 10 wt%, about 5 wt% to about 20 wt%, about 5 wt% to about 15 wt%, about 5 wt% to about 10 wt%, or about 10 wt% to about 20 wt%), based on a total weight of the lubricating compositions. For example, a dispersant may be present in a concentrate of the present disclosure in an amount of up to about 20 wt% (e g., up to about 15 wt%, up to about 10 wt%, up to about 5 wt%, about 1 wt% to about 20 wt%, about 1 wt% to about 15 wt%, about 1 wt% to about 10 wt%, about 1 wt% to about 5 wt%, about 2 wt% to about 20 wt%, about 2 wt% to about 15 wt%, about 2 wt% to about 10 wt%, about 5 wt% to about 20 wt%, about 5 wt% to about 15 wt%, about 5 wt% to about 10 wt%, or about 10 wt% to about 20 wt%), based on a total weight of the concentrate. In another example, a dispersant may be present in a lubricating oil of the present disclosure in an amount of up to about 15 wt% (e.g., up to about 10 wt%, up to about 5 wt%, about 0.02 wt% to about 15 wt%, about 0.02 wt% to about 10 wt%, about 0.02 wt% to about 5 wt%, about 0.02 wt% to about 2 wt%, about 1 wt% to about 15 wt%, about 1 wt% to about 10 wt%, or about 1 wt% to about 5 wt%), based on a total weight of the lubricating oil.

[0053] Detergents

[0054] Detergents may be included in lubricating compositions to assist with removing contaminants like soot from metal surfaces.

[0055] Examples of detergents may include, but are not limited to, calcium phenates, calcium sulfur containing phenates, calcium sulfonates, calcium calixarates, calcium salixarates, calcium salicylates, calcium carboxylic acids, calcium phosphorus acids, calcium mono- and / or dithiophosphoric acids, calcium alkyl phenols, calcium sulfur coupled alkyl phenol compounds, calcium methylene bridged phenols, magnesium phenates, magnesium sulfur containing phenates, magnesium sulfonates, magnesium calixarates, magnesium salixarates, magnesium salicylates, magnesium carboxylic acids, magnesium phosphorus acids, magnesium mono- and / or dithiophosphoric acids, magnesium alkyl phenols, magnesium sulfur coupled alkyl phenol compounds, magnesium methylene bridged phenols, sodium phenates, sodium sulfur containing phenates, sodium sulfonates, sodium calixarates, sodium salixarates, sodium salicylates, sodium carboxylic acids, sodium phosphorus acids, sodium mono- and / or di-thiophosphoric acids, sodium alkyl phenols, sodium sulfur coupled alkyl phenol compounds, sodium methylene bridged phenols, the like, and any combination thereof.

[0056] Detergents may include overbased detergents, neutral detergents, or low-based detergents.

[0057] Detergents may be present in a lubricating composition of the present disclosure in an amount of up to about 20 wt% (e.g., up to about 15 wt%, up to about 10 wt%, up to about 5 wt%, 0 wt% to about 20 wt%, about 0.02 wt% to about 20 wt%, about 0.02 wt% to about 15 wt%, about 0.02 wt% to about 10 wt%, about 0.02 wt% to about 5 wt%, about 0.02 wt% to about 2 wt%, about 1 wt% to about 20 wt%, about 1 wt% to about 15 wt%, about 1 wt% to about 10 wt%, or about 1 wt% to about 5 wt%), based on a total weight of the lubricating compositions. For example, a detergent may be present in a concentrate of the present disclosure in an amount of up to about 20 wt% (e.g., up to about 15 wt%, up to about 10 wt%, up to about 5 wt%, 0 wt% to about 20 wt%, about 1 wt% to about 20 wt%, about 1 wt% to about 15 wt%, about 1 wt% to about 10 wt%, about 1 wt% to about 5 wt%, about 5 wt% to about 20 wt%, about 5 wt% to about 15 wt%, about 5 wt% to about 10 wt%, or about 10 wt% to about 20 wt%), based on a total weight of the concentrate. In another example, a detergent may be present in a lubricating oil of the present disclosure in an amount of up to about 15 wt% (e.g., up to about 10 wt%, up to about 5 wt%, 0 wt% to about 15 wt%, about 0.02 wt% to about 15 wt%, about 0.02 wt% to about 10 wt%, about 0.02 wt% to about 5 wt%, about 0.02 wt% to about 2 wt%, about 1 wt% to about 15 wt%, about 1 wt% to about 10 wt%, or about 1 wt% to about 5 wt%), based on a total weight of the lubricating oil.

