WO2026024971A1 - Lubricating automotive or industrial equipment - Google Patents

Abstract

The disclosed technology relates to a lubricant composition for automotive or industrial equipment containing an oil of lubricating viscosity, a sulfurized olefin, and a metal-containing salixarate detergent, as well as a method of improving corrosion performance by lubricating such automotive or industrial equipment with the lubricant composition.

Description

TITLE

Lubricating Automotive or Industrial Equipment

BACKGROUND

[0001] The disclosed technology relates to a lubricant composition for automotive or industrial equipment containing an oil of lubricating viscosity, a sulfurized olefin, and a metal-containing salixarate detergent, as well as a method of improving corrosion performance by lubricating such automotive or industrial equipment with the lubricant composition.

[0002] Sulfurized olefins are the go-to extreme pressure additives in automotive and industrial lubricants. Sulfurized olefins are known to react with copper to form a variety of copper sulfides and cause copper corrosion issues. Typically lubricant compositions use sulfonate detergents for cleanliness of the formulation. However these sulfonates do not improve copper corrosion performance when sulfurized olefins are present. As such, the use of sulfurized olefin in e-fluids is limited if copper is present due to the increased corrosion and formation of conductive deposits. The ability to formulate with sulfurized olefins without detriment to copper corrosion performance would be extremely beneficial.

SUMMARY

[0003] The use of a metal-containing salixarate detergents in combination with sulfurized olefin was found to be surprisingly beneficial in minimizing copper corrosion while providing protection against gear scuffing, wear and pitting as well as bearing wear and pitting and providing appropriate oxidative stability.

[0004] One aspect of the technology is therefore directed to a lubricant composition containing a sulfurized olefin and metal-containing salixarate detergent.

[0005] Another aspect of the technology encompasses a method of lubricating an automotive or industrial device by supplying thereto the lubricant composition as described, and operating the automotive or industrial device.

DETAILED DESCRIPTION

[0006] Various preferred features and embodiments will be described below by way of non-limiting illustration. One aspect of the invention is a lubricant formulation containing (a) an oil of lubricating viscosity, (b) a sulfurized olefin or mixture thereof, and (c) a metal-containing salixarate detergent. Oil of Lubricating Viscosity

[0007] One component of the disclosed technology is an oil of lubricating viscosity, also referred to as a base oil. The base oil may be selected from any of the base oils in

Groups I-V of the American Petroleum Institute (API) Base Oil Interchangeability Guidelines (2011), namely

Base Oil Category Sulfur (%) Saturates (%) Viscosity Index

Group I >0.03 and/or <90 80 to less than 120

Group II <0.03 and >90 80 to less than 120

Group III <0.03 and >90 >120

Group IV All polyalphaolefins (PAOs)

Group V All others not included in Groups I, II, III or IV

[0008] Groups I, II and III are mineral oil base stocks. Other generally recognized categories of base oils may be used, even if not officially identified by the API: Group II+, referring to materials of Group II having a viscosity index of 110-119 and lower volatility than other Group II oils; and Group III+, referring to materials of Group III having a viscosity index greater than or equal to 130. The oil of lubricating viscosity can include natural or synthetic oils and mixtures thereof. Mixtures of mineral oil and synthetic oils, e.g., polyalphaolefin oils and/or polyester oils, may be used.

[0009] In one embodiment the oil of lubricating viscosity has a kinematic viscosity at 100 °C by ASTM D445 of 1.5 to 7.5, or 2 to 7, or 2.5 to 6.5, or 3 to 6 mm²/s. In one embodiment the oil of lubricating viscosity comprises a poly alpha olefin having a kinematic viscosity at 100 °C by ASTM D445 of 1.5 to 7.5 or any of the other aforementioned ranges.

The Sulfurized Olefin

[0010] The sulfurized olefins employed in the present technology encompass mixtures, the compositions of which are not easily described aside from the reaction used to prepare them. In general, the sulfurized olefins are about 80% polysulfides, mostly di-t- butyl polysulfides, with a range of sulfur atoms of between 3 and 8. The mixtures may be generically represented by the formula: Ri-Sx-IG, where Ri and R2 separately are derived from 2 to 6 carbon atom containing olefins and x is an integer of between 1 and 10, with the proviso that the sulfurized olefin will have a sulfur content of from about 10 to about 75 wt%, or from 10 to 60 wt.% or even from 10 to 50 wt%. [0011] To be more particular, the sulfurized olefins are the reaction products of olefins containing from two to eight carbon atoms reacted with hydrogen sulfide and sulfur under super-atmospheric pressure in the presence of a catalyst.

[0012] Olefinic compounds which may be sulfurized by the method of this invention are diverse in nature and may be substituted or un- substituted. The nature of the substituents if/when the olefin is substituted is not normally a critical aspect of the technology and any such substituent is useful so long as it is or can be made compatible with lubricating environments and does not interfere under the contemplated reaction conditions. Thus, substituted compounds which are so unstable as to deleteriously decompose under the reaction conditions employed are not contemplated. However, certain substituents such as keto or aldehyde can desirably undergo sulfurization. The selection of suitable substituents is within the skill of the art or may be established through routine testing. Typical of such substituents include any of the above-listed moieties as well as hydroxy, amidine, amino, sulfonyl, sulfinyl, sulfonate, nitro, phosphate, phosphite, alkali metal mercapto and the like.

