Benzazepine compounds as antioxidants for lubricating compositions

Abstract

The present invention discloses a lubricating composition, which comprises an oil having lubricating viscosity and a benzazepine compound. A method of using such a lubricating composition is also disclosed.

Description

[0001] The technology of the present disclosure relates to compositions suitable as lubricants and lubricant additive compositions, the compositions comprising benzazepine derived antioxidants, wherein the antioxidants themselves can also be described as benzazepines compounds, and optionally comprise other additives suitable for lubricants, such as antiwear agents, detergents or dispersants.

[0002] Antioxidants are an important class of additives as they are used to provide and / or improve the antioxidant properties of organic compositions, including lubricating compositions containing organic components, by preventing or retarding oxidation and thermal decomposition. Antioxidants can cause an increase in volatility in some applications, which can be undesirable due to required environmental regulations and / or performance standards.

[0003] It is known that substituted diarylamine compounds can be used in oils having lubricating viscosity to reduce oxidative decomposition and improve cleanliness.

[0004] The subject matter described herein provides an ashless antioxidant that has suitable performance properties when used in lubricating formulations, particularly for, e.g., heavy-duty diesel engines and passenger car crankcase engines, and can also reduce regulatory issues.

[0005] There is provided a lubricating composition comprising an oil having lubricating viscosity and a benzazepine compound. In certain embodiments, the benzazepine compound is an ashless benzazepine compound. In certain embodiments, there is provided a lubricating composition comprising an oil having lubricating viscosity and an ashless antioxidant, wherein the ashless antioxidant comprises a benzazepine compound. In certain embodiments, there is provided a lubricating composition comprising an oil having lubricating viscosity and an ashless antioxidant, wherein the ashless antioxidant consists essentially of a benzazepine compound. In certain embodiments, there is provided a lubricating composition comprising an oil having lubricating viscosity and an ashless antioxidant, wherein the ashless antioxidant consists of a benzazepine compound. In certain embodiments, there is provided a lubricating composition comprising an oil having lubricating viscosity and an ashless antioxidant, wherein the ashless antioxidant is a benzazepine compound.

[0006] The present subject matter also provides a lubricating composition suitable for lubricating an internal combustion engine, the lubricating composition comprising: (A) a major amount of an oil having lubricating viscosity; (B) a minor amount of at least one antioxidant, the antioxidant comprising a benzazepine as described herein compound; and (C) a minor amount of at least one other additive, the additive comprising at least one of the following: a viscosity modifier, a pour point depressant, a dispersant, a detergent, an antiwear agent, an antioxidant different from the antioxidant of component (B), a friction modifier, a corrosion inhibitor, a seal swell agent, a metal deactivator or a foam inhibitor.

[0007] The present subject matter also provides a method of lubricating an internal combustion engine, wherein the method comprises the step of providing any one of the lubricating compositions described herein to the engine. Such methods can include methods for improving the oxidation stability of engine oil lubricants (e.g., crankcase lubricants).

[0008] The present subject matter also provides a method for lubricating an internal combustion engine, the method comprising: (A) providing a lubricating composition to the engine, the lubricating composition comprising: (i) an oil having lubricating viscosity; (ii) a minor amount of at least one antioxidant, the antioxidant comprising a benzazepine as described herein compound; and (iii) a minor amount of at least one other additive, the additive comprising at least one of the following: a viscosity modifier, a pour point depressant, a dispersant, a detergent, an antiwear agent, an antioxidant different from the antioxidant of component (ii), a friction modifier, a corrosion inhibitor, a seal swell agent, a metal deactivator or a foam inhibitor.

[0009] The following embodiments of the present subject matter are contemplated :

[0010] 1. A lubricating composition, the lubricating composition comprising an oil having lubricating viscosity and a benzazepine compound.

[0011] 2. The lubricating composition according to embodiment 1, wherein the benzazepine compound is substituted with a second aryl ring, the second aryl ring sharing two carbon atoms with the nitrogen-containing ring of the benzazepine compound.

[0012] 3. The lubricating composition according to embodiment 1 or embodiment 2, wherein the nitrogen-containing ring of the benzazepine compound contains at least one additional heteroatom, wherein the heteroatom is at least one of oxygen, sulfur or nitrogen.

[0013] 4. The lubricating composition according to any one of embodiments 1 to 3, wherein the benzazepine The compound is represented by at least one of the following general formulas IA or IB:

[0014]

[0015]

[0016] wherein R 1 、R 2 and R 3 are each independently hydrogen or a hydrocarbyl group having 1 to 24 carbon atoms, or R 1 and R 2 together form a saturated five- or six-membered carbon ring, an unsaturated five- or six-membered carbon ring or an aromatic ring, any of which is optionally further substituted by a hydrocarbyl group having 1 to 24 carbon atoms; each X is independently O, S or NR 4 ; and R 4 is hydrogen or a hydrocarbyl group having 1 to 18 carbon atoms.

[0017] 5. The lubricating composition according to any one of embodiments 1 to 4, wherein the benzazepine compound comprises a dibenzazepine compound.

[0018] 6. The lubricating composition according to embodiment 5, wherein the dibenzazepine compound

[0019] is represented by at least one of the following general formulas IIA or IIB:

[0020]

[0021] wherein R 1 、R 2 and R 3 are each independently hydrogen or a hydrocarbyl group having 1 to 24 carbon atoms; each X is independently O, S or NR 4 ; and R 4 is hydrogen or a hydrocarbyl group having 1 to 18 carbon atoms.

[0022] 7. The lubricating composition according to any one of embodiments 1 to 6, wherein the benzazepine compound is present in the lubricating composition in an amount of 0.1 wt% to 5.0 wt%, or 0.5 wt% to 3.0 wt%, or 0.8 wt% to 2.5 wt% based on the total weight of the lubricating composition.

[0023] 8. A lubricating composition according to any one of embodiments 1 to 7, wherein the lubricating composition comprises at least 0.3% by weight of at least one additional lubricant additive, the additive comprising at least one of the following: an ashless polyisobutenyl succinimide dispersant, an overbased or neutral metal-based detergent, an antiwear agent, a polymeric viscosity modifier, or an ashless antioxidant other than a benzazepine compound.

[0024] 9. A lubricating composition according to embodiment 8, wherein the ashless polyisobutenyl succinimide dispersant is present in the lubricating composition in an amount of 0.5% to 4.0% by weight, or 0.8% to 3.0% by weight, or 1.1% to 2.3% by weight, or 1.5% to 2.8% by weight, based on the total weight of the lubricating composition.

[0025] 10. A lubricating composition according to embodiment 8 or embodiment 9, wherein the metal-based detergent comprises at least one of a neutral alkaline earth metal detergent or an overbased alkaline earth metal detergent, in an amount of 0.2% to 15% by weight, or 0.3% to 10% by weight, or 0.3% to 8% by weight, or 0.4% to 3% by weight, based on the total weight of the lubricating composition.

[0026] 11. A lubricating composition according to embodiment 10, wherein at least one of the neutral alkaline earth metal detergent or the overbased alkaline earth metal detergent comprises at least one of the following: an alkylbenzene sulfonate detergent, a sulfur-coupled phenate detergent, or an alkyl salicylate detergent.

[0027] 12. A lubricating composition according to any one of embodiments 8 to 11, wherein at least one antiwear agent is present in an amount of 0.05% to 3% by weight, or 0.08% to 1.3% by weight, or 0.08% to 2.1% by weight, or 0.1% to 1.5% by weight, or 0.5% to 0.9% by weight, based on the total weight of the lubricating composition.

[0028] 13. A lubricating composition according to embodiment 12, wherein the at least one antiwear agent comprises a phosphorus-containing compound, and the amount of the phosphorus-containing compound can effectively deliver 200 ppm to 1200 ppm of phosphorus to the lubricating composition.

[0029] 14. A lubricating composition according to embodiment 12 or embodiment 13, wherein the at least one antiwear agent comprises zinc dialkyldithiophosphate.

[0030] 15. A lubricating composition according to embodiment 8, wherein other than the benzazepine The ashless antioxidant of the compound is present in an amount of 0.01% to 5% by weight, or 0.1% to 4% by weight, or 0.2% to 3% by weight, or 0.5% to 2% by weight based on the total weight of the lubricating composition.

[0031] 16. The lubricating composition according to any one of embodiments 1 to 15, wherein the lubricating composition comprises less than 0.1% by weight of a diarylamine antioxidant.

