Corrosion inhibitor compounds and compositions

Abstract

A compound having a structure according to Formula I wherein: A is a hydrocarbyl succinimide; n = 1 to 10; m = 0, 1 or 2; and R is a nitrogen-containing heterocyclic moiety

Description

T-12636-W001CORROSION INHIBITOR COMPOUNDS AND COMPOSITIONSFILED OF THE INVENTION

[0001] The present invention relates to compounds and methods of making them, lubricating oil compositions and fuel compositions comprising such compounds, their use in corrosion inhibition and methods of inhibiting corrosion.BACKGROU ND OF THE INVENTION

[0002] Corrosion is a key issue in many types of engines and machines, given the use of metals and metal alloys such as copper, lead and steel for many of their components. In the automotive industry, corrosion has been and remains a concern in conventional gasoline or diesel internal combustion engines, even as alternative engine technologies and alternatively fueled engines are being developed. For example, hydrogen fueled, methanol fueled, or ammonia fueled engines, which typically operate at lower temperatures, may produce or retain more water compared to conventional gasoline or diesel fueled internal combustion engines which may render metal components more susceptible to corrosion. In hybrid electric vehicles, the engine continually goes through stop-start cycles during normal operation. Therefore, the engine in a hybrid vehicle typically operates for short periods of time, which can lead to the problem of accumulating water (and sometimes fuel) in, for example, the engine oil, as the engine is less able to evaporate water and fuel through prolonged use. Further, there has been a move toward the electrification of vehicle drivelines, either in the form of full electric vehicles, hybrid vehicles or even internal combustion vehicles. While typical transmission oils are formulated to prevent or reduce corrosion of metal parts submerged in the oil, corrosion remains a problem for metal surfaces and electrical equipment that are not submerged. Updates to transmissions have led to more sensors being added that reside in the oil's vapor space. Corrosive species in the vapor phase may interact with these electrical parts and cause corrosion to these elements. Corrosion inhibitory performance for non-submerged electronics is not currently encompassed in vehicle lubricant specifications, but it is anticipated that vapor phase corrosion performance will become increasingly important, particularly with respect to sensitive electronics where even slightT-12636-W001 corrosion can interrupt the function of the electronics. Corrosion has been studied in the vapor phase, however the corrosion phenomena that have thus far been described are primarily due to atmospheric corrosion (e.g. based on humidity, oxidation and salts), while the corrosion with respect to electronics in the headspace above an automotive lubricant will have significantly different set of environmental contributors (e.g., low humidity, low oxygen, volatile lubricant and lubricant degradation products).

[0003] There is therefore a need to develop further improved compounds for corrosion inhibition, which can be utilized in a variety of functional fluids and function in both the oil / fuel phase and the vapor phase.SUMMARY OF THE INVENTION

[0004] In a first aspect of the present invention, there is provided a compound having a structure according to Formula IFormula I wherein: A is a hydrocarbyl succinimide; n = 1 to 10; m = 0, 1 or 2; and R is a nitrogen-containing heterocyclic moiety.

[0005] The nitrogen-containing heterocyclic moiety may be or may comprise a five-membered heterocycle which contains 2, 3 or 4 N atoms.T-12636-W001

[0006] The five-membered ring may be a diazole, triazole, or tetrazole, or isomers thereof.

[0007] R may have a structure according to Formula IIFormula II wherein X is CH or N, Y is C, CH or N, Z is C, CH or N and W is absent or if present, is an aromatic ring, with the proviso that when W is present, Y and Z are C.

[0008] R may be selected fromFormula Ila Formula lib Formula lie Formula lid Formula HeT-12636-W001Formula llj Formula Ilk , and wherein R1is C1-C6 alkyl.

[0009] The hydrocarbyl succinimide may include a polyisobutenyl (PIB) group or an ethylene- propylene copolymer group.10010] The hydrocarbyl group of the hydrocarbyl succinimide may have a number average molecular weight, Mn, of from about 450 to 5000, for example, from about 500 to about 2500, or from about 750 to about 2000, or from about 750 to about 1500, or from about 900 to about 1400.

[0011] The compound may beT-12636-W001T-12636-W001

[0012] In a second aspect of the present invention there is provided a lubricating oil composition comprising a compound according to the first aspect.

[0013] The lubricating oil composition may be an engine lubricant, a transmission oil, a gear oil, a hydraulic fluid, a brake fluid, or a cooling fluid.

[0014] The lubricating oil may be suitable for use in an electric vehicle or hybrid electric vehicle.

[0015] The lubricating oil composition may comprise from about 0.01 wt. % to about 20.0 wt. % of the compound.

[0016] The lubricating oil composition may comprise one or more additives selected from a detergent, dispersant, antioxidant, viscosity modifier, antiwear / extreme-pressure agent, friction modifier, corrosion inhibitor other than the compound according to the first aspect, pour point depressant and foam inhibitor, optionally wherein the total amount of additives comprises no more than about 50 wt. % of the total weight of the lubricating oil composition, for example, from about 1.0 to about 25.0 wt. %.

[0017] In a third aspect of the present invention, there is provided a fuel composition comprising a compound according to the first aspect.

[0018] The fuel may be hydrogen, ammonia, natural gas, gasoline or diesel.

[0019] The fuel composition may comprise from about 0.01 wt. % to about 20.0 wt. % of the compound, based on the total weight of the fuel composition.

[0020] In a fourth aspect of the present invention, there is provided a use of a compound according to the first aspect as a corrosion inhibitor.

[0021] In a fifth aspect of the present invention, there is provided the use of a compound according to the first aspect as a corrosion inhibitor in a lubricating oil composition, for example, a functional automative fluid, or a fuel composition.

[0022] In a sixth aspect of the present invention, there is provided a use of a compound according to the first aspect to inhibit corrosion in a hydrogen, natural gas or ammonia fueled internalT-12636-W001 combustion engine, wherein the compound is present in a lubricating oil composition, for example, a functional automotive fluid, or fuel composition used to operate the engine.

[0023] In a seventh aspect of the present invention, there is provided a use of a compound according to the first aspect to inhibit corrosion in an electric vehicle or hybrid electric vehicle, wherein the compound is present in a lubricating oil composition, for example, a functional automotive fluid, used to operate the electric vehicle or hybrid electric vehicle.

[0024] In an eighth aspect of the present invention, there is provided a use of a compound according to the first aspect to inhibit corrosion in a gasoline or diesel fueled internal combustion engine, wherein the compound is present in a lubricating oil composition, for example, a functional automotive fluid, or fuel composition used to operate the engine.

[0025] In a ninth aspect of the present invention, there is provided a method for inhibiting corrosion in a hydrogen, natural gas or ammonia fueled internal combustion engine comprising operating the engine with a lubricating oil composition, for example, a functional automotive fluid, or fuel composition according to the second or third aspect.

[0026] In a tenth aspect of the present invention, there is provided a method for inhibiting corrosion in an electric vehicle or hybrid electric vehicle comprising operating the electric vehicle or hybrid electric vehicle with a lubricating oil composition, for example, a functional automotive fluid, according to the second aspect.

[0027] In an eleventh aspect of the invention, there is provided a method for inhibiting corrosion in a gasoline or diesel fueled internal combustion engine comprising operating the engine with a lubricating oil composition, for example, a functional automotive fluid, or fuel composition according the second or third aspect.

[0028] In a twelfth aspect of the present invention, there is provided a use or method according to any one of the fourth aspect to the eleventh aspect, wherein the lubricating oil composition or fuel composition is according to the second or third aspect.T-12636-W001

[0029] In a thirteenth aspect of the present invention, there is provided a use or method according to any one of the fourth aspect to the twelfth aspect, wherein the corrosion is metal corrosion, for example, copper, lead and / or steel corrosion, or corrosion of electrical components.

[0030] The corrosion may be copper or lead corrosion, optionally wherein copper and / or lead corrosion is reduced by at least 25 % compared to a directly comparable lubricating oil or fuel composition that does not contain the compound, as determined in accordance with the modified ASTM-D6594 test method described in the description.

[0031] In a fourteenth aspect of the present invention, there is provided a method of making a compound according to the first aspect, comprising reacting a polyamine hydrocarbyl bissuccinimide, an aldehyde and a nitrogen-containing heterocycle, for example, wherein the polyamine hydrocarbyl bis- succinimide is heated to at least 50 °C in a suitable solvent over a first period of time, followed by addition of the aldehyde and nitrogen-containing heterocycle to form a reaction mixture, and heating the reaction mixture at a temperature of at least 50 °C for a second period of time.

[0032] The aldehyde may be paraformaldehyde and the nitrogen-containing heterocycle may be a diazole, triazole, tetrazole, or isomers thereof, such as, 1, 2, 4-triazole, imidazole, pyrazole and the like.DETAI LED DESCRIPTION OF TH E I NVENTION

[0033] To facilitate the understanding of the subject matter disclosed herein, a number of terms, abbreviations or other shorthand as used herein are defined below. Any term, abbreviation or shorthand not defined is understood to have the ordinary meaning used by a skilled artisan contemporaneous with the submission of this application.