[0058] Antioxidants

[0059] Antioxidants may be included in lubricating compositions to retard the oxidative degradation of lubricating oils during service. Such degradation may result in deposits on metal surfaces, the presence of sludge, or a viscosity increase in the lubricating oil.

[0060] Examples of antioxidants may include, but are not limited to, hindered phenols, amines, sulfurized olefins, titanium compounds, molybdenum compounds (e.g., molybdenum dithiocarbamates), the like, and any combination thereof.

[0061] The hindered phenol antioxidant may contain a secondary butyl and / or a tertiary butyl group as a sterically hindering group. The phenol group may be further substituted with a hydrocarbyl group (typically linear or branched alkyl) and / or a bridging group linking to a second aromatic group. Examples hindered phenol antioxidants may include, but are not limited to, 2,6-di-t-butylphenol, 4,4'-methylenebis(2,6-di-t-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,4-dodecyl-2,6-di-tert-butylphenol, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, and n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, the like, and any combination thereof.

[0062] Examples amine antioxidants may include, but are not limited to, alkylated diphenylamine (e.g., dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine), phenylnaphthylamine, alkylated phenylnaphthylamine, the like, and any combination thereof.

[0063] Combinations of any of the foregoing antioxidants may be included in the lubricating compositions of the present disclosure. For examples, an amine antioxidant and a hindered phenolic antioxidant may preferably be used in combination.

[0064] Antioxidants may be present in a lubricating composition of the present disclosure in an amount of up to about 20 wt% (e.g., up to about 15 wt%, up to about 10 wt%, up to about 5 wt%, 0 wt% to about 20 wt%, 0 wt% to about 15 wt%, about 0.02 wt% to about 20 wt%, about 0.02 wt% to about 15 wt%, about 0.02 wt% to about 10 wt%, about 0.02 wt% to about 5 wt%, about 0.02 wt% to about 2 wt%, about 1 wt% to about 20 wt%, about 1 wt% to about 15 wt%, about 1 wt% to about 10 wt%, or about 1 wt% to about 5 wt%), based on a total weight of the lubricating compositions. For example, an antioxidant may be present in a concentrate of the present disclosure in an amount of up to about 20 wt% (e.g., up to about 15 wt%, up to about 10 wt%, up to about 5 wt%, 0 wt% to about 20 wt%, 0 wt% to about 15 wt%, about 1 wt% to about 20 wt%, about 1 wt% to about 15 wt%, about 1 wt% to about 10 wt%, about 1 wt% to about 5 wt%, about 5 wt% to about 20 wt%, about 5 wt% to about 15 wt%, about 5 wt% to about 10 wt%, or about 10 wt% to about 20 wt%), based on a total weight of the concentrate. In another example, an antioxidant may be present in a lubricating oil of the present disclosure in an amount of up to about 10 wt% (e.g., up to about 5 wt%, 0 wt% to about 10 wt%, 0 wt% to about 5 wt%, about 0.01 wt% to about 10 wt%, about 0.01 wt% to about 5 wt%, about 0.01 wt% to about 3 wt%, about 0.1 wt% to about 10 wt%, about 0.1 wt% to about 5 wt%, or about 0.1 wt% to about 3 wt%), based on a total weight of the lubricating oil.

[0065] Viscosity Modifiers

[0066] Viscosity modifiers may be included in lubricating compositions to adjust the viscosity (higher or lower) of the lubricating composition for a desired purpose of use of the lubricating compositions. Viscosity modifiers may provide lubricating compositions with high and low temperature operability by imparting shear stability at elevated temperatures and acceptable viscosity at low temperatures.