[0032] 17. The lubricating composition according to any one of embodiments 1 to 16, wherein the lubricating composition is substantially free of a diarylamine antioxidant.

[0033] 18. The lubricating composition according to embodiment 1, wherein the benzazepine compound comprises at least one of the following: benzazepine dihydrobenzazepine tetrahydrobenzazepine 5H-dibenz[b,f]azepine 10,11-dihydro-5H-dibenz[b,f]azepine or their hydrocarbyl-substituted derivatives.

[0034] 19. A method of lubricating an internal combustion engine, the method comprising providing the lubricating composition according to any one of embodiments 1 to 18 to the internal combustion engine.

[0035] 20. A method of improving the antioxidant properties of a crankcase lubricant, wherein the method comprises lubricating the crankcase with the lubricating composition according to any one of embodiments 1 to 18.

[0036] The various features and embodiments of the subject matter will now be described by way of non-limiting illustration.

[0037] Unless otherwise indicated, the amount of each chemical component described herein does not include any solvents or diluent oils that may typically be present in commercial substances, i.e., on an active chemical basis. Unless otherwise indicated, each chemical or composition mentioned herein should be interpreted as a commercial grade substance, which may contain isomers, by-products, derivatives, and other such substances that are commonly understood to be present in commercial grades.

[0038] As used herein, the terms "hydrocarbyl substituent" or "hydrocarbyl group" are used in their ordinary sense, which is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly connected to the remainder of the molecule and predominantly having hydrocarbon character. Examples of hydrocarbyl groups include: hydrocarbyl substituents, i.e., aliphatic (e.g., alkyl or alkenyl), cycloaliphatic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic, aliphatic and cycloaliphatic-substituted aromatic substituents, as well as cyclic substituents where the ring is completed through another part of the molecule (e.g., two substituents together form a ring); substituted hydrocarbyl substituents, i.e., substituents containing non-hydrocarbon groups which, in the context of the present subject matter, do not change the predominantly hydrocarbon nature of the substituent (e.g., halogens (especially chlorine and fluorine), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso and thioxy); hetero substituents, i.e., substituents which, in the context of the present subject matter, while having predominantly hydrocarbon character, contain atoms other than carbon in the ring or chain formed, which include substituents such as pyridyl, furyl, thienyl and imidazolyl. Heteroatoms include sulfur, oxygen and nitrogen. Generally, for every ten carbon atoms in the hydrocarbyl group, there will be no more than two or no more than one non-hydrocarbon substituent; alternatively, there may be no non-hydrocarbon substituents in the hydrocarbyl group.

[0039] It is known that some of the above substances can interact in the final formulation such that the components of the final formulation can be different from those initially added. For example, metal ions (e.g., metal ions of detergents) can migrate to other acidic or anionic sites of other molecules. The products thus formed, including those formed when using the compositions of the present subject matter in their intended uses, may not be easily described. However, all such conditioned and reaction products are included within the scope of the present subject matter. The present subject matter includes compositions prepared by mixing the components described herein.

[0040] As used herein, the indefinite article "a" / "an" is intended to mean one or more than one. As used herein, the phrase "at least one" means one or more than one of the following terms. Thus, "a" / "an" and "at least one" can be used interchangeably. For example, "at least one of A, B or C" means that in alternative embodiments, only one of A, B or C may be included, and any mixture of two or more of A, B and C may be included.

[0041] As used herein, the term "substantially" means that a given value is within ±10% of a specified value. In other embodiments, the value is within ±5% of the specified value. In other embodiments, the value is within ±2.5% of the specified value. In other embodiments, the value is within ±1% of the specified value.

[0042] As used herein, the term "substantially free of" means that a component does not include any intentional addition of the material from which the component is "substantially free of". For example, the component may include no more than impurity levels of the material from which the component is "substantially free of", which may be the result of an incomplete chemical reaction and / or an unintentional / undesired (but possibly unavoidable) reaction product.

[0043] As used herein, the transitional term "comprising", which is synonymous with "including", "containing", or "characterized by", is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. However, in each use herein of "comprising", it is intended that the term also cover, as alternative embodiments, the phrases "consisting essentially of" and "consisting of", where "consisting of" excludes any element or step not specified, and "consisting essentially of" permits the inclusion of additional unrecited elements or steps that do not substantially affect the essential or basic and novel properties of the composition or method under consideration.

[0044] The present subject matter relates to a lubricating composition comprising an oil having lubricating viscosity and an ashless antioxidant, wherein the ashless antioxidant comprises a benzazepine compound, and methods of using such lubricating compositions, such as methods of lubricating an internal combustion engine using such an antioxidant. The lubricating composition may also comprise a lubricant additive as described herein.

[0045] The lubricating compositions described herein can be used as lubricating compositions in a variety of applications: internal combustion engines, including gasoline engines or spark-ignition engines, such as passenger car engines, diesel engines, or compression-ignition engines, such as heavy-duty diesel truck engines, natural gas-fueled engines, such as stationary power engines, two-stroke engines, aircraft piston engines and turbine engines, marine and railroad diesel engines; power transmissions, such as automatic transmissions, transaxle transmissions or agricultural tractor transmissions; gears, such as industrial gears or automotive gears; metalworking; hydraulic systems; special applications, such as bearings, which may require the lubricating composition to be a grease; and hydrocarbon fuels for internal combustion engines, such as gasoline or diesel fuel.

[0046] One component of the lubricating composition disclosed herein is an oil having lubricating viscosity. As used herein, an oil having lubricating viscosity can include natural oils and / or synthetic oils, oils derived from hydrocracking, hydrogenating, and / or hydrorefining of unrefined oils, refined oils, re-refined oils, or mixtures thereof. A more detailed description of unrefined oils, refined oils, and re-refined oils is provided in WO 2008 / 147704 A1, paragraphs

[0054] to

[0056] . More detailed descriptions of natural and synthetic lubricating oils are found in paragraphs

[0058] and

[0059] of WO 2008 / 147704 A1, respectively. Synthetic oils can also be produced by the Fischer-Tropsch reaction and can be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In certain embodiments, the oil can be prepared by Fischer-Tropsch gas-to-liquid synthesis procedures and other gas-to-liquid procedures.

[0047] Suitable oils can be derived from biological (i.e., natural) sources or produced by biotechnological methods. This includes naturally occurring oils that can be further refined or purified by standard methods, such as vegetable oils and triglyceride oils, and those oils that can be sourced by direct bioconversion of natural chemicals into oils or by biogenesis of precursor molecules of structural units that can be further converted into oils by known methods.

[0048] An oil having lubricating viscosity can also be defined as set forth in subtitle 1.3 of subsection 1.3 of the April 2008 edition of “Appendix E - API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils”, “Base Stock Categories”. The API guidelines are also summarized in US 7,285,516 B2 (see column 11, line 64 to column 12, line 10).

[0049] In certain embodiments, an oil having lubricating viscosity can be an API Group I, II, III, or IV mineral oil, ester, or other synthetic oil, or any mixture thereof.

[0050] The amount of oil having a lubricating viscosity present in the lubricating compositions described herein is typically the balance remaining after subtracting from 100 weight percent the sum of the amounts of the dispersant additive package and any additional additives (if any) in accordance with the present disclosure. Thus, the amount of oil having a lubricating viscosity can vary widely in different embodiments because that amount depends on the amounts of any other ingredients present in the lubricating composition. In certain embodiments, the oil having a lubricating viscosity can be the major portion of the lubricating composition. For example, the amount of oil having a lubricating viscosity present can be from 75 weight percent to 95 weight percent, such as from 80 weight percent to 95 weight percent, or from 80 weight percent to 90 weight percent, based on the total weight of the lubricating composition.

[0051] In certain embodiments, the oil having a lubricating viscosity can have a kinematic viscosity, as measured by standard test method ASTM D 445, of from 2.4 m 2 / s to 6.4 m 2 / s at 100 °C. In certain embodiments, the kinematic viscosity is from 4.0 m 2 / s to 5.0 m 2 / s or from 5.2 m 2 / s to 5.8 m 2 / s or from 6.0 m 2 / s to 6.5 m 2 / s. In certain embodiments, the kinematic viscosity is 6.2 m 2 / s, 5.6 m 2 / s or 4.6 m 2 / s.