[0034] As used herein, the following terms have the following meanings, unless expressly stated to the contrary. In this specification, the following words and expressions, if and when used, have the meanings given below.T-12636-W001

[0035] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of features is not necessarily limited only to those features but may include other features not expressly listed or other features that are inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" refers to an inclusive-or and not to an exclusive-or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

[0036] The use of "a" or "an" is employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the embodiments of the disclosure. This description should be read to include one or at least one and the singular also includes the plural, or vice versa, unless it is clear that it is meant otherwise. The term "averaged," when referring to a value, is intended to mean an average, a geometric mean, or a median value. Group numbers corresponding to columns within the Periodic Table of the elements use the "New Notation" convention as seen in the CRC Handbook of Chemistry and Physics, 81st Edition (2000-2001).

[0037] All percentages reported are weight % on an active ingredient basis (i.e., without regard to carrier or diluent oil) unless otherwise stated.

[0038] The abbreviation "ppm" means parts per million by weight, based on the total weight of the lubricating oil composition or fuel composition.

[0039] The term "metal" refers to transition metals, post-transition metals, alkali metals, alkaline earth metals, metalloids, or mixtures thereof. Transition metals include any metal found in Groups 3-12 of the periodic table, including titanium, iron, copper, zinc, molybdenum, palladium, and platinum. Post-transition metals include aluminum, gallium, tin and lead. Alkali metals include lithium, sodium and potassium. Alkaline earth metals include calcium, barium, magnesium and strontium. Metalloids include silicon, germanium, and antimony.T-12636-W001

[0040] All ASTM standards referred to herein are the most current versions as of the filing date of the present application.

[0041] Unless otherwise specified, all percentages are in weight percent.Compound for use as corrosion inhibitors

[0042] In accordance with the first aspect, the compound has a structure according to Formula IFormula I wherein: A is a hydrocarbyl succinimide; n= 1 to 10; m = 0, 1 or 2; and R is a nitrogen-containing heterocyclic moiety.

[0043] The term "hydrocarbyl" refers to a moiety that includes both carbon and hydrogen atoms ("hydrocarbon"). Hydrocarbyl may refer to saturated or unsaturated moieties, aliphatic or aromatic moieties, cyclic or acyclic moieties, branched or unbranched moieties.

[0044] The term "heterocyclic" refers to a cyclic species which contains one or more heteroatoms, i.e., an atom which is not carbon (C) or hydrogen (H), for example, nitrogen (N), oxygen (O), or sulfur (S).

[0045] The term "nitrogen-containing heterocyclic" refers to a heterocyclic species which contains at least one nitrogen atom.T-12636-W001

[0046] The term "moiety" is used to signify a part or sub-structure of a molecule which contains atoms with a specific chemistry (for example, an alcohol or ester) and is typically used to describe larger, characteristic parts of a molecule. This term may be used interchangeably with the term "functional group".

[0047] The structure according to Formula I may have n = 1 to 9, or n = 1 to 8, or n =1 to 7, or n = 1 to 6, or n = 1 to 5, or n = 1 to 4, or n = 1 to 3, or n = 1 to 2. The structure according to Formula I may have n = 1, or n = 2, or n = 3, or n = 4, or n = 5, or n = 6, or n = 7, or n = 8, or n = 9 or n = 10. The structure according to Formula I may have n = 2.

[0048] The structure according to Formula I may have m = 0. The structure according to Formula I may have m = 1. The structure according to Formula I may have m = 2.

[0049] The structure according to Formula I may have n = 2 and m = 1. The structure according to Formula I may have n =2 and m = 0.

[0050] The nitrogen-containing heterocyclic moiety may comprise a five-membered heterocycle. The nitrogen-containing heterocyclic moiety may be a five-membered heterocycle.

[0051] The nitrogen-containing heterocyclic moiety may comprise a five-membered heterocycle which contains 2, 3 or 4 nitrogen (N) atoms. The nitrogen-containing heterocyclic moiety may comprise a five-membered heterocycle which contains 2 nitrogen (N) atoms. The nitrogen-containing heterocyclic moiety may comprise a five-membered heterocycle which contains 3 nitrogen (N) atoms. The nitrogen-containing heterocyclic moiety may comprise a five — membered heterocycle which contains 4 nitrogen (N) atoms. The nitrogen-containing heterocyclic moiety may be a five-membered heterocycle which contains 2, 3 or 4 nitrogen (N) atoms. The nitrogen-containing heterocyclic moiety may be a five-membered heterocycle which contains 2 nitrogen (N) atoms. The nitrogen-containing heterocyclic moiety may be a five — membered heterocycle which contains 3 nitrogen (N) atoms. The nitrogen-containing heterocyclic moiety may be a five-membered heterocycle which contains- 4 nitrogen (N) atoms.

[0052] The nitrogen-containing heterocyclic moiety may be aromatic. The nitrogen-containing heterocyclic moiety may be an aromatic five-membered heterocycle. The nitrogen-containingT-12636-W001 heterocyclic moiety may be unsubstituted. The nitrogen-containing heterocyclic moiety may be substituted. The nitrogen-containing heterocyclic moiety may have a fused ring. The nitrogen-containing heterocyclic moiety may comprise a five-membered heterocycle with a fused ring. The fused ring may be an aromatic fused ring. The nitrogen-containing heterocyclic moiety may be an unsubstituted, aromatic five-membered heterocycle. The nitrogen-containing heterocyclic moiety may be an aromatic five-membered heterocycle with a fused ring. The fused ring may be a 6-membered fused ring, wherein two of the member atoms are shared with the five-membered heterocyclic moiety. The fused ring may be unsubstituted. The fused ring may be substituted. The fused ring may be substituted with an alkyl group, for example a Cl to C6 alkyl group. The fused ring may be substituted with a methyl group, or an ethyl group, or a propyl group, or a butyl group, or a pentyl group, or a hexyl group. The fused ring may be substituted with a methyl group.

[0053] The five-membered ring may be a diazole, triazole or tetrazole. The term "diazole" refers to a five-membered ring species which comprises 3 carbon atoms and 2 nitrogen atoms. The term "triazole" refers to a five-membered ring species which comprises 2 carbon atoms and 3 nitrogen atoms. The term "tetrazole" refers to a five-membered ring species which comprises- 1 carbon atoms and 4 nitrogen atoms.

[0054] In Formula I, R may have the following structure:Formula II wherein X is CH or N, Y is C, CH or N, and Z is C, CH, or N. W may be present or absent. When present, W is a fused aromatic ring. When W is absent, X is CH or N, Y is CH or N, and Z is C, CH, or N. When W is present, X is CH or N, Y is C, and Z is C. W may be a fused 6-memebred aromatic ring. W may be a fused aromatic hydrocarbyl ring. W may be a fused 6-memebered aromaticT-12636-W001 hydrocarbyl ring, i.e., benzo-fused. The fused ring may be a 6-membered fused ring, wherein two of the member atoms are shared with the five-membered heterocyclic moiety, shown as Z and Y in Formula II. The fused ring may be substituted with a Ci-C3alkyl group, for example, a methyl group, or an ethyl group, or a propyl group, or a butyl group, or a pentyl group, or a hexyl group. The fused ring may be mono- or di-substituted with a Ci-C6alkyl group, for example, a methyl group, or an ethyl group, or a propyl group, or a butyl group, or a pentyl group, or a hexyl group. The fused ring may be mono-substituted with a methyl group, or an ethyl group, or a propyl group, or a butyl group, or a pentyl group, or a hexyl group. The fused ring may be mono-substituted with a methyl group.

[0055] In Formula I, R may be selected from:Formula lieT-12636-W001Formula Hi Formula Ilk, and wherein R1is C1-C6 alkyl.

[0056] The hydrocarbyl group of the hydrocarbyl succinimide may have a number average molecular weight, Mn, of from about 450 g / mol to 5000 g / mol, for example, from about 500 g / mol to about 2500 g / mol, or from about 750 g / mol to about 2000 g / mol, or from about 750 g / mol to about 1500 g / mol, or from about 900 g / mol to about 1400 g / mol. The hydrocarbyl group of the hydrocarbyl succinimide may have a number average molecular weight, Mn, of about 1000 g / mol. The hydrocarbyl group of the hydrocarbyl succinimide may have a number average molecular weight, Mn, of about 1300 g / mol.

[0057] The hydrocarbyl group of the succinimide may be or may comprise an aliphatic hydrocarbyl group. The hydrocarbyl group of the succinimide may be or may comprise an alkyl or alkenyl group. The alkyl or alkenyl may contain greater than about 40 carbon atoms, forT-12636-W001 example, from about greater than 40 carbon atoms up to about 400 carbon atoms, for example, up to about 350 carbon atoms, or up to about 300 carbon atoms, or up to about 250 carbon atoms, or up to about 200 carbon atoms, or up to about 100 carbon atoms. The hydrocarbyl group may be or may comprise a polymeric species. The hydrocarbyl group of the succinimide may be or comprise a polyolefin group such as polyisobutenyl group or an ethylene-propylene copolymer group. The hydrocarbyl group of the succinimide may be or may comprise a polyisobutenyl group.