[0013] Example olefins from which the sulfurized olefin can be prepared can contain from 2 to 30 carbon atoms. In some cases the olefins can contain two to 16 carbon atoms. Often, the olefins can contain two to six carbon atoms. The sulfurized olefin may also be prepared from an olefin containing from three to five carbon atoms. The olefin can be butylene. The olefin can also be isobutylene. Amylene may also be employed as the olefin. The olefin may also be isoamylene. The olefin may also be diisobutylene. The olefin may also be cyclohexene ester derived. Sulfurized olefins suitable for use herein may be prepared from mixtures of any of the foregoing olefins.

[0014] The other two reagents which are essential in the method for preparing the sulfurized olefin, sulfur and hydrogen sulfide, are well known and are commercially available. Commercial sources of all these reagents are normally used, and impurities normally associated therewith may be present without adverse results.

[0015] The amounts of sulfur and hydrogen sulfide per mole of olefinic compound are, respectively, about 0.3-2.0 gram-atoms and about 0.1-1.5 moles. The preferred ranges are about 0.5-1.5 gram-atoms and about 0.4-1.25 moles respectively, and the most desirable ranges are about 0.7- 1.2 gram-atoms and about 0.4-0.8 mole respectively. [0016] The temperature range in which the sulfurization reaction is carried out is generally about 50°-350° C. The preferred range is about 100°-200° C, with about 125°- 180° C being especially suitable. The reaction is conducted under superatmospheric pressure; this may be and usually is autogenous pressure (i.e., the pressure which naturally develops during the course of the reaction) but may also be externally applied pressure. The exact pressure developed during the reaction is dependent upon such factors as the design and operation of the system, the reaction temperature, and the vapor pressure of the reactants and products and it may vary during the course of the reaction. [0017] It is frequently advantageous to incorporate materials useful as sulfurization catalysts in the reaction mixture. These materials may be acidic, basic or neutral. Useful neutral and acidic materials include acidified clays such as "Super Filtrol", p-toluenesul- fonic acid, dialkyl-phosphorodithioic acids, and phosphorus sulfides such as phosphorus pentasulfide. The preferred catalysts are basic materials. These may be inorganic oxides and salts such as sodium hydroxide, calcium oxide and sodium sulfide. The most desirable basic catalysts, however, are nitrogen bases including ammonia and amines. The amines includes primary, secondary and tertiary hydrocarbyl amines wherein the hydro- carbyl radicals are alkyl, aryl, aralkyl, alkaryl or the like and contain about 1-20 carbon atoms. Suitable amines include aniline, benzylamine, dibenzylamine, dodecylamine, naphthylamine, tallow amines, N-ethyldipropylamine, N-phenylbenzylamine, N,N-di- ethylbutylamine, m-toluidine and 2,3 -xylidine. Also useful are heterocyclic amines such as pyrrolidine, N-methylpyrrolidine, piperidine, pyridine and quinoline.

[0018] The preferred basic catalysts include ammonia and primary, secondary, or tertiary alkylamines having about 1-8 carbon atoms in the alkyl radicals. Representative amines of this type are methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, di-n-butylamine, tri-n-butylamine, tri-sec-hexylamine and tri-n-octylamine. Mixtures of these amines can be used, as well as mixtures of ammonia and amines.

[0019] The amount of catalytic material used is generally about 0.05-2.0% of the weight of the olefinic compound. In the case of the preferred ammonia and amine catalysts, about 0.0005-0.5 mole per mole of olefin is preferred, and about 0.001-0.1 mole is especially desirable.

[0020] The exact chemical nature of the sulfurized olefins is not known with certainty, and it is most convenient to describe them in terms of the method for their preparation. It appears, however, that when prepared from olefins containing less than 7 carbon atoms, they comprise principally disulfides, trisulfides and tetrasulfides. The sulfur content of these sulfurized compositions is usually about 2-60% by weight, preferably about 25-60% and most desirably about 40-50%. [0021] The foregoing sulfurized olefins are known in the art and further details can be found, for example, in U.S. 4,119,549; U.S. 4,191,659 and U.S. 4,344,854.

[0022] The foregoing sulfurized olefins are distinguishable from oligomeric polysulfides of C4Sx(C4S_y)bC4, where b can be 0 to 8, and x and y can be 1 to 3, such as those prepared by the processes taught, for example, in U.S. Patent Nos. 2,708,199 and 3,697,499. Briefly, such oligomeric polysulfides are prepared by forming an adduct between 1 to 2 moles of olefin and a sulfur halide, followed by reacting the adduct with an alkali metal sulfide, optionally in the presence of free sulfur.