[0052] The lubricating compositions described herein can be in the form of concentrates and / or fully formulated lubricants. If the lubricating composition is in the form of a concentrate (which can be combined with additional oil to form a finished lubricant in whole or in part), the ratios of the components disclosed herein to the oil having a lubricating viscosity and / or to a diluent oil include the range of from 1:99 to 99:1 by weight or from 80:20 to 10:90 by weight.

[0053] The ashless antioxidants described herein include benzotriazole compounds and / or compounds derived from benzotriazole . Benzotriazole compounds are heterocyclic compounds containing a benzene ring fused to an azole ring. Benzotriazole compounds can be further substituted with hydrocarbyl groups, including dibenzotriazole compounds containing a second aromatic ring fused to the azole ring. Benzotriazole compounds can also be selected such that the azole The ring can be unsaturated, or fully or partially saturated. In certain embodiments, the azo ring may also contain heteroatoms such as oxygen, sulfur, and / or nitrogen. As used herein, the term "benzoazepine compound" is intended to mean any of the compounds described in this paragraph.

[0054] In certain embodiments, the benzoazepine compound is represented by at least one of the following general formulas IA or IB:

[0055]

[0056] Wherein, with respect to general formulas IA and IB: R 1 , R 2 and R 3 are each independently hydrogen or a hydrocarbyl group having 1 to 24 carbon atoms, or R 1 and R 2 together form a saturated five- or six-membered carbocyclic ring, an unsaturated five- or six-membered carbocyclic ring, or an aromatic ring, any of which is optionally further substituted with a hydrocarbyl group having 1 to 24 carbon atoms; each X is independently O, S, or NR 4 ; and R 4 is hydrogen or a hydrocarbyl group having 1 to 18 carbon atoms.

[0057] In certain embodiments, the benzoazepine compound can be a dibenzoazepine compound, wherein the dibenzoazepine compound is optionally represented by at least one of the following general formulas IIA or IIB:

[0058]

[0059] Wherein, with respect to general formulas IIA and IIB: R 1 , R 2 and R 3 are each independently hydrogen or a hydrocarbyl group having 1 to 24 carbon atoms; each X is independently O, S, or NR 4 ; and R 4 is hydrogen or a hydrocarbyl group having 1 to 18 carbon atoms.

[0060] The ashless antioxidant can be present in the lubricating compositions described herein in an amount of 0.1 wt% to 5.0 wt%, such as 0.5 wt% to 3.0 wt%, or 0.8 wt% to 2.5 wt%, or 0.5 wt% to 1.5 wt%, based on the total weight of the lubricating composition.

[0061] In addition to containing the benzoazepine In addition to the ashless antioxidants of the compounds, the lubricating compositions described herein may further comprise one or more of the following: polyisobutenyl succinimide dispersants, overbased detergents, neutral detergents, antioxidants different from the ashless antioxidants described herein, antiwear agents, friction modifiers, corrosion inhibitors, polymer viscosity modifiers, and / or foam inhibitors. In certain embodiments, a fully formulated lubricating oil may contain one or more of these additives and is typically a package of multiple such additives.

[0062] The lubricating compositions described herein may further comprise a dispersant. In certain embodiments, the dispersant may be a polyalkenyl succinimide dispersant. Dispersants are generally well-known in the lubricant art and typically include those referred to as ashless dispersants and polymeric dispersants. Ashless dispersants are called "ashless" because, when employed, they do not contain metals and thus generally do not contribute to the sulfated ash when added to a lubricant. However, once they are added to a lubricant containing metal species, they may interact with the surrounding metals. Ashless dispersants may be characterized by polar groups attached to relatively high molecular weight hydrocarbon chains. Suitable ashless dispersants include N-substituted long-chain alkenyl succinimides having a variety of chemical structures, including those represented by the following general formula III:

[0063]

[0064] wherein, with respect to general formula III: each R 1 is independently an alkyl group, such as a polyisobutylene group having a molecular weight (M n ) of from 500 grams per mole to 5000 grams per mole based on the polyisobutylene precursor, and each R 2 is independently an alkylene group, such as an ethylene (C2H4) group.

[0065] Such molecules may be derived from the reaction of an alkenyl acylating agent with a polyamine, and in addition to the simple imide structure shown above, there may be a variety of covalent bonds between the two moieties, including a variety of amides and quaternary ammonium salts. In the above general formula, the amine moiety is shown as an alkylene polyamine, but other aliphatic and aromatic monoamines and polyamines may also be used. Additionally, the R 1 groups of general formula III may have various bonding modes on the imide structure, including various ring bonds. The ratio of the carbonyl group of the acylating agent to the nitrogen atom of the amine may be from 1:0.5 to 1:3, and in other cases from 1:1 to 1:2.75 or from 1:1.5 to 1:2.5. Succinimide dispersants are more fully described in US 4,234,435, US 3,172,892, and EP 0 355 895 A2 / B1.

[0066] In certain embodiments, the dispersant is prepared by a process involving the presence of a small amount of chlorine or other halogen, as described in US 7,615,521 B2 (see, for example, column 4, lines 18 - 60 and Preparation Example A). Such dispersants typically have some cycloaliphatic structure in the linkage of the hydrocarbyl substituent to the acidic or amide "head" group. In other embodiments, the dispersant is prepared by a thermal process involving an "ene" reaction without the use of any chlorine or other halogen, as described in US 7,615,521 B2; dispersants prepared in this manner are typically derived from highly vinylidene (i.e., greater than 50% terminal vinylidene) polyisobutene (see column 4, lines 61 to column 5, line 30 and Preparation Example B). Such dispersants typically do not contain the above-described cycloaliphatic structure at the point of attachment. In certain embodiments, the dispersant is prepared by free radical catalyzed polymerization of highly vinylidene polyisobutene with an ethylenically unsaturated acylating agent, as described in US 8,067,347 B2.

[0067] Some dispersants for use in the lubricating compositions of the present invention can be derived from highly vinylidene polyisobutene as a polyolefin, i.e., having greater than 50%, 70% or 75% terminal vinylidene groups (α and β isomers). In certain embodiments, the succinimide dispersant can be prepared by a direct alkylation route. In other embodiments, it can comprise a mixture of direct alkylation and chloro route dispersants.

[0068] Dispersants suitable for use in the lubricating compositions described herein include succinimide dispersants. In certain embodiments, the dispersant can be present as a single dispersant. In certain embodiments, the dispersant can be present as a mixture of two or three different dispersants, at least one of which can optionally be a succinimide dispersant.

[0069] The succinimide dispersant can be an imide of at least one aliphatic polyamine having two to eight nitrogen atoms. The aliphatic polyamine can be ethylenepolyamine, propylenepolyamine, butylenepolyamine or mixtures thereof. In certain embodiments, the aliphatic polyamine can be ethylenepolyamine. In certain embodiments, the aliphatic polyamine can be ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine residue or mixtures thereof.

[0070] The succinimide dispersant can be an aromatic amine, a derivative of an aromatic polyamine, or a mixture thereof. The aromatic amine can be 4-aminodiphenylamine (ADPA) (also known as N-phenyl-p-phenylenediamine), a derivative of ADPA (as described in US 2011 / 0306528 A1 and US 2010 / 0298185 A1), nitroaniline, aminocarbazole, aminoindazolone, aminopyrimidine, 4-(4-nitrophenylazo)aniline, or a combination thereof. In certain embodiments, the dispersant is a derivative of an aromatic amine, wherein the aromatic amine has at least three non-consecutive aromatic rings.

[0071] The succinimide dispersant can be a polyetheramine, a derivative of a polyether polyamine, or a mixture thereof. Typical polyetheramine compounds contain at least one ether unit and are end-capped with at least one amine moiety chain. The polyether polyamine can be based on polymers derived from C2-C6 epoxides (such as ethylene oxide, propylene oxide, and butylene oxide). Examples of polyether polyamines are sold under the trade name and are commercially available from Huntsman Corporation.

[0072] The dispersant can also be post-treated by conventional methods, such as by reaction with any of a variety of reagents. These reagents include boron compounds, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds. In certain embodiments, the succinimide dispersant can be post-treated with boron to obtain a boricated dispersant. In certain embodiments, the succinimide dispersant includes at least one boron-containing dispersant and at least one boron-free dispersant. In one embodiment, the lubricating composition is free or substantially free of boron-containing succinimide dispersants.