[0058] The term "alkyl" refers to a saturated hydrocarbon species, which may be straight chained or branched. Unless specified, the alkyl is unsubstituted.

[0059] The term "alkenyl" refers to an unsaturated hydrocarbon species which contains at least one carbon-carbon double bond, and which may be straight chained or branched. Unless specified, the alkenyl is unsubstituted.

[0060] The hydrocarbyl succinimide may be a polyisobutenyl succinimide. The polyisobutenyl (PIB) group of the polyisobutenyl succinimide may have a number average molecular weight, Mn, of from about 450 g / mol to 5000 g / mol, for example, from about 500 g / mol to about 2500 g / mol, or from about 750 g / mol to about 2000 g / mol, or from about 750 g / mol to about 1500 g / mol, or from about 900 g / mol to about 1400 g / mol. The polyisobutenyl (PIB) group of the polyisobutenyl succinimide may have a number average molecular weight, Mn, of about 1000 g / mol. The polyisobutenyl (PIB) group of the polyisobutenyl succinimide may have a number average molecular weight, Mn, of about 1300 g / mol.

[0061] The compound may have a structure according to one of the following Formula:T-12636-W001wherein: each R is independently a hydrocarbyl group, n = 1 to 10 and m= 0, 1, or 2.

[0062] The compound may be:T-12636-W001The polyisobutenyl ( PI B) group of the structure of Formula IV to VIII may have a number average molecular weight, Mn, of from about 450 g / mol to 5000 g / mol, for example, from about 500T-12636-W001 g / mol to about 2500 g / mol, or from about 750 g / mol to about 2000 g / mol, or from about 750 g / mol to about 1500 g / mol, or from about 900 g / mol to about 1400 g / mol. The PIB group of the polyisobutenyl succinimide may have a number average molecular weight, Mn, of about 1000 g / mol. The PIB group of the polyisobutenyl succinimide may have a number average molecular weight, Mn, of about 1300 g / mol. The PIB of the structure of Formula IV to VII may have a number average molecular weight, Mn, of about 1000 g / mol. The PIB of the structure of Formula IV to VII may have a number average molecular weight, Mn, of about 1300 g / mol.Lubricating Oil Composition

[0063] In accordance with the second aspect, there is provided a lubricating oil composition comprising a compound according to the first aspect, for example, according to any one of the various embodiments of the first aspect described above.

[0064] The lubricating oil composition may be (i.e., formulated as) a engine lubricant. The lubricating oil composition may be (i.e., formulated as) a transmission oil. The lubricating oil composition may be (i.e., formulated as) a gear oil. The lubricating oil composition may be (i.e., formulated as) a hydraulic fluid. The lubricating oil composition may be (i.e., formulated as) a brake fluid. The lubricating oi composition may be (i.e., formulated as) a cooling fluid, for example, for an immersion cooling system.

[0065] The lubricating oil composition may be suitable for use in an electric vehicle or a hybrid electric vehicle.

[0066] The lubricating oil composition may be suitable for use in vehicles with an internal combustion engine fueled by gasoline or diesel.

[0067] The lubricating oil composition may be suitable for use in vehicles with an internal combustion engine fueled by hydrogen.

[0068] The lubricating oil composition may be suitable for use in vehicles with an internal combustion engine fueled by natural gas.T-12636-W001

[0069] The lubricating oil composition may be suitable for use in vehicles with an internal combustion engine fueled by ammonia.

[0070] The lubricating oil composition may comprise from about 0.01 wt. % to about 20.0 wt. % of the compound, including mixtures thereof, based on the total weight of the lubricating oil composition. The lubricating oil composition may comprise from about 0.025 wt.% to about 17.50 wt.%, or 0.05 wt.% to about 15.0 wt.%, or about 0.075 wt.% to about 12.50 wt.%, or about 0.1 wt.% to about 10 wt.%, or about 0.2 wt.% to about 7.5 wt.%, or about 0.25 wt.% to about 5.0 wt.%, or about 0.3 wt.% to about 2.5 wt.%, or about 0.35 wt.% to about 1.00 wt.%, or about 0.40 wt.% to about 0.75 wt.% of the compound, including mixtures thereof, based on the total weight of the lubricating oil composition. The lubricating oil composition may comprise about 0.05 wt.% to about 2.50 wt.%, or about 0.075 wt.% to about 2.000 wt.%, or about 0.1 wt.% to about 1.5 wt.%, or about 0.2 wt.% to about 1.0 wt.%, or about 0.3 wt.% to about 0.8 wt.% of the compound, including mixtures thereof, based on the total weight of the lubricating oil composition.

[0071] The lubricating oil may comprise an oil of lubricating viscosity (sometimes referred to as "base stock" or "base oil"). The oil of lubricating viscosity may act as the primary liquid constituent of the lubricating oil composition, into which compound, other optional additives and possibly other oils are blended, for example to produce a final lubricant (or lubricating oil composition). A base oil, which is useful for making concentrates as well as for making lubricating oil compositions therefrom, may be selected from natural (vegetable, animal or mineral) lubricating oils, synthetic lubricating oils or mixtures thereof.

[0072] Oils used as the base oil will be selected or blended depending on the desired end use and the additives in the finished oil to give the desired grade of engine oil. In one embodiment, the lubricating oil composition is a multi-grade oil for heavy duty or passenger car. The multigrade oil may have a Society of Automotive Engineers (SAE) viscosity grade of OW-8, 0W- 12, 0W- 16, 0W-20, 0W-30, 0W-40, 0W-50, 0W-60, 5W, 5W-20, 5W-30, 5W-40, 5W- 50, 5W-60, 10W, 10W-20, 10W-30, 10W-40, 10W-50, 15W, 15W-20, 15W-30, 15W-40, 20W-40 or 20W-50. The lubricating oil composition may have an SAE grade of 15W-40.

[0073] Definitions for the base stocks and base oils in this disclosure are the same as those found in American Petroleum Institute (API) Publication 1509 Annex E ("API Base Oil InterchangeabilityT-12636-W001Guidelines for Passenger Car Motor Oils and Diesel Engine Oils / ' February 2022). Group I base stocks contain less than 90% saturates and / or greater than 0.03% sulfur and have a viscosity index greater than or equal to 80 and less than 120 using the test methods specified in Table E-l. Group II base stocks contain greater than or equal to 90% saturates and less than or equal to 0.03% sulfur and have a viscosity index greater than or equal to 80 and less than 120 using the test methods specified in Table E-l. Group III base stocks contain greater than or equal to 90% saturates and less than or equal to 0.03% sulfur and have a viscosity index greater than or equal to 120 using the test methods specified in Table E-l. Group IV base stocks are polyalphaolefins (PAO). Group V base stocks include all other base stocks not included in Group I, II, III, or IV.

[0074] Natural oils include animal oils, vegetable oils (e.g., castor oil and lard oil), and mineral oils. Animal and vegetable oils possessing favorable thermal oxidative stability can be used. Of the natural oils, mineral oils are preferred. Mineral oils vary widely as to their crude source, for example, as to whether they are paraffinic, naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal or shale are also useful. Natural oils vary also as to the method used for their production and purification, for example, their distillation range and whether they are straight run or cracked, hydrorefined, or solvent extracted.

[0075] Synthetic oils include hydrocarbon oil. Hydrocarbon oils include oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene isobutylene copolymers, ethylene-olefin copolymers, and ethylene-alphaolefin copolymers). Polyalphaolefin (PAO) oil base stocks are commonly used synthetic hydrocarbon oil. By way of example, PAOs derived from C8 to C14 olefins, e.g., C8, CIO, C12, C14 olefins or mixtures thereof, may be utilized.

[0076] Other useful fluids for use as base oils include non-conventional or unconventional base stocks that have been processed, preferably catalytically, or synthesized to provide high performance characteristics.

[0077] Non-conventional or unconventional base stocks / base oils include one or more of a mixture of base stock(s) derived from one or more Gas-to-Liquids (GTL) materials, as well as isomerate / isodewaxate base stock(s) derived from natural wax or waxy feeds, mineral and or nonmineral oil waxy feed stocks such as slack waxes, natural waxes, and waxy stocks such as gas oils, waxy fuels hydrocracker bottoms, waxy raffinate, hydrocrackate, thermal crackates, or otherT-12636-W001 mineral, mineral oil, or even non-petroleum oil derived waxy materials such as waxy materials received from coal liquefaction or shale oil, and mixtures of such base stocks. Other base oils include Coal to liquid (CTL) products and alkyl-naphthalene.

[0078] Base oils for use in the lubricating oil compositions of present disclosure are any of the variety of oils corresponding to API Group I, Group II, Group III, Group IV, and Group V oils, and mixtures thereof, preferably API Group II, Group III, Group IV, and Group V oils, and mixtures thereof, more preferably the Group III to Group V base oils due to their exceptional volatility, stability, viscometric and cleanliness features.