[0023] The amount of sulfurized olefin in the lubricant formulation may be 0.01 to 10 percent by weight. Alternative amounts of the sulfurized olefin may be 0.1 to 8 percent, or 0.2 to 6 percent, or 0.5 to 5 percent by weight. The amount of sulfurized olefin can also be 0.1 to 2 percent by weight, 0.1 to 1 percent by weight, or 0.1 to 1 percent by weight, or even 0.1 -0.5 percent by weight, or 0.2 to 0.5 percent by weight, or 0.2 to 1 percent by weight. The amount of sulfurized olefin present may be suitable to provide sulfur to the lubricant formulation in an amount of 0.5 to 3 wt% sulfur. The amount may also be suitable to provide the lubricant formulation from 0.75 to 2.75 wt% sulfur. The amount may also be suitable to provide the lubricant formulation from 1 to 2.5 wt% sulfur.

[0024] It will be understood by the skilled person that the sulfurized olefin will typically comprise a mixture of various individual chemical species. Reference herein to a sulfurized olefin will be understood by those of ordinary skill to encompass mixtures of such compounds as may be prepared by the described syntheses.

Metal-containing salixarate detergent

[0025] Metal containing salixarate detergents are typically those of having m units of salicylic acid type compounds of formula (la)

(la) and n units of pheno! tvoe compounds of formida !!b)

(lb) joined together to form a ring, wherein each Y is a divalent bridging group which may be the same or different in each unit; RO is H or an alkyl group of 1 to 6 carbon atoms; R5 is H or an alkyl group of 1 to 60 carbon atoms; j is 1 or 2; R3 is hydrogen, a hydrocarbyl or a hetero-substituted, hydorcarbyl group; either R1 is hydroxy and R2 and R4 are independently either hydrogen, hydrocarbyl or hetero-substituted hydrocarbyl, or R2 and R4 are hydroxyl and R1 is either hydrogen, hydrocarbyl or hetero-substituted hydrocarbyl; m is from 1 to 8; n is at least 3; and m+n is 4 to 20.

[0026] When more than one salicylic acid type unit is present in the ring (ie m>l), the salicylic acid type units (formula (la)) and phenol type units (formula (lb)) are distributed randomly, although this does not exclude the possibility that in some rings there may be several salicylic acid type units joined together in a row.

[0027] Each Y may independently be represented by the formula (CHR6)d in which R6 is either hydrogen or hydrocarbyl and d is an integer which is at least 1. In one embodiment, R6 contains 1 to 6 carbon atoms, and in one embodiment it is methyl. In one embodiment, d is from 1 to 4. Y may optionally be sulphur rather than (CHR6)d in up to 50% of the units, such that the amount of sulphur incorporated in the molecule is up to 50 mole %. In one embodiment, the amount of sulphur is between 8 and 20 mole %, and in one embodiment the compound is sulphur-free.

[0028] Regarding R1 to R6, the term “hydrocarbyl” includes (C1-C60) alkyl such as t-butyl, t-amyl, s-butyl, isopropyl, octyl, nonyl, dodecyl and octadecyl. Alternatively the hydrocarbyl group may be derived from a polyolefin, for example polyethylene, polypropylene, polybutylene or a polyolefin copolymer, for example an ethyl ene/propylene copolymer, preferably derived from a polyisobutene. Examples include dodecyl and octadecyl. Alternatives include isoprene-butadiene, styrene-isoprene or styrene-butadiene block copolymers such as those disclosed in WO 96/40846, or ethylene-propylene and ethylene- butene-1 copolymers having molecular weights from 1500 to 2500 or 7500, as disclosed in U.S. Pat. No. 5,567,344 and U.S. Pat. No.5, 578, 237. Mixtures of all the above may also be employed. Any hetero- substituted hydrocarbyl group has the heteroatom, preferably — O — or =NH, interrupting a chain of carbon atoms, such as an alkoxy-alkyl group of 2- 20 carbons.

[0029] In one embodiment, Y is CH2; R1 is hydroxyl; R2 and R4 are independently either hydrogen, hydrocarbyl or hetero- substituted hydrocarbyl; R3 is either hydrocarbyl or hetero- substituted hydrocarbyl; R0 is H; R5 is an alkyl group of 6 to 50 carbon atoms, and in one embodiment 4 to 40 carbon atoms, and in one embodiment 6 to 25 carbon atoms; and m+n has a value of at least 5, and in one embodiment at least 6, and in one embodiment at least 8, where m is 1 or 2, and in one embodiment m is 1.

[0030] In one embodiment, R2 and R4 are hydrogen; R3 is hydrocarbyl, and in one embodiment alkyl of greater than 4 carbon atoms, and in one embodiment greater than 9 carbon atoms; R5 is hydrogen; and m+n is from 6 to 12; m is 1 or 2. A particularly preferred salixarene is dodecyl-salicylic calix[8]arene, which has the structure.

[0031] In one embodiment, the salixarate is the same as the foregoing except that it has two salicylic acid type units rather than one in an 8-unit ring as above.