[0073] The polyalkenyl succinimide dispersant may be present in an amount of from 1.2 wt% to 4 wt%, or from 1.5 wt% to 3.8 wt%, or from 0.5 wt% to 4.0 wt%, or from 0.8 wt% to 3.0 wt%, or from 1.1 wt% to 2.3 wt%, or from 1.5 wt% to 2.8 wt%, or from 1.2 wt% to 3 wt%, or from 2.0 wt% to 3.5 wt% based on the total weight of the lubricating composition. If a mixture of two or more dispersants contains a succinimide dispersant, each of these dispersants may independently be present in the composition in an amount of from 0.01 wt% to 4 wt%, or from 0.1 wt% to 3.5 wt%, or from 0.5 wt% to 3.5 wt%, or from 1.0 wt% to 3.0 wt%, or from 0.5 wt% to 2.2 wt% based on the total weight of the lubricating composition, provided that the total amount of the dispersants is as described above. In certain embodiments, the polyalkenyl succinimide dispersant is a polyisobutylene succinimide. In certain embodiments, the polyalkenyl succinimide dispersant is a polyisobutylene succinimide and is present in the lubricating composition in an amount of from 1.2 wt% to 4 wt% based on the total weight of the lubricating composition.

[0074] In certain embodiments, the polyalkenyl succinimide dispersant described above is a boron-containing succinimide dispersant, and the amount thereof is from 1.2 wt% to 4 wt% based on the total weight of the lubricating composition, or at the treatment rate of the polyalkenyl succinimide dispersant described above. In another embodiment, the polyalkenyl succinimide dispersant is a mixture of a boron-free and a boron-containing succinimide dispersant. When both the boron-containing dispersant and the boron-free dispersant are present, the ratio of one or more boron-containing dispersants to one or more boron-free dispersants may be from 4:1 to 1:4 by weight, or from 3:1 to 1:3 by weight, or from 2:1 to 1:3 by weight, or from 1:1 to 1:4 by weight. In certain embodiments, one or more boron-containing dispersants are present in an amount of from 0.8 wt% to 2.1 wt% and one or more boron-free dispersants are present in an amount of from 0.8 wt% to 4 wt% based on the total weight of the lubricating composition.

[0075] In certain embodiments, the lubricating compositions described herein may comprise a metal-containing detergent. The metal-containing detergent may be a overbased detergent. Overbased detergents (sometimes referred to as overbased or superbasic salts) are characterized by a metal content that exceeds the metal content required for neutralization according to the stoichiometry of the metal and a particular acidic organic compound that reacts with the metal. Overbased detergents may comprise sulfur-free phenates, sulfur-containing phenates, sulfonates, salixarates, salicylates, and / or mixtures thereof.

[0076] Overbased detergents may comprise sodium, calcium, magnesium salts of phenates, sulfur-containing phenates, sulfonates, salixarates, and / or salicylates, and / or mixtures thereof. Overbased phenates and salicylates typically have a total base number (TBN) of from 180 to 450. Overbased sulfonates typically have a total base number of from 250 to 600 or from 300 to 500. Overbased detergents are known in the art. In certain embodiments, the sulfonate detergent may be a predominantly linear alkylbenzene sulfonate detergent having a metal ratio of at least 8, as described in paragraphs

[0026] to

[0037] of US 2005 / 0065045 A1. Linear alkylbenzene sulfonate detergents may be particularly useful for helping to improve fuel economy. The linear alkyl group may be attached to the benzene ring at any position along the straight chain of the alkyl group (but typically at the 2, 3, or 4 position of the straight chain, and in some cases, predominantly at the 2 position), resulting in a linear alkylbenzene sulfonate detergent. The overbased detergent may be present in an amount of from 0 wt% to 15 wt%, or greater than 0 wt% to 15 wt%, or from 0.2 wt% to 15 wt%, or from 0.3 wt% to 10 wt%, or from 0.3 wt% to 8 wt%, or from 0.4 wt% to 3 wt%, or from 0.2 wt% to 3 wt% based on the total weight of the lubricating composition. For example, in a heavy-duty diesel engine, the detergent may be present in an amount of from 2 wt% to 3 wt% based on the total weight of the lubricating composition. For example, in a passenger car engine, the detergent may be present in an amount of from 0.2 wt% to 1 wt% based on the total weight of the lubricating composition.

[0077] The metal-containing detergent provides sulfate ash to the lubricating composition. The sulfated ash may be determined by ASTM D874. In certain embodiments, the lubricating compositions described herein may comprise a metal-containing detergent, and the amount of the metal-containing detergent may deliver at least 0.4 wt% of sulfated ash to the total lubricating composition. In another embodiment, the metal-containing detergent may be present in an amount that delivers at least 0.6 wt% of sulfated ash, or at least 0.75 wt% of sulfated ash, or at least 0.9 wt% of sulfated ash to the total lubricating composition.

[0078] In certain embodiments, the lubricating compositions described herein may further comprise an antiwear agent. Examples of antiwear agents include phosphorus-containing antiwear / extreme pressure agents (such as metal thiophosphates), phosphate esters and their salts, phosphorus-containing carboxylic acids, phosphorus-containing esters, phosphorus-containing ethers, phosphorus-containing amides, and phosphites. In certain embodiments, the amount of the phosphorus antiwear agent present may deliver from 0.01 wt% to 0.2 wt%, or from 0.015 wt% to 0.15 wt%, or from 0.02 wt% to 0.1 wt%, or from 0.025 wt% to 0.08 wt%, or from 0.01 wt% to 0.05 wt% of phosphorus to the total lubricating composition. In certain embodiments, the antiwear agent is zinc dialkyldithiophosphate.

[0079] Zinc dialkyldithiophosphate can be described as primary zinc dialkyldithiophosphate or secondary zinc dialkyldithiophosphate, depending on the structure of the alcohol used in its preparation. In certain embodiments, the lubricating compositions described herein may comprise primary zinc dialkyldithiophosphate. In certain embodiments, the lubricating compositions described herein may comprise secondary zinc dialkyldithiophosphate. In certain embodiments, the lubricating compositions described herein may comprise a mixture of primary zinc dialkyldithiophosphate and secondary zinc dialkyldithiophosphate, optionally wherein the ratio (by weight) of primary zinc dialkyldithiophosphate to secondary zinc dialkyldithiophosphate is at least 1:1, or at least 1:1.2, or at least 1:1.5, or at least 1:2, or at least 1:10. In certain embodiments, the lubricating compositions described herein may comprise a mixture of primary zinc dialkyldithiophosphate and secondary zinc dialkyldithiophosphate, wherein the secondary zinc dialkyldithiophosphate is at least 50 wt% (such as at least 60 wt%, at least 70 wt%, at least 80 wt%, or at least 90 wt%) of the primary zinc dialkyldithiophosphate. In certain embodiments, the lubricating compositions described herein are substantially free of, or do not contain, primary zinc dialkyldithiophosphate.

[0080] The phosphorus antiwear agent may be present in an amount of from 0.05 wt% to 3 wt%, or from 0.08 wt% to 1.3 wt%, or from 0.08 wt% to 2.1 wt%, or from 0.1 wt% to 1.5 wt%, or from 0.5 wt% to 0.9 wt% based on the total weight of the lubricating composition.

[0081] In certain embodiments, the lubricating compositions described herein may comprise a benzazepine different from that described above Additional antioxidants for the ashless antioxidants of the compound. Such additional antioxidants (which may also be ashless antioxidants) may include one or more of the following: arylamines, diarylamines, alkylated arylamines, alkylated diarylamines, phenols, hindered phenols, or sulfurized olefins. Such additional antioxidants may be present in an amount of 0.01 wt% to 5 wt%, or 0.1 wt% to 4 wt%, or 0.2 wt% to 3 wt%, or 0.5 wt% to 2 wt% based on the total weight of the lubricating composition.

[0082] The diarylamine or alkylated diarylamine may be phenyl-α-naphthylamine (PANA), alkylated diphenylamine, alkylated phenylnaphthylamine, or a mixture thereof. The alkylated diphenylamine may include dinonyl diphenylamine, nonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine, didecyl diphenylamine, decyl diphenylamine, or a mixture thereof. In certain embodiments, the diphenylamine may include nonyl diphenylamine, dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine, or a mixture thereof. In one embodiment, the alkylated diphenylamine may include nonyl diphenylamine and / or dinonyl diphenylamine. The alkylated diarylamine may include octyl, dioctyl, nonyl, dinonyl, decyl, or didecyl phenylnaphthylamine.