[0079] The base oil may be a renewable base oil. Renewable as used herein means any biologically derived composition, including fatty alcohols, olefins, oroligomers. Such compositions may be made, for nonlimiting example, from biological organisms designed to manufacture specific oils, as discussed in WO 2012 / 141784, but do not include petroleum distilled or processed oils such as, for non-limiting example, mineral oils. A suitable method to assess materials derived from renewable resources is through "Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis" (ASTM D6866-12 or ASTM D6866-11). Counts from 14C in a sample can be compared directly or through secondary standards to SRM 4990C. A measurement of 0% 14C relative to the appropriate standard indicates carbon originating entirely from fossils (e.g., petroleum based). A measurement of 100% 14C indicates carbon originating entirely from modern sources (see, e.g., WO 2012 / 141784, incorporated herein by reference).

[0080] The lubricating oil composition will typically comprise at least about 50 wt. % of base oil based on the total weight of the lubricating oil composition, for example, at least about 60 wt.%, or at least about 70 wt. %, or at least about 80 wt. %, or from about 50 wt. % to about 99 wt. %, or from about 50 wt. % to about 95 wt. %, or from about 50 wt. % to about 90 wt.%, or from about 60 wt. % to about 90 wt. %, or from about 70 wt. % to about 90 wt. %, or from about 80 wt. % to about 90 wt.%.

[0081] The lubricating oil composition may have a high temperature shear (HTHS) viscosity at 150° C (measure in accordance with ASTM D4683) of 5.2 cP or less, such as 5.1 cP or less, 5.0 cP or less, 4.5 cP or less, 4.0 cP or less, 3.9 cP or less, 3.8 cP or less, 3.7 cP or less, 3.6 cP or less, 3.5T-12636-W001 cP or less, 3.4 cP or less, 3.3 cP or less, 3.2 cP or less, 3.1 cP or less, 3.0 cP or less, 2.9 cP or less, 2.8 cP or less, 2.7 cP or less, 2.6 cP or less, 2.5 cP or less, 2.4 cP or less, 2.3 cP or less, 2.2 cP or less, 2.1 cP or less, 2.0 cP or less, 1.9 cP or less, 1.8 cP or less, 1.7 cP or less, 1.6 cP or less, 1.5 cP or less, 1.4 cP or less, 1.3 cP or less, 1.2 cP or less, 1.1 cP or less, or 1.0 cP or less. In some embodiments, the lubricating oil composition may have a HTHS at 150°C from 1.0 to 5.2 cP, such as from 1.0 to 4.5 cP, 1.0 to 4.0 cP, 1.0 to 2.9 cP, 1.3 to 2.9 cP, 1.0 to 2.6 cP, 1.3 to 2.6 cP, 1.0 cP to 2.3 cP, 1.3 cP to 2.3 cP, 1.0 cP to 2.0 cP, 1.3 cP to 2.3 cP, 1.0 cP to 1.7 cP, or 1.3 cP to 1.7 cP. The lubricating oil composition may have a viscosity index of at least 135 (e.g., 135 to 400, or 135 to 250), at least 150 (e.g., 150 to 400, 150 to 250), at least 165 (e.g., 165 to 400, or 165 to 250), at least 190 (e.g., 190 to 400, or 190 to 250), or at least 200 (e.g., 200 to 400, or 200 to 250).

[0082] The base oil may have a kinematic viscosity at 100 °C (measured in accordance with ASTM D445) in a range of 1.4 to 20 mm2 / s such as 3 to 12 mm2 / s, such as 3 to 11 mm2 / s, 3 to 10 mm2 / s, 3 to 9 mm2 / s, 3 to 8 mm2 / s, 3 to 7 mm2 / s, 3 to 6 mm2 / s, 3 to 5 mm2 / s, 3 to 4 mm2 / s, 4 to 12 mm2 / s, 4 to 11 mm2 / s, 4 to 10 mm2 / s, 4 to 9 mm2 / s, 4 to 8 mm2 / s, 4 to 7 mm2 / s, 4 to 6 mm2 / s, 4 to 5 mm2 / s, 5 to 12 mm2 / s, 5 to 11 mm2 / s, 5 to 10 mm2 / s, 5 to 9 mm2 / s, 5 to 8 mm2 / s, 5 to 7 mm2 / s, 5 to 6 mm2 / s, 6 to 12 mm2 / s, 6 to 11 mm2 / s, 6 to 10 mm2 / s, 6 to 9 mm2 / s, 6 to 8 mm2 / s, 6 to 7 mm2 / s, 7 to 12 mm2 / s, 7 to 11 mm2 / s, 7 to 10 mm2 / s, 7 to 9 mm2 / s, 7 to 10 mm2 / s, 7 to 9 mm2 / s, 7 to 8 mm2 / s, 8 to 12 mm2 / s, 8 to 11 mm2 / s, 8 to 10 mm2 / s, 8 to 9 mm2 / s, 9 to 12 mm2 / s, 9 to 11 mm2 / s, 9 to 10 mm2 / s, 10 to 12 mm2 / s, 10 to 11 mm2 / s, or 11 to 12 mm2 / s. More generally, the base oil may be selected with a suitable kinematic viscosity depending on the intended use of the lubricating oil composition, e.g., as a crankcase lubricant, or a transmission oil, or a brake fluid, etc.

[0083] The lubricating oil composition may comprise one or more further additives. Such additives when present are either dispersed or dissolved in the lubricating oil composition. The one or more further additives may be selected from a detergent, dispersant, e.g., ashless dispersants, antioxidant, viscosity modifier, anti-wear / extreme-pressure agent, molybdenum succinimide, friction modifier, corrosion inhibitor other than the compound according to the first aspect, pour point depressant, foam inhibitor, dehazing agents, demulsifying agents, co-solvents, package compatibilizers, dyes and the like and mixtures thereof.T-12636-W001

[0084] The lubricating oil may further comprise one or more detergents. Detergents utilized in lubricating oil compositions generally comprise a polar head comprising a metal salt of an organic acid and a hydrophobic, oil-soluble tail. The detergent may be a metal detergent. The metal may be an alkali or alkaline earth metal. The metal may be Li, Na, K, Mg, or Ca, or a combination thereof. The metal may be Mg or Ca, or a combination thereof. The one or more detergents may be selected from a metal sulfonate, metal phenate, metal salicylate, or metal alkyl hydroxybenzoate or combinations thereof. The one or more detergents may be selected from a metal sulfonate, a metal phenate or a combination thereof. The metal of the one or more detergents selected from a metal sulfonate, a metal phenate or a combination thereof may be Ca or Mg. The lubricating oil composition may comprise a Ca phenate detergent. The lubricating oil composition may comprise a Mg sulfonate detergent. The lubricating oil composition may comprise a Ca sulfonate detergent.

[0085] The one or more detergents may be neutral. Detergents that contain a stoichiometric amount of the metal are described as neutral. The one or more metal detergents may be overbased. Detergents that contain an excess of metal (i.e., greater than stoichiometric amount) are described as overbased. The one or more detergents may be overbased and have a TBN of 10 to 650 mg KOH / g, such as 10 to 600 mg KOH / g, 10 to 550 mg KOH / g, 10 to 500 mg KOH / g, 10 to 450 mg KOH / g, 10 to 400 mg KOH / g, 10 to 350 mg KOH / g, 10 to 300 mg KOH / g, 10 to 250 mg KOH / g, 10 to 200 mg KOH / g, 10 to 150 mg KOH / g, 10 to 100 mg KOH / g, 10 to 50 mg KOH / g, 10 to 40 mg KOH / g, 10 to 30 mg KOH / g, 10 to 20 mg KOH / g, 50 to 650 mg KOH / g, 50 to 600 mg KOH / g, 50 to 550 mg KOH / g, 50 to 500 mg KOH / g, 50 to 450 mg KOH / g, 50 to 400 mg KOH / g, 50 to 350 mg KOH / g, 50 to 300 mg KOH / g, 50 to 250 mg KOH / g, 50 to 200 mg KOH / g, 50 to 150 mg KOH / g, 50 to 100 mg KOH / g, 100 to 650 mg KOH / g, 100 to 600 mg KOH / g, 100 to 550 mg KOH / g, 100 to 500 mg KOH / g, 100 to 450 mg KOH / g, 100 to 400 mg KOH / g, 100 to 350 mg KOH / g, 100 to 300 mg KOH / g, 100 to 250 mg KOH / g, 100 to 200 mg KOH / g, 100 to 150 mg KOH / g, 150 to 650 mg KOH / g, 150 to 600 mg KOH / g, 150 to 550 mg KOH / g, 150 to 500 mg KOH / g, 150 to 450 mg KOH / g, 150 to 400 mg KOH / g, 150 to 350 mg KOH / g, 150 to 300 mg KOH / g, 150 to 250 mg KOH / g, 150 to 200 mg KOH / g, 200 to 650 mg KOH / g, 200 to 600 mg KOH / g, 200 to 550 mg KOH / g, 200 to 500 mg KOH / g, 200 to 450 mg KOH / g, 200 to 400 mg KOH / g, 200 to 350 mg KOH / g, 200 to 300 mg KOH / g, , 250 to 650 mg KOH / g, 250 to 600 mg KOH / g, 250 to 550 mg KOH / g, 250 to 500 mg KOH / g, 250 to 450 mg KOH / g, 250 to 400 mg KOH / g, 250 to 350 mg KOH / g, 250 to 300 mg KOH / g, 300 toT-12636-W001650 mg KOH / g, 300 to 600 mg KOH / g, 300 to 550 mg KOH / g, 300 to 500 mg KOH / g, 300 to 450 mg KOH / g, 300 to 400 mg KOH / g, 350 to 650 mg KOH / g, 350 to 600 mg KOH / g, 350 to 550 mg KOH / g, 350 to 500 mg KOH / g, 350 to 450 mg KOH / g, 350 to 400 mg KOH / g, 400 to 650 mg KOH / g, 400 to 600 mg KOH / g, 400 to 550 mg KOH / g, 400 to 500 mg KOH / g, 400 to 450 mg KOH / g.