[0032] The detergent may be borated or non-borated.

[0033] In one embodiment the metal -containing salixarate detergent may be a sodium, potassium, calcium, or magnesium containing detergent, or mixtures thereof. In one embodiment of the present invention, the detergent is a calcium-containing salixarate detergent.

[0034] Such detergents and the preparation thereof are well known in the art but may also include those hereafter developed. The TBN and metal ratios may however, differ slightly. A more detailed description of the expressions “metal ratio”, TBN and “soap content” are known to a person skilled in the art and explained in standard textbooks, such as, for example, “Chemistry and Technology of Lubricants”, Third Edition, Edited by R. M. Mortier and S. T. Orszulik, Copyright 2010, pages 219 to 220 under the subheading 7.2.5. Detergent Classification.

[0035] The metal-containing salixarate detergent may be a non-overbased detergent (may also be referred to as a neutral detergent). The TBN of a non-overbased detergent may be 20 to less than 200, or 30 to 100, or 35 to 50 mg KOH/g. The TBN of a non- overbased detergent, on a diluent oil free basis, may also be 20 to 175, or 30 to 100 mg KOH/g.

[0036] As used herein the TBN values quoted and associated range of TBN is on “an as is basis,” i.e., containing conventional amounts of diluent oil. Conventional amounts of diluent oil typically range from 30 wt % to 60 wt % (often 40 wt % to 55 wt %) of the detergent component.

[0037] The metal-containing detergent may be an overbased detergent, having, for example, a TBN of greater than 200 mg KOH/g (typically 250 to 600, or 300 to 500 mg KOH/g).

[0038] The overbased metal-containing detergent may be formed by the reaction of a basic metal compound, for example, containing sodium, potassium, calcium or magnesium, and an acidic detergent substrate.

[0039] The basic metal compound is used to supply basicity to the detergent. The basic metal compound is a compound of a hydroxide or oxide of the metal.

[0040] The oxides and/or hydroxides may be used alone or in combination. The oxides or hydroxides may be hydrated or dehydrated, although hydrated is typical. In one embodiment the basic metal compound may be calcium hydroxide, which may be used alone or mixtures thereof with other metal basic compounds. Calcium hydroxide is often referred to as lime. In one embodiment the calcium basic compound may be calcium oxide which may be used alone or mixtures thereof with other metal basic compounds. [0041] The metal-containing detergent can be included in an amount to deliver up to 2000 ppm metal, e.g., sodium, potassium, calcium, or magnesium, to the composition, or from 100 ppm to 1000 ppm, or 100 ppm to 600 ppm metal, or from 100 ppm to 250 ppm, or even from 400 ppm to 750 ppm of metal.

Corrosion Inhibitor

[0042] The lubricant formulation can also include a corrosion inhibitor. The corrosion inhibitor may also be described as a metal deactivator or a yellow-metal passivator. [0043] Examples of a corrosion inhibitor include triazoles, such as benzotriazoles and 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles, 2-alkyldithiobenzo- thiazoles, 2-(N,N-dialkyldithiocarbamoyl)benzothiazoles, 2,5-bis(alkyl-dithio)-l,3,4- thiadiazoles, 2,5-bis(N,N-dialkyldithiocarbamoyl)-l,3,4-thiadiazoles, 2-alkyldithio-5- mercapto thiadiazoles or mixtures thereof. In one embodiment the corrosion inhibitor includes a benzotri azole. In one embodiment the corrosion inhibitor includes a 2,5- bis(alkyl-dithio)-l,3,4-thiadiazole.

[0044] Examples of suitable hydrocarbyl benzotriazoles further reacted with an aldehyde and an amine include N,N-bis(2-ethylhexyl)-ar-methyl-lH-benzotriazole-l- m ethanamine, N,N-bis(2-ethylhexyl)-4-methyl-lH-benzotriazole-l-m ethanamine, N,N- bis(2-ethylhexyl)-4-methyl-lH-benzotriazole-l-methanamine, 2H-benzotriazole-2- m ethanamine, N-(4-methoxyphenyl)-lH-benzotriazole-l-m ethanamine, N,N-di- dodecyl-lH-benzotriazole-l-m ethanamine, N-(lH-benzotriazol-l-ylmethyl)-N-(2- ethylhexyl)-lH-benzotriazole-l-methanamine, N-methyl-N-phenyl-lH-benzotriazole- 1-methanamine, 4,5,6,7-tetrahydro-N,N-ditridecyl-lH-benzotriazole-l-methanamine, N,N-dioctadecyl- IH-benzotri azole- 1-methanamine, 5-methyl-N,N-dioctyl-lH-ben- zotriazole-l-methanamine, N,N-dibutyl-lH-benzotriazole- 1-methanamine, N-(4- m ethylphenyl)- IH-benzotriazole- 1-methanamine, N,N-bis(2-ethylhexyl)-lH-benzotria- zole- 1-methanamine, N,N-dioctyl-2H-benzotriazole-2-methanamine, N-dodecyl-lH- benzotriazole- 1-methanamine, N-phenyl-lH-benzotriazole- 1-methanamine, N,N-di- dodecyl-4, 5, 6, 7-tetrahydro-lH-benzotriazole- 1-methanamine, N,N-bis(2-ethylhexyl)- 5 -methyl- IH-benzotriazole- 1-methanamine, N-octadecyl-lH-benzotriazole-l-m ethanamine, N,N-didodecyl-2H-benzotriazole-2-methanamine, N,N-dioctyl-lH-benzotria- zole- 1-methanamine, N-(2-ethylhexyl)- IH-benzotriazole- 1-methanamine, 4,5,6,7-tetra- hydro-N,N-ditetradecyl-lH-benzotriazole-l-methanamine, or mixtures thereof. In one embodiment the corrosion inhibitor includes N,N-bis(2-ethylhexyl)-4-methyl-lH-ben- zotriazole-l-methanamine or N,N-bis(2-ethylhexyl)-ar-m ethyl- IH-benzotri azole- 1- m ethanamine.