[0083] The diarylamine antioxidant may be present in the lubricating composition in an amount of 0.1 wt% to 10 wt%, or 0.35 wt% to 5 wt%, or 0.4 wt% to 1.2 wt%, or 0.5 wt% to 2 wt% based on the total weight of the lubricating composition. In certain embodiments, the lubricating composition may contain less than 0.2 wt%, or less than 0.1 wt%, or less than 0.05 wt% of the diarylamine antioxidant based on the total weight of the lubricating composition; in one embodiment, the lubricating composition does not contain or is substantially free of the diarylamine antioxidant.

[0084] The phenolic antioxidant may be a simple alkylphenol, a hindered phenol, and / or a coupled phenolic compound.

[0085] The hindered phenol antioxidant may contain secondary butyl and / or tertiary butyl groups as steric hindrance groups. The phenolic group may generally be further substituted with a hydrocarbon group (such as a straight-chain or branched-chain alkyl group) and / or a bridging group connecting 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, 4-butyl-2,6-di-tert-butylphenol, 4-dodecyl-2,6-di-tert-butylphenol, or butyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. In certain embodiments, the hindered phenol antioxidant may be an ester and may include, for example, Irganox from BASF TML-135. In certain embodiments, the phenolic antioxidant comprises a hindered phenol. In certain embodiments, the hindered phenol is derived from 2,6-di-tert-butylphenol.

[0086] In certain embodiments, the lubricating composition described herein may comprise from 0.01 wt% to 5 wt%, or from 0.1 wt% to 4 wt%, or from 0.2 wt% to 3 wt%, or from 0.5 wt% to 2 wt% of a phenolic antioxidant, based on the total weight of the lubricating composition.

[0087] Sulfurized olefins are well-known commercial materials, and those sulfurized olefins that are substantially free of nitrogen (i.e., free of nitrogen functional groups) are readily available. The nature of the olefin compounds that can be sulfurized is diverse. They contain at least one olefin double bond, which is defined as a non-aromatic double bond; i.e., a double bond connecting two aliphatic carbon atoms. These materials typically have thioether bonds containing from 1 to 10 sulfur atoms, such as from 1 to 4 or 1 or 2 sulfur atoms.

[0088] The additional (such as ashless) antioxidants described above can be used alone or in combination. In certain embodiments, two or more different additional antioxidants can be used in combination such that there is at least 0.1 wt% of each of at least two antioxidants, and optionally the combined amount of the additional antioxidants is from 0.5 wt% to 5 wt% based on the total weight of the lubricating composition. In certain embodiments, there can be from 0.25 wt to 3 wt of each additional antioxidant based on the total weight of the lubricating composition.

[0089] In certain embodiments, the lubricating composition described herein may comprise a molybdenum compound. The molybdenum compound can be molybdenum dialkyldithiophosphate, molybdenum dithiocarbamate, an amine salt of a molybdenum compound, or a mixture thereof. The molybdenum compound can provide from 0 ppm to 1000 ppm, or from 5 ppm to 1000 ppm, or from 10 ppm to 750 ppm, or from 5 ppm to 300 ppm, or from 20 ppm to 250 ppm, or from 350 ppm to 900 ppm of molybdenum based on the total lubricating composition.

[0090] The lubricating composition described herein may further comprise a polymeric viscosity modifier. It is known that polymeric viscosity modifiers can be functionalized or derivatized; functionalized polymeric viscosity modifiers are also known as dispersant viscosity modifiers (DVM). The polymeric viscosity modifier can be an olefin (co)polymer, a poly(meth)acrylate (PMA), or a mixture thereof. In certain embodiments, the polymeric viscosity modifier is an olefin (co)polymer.

[0091] The olefin polymer can be derived from isobutene or isoprene. In certain embodiments, the olefin polymer is made from ethylene and C3-C 10Preparation of higher olefins within the range of α-olefins; for example, olefin polymers can be prepared from ethylene and propylene.

[0092] In certain embodiments, the olefin polymer can be 15 mol% to 80 mol% (such as 30 mol% to 70 mol%) of ethylene and 20 mol% to 85 mol% (such as 30 mol% to 70 mol%) of C3-C 10 polymers of monoolefins (such as propylene). Terpolymer variants of olefin copolymers can also be used and can contain up to 15 mol% of non-conjugated dienes or trienes. The non-conjugated diene or triene can have 5 to 14 carbon atoms. The non-conjugated diene or triene monomer can be characterized by the presence of vinyl groups in the structure and can include cyclic and bicyclic compounds. Representative dienes include 1,4-hexadiene, 1,4-cyclohexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 1,5-heptadiene, and 1,6-octadiene.

[0093] In certain embodiments, the olefin copolymer can be a copolymer of ethylene, propylene, and butene. The polymer can be prepared by polymerizing a mixture of monomers including ethylene, propylene, and butene. These polymers can be referred to as copolymers or terpolymers. The terpolymer can contain 5 mol% to 20 mol%, or 5 mol% to 10 mol% of structural units derived from ethylene; 60 mol% to 90 mol%, or 60 mol% to 75 mol% of structural units derived from propylene; and 5 mol% to 30 mol%, or 15 mol% to 30 mol% of structural units derived from butene. Butene can include any isomer or mixture thereof, such as n-butene, isobutene, or a mixture thereof. Butene can include 1-butene. Commercial sources of butene can include 1-butene as well as butene-2 and butadiene. Butene can include a mixture of 1-butene and isobutene, where the weight ratio of 1-butene to isobutene is about 1:0.1 or less. Butene can include 1-butene and be free or substantially free of isobutene.

[0094] In certain embodiments, the olefin copolymer can be a copolymer of ethylene and butene. The polymer is prepared by polymerizing a monomer mixture containing ethylene and butene, where the monomer composition is free or substantially free of propylene monomer (i.e., contains less than 1 wt% of intentionally added propylene monomer). The copolymer can contain 30 mol% to 50 mol% of structural units derived from butene; and 50 mol% to 70 mol% of structural units derived from ethylene. Butene can include a mixture of 1-butene and isobutene, where the weight ratio of 1-butene to isobutene is about 1:0.1 or less. Butene can include 1-butene and be free or substantially free of isobutene.

[0095] Useful olefin polymers, such as ethylene-α-olefin copolymers, have a number average molecular weight of from 4,500 g / mol to 500,000 g / mol (e.g., from 5,000 g / mol to 100,000 g / mol, or from 7,500 g / mol to 60,000 g / mol, or from 8,000 g / mol to 45,000 g / mol).

[0096] In certain embodiments, the lubricating compositions described herein may include a poly(meth)acrylate polymer viscosity modifier. As used herein, the term “(meth)acrylate” and its cognates mean methacrylate and / or acrylate.

[0097] In certain embodiments, the poly(meth)acrylate polymer is prepared from a monomer mixture comprising (meth)acrylate monomers having alkyl groups of different lengths. The (meth)acrylate monomers may contain an alkyl group that is a straight or branched chain group. The alkyl group may contain from 1 to 24 carbon atoms, such as from 1 to 20 carbon atoms.

[0098] The poly(meth)acrylate polymer may be formed from monomers derived from saturated alcohols such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-methylpentyl (meth)acrylate, 2-propylheptyl (meth)acrylate, 2-butyl octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, 2-tert-butylheptyl (meth)acrylate, 3-isopropylheptyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth)acrylate, 2-methyldodecyl (meth)acrylate, tridecyl (meth)acrylate, 5-methyltridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, 2-methylhexadecyl (meth)acrylate, heptadecyl (meth)acrylate, 5-isopropylheptadecyl (meth)acrylate, 4-tert-butyloctadecyl (meth)acrylate, 5-ethyloctadecyl (meth)acrylate, 3-isopropyloctadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, (meth)acrylates derived from unsaturated alcohols such as oleyl (meth)acrylate, and / or (meth)acrylate cycloalkyl esters such as 3-vinyl-2-butylcyclohexyl (meth)acrylate or borneol (meth)acrylate.