[0086] The term "Total Base Number" or "TBN" as used herein refers to the amount of base equivalent to milligrams of KOH in one gram of sample. Thus, higher TBN numbers reflect more alkaline products, and therefore greater alkalinity. TBN may be determined using the ASTM D2896 test.

[0087] The one or more detergents may comprise an overbased Ca phenate detergent. The overbased Ca phenate detergent may have a TBN of about 50 mg KOH / g to about 600 mg KOH / g, about 100 mg KOH / g to about 500 mg KOH / g, for example, about 150 mg KOH / g to about 400 mg KOH / g, about 200 mg KOH / g to about 300 mg KOH / g, or about 240 mg KOH / g to about 280 mg KOH / g.

[0088] The one or more detergents may comprise an overbased Mg sulfonate detergent. The overbased Mg sulfonate detergent may have a TBN of about 50 mg KOH / g to about 800 mg KOH / g, for example, about 100 mg KOH / g to about 700 mg KOH / g, about 200 mg KOH / g to about 600 mg KOH / g, about 300 mg KOH / g to about 500 mg KOH / g, or about 350 mg KOH / g to about 450 mg KOH / g.

[0089] The one or more detergents may comprise an overbased Ca sulfonate detergent. The overbased Ca sulfonate detergent may have a TBN of about 50 mg KOH / g to about 300 mg KOH / g, for example about 70 mg KOH / g to about 280 mg KOH / g, about 90 mg KOH / g to about 260 mg KOH / g, about 100 mg KOH / g to about 240 mg KOH / g, about 120 mg KOH / g to about 220 mg KOH / g, about 140 to about 200 mg KOH / g, or about 160 mg KOH / g to about 180 mg KOH / g.

[0090] The one or more detergents may individually be present in the lubricating oil composition in an amount of about 100 ppm to about 2500 ppm, such as about 100 ppm to about 2500 ppm, or about 150 ppm to about 1800 ppm, or about 200 ppm to about 1500 ppm, or about 300 ppm to about 1100 ppm, or about 350 ppm to about 1000 ppm, or about 400 ppm to about 900 ppm in terms of metal content.T-12636-W001

[0091] The one or more detergents may comprise an overbased Ca phenate detergent present in the lubricating oil composition in an amount of about 100 ppm to about 2000 ppm, for example, about 200 ppm to about 1800 ppm, about 300 ppm to about 1600 ppm, about 400 ppm to about 1400 ppm, about 500 ppm to about 1200 ppm, about 600 ppm to about 1000 ppm, about 700 ppm to 1000 ppm, about 750 ppm to about 950 ppm, or about 800 ppm to about 900 ppm in terms of calcium content.

[0092] The one or more detergents may comprise an overbased Mg sulfonate detergent present in the lubricating oil composition in an amount of about 100 ppm to about 1500 ppm, for example, about 200 ppm to about 1250 ppm, about 300 ppm to about 1000 ppm, about 400 ppm to about 900 ppm, about 500 ppm to about 800 ppm, about 550 ppm to about 750 ppm, or about 600 ppm to about 700 ppm, in terms of magnesium content.

[0093] The one or more detergents may comprise an overbased Ca sulfonate detergent present in the lubricating oil composition in an amount of about 100 ppm to about 900 ppm, for example about 150 ppm to about 800 ppm, about 200 ppm to about 700 ppm, about 250 ppm to about 600 ppm, about 300 ppm to about 500 ppm, or about 350 ppm to about 450 ppm, in terms of calcium content.

[0094] The lubricating oil composition may comprise one or more detergents such that the total amount of metal from the one or more detergents is less than about 4000 ppm, for example, less than about 3000 ppm, or less than about 2500 ppm, or less than about 2000 ppm, for example, from about 500 ppm to about 3000 ppm, or from about 750 ppm to 2500 ppm, or from about 1000 to about 2000 ppm, or from about 1500 ppm to about 2000 ppm. The total metal content may be all calcium, all magnesium or a mixture of magnesium and calcium, for example, in a ratio of calcium to magnesium of from about 10:1 to about 1:10, for example, from about 10:1 to about 1:5, or from about 10:1 to about 10:1 to about 1:1, or from about 5:1 to about 1:1 or from about 3:1 to 1:1 or from about 3:1 to about 3:2, or from about 3:1 to about 2:1.

[0095] The lubricating oil composition may comprise up to about 20.0 wt. % of detergent, based on the total weight of the lubricating oil composition, for example, from about 0.1 to about 20.0 wt. %, or from about 0.1 to 15.0 wt.%, or from about 0.1 to 10.0 wt. %, or from about 0.2 to aboutT-12636-W0017.5 wt. %, or from about 0.5 to about 5.0 wt. %, or from about 0.5 to about 3,0 wt.%, or from about 0.5 to about 2.0 wt. %.

[0096] The lubricating oil may further comprise one or more dispersants. The one or more dispersants may be selected from hydrocarbyl succinimides, mixed ester / amides of hydrocarbyl- substituted succinic acid, hydroxyesters of hydrocarbyl-substituted succinic acids, and Mannich condensation products of hydrocarbyl-substituted phenols, formaldehydes, polyamines or combinations thereof. The one or more dispersants may be selected from condensation products of polyamines and hydrocarbyl-substituted phenyl acids. The one or more dispersants may be bis-succinimide dispersants derived from polyalkenyl succinic anhydrides, such as polyisobutenyl succinic anhydride (PIBSA).

[0097] The one or more dispersants may be post-treated by conventional methods by reaction with any of a variety of agents. Among these agents are boron compounds (e.g., boric acid) and cyclic carbonates (ethylene carbonate).

[0098] The one or more dispersants may be a non-borated succinimide dispersant, a borated succinimide dispersant or a combination thereof.

[0099] The one or more dispersants may be present in an amount of about 0.1 wt.% to about 10 wt.% based on the total weight of the lubricating oil composition, for example, about 0.25 wt.% to about 9.5 wt.%, about 0.5 wt.% to about 9.0 wt.%, about 0.75 wt.% to about 8.5 wt.%, about 1.0 wt.% to about 8.0 wt.%, about 1.5 wt.% to about 7.5 wt.%, about 2.0 wt.% to about 6.5 wt.%, about 2.5 wt.% to about 5.5 wt.%, about 3.5 wt.% to about 4.5 wt.%.

[0100] The lubricating composition may comprise one or more antioxidants. The one or more antioxidants may be selected from alkylated phenols or diarylamines, sulfur-containing antioxidants, or combinations thereof. The one or more antioxidants may include phenolic antioxidants which may be selected from 2,6-di-tert-butylphenol, mixtures of tert-butylated phenols, 2,6-di-tert-butyl-4-methylphenol, ,6-di-tert-butyl-p-cresol, and 2,6-di-tert-butyl-4-(2- octyl-3-propanoic) phenol, 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4- methyl-6-tert-butylphenol), and mixed methylene-bridged polyalkyl phenols, 4,4'-thiobis(2- methyl-6-tert-butylphenol) and combinations thereof. The one or more antioxidants may includeT-12636-W001 aminic antioxidants which may be selected from 3-hydroxydiphenylamine, N-phenyl-1,2- phenylenediamine, N-phenyl-l,4-phenylenediamine, mono / dibutyldiphenylamine, mono / dioctyldiphenylamine, mono / dinonyldiphenylamine, mono / ditetradecyldiphenylamine, phenyl-alpha-naphthylamine, and combinations thereof. The one or more antioxidants may include a sulfur-containing antioxidants which may be selected from, sulfurized olefins derived from C4-C25 alpha-olefins and a sulfur source such as elemental sulfur, sulfur monochloride, sulfur dichloride, sodium sulfide, sodium polysulfide, and combinations thereof.

[0101] The one or more antioxidants may be present in an amount of about 0.1 wt.% to about 10.0 wt.%, based on the total weight of the lubricating oil compositions, for example, about 0.25 wt.% to about 9.5 wt.%, about 0.5 wt.% to about 9.0 wt.%, about 0.75 wt.% to about 8.5 wt.%, about 1.0 wt.% to about 8.0 wt.%, about 1.25 wt.% to about 7.0 wt.%, about 1.5 wt.% to about 6.00wt.%, about 1.75 wt.% to about 5.0 wt.%, about 2.0 wt.% to about 4.0 wt.%, or about 2.0 wt.% to about 3.0 wt.%.