[0067] Examples of viscosity modifiers may include, but are not limited to, polymethacrylates, polyacrylates, polyolefins (e.g., ethylene-propylene copolymer), styrene copolymers (e.g., styrenediene copolymer and styrene-isoprene copolymer), styrene-maleic ester copolymers, hydrogenated styrene-diene copolymers, olefingraft-polymethacrylate polymers, polyisobutylenes, hydrogenated polyisoprene star polymers, the like, and any combination thereof.

[0068] Viscosity modifiers may have a molecular weight of about 10,000 g / mol to about 1,500,000 g / mol (e.g., about 20,000 g / mol to about 1,200,000 g / mol, or about 50,000 g / mol to about 1,000,000 g / mol.

[0069] Viscosity modifiers may be present in a lubricating composition of the present disclosure in an amount of up to about 25 wt% (e.g., up to about 20 wt%, up to about 15 wt%, up to about 10 wt%, up to about 5 wt%, 0 wt% to about 25 wt%, 0 wt% to about 20 wt%, 0 wt% to about 15 wt%, about 0.1 wt% to about 25 wt%, about 0.1 wt% to about 20 wt%, about 0.1 wt% to about 15 wt%, about 0.1 wt% to about 10 wt%, about 0.1 wt% to about 5 wt%, about 1 wt% to about 25 wt%, about 1 wt% to about 20 wt%, about 1 wt% to about 15 wt%, about 1 wt% to about 10 wt%, about 1 wt% to about 5 wt%, about 5 wt% to about 25 wt%, about 5 wt% to about 20 wt%, or about 5 wt% to about 15 wt%), based on a total weight of the lubricating compositions.

[0070] Corrosion Inhibitors

[0071] Corrosion inhibitors may be included in lubricating compositions to protect lubricated metal surfaces against chemical attack by water or other contaminants.

[0072] Examples of corrosion inhibitors may include, but are not limited to, amine compounds, alkanolamine compounds, amide compounds, carboxylic acid compounds, zinc dithiophosphates, metal phenolates, basic metal sulfonates, the like, and any combination thereof.

[0073] Corrosion inhibitors may be present in a lubricating composition of the present disclosure in an amount of up to about 5 wt% (e.g., up to about 4 wt%, up to about 3 wt%, up to about 2 wt%, 0 wt% to about 5 wt%, 0 wt% to about 2 wt%, about 0.01 wt% to about 5 wt%, or about 0.01 wt% to about 2 wt%), based on a total weight of the lubricating compositions.

[0074] Antiwear Agents

[0075] Examples of antiwear agents may include, but are not limited to, metal thiophosphates (e.g., dialkyldithiophosphate); phosphoric acid esters and salts thereof; phosphorus-containing carboxylic acids, esters, ethers, and amides; phosphites; borate esters; dithiocarbamatecompounds; molybdenum-containing compounds; sulfurized olefins; tartrate esters; tartramides; tartrimides (e.g., oleyl tartrimide); the like; and any combination thereof.

[0076] Antiwear agents may be present in a lubricating composition of the present disclosure in an amount of up to about 15 wt% (e.g., up to about 10 wt%, up to about 5 wt%, up to about 2 wt%, 0 wt% to about 15 wt%, 0 wt% to about 10 wt%, 0 wt% to about 5 wt%, 0 wt% to about 2 wt%, about 0.5 wt% to about 15 wt%, about 0.5 wt% to about 10 wt%, about 0.5 wt% to about 5 wt%, or about 0.1 wt% to about 2 wt%), based on a total weight of the lubricating compositions.

[0077] Metal Deactivators

[0078] Examples of metal deactivators may include, but are not limited to, benzotriazole compounds, tolyltriazole compounds (e.g., tolyltriazole and 1,2,4-triazoles), imidazole compounds, benzimidazole compounds (e.g., 2-alkyldithiobenzimidazoles and 2-alkyldithiobenzothiazoles), thiadiazole compounds (e.g., dimercaptothiadiazole derivatives), pyrimidine compounds, the like, and any combination thereof.