[0099] Other examples of monomers include (meth)acrylic acid alkyl esters having groups derived from long-chain alcohols, which can be obtained, for example, by reacting (meth)acrylic acid (by direct esterification) or methyl (meth)acrylate (by transesterification) with long-chain fatty alcohols, in which reaction a mixture of esters (such as (meth)acrylates) with alcohol groups of various chain lengths is typically obtained. These fatty alcohols include Oxo 7911, Oxo 7900 and Oxo 1100; those from ICI 79; those from Sasol 1620, 610 and 810; those from Ethyl Corporation 610 and 810; those from Shell AG 79, 911 and 25L; those from Condea Augusta, Milan 125; those from Cognis and and those from Ugine Kuhlmann 7-11 and 91.

[0100] In certain embodiments, the poly(meth)acrylate polymer comprises a dispersant monomer; the dispersant monomer includes those monomers that can copolymerize with the (meth)acrylate monomer and contain one or more heteroatoms in addition to the carbonyl group of the (meth)acrylate. The dispersant monomer can contain a nitrogen-containing group, an oxygen-containing group, or a mixture thereof.

[0101] The nitrogen-containing compound can be (meth)acrylamide or a nitrogen-containing (meth)acrylate monomer. Examples of suitable nitrogen-containing compounds include N,N-dimethylacrylamide, N-vinylcarboxamide (such as N-vinylformamide), vinylpyridine, N-vinylacetamide, N-vinylpropionamide, N-vinylhydroxyacetamide, N-vinylimidazole, N-vinylpyrrolidone, N-vinylcaprolactam, dimethylaminoethyl acrylate (DMAEA), dimethylaminoethyl methacrylate (DMAEMA), dimethylaminobutyl acrylamide, dimethylaminopropyl methacrylate (DMAPMA), dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, dimethylaminoethyl acrylamide, or a mixture thereof.

[0102] The dispersant monomer may be present in an amount of up to 5 mol% of the monomer composition of the (meth)acrylate polymer. In one embodiment, the poly(meth)acrylate is present in the polymer composition in an amount of 0 mol% to 5 mol%, or 0.5 mol% to 4 mol%, or 0.8 mol% to 3 mol%.

[0103] In certain embodiments, the poly(meth)acrylate is free or substantially free of the dispersant monomer.

[0104] In certain embodiments, the poly(meth)acrylate comprises a block copolymer or a gradient block copolymer. The block copolymer is formed from a monomer mixture comprising one or more (meth)acrylate monomers, wherein, for example, a first (meth)acrylate monomer forms a discrete block of the polymer that is linked to a second discrete block of the polymer formed from a second (meth)acrylate monomer. While the block copolymer has substantially discrete blocks formed from the monomers in the monomer mixture, the gradient block copolymer may consist of a relatively pure first monomer at one end and a relatively pure second monomer at the other end, with the middle of the gradient block copolymer being more of a gradient composition of the two monomers.

[0105] In certain embodiments, the poly(meth)acrylate polymer (P) may be a block copolymer or a gradient block copolymer that comprises at least one polymer block (B1) that is insoluble or substantially insoluble in the base oil and a second polymer block (B2) that is soluble or substantially soluble in the base oil.

[0106] In certain embodiments, the poly(meth)acrylate polymer may have a structure selected from linear, branched, hyperbranched, crosslinked, star (also referred to as "radial") or combinations thereof. Star or radial refers to a multi-arm polymer. Such polymers include (meth)acrylate-containing polymers having three or more arms or branches, which in some embodiments may contain at least 20 (such as at least 50, 100, 200, 350, 500 or 1000) carbon atoms. The arms are typically attached to a polyvalent organic moiety that serves as a "core" or "coupling agent". The multi-arm polymer may be referred to as a radial or star polymer or even a "comb" polymer or a polymer having multiple arms or branches in other ways as described herein.

[0107] Random, block, or otherwise linear poly(meth)acrylates can have a weight-average molecular weight (Mw) of from 1,000 Daltons to 400,000 Daltons, from 1,000 Daltons to 150,000 Daltons, or from 15,000 Daltons to 100,000 Daltons. In certain embodiments, the poly(meth)acrylate can be a linear block copolymer having an Mw of from 5,000 Daltons to 40,000 Daltons or from 10,000 Daltons to 30,000 Daltons.

[0108] Radial, crosslinked, or star copolymers can be derived from linear random or diblock copolymers having the molecular weights described above. The star polymers can have a weight-average molecular weight of from 10,000 Daltons to 1,500,000 Daltons, or from 40,000 Daltons to 1,000,000 Daltons, or from 300,000 Daltons to 850,000 Daltons.

[0109] The lubricating compositions described herein can comprise from 0.05 wt% to 2 wt%, or from 0.08 wt% to 1.8 wt%, or from 0.1 wt% to 1.2 wt% of one or more polymer viscosity modifiers as described herein, based on the total weight of the lubricating composition.

[0110] In certain embodiments, the polymer viscosity modifier can include DVM. DVM can be present in an amount of from 0 wt% to 5 wt%, or from 0 wt% to 4 wt%, or greater than 0 wt% to 5 wt%, or greater than 0 wt% to 4 wt%, or from 0.05 wt% to 2 wt%, based on the total weight of the lubricating composition.

[0111] Suitable DVMs include: functionalized polyolefins, such as ethylene-propylene copolymers that have been functionalized with acylating agents such as maleic anhydride and amines; poly(meth)acrylates functionalized with amines; or esterified styrene-maleic anhydride copolymers reacted with amines. Descriptions of DVMs are provided in WO 2006 / 015130 A1 or US 4,863,623, US 6,107,257, US 6,107,258, and US 6,117,825. In certain embodiments, the DVM can include those described in US 4,863,623 (see column 2, lines 15 to column 3, line 52) or WO 2006 / 015130 A1 (see paragraph

[0008] on page 2 and the preparation examples as described in paragraphs

[0065] to

[0073] ).

[0112] Suitable amines for forming the DVM include aliphatic amines, aliphatic polyamines, aromatic amines, aromatic polyamines, polyether compounds, polyetheramines (such as those described above), and combinations thereof. Aliphatic polyamines can be ethylenepolyamines, propylenepolyamines, butylenepolyamines, or mixtures thereof. In certain embodiments, the aliphatic polyamine can be an ethylenepolyamine. In certain embodiments, the aliphatic polyamine can be ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine residues, or mixtures thereof.

[0113] Aromatic amines can be 4-aminodiphenylamine (ADPA) (also known as N-phenylphenylenediamine), derivatives of ADPA (as described in US2011 / 0306528 A1 and US 2010 / 0298185 A1), nitroaniline, aminocarbazole, aminoindazolinone, aminopyrimidine, 4-(4-nitrophenylazo)aniline, or combinations thereof. In certain embodiments, the DVM can be a derivative of an aromatic amine, optionally wherein the aromatic amine has at least three non-consecutive aromatic rings.

[0114] The DVM can be a derivative of a polyetheramine or a polyether polyamine. Suitable polyetheramine compounds contain at least one ether unit and can be chain-terminated by at least one amine moiety. Polyether polyamines can be based on polymers derived from C2-C6 epoxides (such as ethylene oxide, propylene oxide, and butylene oxide). Examples of commercially available polyether polyamines are sold under the trade name and are commercially available from Huntsman Corporation.

[0115] In certain embodiments, the lubricating compositions described herein can further comprise a friction modifier. Examples of suitable friction modifiers include long-chain fatty acid derivatives of amines, fatty esters, or epoxides; fatty imidazolines, such as condensation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkyl phosphates; fatty alkyl tartrates; fatty alkyl tartrimides; and / or fatty alkyl tartramides. As used herein, the term fatty can mean having a C8-C 22 straight-chain alkyl group.

[0116] These friction modifiers can also encompass materials such as sulfurized fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil, and / or monoesters of polyols and aliphatic carboxylic acids.

[0117] In certain embodiments, the friction modifier can include at least one of the following: long-chain fatty acid derivatives of amines, long-chain fatty esters, or long-chain fatty epoxides; fatty imidazolines; amine salts of alkyl phosphates; fatty alkyl tartrates; fatty alkyl tartrimides; or fatty alkyl tartramides.

[0118] In certain embodiments, the friction modifier can be a long-chain fatty acid ester. In certain embodiments, the long-chain fatty acid ester can be a monoester, diester, or a mixture thereof, and in certain embodiments, the long-chain fatty acid ester can be a triglyceride. In certain embodiments, the friction modifier can be glycerol monooleate.