[0102] The lubricating composition may comprise one or more viscosity modifiers (also known as viscosity index improvers). The one or more viscosity modifiers may be selected from polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutenes, hydrogenated styrene-isoprene polymers, styrene / maleic ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkyl styrenes, hydrogenated alkenyl aryl conjugated diene copolymers, or combinations thereof.

[0103] The one or more viscosity modifiers may be present in an amount of about 0.1 wt. % to about 20 wt. %, based on the total weight of the lubricating oil composition, for example, about 0.1 wt. % to about 15.0 wt. %, about 0.1 wt.% to about 10.0 wt. %, about 0.1 wt. % to about 5.0 wt. %, or about 0.5 wt. % to about 5.0 wt.

[0104] The lubricating composition may comprise one or more antiwear agents. The one or more antiwear agents may be selected from metal thiosphosphates, metal dialkyldithiophosphates, phosphoric acid esters or salts thereof, phosphate esters, phosphites, phosphonates, sulfurized olefins, thiocarbamate-containing compounds including, thiocarbamate esters, alkylene-coupled thiocarbamates, bis(S-alkyldithiocarbamyl) disulfides and combinations thereof. The one or moreT-12636-W001 antiwear agents may comprise a metal dialkyldithiophosphate, for example, a zinc dialkyldithiophosphate.

[0105] The one or more antiwear agents may be or comprise a zinc dialkyldithiophosphate which may be present in the lubricating oil composition in an amount of 100 ppm to about 2000 ppm, such as about 150 ppm to about 1800 ppm, about 200 ppm to about 1500 ppm, about 300 ppm to about 1250 ppm, about 400 ppm to about 1000 ppm, about 500 ppm to about 900 ppm, about 600 ppm to about 800 ppm, or about 700 to about 800 ppm in terms of phosphorus.

[0106] The zinc dithiophosphate may have the following formula:Zn[S-P(=S)(OR1)(OR2)]2, wherein R1and R2may be the same or different hydrocarbyl radicals having from 1 to 18 (e.g., 2 to 12) carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals. The R1and R2groups may be alkyl groups having from 2 to 8 carbon atoms (e.g., the alkyl radicals may be ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, or 2-ethylhexyl). The zinc dihydrocarbyl dithiophosphate can therefore include zinc dialkyl dithiophosphates (ZDDP). The zinc dialkyl dithiophosphate can be a primary zinc dialkyl dithiophosphate containing primary alkyl groups, or secondary zinc dialkyl dithiophosphate containing secondary alkyl groups, or mixtures thereof.

[0107] The lubricating composition may comprise one or more friction modifiers. The one or more friction modifiers may comprise metal containing and metal-free friction modifiers and may include, but are not limited to, imidazolines, aliphatic fatty acid amides, aliphatic amines, succinimides, alkoxylated aliphatic amines, ether amines, alkoxylated ether amines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, amino guanidine, alkanolamides, phosphonates, metal-containing compounds, glycerol esters, sulfurized fatty compounds and olefins, sunflower oil other naturally occurring plant or animal oils, dicarboxylic acid esters, esters or partial esters of a polyol and one or more aliphatic or aromatic carboxylic acids, and combinations thereof.

[0108] The lubricating composition may comprise one or more further rust or corrosion inhibitors, other than the compound of the first aspect. Metal passivators are a type of corrosion inhibitor that binds to the surface of a metal to form a protective film, thereby passivating the metal surface.T-12636-W001

[0109] The one or more rust or corrosion inhibitors may be selected from ether amines, polyethoxylated compounds, mono- and polycarboxylic acids derived from fatty acids, and combinations thereof. Metal passivators may be selected from thiazoles, triazoles, and thiadiazoles such as benzotriazole, tolyltriazole, decyltriazole, dodecyltriazole, 2-mercaptobenzotriazole, 2,5-dimercapto-l,3,4-thiadiazoles, and combinations thereof.

[0110] The lubricating composition may comprise one or more foam inhibitors. Foam inhibitors are used to reduce or prevent stable foams in the lubricating composition. The one or more foam inhibitors may be selected from silicon-based polymers such as polysiloxanes. The one or more foam inhibitors may be selected from non-silicon-based organic polymers such as polyacrylates such as ethyl acrylate / 2-ethylhexylacrylate copolymers.

[0111] The one or more foam inhibitors may be present in the lubricating oil composition in an amount of about 1 ppm to about 100 ppm, for example, 2 ppm to about 90 ppm, about 5 ppm to about 80 ppm, about 7 ppm to about 70 ppm, about 10 ppm to about 60 ppm, about 15 ppm to about 50 ppm, about 20 ppm to about 40 ppm, or about 20 ppm to about 30 ppm.

[0112] The lubricating oil composition may comprise metal detergent (e.g., calcium and / or magnesium detergent), dispersant (e.g., borated and / or non-borated succinimide dispersant), antiwear agent (e.g., zinc dialkyldithiophosphate), molybdenum succinimide, antioxidant (e.g., phenolic antioxidant) and optionally foam inhibitor (e.g., silicon-based foam inhibitor). The amounts of each of these additives may be as described above for each individual additive.

[0113] The lubricating oil composition may comprise a total amount of additives of no more than about 50 wt. % of the total weight of the lubricating oil composition. For example, the lubricating oil composition may comprise from about 1.0 to about 25.0 wt. %., about 2.0 wt.% to about 20 wt.%, about 3.0 wt.% to about 15 wt.%, about 4.0 wt.% to about 12.5 wt.%, about 5.0 wt.% to about 10 wt.%.

[0114] Unless otherwise stated, each of the foregoing additives, when used, is used at a functionally effective amount to impart the desired properties to the lubricant. Thus, for example, if an additive is an ashless dispersant, a functionally effective amount of this ashless dispersantT-12636-W001 would be an amount sufficient to impart the desired dispersancy characteristics to the lubricant. Generally, the concentration of each of these additives, when used, may range, unless otherwise specified, from about 0.001 to about 20 wt. %, such as about 0.01 to about 10 wt. %.Fuel composition

[0115] There is provided a fuel composition comprising a compound according to the first aspect.

[0116] The fuel may be hydrogen. The fuel may be ammonia. The fuel may be natural gas. The fuel may be gasoline. The fuel may be diesel.

[0117] Gasoline fuel refers to a composition containing at least predominantly C4-Ci2hydrocarbons. In one embodiment, gasoline or gasoline boiling range components is further defined to refer to a composition containing at least predominantly C4-Ci2hydrocarbons and further having a boiling range of from about 37.8°C (100°F) to about 204°C (400°F). In an alternative embodiment, gasoline is defined to refer to a composition containing at least predominantly C4-C12hydrocarbons, having a boiling range of from about 37.8°C (100°F) to about 204°C (400°F), and further defined to meet ASTM D4814.

[0118] Diesel fuel refers to middle distillate fuels containing at least predominantly Ci0-C25hydrocarbons. In one embodiment, diesel is further defined to refer to a composition containing at least predominantly Ci0-C2s hydrocarbons, and further having a boiling range of from about 165.6°C (330°F) to about 371.1°C (700°F). In an alternative embodiment, diesel is as defined above to refer to a composition containing at least predominantly Cio-C2s hydrocarbons, having a boiling range of from about 165.6°C (330°F) to about 371.1°C (700°F), and further defined to meet ASTM D975.

[0119] The fuel may be present in a major amount by weight % of the total fuel composition. The fuel may be present in about 50 wt. % or greater, 55 wt. % or greater, 60 wt. % or greater, 65 wt. % or greater, 70 wt. % or greater, 75 wt. % or greater, 80 wt. % or greater, 85 wt. % or greater, 90 wt. % or greater, 95 wt. % or greater or between any range from about 50 wt. % to up to below 100 wt. %.T-12636-W001

[0120] The fuel composition may comprise from about 0.01 wt. % to about 20.0 wt. % of the compound, based on the total weight of the fuel composition. The fuel composition may comprise from about 0.025 wt.% to about 17.50 wt.%, 0.05 wt.% to about 15.0 wt.%, about 0.075 wt.% to about 12.50 wt.%, about 0.1 wt.% to about 10 wt.%, about 0.2 wt.% to about 7.5 wt.%, about 0.25 wt.% to about 5.0 wt.%, about 0.3 wt.% to about 2.5 wt.%, about 0.35 wt.% to about 1.00 wt.%, or about 0.40 wt.% to about 0.75 wt.%. The fuel composition may comprise about 0.05 wt.% to about 2.50 wt.%, about 0.075 wt.% to about 2.000 wt.%, about 0.1 wt.% to about 1.5 wt.%, about 0.2 wt.% to about 1.0 wt.%, or about 0.3 wt.% to about 0.8 wt.%.