[0079] Metal deactivators may be present in a lubricating composition of the present disclosure in an amount of up to about 5 wt% (e.g., up to about 4 wt%, up to about 3 wt%, up to about 2 wt%, 0 wt% to about 5 wt%, 0 wt% to about 2 wt%, about 0.01 wt% to about 5 wt%, or about 0.01 wt% to about 2 wt%), based on a total weight of the lubricating compositions.

[0080] Foam Inhibitors

[0081] Examples of foam inhibitors (or anti-foam agents) may include, but are not limited to, copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; silicones; polysiloxanes (e.g., silicon oil and polydimethyl siloxane); the like; and any combination thereof.

[0082] Foam inhibitors may be present in a lubricating composition of the present disclosure in an amount of up to about 5 wt% (e.g., up to about 4 wt%, up to about 3 wt%, up to about 2 wt%, 0 wt% to about 5 wt%, 0 wt% to about 2 wt%, about 0.01 wt% to about 5 wt%, or about 0.01 wt% to about 2 wt%), based on a total weight of the lubricating compositions.

[0083] Demulsifiers

[0084] Examples of demulsifiers may include, but are not limited to, trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides, ethylene oxi de-propylene oxide polymers, the like, and any combination thereof.

[0085] Demulsifiers may be present in a lubricating composition of the present disclosure in an amount of up to about 5 wt% (e.g., up to about 4 wt%, up to about 3 wt%, up to about 2 wt%,0 wt% to about 5 wt%, 0 wt% to about 2 wt%, about 0.01 wt% to about 5 wt%, or about 0.01 wt% to about 2 wt%), based on a total weight of the lubricating compositions.

[0086] Pour Point Depressants

[0087] Examples of pour point depressants may include, but are not limited to, polymethacrylates, polyacrylates, polyarylamides, acrylate- styrene copolymers, esterified olefin copolymers, alkylated polystyrene, vinyl acetate-fumarate copolymers, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, terpolymers of dialkylfumarates, the like, and any combination thereof.

[0088] Pour point depressants may be present in a lubricating composition of the present disclosure in an amount of up to about 5 wt% (e.g., up to about 4 wt%, up to about 3 wt%, up to about 2 wt%, 0 wt% to about 5 wt%, 0 wt% to about 2 wt%, about 0.01 wt% to about 5 wt%, or about 0.01 wt% to about 2 wt%), based on a total weight of the lubricating compositions.

[0089] Seal Compatibility Agents

[0090] Seal compatibility agents may be included in lubricating compositions to help swell elastomeric seals by causing a chemical reaction in the lubricating oil or physical change in the elastomer.

[0091] Examples of seal compatibility agents may include, but are not limited to, organic phosphates, aromatic esters, aromatic hydrocarbons, polybutenyl succinic anhydride, the like, and any combination thereof.

[0092] Seal compatibility agents may be present in a lubricating composition of the present disclosure in an amount of up to about 5 wt% (e.g., up to about 4 wt%, up to about 3 wt%, up to about 2 wt%, 0 wt% to about 5 wt%, 0 wt% to about 2 wt%, about 0.01 wt% to about 5 wt%, or about 0.01 wt% to about 2 wt%), based on a total weight of the lubricating compositions.

[0093] Use of Lubricating Compositions

[0094] The lubricating compositions (e.g., concentrates once diluted and lubricating oils) of the present disclosure may be suitable for use as automotive crank case lubricants, automotive gear oils, transmission oils, marine cylinder oils, marine trunk piston engine oils, passenger vehicle engine oils, commercial vehicle engine oils, lubricants for hybrid vehicles, lubricants for plug-in hybrid vehicles, lubricants for battery electric vehicles, automotive greases, and many industrial lubricants such as circulation lubricants, industrial gear lubricants, onshore wind turbinelubricants, offshore wind turbine lubricants, paper machine oils, industrial greases, compressor oils, pump oils, refrigeration lubricants, hydraulic lubricants, and metal working fluids.