[0119] The friction modifier can be present in an amount of from 0 wt% to 6 wt%, or 0.05 wt% to 4 wt%, or 0.1 wt% to 2 wt% based on the total weight of the lubricating composition.

[0120] Other performance additives (such as corrosion inhibitors, including those described in WO 2006 / 047486 A1), octyloctanamide, dodecenyl succinic acid or anhydride, and condensation products of fatty acids (such as oleic acid) with polyamines can be present in the lubricating compositions described herein. In certain embodiments, the corrosion inhibitor includes (a registered trademark of The Dow Chemical Company) corrosion inhibitor. The corrosion inhibitor can be a homopolymer or copolymer of propylene oxide. The corrosion inhibitor is described in more detail in the product manual published by The Dow Chemical Company (Form No. 118-01453-0702AMS, entitled "SYNALOX Lubricants, High-Performance Polyglycols for Demanding Applications").

[0121] The lubricating compositions described herein can also contain: metal deactivators, which include derivatives of benzotriazole (usually tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, and / or 2-alkyldithiobenzothiazole; foam inhibitors, which include copolymers of ethyl acrylate and 2-ethylhexyl acrylate, and / or copolymers of ethyl acrylate, 2-ethylhexyl acrylate, and vinyl acetate; demulsifiers, which include trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides, and / or (ethylene oxide / propylene oxide) polymers; and pour point depressants, which include esters of maleic anhydride-styrene, polymethacrylates, polyacrylates, and / or polyacrylamides.

[0122] Suitable pour point depressants can include polyalphaolefins, esters of maleic anhydride-styrene, poly(meth)acrylates, polyacrylates, and / or polyacrylamides.

[0123] In certain embodiments, the lubricating compositions described herein can have a composition as described in the table below:

[0124]

[0125] The benzazepines described herein compounds can be used in lubricating compositions formulated to lubricate mechanical devices. Such mechanical devices include, but are not limited to, internal combustion engines (e.g., spark-ignition internal combustion engines or compression-ignition internal combustion engines) and driveline devices (such as automatic transmissions, manual transmissions, dual-clutch transmissions, or axles or differentials). Compression-ignition internal combustion engines can include heavy-duty diesel engines.

[0126] Diesel engines can be classified by their gross vehicle weight rating (GVWR). GVWR includes the maximum rated weight of the vehicle and its cargo (including passengers). GVWR can be applied to trucks or trailers, but not to a combination of both, which is a separate rating called the gross combination weight rating (GCWR). The GVWRs of various classes of diesel engines are listed in the table below:

[0127] Category GVWR (lbs) Class 1 0 lbs - 6,000 lbs Class 2A 6,001 lbs - 8,500 lbs Class 2B 8,501 lbs - 10,000 lbs Class 3 10,001 lbs - 14,000 lbs Class 4 14,001 lbs - 16,000 lbs Class 5 16,001 lbs - 19,500 lbs Class 6 19,5001 lbs - 26,000 lbs Class 7 26,001 lbs - 33,000 lbs Class 8 Over 33,000 lbs

[0128] Light-duty vehicles are classified as those belonging to Classes 1 to 3. Class 2A vehicles are commonly referred to as "light" vehicles, and Class 2B vehicles are commonly referred to as "light heavy-duty" vehicles. Medium-duty vehicles are those belonging to Classes 4 to 6. Heavy-duty vehicles are those classified as Classes 7 and 8.

[0129] The lubricating compositions described herein having an ashless antioxidant comprising the disclosed benzazepines compounds can be used as lubricants for diesel engines in all Classes 1 to 8 engines. In certain embodiments, the lubricating composition is used in Class 8 engines. Examples

[0130] The subject matter disclosed herein can be better understood with reference to the following examples, which are provided only to further illustrate the subject matter disclosed herein. The exemplary examples should not be construed as limiting the subject matter in any way.

[0131] A series of benzazepines were evaluated for their ability to reduce the oxidative degradation of lubricating compositions. The procedures for alkylating selected commercially available benzazepines are described below, and examples of suitable (di)benzazepines compounds are summarized below (Table 1).

[0132] Example A (2,8-dinonyl-10,11-dihydro-5H-dibenzo[b,f]azepine ):A 1 L four-necked flask was equipped with an overhead stirrer, a nitrogen under-surface tube (providing 0.1 cfh N2), and a Dean-Stark water separator with a water condenser at the top. Propylene trimer (182 g, 1.46 mol) was added to the flask. The flask was heated to 85 °C, and then 10,11-dihydro-5H-dibenz[b,f]azepine (95 g, 487 mmol) was added to the flask and slurried. The reaction was further heated to 100 °C, and then acidic clay (28.5 g) was added. The reaction was heated to reflux at 150 °C and maintained for 12 hours. The reaction mixture was filtered through diatomaceous earth, and then the residual olefins were removed at 170 °C. The reaction mixture was filtered again to obtain the product in the form of a viscous yellow oil (91.1 g, 41.8%). %N ~ 3.4%, TBN ~ 125 mg KOH / gram of material.

[0133] Example B (2,8-bis(4,6-dimethylheptan-2-yl)-5H-dibenz[b,f]azepine ):A 1 L four-necked flask was equipped with an overhead stirrer, an N2 line, a thermocouple well, and a Friedrich condenser. 5H-Dibenz[b,f]azepine (100 g, 512 mmol) and acetic anhydride were added to the flask and heated to 125 °C. After 4 hours, the volatiles were removed by vacuum stripping. Propylene trimer (196 g, 1.55 mol) was added to the flask, and the material was heated to 80 °C. Then aluminum trichloride was added and the reaction was heated to 150 °C and maintained for 9 hours. The reaction was cooled to 80 °C and 10 g of water was slowly added, followed by 170 g of a 45% KOH solution (aqueous). The mixture was heated and maintained at 110 °C for 7 hours, and then the mixture was phase-separated. The aqueous layer was drained and the organic layer was stripped to remove excess propylene trimer. Upon cooling, the product solidified into a brown solid (113 g, 93%). %N ~ 5.9%.

[0134] The following Tables 1A and 1B provide exemplary benzazepines according to the subject matter of the present invention, the preparation of which is similar to Example A / Example B above, with reference to one of the following Structures I or II (in Table 1A, (B) refers to a branched hydrocarbon group and (L) refers to a straight-chain hydrocarbon group): compounds, the preparation of which is similar to the above Example A / Example B, with reference to one of the following Structures I or II (in Table 1A, (B) refers to a branched hydrocarbon group and (L) refers to a straight-chain hydrocarbon group):

[0135]

[0136] Table 1A

[0137] Structure Example X <![CDATA[R1]]> <![CDATA[R2]]> <![CDATA[R3]]> <![CDATA[R4]]> I A <![CDATA[-CH2-]]> <![CDATA[-C9H 19 (B)]]> -H <![CDATA[-C9H 19 (B)]]> -H II B -CH- <![CDATA[-C9H 19 (B)]]> -H <![CDATA[-C9H 19 (B)]]> -H I C <![CDATA[-CH2-]]> <![CDATA[-C 10 H 21 (L)]]> -H <![CDATA[-C 10 H 21 (L)]]> -H I D <![CDATA[-CH2-]]> <![CDATA[-C9H 19 (B)]]> -H <![CDATA[-C9H 19 (B)]]> <![CDATA[-CH2CH=CH2]]> I E <![CDATA[-CH2-]]> <![CDATA[-C9H 19 (B)]]> <![CDATA[-C9H 19 (B)]]> <![CDATA[-C9H 19 (B)]]> -H I F <![CDATA[-CH2-]]> <![CDATA[-C9H 19 (B)]]> -H <![CDATA[-C9H 19 (B)]]> <![CDATA[-CH3]]> I G <![CDATA[-CH2-]]> <![CDATA[-C 12 H 25 (B)]]> -H <![CDATA[-C 12 H 25 (B)]]> -H II H -CH- <![CDATA[-C 12 H 25 (B)]]> -H <![CDATA[-C 12 H 25 (B)]]> -H I I -NH- <![CDATA[-C9H 19 (B)]]> -H <![CDATA[-C9H 19 (B)]]> -H I J -O- <![CDATA[-C9H 19 (B)]]> -H <![CDATA[-C9H 19 (B)]]> -H II K -N- <![CDATA[-C9H 19 (B)]]> -H <![CDATA[-C9H 19 (B)]]> -H

[0138] Table 1B

[0139]

[0140]

[0141] Lubricating compositions: A series of 5W-30 lubricating compositions were prepared with various benzazepine compounds described herein and conventional crankcase additives such as ashless polyisobutenyl succinimide dispersants, overbased alkaline earth metal detergents, zinc dialkyldithiophosphate (ZDDP), additional ashless antioxidants, polymeric viscosity modifiers, and other common additives as shown in Table 2.