[0121] The fuel composition may comprise one or more further additives. The one or more further additives may be selected from antioxidants, metal deactivators, demulsifiers, oxygenates, antiknock agents, dispersants, detergents, pour point depressants and flow improvers.Uses of and methods utilizing the compound to inhibit corrosion

[0122] In accordance with the fourth to thirteenth aspects, the compound according to the first aspect may be used as a corrosion inhibitor (i.e., to improve (i.e., inhibit / reduce) corrosion, for example, in a lubricating oil composition, for example, a functional automative fluid, or a fuel composition. As such, the lubricating oil or fuel may be formulated to maintain, enhance or improve corrosion performance. The compounds may be used as corrosion inhibitors to reduce corrosion of metal parts, i.e., corrodible metal components, such as those made from or comprising the likes of iron, aluminum, copper, zinc, tin, lead and their alloys, as well as steel. Metal parts include the likes of cam followers and bearings. The compounds may be used to reduce corrosion of electrical components, e.g., sensors and the like.

[0123] The lubricating oil composition may be a functional automotive fluid, for example, an engine lubricant, hydraulic medium or coolant. The lubricating oil composition may be a crankcase lubricant. The lubricating oil composition may be a transmission oil. The lubricating oil composition may be a gear oil. The lubricating oil composition may be a hydraulic fluid. The lubricating oil composition may be a brake fluid. The lubricating oil composition may be a cooling fluid, for example, for an immersion cooling system.T-12636-W001

[0124] The fuel composition may be gasoline or diesel. The fuel composition may be natural gas based. The fuel composition may be hydrogen based. The fuel composition may be ammonia based. Other fuel types include methanol-based fuels or jet fuel. The compounds of the first aspect may act to reduce corrosion in parts of the engine as the fuel is delivered for combustion, or during combustion. Compounds in the fuel may also end up in the engine lubricant, for example, via engine blow-by when a mixture of air-fuel or combustion gases leak between the engine's pistons and cylinder wall into the crankcase.

[0125] Without wishing to be bound by theory, it is believed that the compounds of the present invention are able to inhibit corrosion in the vapor phase under performance conditions (i.e., engine environment temperatures) whereby a portion of the compound, i.e., the R moiety of the structure of Formula I, for example, the triazole or imidazole species, may cleave from the compound, and can volatilize such that it exists in the vapor phase and can therefore act as a corrosion inhibitor in the vapor phase as well as the oil phase. As such, the compounds may be used / implemented in a method to inhibit corrosion in an electric vehicle or hybrid electric vehicle, wherein the compound is present in a lubricating oil composition, used to operate the hybrid electric vehicle. The lubricating oil composition may be an electric vehicle drive line fluid (EDF).

[0126] The compound may be present in the lubricating oil composition, for example, a functional automotive fluid, or fuel composition used to operate the engine in suitable amounts to maintain, inhibit, reduce or otherwise improve corrosion performance. Reference is made to the description of the lubricating oil compositions and fuel compositions above and the various embodiments describing suitable amounts of the compound.

[0127] The corrosion to be inhibited may be copper corrosion. The corrosion to be inhibited may be lead corrosion. The corrosion to be inhibited may be copper and lead corrosion Copper corrosion may be reduced by at least 5 %, for example, at least 10 %, or at least 15 %, or at least 20 %, or at least 25 % compared to a directly comparable lubricating oil or fuel composition that does not contain the compound, as may be determined using a suitable test method, such as the modified ASTM D6594 test method describe herein. As described in the examples section below, the test is modified through the addition of water to the test oil. Copper corrosion may be reduced by as much as 30 %, for example, by as much as 40 %, by as much as 50 %, or by as much as 60 %. Lead corrosion may be reduced by at least 5 %, for example, at least 10 %, or at least 15T-12636-W001%, or at least 20 %, or at least 25 % compared to a directly comparable lubricating oil or fuel composition that does not contain the compound, as may be determined using a suitable test method, such as the modified ASTM D6594 test method describe herein. Lead corrosion may be reduced by as much as 30 %, for example, by as much as 40 %, by as much as 50 %, or by as much as 60 %. Copper and / or lead corrosion may be reduced by up to about 75 %, or by up to about 50 %, or by up to about 40 %, or by up to about 30 %. Copper corrosion may be less than 75 ppm, as determined in accordance with the modified ASTM D6594 test method, for example, less than 50 ppm, or less than 40 ppm, or less than 35 ppm, or less than 30 ppm, or less than 25 ppm. Lead corrosion may be less than 100 ppm, for example, less than 75 ppm, as determined in accordance with the modified ASTM D6594 test method, for example, less than 50 ppm, or less than 40 ppm, or less than 35 ppm, or less than 30 ppm, or less than 20 ppm.Method of making the compound

[0128] In accordance with the fourteenth aspect of the present invention, there is provided a method of making a compound according to the first aspect, comprising reacting a polyamine hydrocarbyl bis-succinimide, an aldehyde and a nitrogen-containing heterocycle.

[0129] The aldehyde may be any suitable aldehyde. The aldehyde may be paraformaldehyde. The nitrogen-containing heterocycle may be any suitable heterocycle which is capable of reacting with the polyamine hydrocarbyl bis-succinimide and aldehyde forming the R groups of Formula I. The nitrogen-containing heterocycle may be a diazole, triazole, tetrazole or an isomer thereof, such as, 1, 2, 4-triazole or 1, 2, 3-trizaole, imidazole, pyrazole, and the like.

[0130] The polyamine hydrocarbyl bis-succinimide materials may be made by reacting a hydrocarbyl-substituted dicarboxylic acid material with a molecule containing amine functionality. Examples of suitable polyamines include polyalkylene polyamines, hydroxysubstituted polyamines and polyoxyalkylene polyamines. The succinimide may be post-treated (e.g., with a boronating agent, epoxide, ethylene carbonate, or a cyclic carbonate). Succinimides are generally basic and typically contribute to the TBN of a lubricating oil composition to which they are added, without introducing additional sulfated ash.T-12636-W001

[0131] The following non-limiting examples are illustrative of the present invention. Brief descriptions of how the examples were prepared are provided.EXAMPLESCompound SynthesisSynthesis of Compound A (Formula IV)

[0132] A 2 L flask was equipped with an overhead stirrer, Dean-Stark apparatus, nitrogen sparge tube inlet, and thermocouple was charged with the polyamine 1000MW PIB bis-succinimide shown in the reaction scheme above (996 g, 433 mmol, TBN 38 mg KOH / g) and paraformaldehyde (59.61 g, 866 mmol) at room temperature under N2atmosphere. The reaction mixture was then heated with stirring to 90 °C over a period of 3 hr. Imidazole (27.42 g, 866 mmol) was charged to the reaction mixture; the temperature was increased to 100 °C and held for 2 hr. Once complete, the reaction was cooled to 85 °C and held under vacuum to remove water.Synthesis of Compound B (Formula V)

[0133] A 2 L flask was equipped with an overhead stirrer, Dean-Stark apparatus, nitrogen sparge tube inlet, and a thermocouple was charged with the polyamine 1000 MW PIB bis-succinimide shown in the reaction scheme above (1000 g, 434 mmol, TBN 38 mg KOH / g.) and paraformaldehyde (26.12 g, 869 mmol) at room temperature under N2atmosphere. The reaction mixture was then heated with stirring to 65 °C over a period of 3 hr. 1,2,4-triazole (60.1 g, 869T-12636-W001 mmol.) was charged to the reaction mixture; the temperature was increased to 95 °C and held for2 hr. Once complete, the reaction was cooled to 85 °C and held under vacuum to remove water.Synthesis of Compound C (Formula VI)

[0134] A 2 L flask was equipped with an overhead stirrer, Dean-Stark apparatus, nitrogen sparge tube inlet, and thermocouple was charged with the polyamine 1000MW PIB bis-succinimide shown in the reaction scheme above (937.6 g, 338 mmol, TBN 36.5 mg KOH / g) at room temperature under N2atmosphere. 500 mL of hexane was added to the flask, and the reaction mixture was heated with stirring to 65 °C. Paraformaldehyde (21.38 g, 676 mmol) and imidazole (47.00 g, 676 mmol) were then added to the reaction mixture, which was held at 65 °C and stirred for 12 hr. Once complete, the reaction was held under vacuum to remove water and hexane.Synthesis of Compound D (Formula VII)

[0135] A 2 L flask was equipped with an overhead stirrer, Dean-Stark apparatus, nitrogen sparge tube inlet, and thermocouple was charged with the polyamine 1300 MW PIB bis-succinimide shown in the reaction scheme above (951.0 g, 247 mmol, TBN 52.7 mg KOH / g) and 500 mL hexane at room temperature under N2atmosphere. The reaction mixture was heated with stirring to 65 °C. Once at 65 °C, paraformaldehyde (15.68 g, 495 mmol) and 1,2,4-triazole (34.88 g, 495 mmol) were charged to the reaction mixture. The reaction was held at 65 °C and stirred for 5 hr. Once complete, the reaction mixture was heated to 75 °C and held under vacuum to remove water and hexane.T-12636-W001Synthesis of Compound E

[0136] A 2 L flask was equipped with an overhead stirrer, Dean-Stark apparatus, nitrogen sparge tube inlet, and thermocouple was charged with the polyamine 1300MW PIB bis-succinimide shown in the reaction scheme above (919.6 g, 239 mmol, TBN 52.7 mg KOH / g) at room temperature under N? atmosphere, followed by 500 mL of hexane. The reaction mixture was then heated with stirring to 65 °C over a period of 1 hr. Imidazole (33.226 g, 478 mmol) and paraformaldehyde (15.127 g, 478 mmol) were charged to the reaction mixture; the temperature was held at 65 °C for 19 hr. Once complete, the reaction was held at 65 °C under vacuum to remove water and hexane.Lubricating Oil CompositionBaseline 1