[0045] Examples of suitable hydrocarbyl 1,2,4-triazoles further reacted with an amine include N,N-Bis(l-methylethyl)-lH-l,2,4-triazole-l-methanamine, N,N-diisobu- tyl- 1H-1, 2, 4-triazole-l-m ethanamine, N, N-di cyclohexyl- 1H- 1,2, 4-tri azole- 1-m ethanamine, N,N-bis(2-ethylhexyl)-lH-l,2,4-Triazole-l-methanamine, 1 -(( 1H- 1,2, 4-tri azol - l-yl)methyl)piperidine, N,N-bis(tridecyl)-lH-l,2,4-Triazole-l-methanamine, N,N-di- m ethyl- 1-(1H- 1,2, 4-tri azol- l-yl)methanamine, N,N-dibutyl-lH- 1,2, 4-tri azole- 1-m ethanamine, N,N-dicoco-l-(lH- 1,2, 4-tri azol- l-yl)methanamine, N-((lH-l,2,4-triazol-l- yl)methyl)octan-3 -amine.

[0046] In different embodiments the corrosion inhibitor is a triazole. Triazole corrosion inhibitors may be present, alone, or as mixtures with other triazoles or other azole corrosion inhibitors, in ranges including about 0.005 or 0.01 wt % to about 0.1 wt %, or about 0.03 wt % to about 0.08 wt %, or about 0.04 wt % to about 0.068 wt %, or about 0.045 wt % to about 0.057 wt % of the lubricant additive composition.

[0047] In an embodiment the corrosion inhibitor can be a thiadiazole, such as a 1,3,4- thiadiazole. In embodiments, the 1,3,4-thiadiazole can include substituents at the 2 and 5 positions of the thiadiazole ring, such as, for example, alkyldi sulfaneyl moi eties. Such corrosion inhibitors can include those of formula wherein Ri and R2 are independently al yl groups with 1 to 12 carbons.

[0048] Examples of a thiadiazole include 2,5-dimercapto-l,3,4-thiadiazole, or oligomers thereof, a hydrocarbyl-substituted 2,5-dimercapto-l,3,4-thiadiazole, a hydro- carbylthio-substituted 2,5-dimercapto-l,3,4-thiadiazole, or oligomers thereof. The oligomers of hydrocarbyl-substituted 2,5-dimercapto-l,3,4-thiadiazole typically form by forming a sulfur- sulfur bond between 2,5-dimercapto-l,3,4-thiadiazole units to form oligomers of two or more of said thiadiazole units. Further examples of thiadiazole compounds are found in WO 2008,094759, paragraphs 0088 through 0090. The thiadiazoles can be included at concentrations of from about 0.01 to about 2 wt%, or about 0.05 to about 1.5 wt%, or even 0.1 to about 1 wt%.

[0049] In one embodiment, the corrosion inhibitor can include (i) a 2,5-bis(alkyl- dithio)-l,3,4-thiadiazole, (ii) a benzotriazole containing a hydrocarbyl substitution on at least one of the following ring positions 4- or 5- or 6- or 7-, or (iii) a benzotriazole containing a hydrocarbyl substitution (typically a benzotriazole further reacted with an aldehyde and an amine) at least one of the following ring positions 1- or 2-.

[0050] In one embodiment, the corrosion inhibitor can include 2,5-bis(alkyl-dithio)-

1.3.4-thiadiazoles. In different embodiments the alkyl groups of 2,5-bis(alkyl-dithio)-

1.3.4-thiadiazoles contain 1 to about 30, or about 2 to about 25, or 4 to about 20, or about 6 to about 16 carbon atoms. Examples of suitable 2,5-bis(alkyl-dithio)-l,3,4- thiadiazoles include 2,5-bis(tert-octyldithio)-l,3,4-thiadiazole, 2,5-bis(tert-nonyl- dithio)-l,3,4-thiadiazole, 2,5-bis(tert-decyldithio)-l,3,4-thiadiazole, 2,5-bis(tert-un- decyldithio)-l,3,4-thiadiazole, 2,5-bis(tert-dodecyldithio)-l,3,4-thiadiazole, or mixtures thereof.