[0142] Table 2 1

[0143]

[0144] *Calculated value

[0145] 1. Unless otherwise specified, all treatment rates are oil-free

[0146] 2. Polyisobutenyl succinimide (TBN 26 mg KOH / g) prepared from highly vinylidene PIB

[0147] 3. Borated polyisobutenyl succinimide (TBN 27 mg KOH / g; 0.8% B) prepared from highly vinylidene PIB

[0148] 4. Overbased magnesium alkylbenzene sulfonate (TBN 700 mg KOH / g)

[0149] 5. Overbased calcium alkylsalicylate (TBN 300 mg KOH / g)

[0150] 6. Other additives include pour point depressants and foam inhibitors

[0151] Antioxidant properties were evaluated by measuring the oxidation induction time using pressure differential scanning calorimetry (CEC L85), forming deposits using the Komatsu heat pipe test (KHT), MHT TEOST (ASTM D7097), microcoking test (MCT), and oxidation stability in the presence of biodiesel (according to ACEA 2016: CEC L109). The relative performance of the azepine derivatives in the tests was compared with formulations without antioxidants and with alkylated diphenylamine as shown in Table 3.

[0152] ​​The MCT involves placing 0.6 mL of a lubricating composition in a groove of an aluminum alloy plate that is heated at one end (hot spot) and regulated at the other end (cold spot). At the end of the test, the deposit formation is determined and scored on a scale of 1 - 10 according to the CEC M - 02 - A - 78 operating procedure. A higher score indicates better deposit performance.

[0153] The KHT measures the tendency of a lubricating composition to form deposits under high - temperature conditions. In KHT, a higher score means better deposit control performance. The KHT test uses a heated glass tube through which a sample lubricating composition (5 mL total sample) is pumped at a rate of 0.31 mL per hour for 16 hours with an air flow of 10 mL per minute. At the end of the test, the deposits in the glass tube are scored on a scale of 0 (very heavy deposit layer) to 10 (no deposit layer).

[0154] Table 3

[0155]

[0156] #imgpt93#

[0157] Unless otherwise specified in the examples or explicitly stated or required by the context, all numerical quantities in this specification that specify amounts of substances, reaction conditions, molecular weights, numbers of carbon atoms, etc. should be understood to be modified by the word "about". As used herein, the term "about" means that the value of a given quantity is within ±20% of the specified value. In other embodiments, the value is within ±15% of the specified value. In other embodiments, the value is within ±10% of the specified value. In other embodiments, the value is within ±5% of the specified value. In other embodiments, the value is within ±2.5% of the specified value. In other embodiments, the value is within ±1% of the specified value. In other embodiments, the value is within the range of the explicitly described value, and based on the disclosure provided herein, the explicitly described value will be understood by one of ordinary skill in the art to behave substantially similarly to a composition including the literal amounts described herein.

[0158] It should be understood that the upper and lower limits of the quantities, ranges, and ratios described herein can be combined independently, and any quantity within the disclosed range is considered to provide the minimum or maximum of a narrower range in an alternative embodiment (of course, provided that the minimum amount of the range must be less than the maximum amount of the same range). Similarly, the ranges and amounts of each element of the subject matter disclosed herein can be used in conjunction with the ranges or amounts of any other element.

[0159] The present disclosure is not limited to the specific embodiments described in this application, which are intended to illustrate various aspects. Many modifications and variations can be made without departing from the spirit and scope of the invention, which will be apparent to those skilled in the art. In addition to those enumerated herein, functionally equivalent methods and components within the scope of the present disclosure will be apparent to those skilled in the art based on the foregoing description. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is limited only by the terms of the appended claims and the full scope of equivalents thereof as given by such claims. It should be understood that the present disclosure is not limited to specific methods, reagents, compounds, or compositions, which can of course vary. It should also be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

Claims

1. A lubricating composition, the lubricating composition comprising an oil having lubricating viscosity and a benzazepine compound, wherein the benzazepine compound includes a dibenzazepine compound, the dibenzazepine compound is represented by at least one of the following general formulas IIA or IIB: wherein R 1 , R 2 and R 3 are each independently hydrogen or a hydrocarbyl group having 1 to 24 carbon atoms; each X is independently O, S or NR 4 ; and R 4 is hydrogen or a hydrocarbyl group having 1 to 18 carbon atoms.

2. The lubricating composition according to claim 1, wherein the benzazepine compound is present in the lubricating composition in an amount of 0.1% to 5.0% by weight based on the total weight of the lubricating composition.

3. The lubricating composition according to claim 1, wherein the lubricating composition comprises at least 0.3% by weight of at least one additional lubricant additive, the additive comprising at least one of the following: an ashless polyisobutenyl succinimide dispersant, an overbased or neutral metal-based detergent, an antiwear agent, a polymeric viscosity modifier, or an ashless antioxidant different from benzazepine compounds.

4. The lubricating composition according to claim 2, wherein the lubricating composition comprises at least 0.3% by weight of at least one additional lubricant additive, the additive comprising at least one of the following: ashless polyisobutenyl succinimide dispersants, overbased or neutral metal-based detergents, antiwear agents, polymeric viscosity modifiers or ashless antioxidants different from benzazepine compounds.

5. The lubricating composition according to claim 3, wherein the ashless polyisobutenyl succinimide dispersant is present in the lubricating composition in an amount of 0.5% to 4.0% by weight based on the total weight of the lubricating composition.

6. The lubricating composition according to claim 4, wherein the ashless polyisobutenyl succinimide dispersant is present in the lubricating composition in an amount of 0.5% to 4.0% by weight based on the total weight of the lubricating composition.

7. The lubricating composition according to claim 3, wherein the metal-based detergent comprises at least one of a neutral alkaline earth metal detergent or an overbased alkaline earth metal detergent, in an amount of 0.2% to 15% by weight based on the total weight of the lubricating composition.

8. The lubricating composition according to claim 5, wherein the metal-based detergent comprises at least one of a neutral alkaline earth metal detergent or an overbased alkaline earth metal detergent, in an amount of 0.2% to 15% by weight based on the total weight of the lubricating composition.

9. The lubricating composition according to claim 7, wherein at least one of the neutral alkaline earth metal detergent or the overbased alkaline earth metal detergent comprises at least one of the following: an alkylbenzene sulfonate detergent, a sulfur-coupled phenate detergent, or an alkyl salicylate detergent.

10. The composition according to any one of claims 3 to 9, wherein at least one antiwear agent is present in an amount of 0.05% to 3% by weight based on the total weight of the lubricating composition.

11. The lubricating composition according to claim 10, wherein the at least one antiwear agent comprises a phosphorus-containing compound, and the amount of the phosphorus-containing compound is effective to deliver 200 ppm to 1200 ppm of phosphorus to the lubricating composition.

12. The lubricating composition according to claim 10, wherein the at least one antiwear agent comprises zinc dialkyldithiophosphate.

13. The lubricating composition according to claim 11, wherein the at least one antiwear agent comprises zinc dialkyldithiophosphate.

14. The lubricating composition according to claim 3, wherein the ashless antioxidant different from the benzazepine compound is present in an amount of 0.01% to 5% by weight based on the total weight of the lubricating composition.

15. The lubricating composition according to any one of claims 1 to 9, wherein the lubricating composition comprises less than 0.1% by weight of a diarylamine antioxidant.

16. The lubricating composition according to any one of claims 1 to 9, wherein the lubricating composition does not contain a diarylamine antioxidant.

17. The lubricating composition according to claim 1, wherein the benzazepine compound comprises at least one of the following: 5H-dibenz[b,f]azepine ; 10,11-dihydro-5H-dibenz[b,f]azepine ; or their hydrocarbyl-substituted derivatives.

18. A method of lubricating an internal combustion engine, the method comprising providing to the internal combustion engine a lubricating composition according to any one of claims 1 to 17.

19. A method of improving the antioxidant properties of a crankcase lubricant, wherein the method comprises lubricating the crankcase with a lubricating composition according to any one of claims 1 to 17.

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