[0137] An SAE 15W-40 lubricating oil was prepared by blending the following components together with Group II base oils:A) a borated and non-borated succinimide dispersantB) an overbased Ca phenate detergent with a TBN of 260C) an overbased Mg sulfonate with a TBN of 400D) an overbased Ca sulfonate detergent with a TBN of 17E) an anti-wear agentF) a molybdenum succinimideG) an antioxidantH) a foam inhibitorComparative Example 1 corresponds to Baseline 1 without the addition of further additives.T-12636-W001Example 1 corresponds to Baseline 1 with the addition of 0.4 wt.% of Compound A (Formula IV).Example 2 corresponds to Baseline 1 with the addition of 0.75 wt.% of Compound A (Formula IV).Modified High Temperature Corrosion Bench Test, HTCBT (ASTM D6594)

[0138] The ASTM D6594 HTCBT test is used to test diesel engine lubricants to determine their tendency to corrode various metals, specifically alloys of lead and copper commonly used in cam followers and bearings. Four metal specimens of copper, lead, tin and phosphor bronze are immersed in a measured amount of engine oil. The oil, at an elevated temperature (170 °C), is blown with air (5 l / h) for a period of time (168 h) with 2% of water. When the test is completed, the copper specimen and the stressed oil are examined to detect corrosion and corrosion products, respectively. The concentrations of copper, lead, and tin in the new oil and stressed oil and the respective changes in metal concentrations are reported.Table 1Modified Copper Strip Corrosion Test (ASTM D130)

[0139] The copper strip corrosion test is designed to assess the relative degree of corrosivity of a petroleum product. A freshly polished copper strip is immersed in a specific volume of the sample being tested and heated under conditions of temperature and time that are specific to the class of material being tested. At the end of the heating period, the copper strip is removed,T-12636-W001 washed and the color and tarnish level assessed against the ASTM Copper Strip Corrosion Standard, summarized in Table 2 below.

[0140] To assess the vapor phase corrosivity of the lubricating oil, a modified ASTM D130 method is utilized. A freshly polished copper strip is placed inside of a 100 mLjar, filled with lubricating oil to half-immerse the copper strip, sealed with a cork stopper and placed inside a temperature- controlled oven. Corrosion of the vapor space (i.e. unimmersed) portion of the copper strip is assed per the ASTM Copper Strip Corrosion Standard.Table 22The ASTM Copper Corrosion Standard is a colored reproduction of strip characteristic of these descriptions.Table 3T-12636-W001Compound A corresponds to the compound of Formula IV,Compound C corresponds to the compound of Formula VI ,4Compound F corresponds to the compound of Formula VIII (PIB MW 1000), shown below:Formula VIII

Claims

T-12636-W001Claims1. A compound having a structure, wherein A according to Formula IFormula I wherein:A is a hydrocarbyl succinimide; n = 1 to 10; m = 0, 1 or 2; andR is a nitrogen containing heterocyclic moiety.

2. A compound according to claim 1, wherein the nitrogen-containing heterocyclic moiety is or comprises a five-membered heterocycle which contains 2, 3 or 4 N atoms.

3. A compound according to claim 2, wherein the five-membered ring is a diazole, triazole or, tetrazole, or isomers thereof.

4. A compound according to any preceding claim, where R has a structure according to Formula IIT-12636-W001Formula II wherein X is CH or N, Y is C, CH or N, Z is C, CH, or N and W is absent or if present, is an aromatic ring, with the proviso that when W is present, Y and Z are C.

5. A compound according to claim 4, wherein R is selected fromFormula lieT-12636-W001Formula llj Formula Ilk , and wherein R1is C1-C6 alkyl.

6. A compound according to any preceding claim, wherein the hydrocarbyl succinimide includes a polyisobutenyl (PIB) group or ethylene-propylene copolymer.

7. A compound according to any preceding claim, wherein the hydrocarbyl group of the hydrocarbyl succinimide has a number average molecular weight, Mn, of from about 450 to 5000, for example, from about 500 to about 2500, or from about 750 to about 2000, or from about 750 to about 1500, or from about 900 to about 1400.

8. A compound according to any preceding claim, wherein the compound isT-12636-W0019. A lubricating oil composition comprising a compound according to any preceding claim.T-12636-W00110. The lubricating oil composition according to claim 9, wherein the lubricating oil composition is an engine lubricant, a transmission oil, a gear oil, a hydraulic fluid, a brake fluid, or a cooling fluid.

11. The lubricating oil composition according to claims 9 or 10, wherein the lubricating oil is suitable for use in an electric vehicle or hybrid electric vehicle.

12. The lubricating oil composition according to any one of claims 9-11, wherein the lubricating oil composition comprises at least about 50 wt. % of a base oil of lubricating viscosity and from about 0.01 wt. % to about 20.0 wt. % of the compound, based on the total weight of the lubricating oil composition.

13. The lubricating oil composition according to any one of claims 9-12, wherein the lubricating oil composition comprises one or more additives selected from a detergent, dispersant, antioxidant, molybdenum succinimide, viscosity modifier, antiwear / extreme-pressure agent, friction modifier, corrosion inhibitor other than according to claim 1, pour point depressant and foam inhibitor, optionally wherein the total amount of additives comprises no more than about 50 wt. % of the total weight of the lubricating oil composition, for example, from about 1.0 to about 25.0 wt. %.

14. The lubricating oil composition according to any one of claims 9-13, wherein the lubricating oil composition comprises metal detergent (e.g., calcium and / or magnesium detergent), dispersant (e.g., borated and / or non-borated succinimide dispersant), antiwear agent, molybdenum succinimide, antioxidant and optionally foam inhibitor, further optionally wherein total the total amount of metal from the metal detergent is from about 750 ppm to 2500 ppm, , optionally wherein the total metal content is all calcium, all magnesium or a mixture of magnesium and calcium, for example, in a ratio of calcium to magnesium of from about 10:1 to about 1:10, for example, from about 10:1 to about 1:5, or from about 10:1 to about 10:1 to about 1:1, or from about 5:1 to about 1:1 or from about 3:1 to 1:1 or from about 3:1 to about 3:2, or from about 3:1 to about 2:1.

15. Use of a compound according to any one of claims 1-8 as a corrosion inhibitor.

16. Use of a compound according to any one of claims 1-8 as a corrosion inhibitor in a lubricating oil composition or a fuel composition.T-12636-W00117. Use of a compound according to any one of claims 1-8 to inhibit corrosion in a hydrogen, natural gas or ammonia fueled internal combustion engine, wherein the compound is present in a lubricating oil composition used to operate the engine.

18. Use of a compound according to any one of claims 1-8 to inhibit corrosion in an electric vehicle or hybrid electric vehicle, wherein the compound is present in a lubricating oil composition, used to operate the electric vehicle or hybrid electric vehicle.

19. Use of a compound according to any one of claims 1-8 to inhibit corrosion in a gasoline or diesel fueled internal combustion engine, wherein the compound is present in a lubricating oil composition, or fuel composition used to operate the engine.

20. A method for inhibiting corrosion in a hydrogen, natural gas or ammonia fueled internal combustion engine comprising operating the engine with a lubricating oil composition according to any of claims 9-14.

21. A method for inhibiting corrosion in an electric vehicle or hybrid electric vehicle comprising operating the electric vehicle or hybrid electric vehicle with a lubricating oil composition according to any of claims 9-14.

22. A method for inhibiting corrosion in a gasoline or diesel fueled internal combustion engine comprising operating the engine with a lubricating oil composition according to any of claims 9- 14.

23. Use or method according to any one of claims 15-22, wherein the lubricating oil composition is according to any one of claims 9-14.

24. Use or method according to any one of claims 15-23, wherein the corrosion is metal corrosion, for example, copper, lead and / or steel corrosion, or corrosion of electrical components.

25. Use or method according to claim 24, wherein the corrosion is copper or lead corrosion, optionally wherein copper and / or lead corrosion is (i) reduced by at least 25 % compared to a directly comparable lubricating oil or fuel composition that does not contain the compound, or (ii) is lessT-12636-W001 than 75 ppm, as determined in accordance with the modified ASTM D6594 test method described in the description.

26. A method of making a compound according to claim 1, comprising reacting a polyamine hydrocarbyl bis-succinimide, an aldehyde and a nitrogen-containing heterocycle, for example, wherein the polyamine hydrocarbyl bis-succinimide is heated to at least 50 °C in a suitable solvent over a first period of time, followed by addition of the aldehyde and nitrogen-containing heterocycle to form a reaction mixture, and heating the reaction mixture at a temperature of at least 50 °C for a second period of time.

27. The method of claim 26, wherein the aldehyde is paraformaldehyde and the nitrogen-containing heterocycle is a diazole, a triazole, tetrazole or isomers thereof, such as, 1, 2, 4-triazole, imidazole, or pyrazole.

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