[0051] The corrosion inhibitor may be used alone or in combination with two, three or more corrosion inhibitors. In one embodiment the corrosion inhibitor includes a mixture of (i) a 2,5-bis(alkyl-dithio)-l,3,4-thiadiazole, (ii) a benzotriazole containing a hydrocarbyl substitution on at least one of the following ring positions 4- or 5- or 6- or 7- , and (iii) a benzotriazole containing a hydrocarbyl substitution (typically a benzotriazole further reacted with an aldehyde and an amine) on at least one of the following ring positions, 1- or 2-.

[0052] In different embodiments the corrosion inhibitor is a thiadiazole. Thiadiazole corrosion inhibitors may be present alone or in mixtures with other thiadiazole corrosion inhibitors or other azole corrosion inhibitors in ranges including about 0.01 wt % to about 1 wt %, or about 0.05 wt % to about 0.9 wt %, or about 0.1 wt % to about 0.8 wt %, or about 0.2 wt % to about 0.7 wt % of the lubricant additive composition or 0.2 wt % to about 0.5 wt % or 0.25 wt % to about 0.35 wt % of the lubricant additive composition.

[0053] Other corrosion inhibitors include various oxygenated materials that may be formed by partial oxidation of waxes or oils. Examples include paraffinic oil oxidates, wax oxidates, and petroleum oxidates. Other corrosion inhibitors include organic boron compounds such as long chain alkenyl amide borates. Yet others include alkali metal sulfonates such as sodium sulfonates and sodium alkylbenzenesulfonates. [0054] Other corrosion inhibitors include esters of hydroxy-acids such as tartaric acid, citric acid, malic acid, lactic acid, oxalic acid, glycolic acid, hydroxypropionic acid, and hydroxyglutaric acid. Examples of these include esters, including tartrate esters (that is, especially the diesters), formed from Ce-12 or Ce-io or Cs-io alcohols, e.g., isotridecyl tartrate, 2-ethylhexyl tartrate, and mixed tartrate esters of C12-14 linear alcohol/Ci3 branched alcohol (e.g., 80-95:20-5 ratios or 90: 10 ratio). Amides and imides of such materials may also be useful.

[0055] Yet other corrosion inhibitors include polyethers. These include polyalkylene oxides such as polyethylene oxide, polypropylene oxide, and copolymers of ethylene oxide and propylene oxide. Such polyethers may be capped at one end with an alkyl group such as a butyl group. Materials of this type are commercially available and are believed to be butyl-capped polypropylene oxides or butyl-capped ethylene oxidepropylene oxide copolymers. Such materials, if they contain a hydroxy group at one end of the chain, may also be referred to as polyether alcohols or polyether polyols.

[0056] In one embodiment the corrosion inhibitor can be a poly ether. In other embodiments the corrosion inhibitor can be one or more of a fatty amine, a condensate of a hydroxyamine with a fatty acid, a carboxylic acid, ester, or salt, a sarcosine derivative, a triazole compound, an ethyoxylated phenol, a partially oxidized wax or oil, a long chain alkenyl amide borate, an ester of a hydroxy acid, or a sodium sulfonate.

[0057] The corrosion inhibitor can be present from 0.02 to 2 percent by weight of the lubricant formulation and in alternative embodiments 0.05 to lwt% or 0.1 to 0.5wt% or 0.1 to 0.2wt% or even 0.05 to 2 wt%.

Other Additives

[0058] The lubricant formulation can also contain other additives. For example, the lubricant can include phosphate and/or thiophosphate compound, and as post treated dispersants.

[0059] Other materials may be present in the lubricant formulation in their conventional amounts including, for example, viscosity modifiers, dispersants, pour point additives, extreme pressure agents, antifoams, friction modifiers, dyes, fragrances, and antioxidants, and color stabilizers, for example.

[0060] Friction modifiers are known and can include fatty amines, esters, especially glycerol esters such as glycerol monooleate, borated glycerol esters, fatty phosphites, fatty acid amides, fatty epoxides, borated fatty epoxides, alkoxylated fatty amines, borated alkoxylated fatty amines, metal salts of fatty acids, sulfurized olefins, fatty imidazolines, condensation products of carboxylic acids and polyalkylene-polyamines, amine salts of alkylphosphoric acids.