[0095] Methods may include supplying to an engine or other equipment (e.g., compressor, pump, wind turbine, etc.) a lubricating composition of the present disclosure. In some instances, methods may include producing a lubricating composition described herein from a concentrate described herein, which may include diluting the concentrate and / or adding additives to the concentrate.

[0096] The lubricant composition for an internal combustion engine may be suitable for any engine lubricant irrespective of the sulfur, phosphorus, or sulphated ash (ASTM D-874) content. The sulfur content of the lubricant compositions of the present disclosure may be 1 wt% or less, or 0.8 wt% or less, or 0.5 wt% or less, or 0.3 wt% or less. The phosphorus content of the lubricant compositions of the present disclosure may be 0.2 wt% or less, or 0.12 wt% or less, or 0.1 wt% or less, or 0.085 wt% or less, or 0.08 wt% or less, or even 0.06 wt% or less, 0.055 wt% or less, or 0.05 wt% or less. The total sulphated ash content of the lubricant compositions of the present disclosure may be 2 wt% or less, or 1.5 wt% or less, or 1.1 wt% or less, or 1 wt% or less, or 0.8 wt% or less, or 0.5 wt% or less, or 0.4 wt% or less.

[0097] Example Embodiments

[0098] Nonlimiting example embodiments of the present disclosure include the following.

[0099] Embodiment 1. A composition comprising:Compound (I) wherein A is H, methyl, ethyl, or any combination thereof; and n is 3-10.

[0100] Embodiment 2. A composition comprising:Compound (II) wherein A is H, methyl, ethyl, or any combination thereof; n is 3-10; and R is polyisobutyl.

[0101] Embodiment 3. A composition comprising:Compound (III) wherein A is H, methyl, ethyl, or any combination thereof; n is 3-10; R1 is a C1-C6 alkyl; and R is polyisobutyl.

[0102] Embodiment 4. A composition comprising:Compound (IV) wherein A is H, methyl, ethyl, or any combination thereof; n is 3-10; m is 3-10; R1 is a C1-C6 alkyl; and R is polyisobutyl.

[0103] Embodiment 5. A composition comprising: two or more of Compounds (II), (III), and (IV) of Embodiments 2-4 in combination.

[0104] Embodiment 6. A method comprising: reacting Compound (I) of Embodiment 1 with polyisobutylene succinimide.

[0105] Embodiment 7. A method comprising: reacting Compound (I) of Embodiment 1 with a hydrocarbyl-substituted phenol and one or more aldehydes.

[0106] Embodiment 8. A lubricating composition comprising: at least 30 wt% of a base oil, based on a total weight of the lubricating composition; and 1 wt% to 20 wt% of a dispersant, based on the total weight of the lubricating composition, wherein the dispersant comprises one or more of Compounds (II), (III), and (IV) of Embodiments 2-4.

[0107] Embodiment 9. The lubricating composition of Embodiment 8, wherein the base oil is present at 30 wt% to 70 wt%, based on the total weight of the lubricating composition.

[0108] Embodiment 10. The lubricating composition of Embodiment 8, wherein the base oil is present at 50 wt% to 99 wt%, based on the total weight of the lubricating composition.

[0109] Embodiment 11. The lubricating composition of any one of Embodiments 8-10 further comprising: up to 20 wt% of a detergent, based on the total weight of the lubricatingcomposition; and up to 20 wt% of an antioxidant, based on the total weight of the lubricating composition; wherein the detergent and / or the antioxidant are present in a non-zero amount.

[0110] Embodiment 12. The lubricating composition of any one of Embodiments 8-11 further comprising one or more of: a supplementary dispersant, a viscosity modifier, a corrosion inhibitor, an antiwear agent, a metal deactivator, a foam inhibitor, a demulsifier, a pour point depressant, and a seal compatibility agent.[OHl] Embodiment 13. A method comprising: supplying to an engine a lubricating composition any one of Embodiments 8-12.