[0061] A lubricant formulation, as used herein, refers to a lubricant formulation having sufficient levels of additive to lubricate an industrial gear or driveline power transmitting device, including an automotive gear, such as a gear, bearing or axle, or a transmission. In this regard, a lubricant formulation can be distinguished from other lubricants, such as engine oil lubricants, based on levels of sulfur and phosphorus. The lubricant formulation can have a total sulfur level of about 0.2 to about 5 wt.% based on the weight of the lubricant formulation. In some embodiments, the total sulfur level can be from about 0.8 to about 4 wt.%, or even about 0.9 to about 3.5 wt.% or about 1 to about 3 wt.%. The lubricant formulation can have a total sulfur level of about 0.2 wt.% or greater based on the weight of the lubricant formulation. In some embodiments, the total sulfur level can be from about 0.4 wt.% or greater, or even about 0.6 wt.%. The lubricant formulation can have a total sulfur level of about 700 ppm to 5000 ppm, 700 ppm to 4000 ppm, 700 ppm to 3000 ppm, or 700 to 2000 ppm, or 800 ppm to 2000 ppm, or even 1000 ppm to 4000 ppm, or even 2000 ppm to 5000 ppm.

[0062] The lubricant formulation can also have a total phosphorus level of about 0.01 to about 0.5 wt.%, or 0.03 to about 0.35 wt.%, or even about 0.05 to about 0.3 wt.% or even 100 ppm to 3000 ppm, or lOOppm to 2000 ppm, or even 100 ppm to lOOOppm.

[0063] The phosphorus can be brought to the lubricant formulation, for example, from the amine alkyl(thio)phosphate discussed above, or other phosphorus containing compounds. Such other phosphorus containing compounds can include, for example, phosphites or phosphonates. Suitable phosphites or phosphonates include those having at least one hydrocarbyl group with 3 or 4 or more, or 8 or more, or 12 or more, carbon atoms. The phosphite may be a mono-hydrocarbyl substituted phosphite, a di- hydrocarbyl substituted phosphite, or a tri -hydrocarbyl substituted phosphite. The phosphonate may be a mono-hydrocarbyl substituted phosphonate, a di -hydrocarbyl substituted phosphonate, or a tri-hydrocarbyl substituted phosphonate.

[0064] In one embodiment the phosphite is sulphur-free i.e., the phosphite is not a thiophosphite.

[0065] The phosphite or phosphonate may be represented by the formulae: wherein at least one R may be a hydrocarbyl group containing at least 3 carbon atoms and the other R groups may be hydrogen. In one embodiment, two of the R groups are hydrocarbyl groups, and the third is hydrogen. In one embodiment every R group is a hydrocarbyl group, i.e., the phosphite is a tri -hydrocarbyl substituted phosphite. The hydrocarbyl groups may be alkyl, cycloalkyl, aryl, acyclic or mixtures thereof.

[0066] In the art, a phosphonate (i.e., formula XI with R = hydrocarbyl) may also be referred to as a phosphite ester. Where one of the R groups in formula XII is an H group, the compound would generally be considered a phosphite, but such a compound can often exist in between the tautomers of formula XI and XII, and thus, could also be referred to as a phosphonate or phosphite ester. For ease of reference, the term phosphite, as used herein, will be considered to encompass both phosphites and phospho- nates.

[0067] The R hydrocarbyl groups may be linear or branched, typically linear, and saturated or unsaturated, typically saturated.

[0068] In one embodiment, the other phosphorus-containing compound can be a C3- 8 hydrocarbyl phosphite, or mixtures thereof, i.e., wherein each R may independently be hydrogen or a hydrocarbyl group having 3 to 8, or 4 to 6 carbon atoms, typically 4 carbon atoms. Typically the C3-8 hydrocarbyl phosphite comprises dibutyl phosphite.

[0069] In one embodiment, the phosphorus-containing compound can be a C12-22 hydrocarbyl phosphite, or mixtures thereof, i.e., wherein each R may independently be hydrogen or a hydrocarbyl group having 12 to 24, or 14 to 20 carbon atoms, typically 16 to 18 carbon atoms. Typically the C 12-22 hydrocarbyl phosphite comprises a C16-18 hydrocarbyl phosphite. Examples of alkyl groups for R³, R⁴ and R⁵ include octyl, 2- ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonadecyl, eicosyl or mixtures thereof. The C 12-22 hydrocarbyl phosphite may be present in the lubricant formulation at about 0.05 wt.% to about 4.0 wt.% of the lubricant formulation, or from about 0.05 wt.% to about 3 wt.%, or from about 0.05 wt.% to about 1.5 wt.%, or from about 0.05 wt.% to about 1 wt.%, or from about 0.1 wt.% to about 0.5 wt.% of the lubricant formulation.

[0070] In some embodiments, the other phosphorus containing compound can include both a C3-8 and a C12 to C24 hydrocarbyl phosphite.

[0071] In one embodiment, the phosphite ester comprises the reaction product of (a) a monomeric phosphoric acid or an ester thereof with (b) at least two alkylene diols; a first alkylene diol (i) having two hydroxy groups in a 1,4 or 1,5 or 1,6 relationship; and a second alkylene diol(ii) being an alkyl -substitute 1,3 -propylene glycol.