[0112] While the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

[0113] The present disclosure will now be further described with reference to the following non-limiting examples.

[0114] EXAMPLES

[0115] Example 1. Synthesis of Compound (I-A)Compound (I-A) where n is 3-10.

[0116] 1.5 kg of N-phenyl-l-naphthylamine was mixed with 30 g of 45% KOH solution. After removing water from the mixture at 120 °C, 1.2 kg of propylene oxide were added to the mixture. After the alkylation reaction was completed, 36 g of MAGNESOL® (magnesium silicate, available from The Dallas Group of America) was used to remove the potassium ions. After filtration, the polyol intermediate was reacted with ammonia and hydrogen in a fixed bed reactor with a metal-based amination catalyst. After purification, the product was a transparent, clear liquid.

[0117] The structure of Compound (I-A) was confirmed using liquid chromatorgraphy-mass spectroscopy analysis. The flash point of Compound (I-A) is greater than 200 °C. Primary amine number of Compound (I-A) was about 1.84 meq / g, and the total acylatables value was about 1.87 meq / g. Based on these results, the calculated polyol conversion is about 98.2%.

[0118] Example 2. Synthesis of Compound (II-A)Compound (II-A) where n is 3-10; and R is polyisobutyl.

[0119] 244 g of polyisobutylene succinic anhydride and 107.2 g of Compound (I-A) were reacted at 170 °C by removing water for 2 hours. After cooling to ambient temperature, the product was a viscous fluid. After purification, the viscosity of Compound (II-A) was measure at 10069 cSt at 40 °C. The structure of Compound (II-A) was confirmed using liquid chromatography-mass spectroscopy analysis.

Claims

WHAT IS CLAIMED IS:

1. A composition comprising:Compound (I) wherein A is H, methyl, ethyl, or any combination thereof; and n is 3-10.

2. A composition comprising:Compound (II) wherein A is H, methyl, ethyl, or any combination thereof; n is 3-10; and R is polyisobutyl.

3. A composition comprising:Compound (TIT)wherein A is H, methyl, ethyl, or any combination thereof; n is 3-10; Rl is a C1-C6 alkyl; and R is polyisobutyl.

4. A composition comprising:R: polyisobutylRl: Cl-6 alkylA: H, methyl , ethyl or the eoinbinationCompound (IV) wherein A is H, methyl, ethyl, or any combination thereof; n is 3-10; m is 3-10; Rl is a C1-C6 alkyl; and R is polyisobutyl.

5. A composition comprising:two or more of Compounds (IT), (III), and (TV) of claims 2-4 in combination.

6. A method comprising:reacting Compound (I) of claim 1 with polyisobutylene succinimide.

7. A method comprising:reacting Compound (I) of claim 1 with a hydrocarbyl -substituted phenol and one or more aldehydes.

8. A lubricating composition comprising:at least 30 wt% of a base oil, based on a total weight of the lubricating composition; and 1 wt% to 20 wt% of a dispersant, based on the total weight of the lubricating composition, wherein the dispersant comprises one or more of Compounds (II), (III), and (IV) of claims 2-4.

9. The lubricating composition of claim 8, wherein the base oil is present at 30 wt% to 70 wt%, based on the total weight of the lubricating composition.

10. The lubricating composition of claim 8, wherein the base oil is present at 50 wt% to 99 wt%, based on the total weight of the lubricating composition.

11. The lubricating composition of any one of claims 8-10 further comprising:up to 20 wt% of a detergent, based on the total weight of the lubricating composition; and up to 20 wt% of an antioxidant, based on the total weight of the lubricating composition; wherein the detergent and / or the antioxidant are present in a non-zero amount.

12. The lubricating composition of any one of claims 8-11 further comprising one or more of: a supplementary dispersant, a viscosity modifier, a corrosion inhibitor, an antiwear agent, a metal deactivator, a foam inhibitor, a demulsifier, a pour point depressant, and a seal compatibility agent.

13. A method compri sing :supplying to an engine a lubricating composition any one of claims 8-12.

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