[0072] Sulfur containing phosphites can include, for example, a material represented by the formula [R¹O(OR²)(S)PSC2H4(C)(O)OR⁴O]_nP(OR⁵)2-n(O)H, wherein R¹ and R² are each independently hydrocarbyl groups of 3 to 12 carbon atoms, or 6 to 8 carbon atoms, or wherein R¹ and R² together with the adjacent O and P atoms form a ring containing 2 to 6 carbon atoms; R⁴ is an alkylene group of 2 to 6 carbon atoms or 2 to 4 carbon atoms; R⁵ is hydrogen or a hydrocarbyl group of 1 to about 12 carbon atoms; and n is 1 or 2. The C12-22 hydrocarbyl phosphite may be present in the lubricant formulation at about 0.05 wt.% to about 1.5 wt.% of the lubricant formulation, or from about 0.1 wt.% to about 1.0 wt.% of the lubricant formulation.

[0073] In one embodiment, the other phosphorus containing compound can be a phosphorus containing amide. Phosphorus containing amides can be prepared by reaction of dithiophosphoric acid with an unsaturated amide. Examples of unsaturated amides include acrylamide, N,N’ -methylene bisacrylamide, methacrylamide, crotonamide and the like. The reaction product of the phosphorus acid and the unsaturated amide may be further reacted with a linking or a coupling compound, such as formaldehyde or paraformaldehyde. The phosphorus containing amides are known in the art and are disclosed in U.S. Pat. Nos. 4,670,169, 4,770,807 and 4,876,374 which are incorporated by reference for their disclosures of phosphorus amides and their preparation.

[0074] The lubricant formulation may have a kinematic viscosity at 100 °C by ASTM D445 of between 1.5 or 2 and 25 cSt. The lubricant formulation may have a kinematic viscosity at 100 °C by ASTM D445 of between 2 and 15 cSt. The lubricant formulation may have a kinematic viscosity at 100 °C by ASTM D445 of between 2 and 12 cSt. The lubricant formulation may have a kinematic viscosity at 100 °C by ASTM D445 of between 2 and 9 cSt. The lubricant formulation may have a kinematic viscosity at 100 °C by ASTM D445 of between 2 and 7 cSt. The lubricant formulation may have a kinematic viscosity at 100 °C by ASTM D445 of between 2 and 6 cSt. The lubricant formulation may have a kinematic viscosity at 100 °C by ASTM D445 of between 2 and 5 cSt. The lubricant formulation may have a kinematic viscosity at 100 °C by ASTM D445 of between 3 and 6.5 cSt. The lubricant formulation may have a kinematic viscosity at 100 °C by ASTM D445 of between 3 and 5.5 cSt or even 2.5 and 5 cSt, or 2.5 to 4 cSt or 7 to 18 cSt, 7 to 15 cSt, or even 7 to 12 cSt, or even 9 to 12 cSt.

[0075] The lubricant additive composition will be suitable for lubricating automotive or industrial equipment.

[0076] Automotive equipment includes the driveline equipment. The lubricant formulation may be employed in the driveline of an electric vehicle, and in particular, a gearbox of an electric motor in the electric vehicle when in the form of a lubricant formulation. In particular, the lubricant additive composition will be suitable for lubricating a transmission in a vehicle with an electric motor, which may be a full electric vehicle or a hybrid-electric vehicle having both an electric motor and an engine powered by hydrocarbon or other fuels.

[0077] In particular, the disclosed technology provides a method of lubricating a driveline power transmitting device, comprising supplying thereto a lubricant formulation as described herein, that is, containing base oil, sulfurized olefin, and metal -containing salixarate detergent and operating the driveline power transmitting device for a sufficient period to allow the lubricant formulation to achieve the improved results as described herein.

[0078] In particular, the disclosed technology provides a method of lubricating a driveline power transmitting device, comprising supplying thereto a lubricant formulation as described herein, that is, containing sulfurized olefin, corrosion inhibitor and metalcontaining salixarate detergent, and operating the driveline power transmitting device for a sufficient period to allow the lubricant formulation to achieve the improved results as described herein.

[0079] The driveline power transmitting device may comprise at least two gears as in a gearbox of a vehicle (e.g., a manual transmission) or in an axle or differential, or in other driveline power transmitting devices. The driveline power transmitting device may also include bearings. The rolling elements of the bearings may be cylindrical or ball in design. Lubricated gears may include amboid, or spiral bevel, or more commonly hypoid gears, such as those for example in a drive axle. The axles may have a gear ratio of 2:1 to 8: 1, and the ring gear maybe be approximately 13 to 64 cm in diameter. The axle may incorporate an open differential or some type of traction enabling device. The axle may be part of a drivetrain with one or more drive axles, such as a tandem or tridem design, in which the axles may be coupled together with a power divider. Application of these axles includes light, medium and heavy duty vehicles (e.g. vocational or line haul service), and could be used on or off highway. The axle may be from a traditional petroleum powered vehicle, may be from an electrically driven vehicle, or a hybrid thereof. The electrically driven axle can combine an electric motor, power electronics and transmission in a unit directly powering the vehicle's axle.

[0080] One aspect is a method of lubricating an electric vehicle comprising supplying to a driveline of the electric vehicle a lubricant formulation containing sulfurized olefin and salixarate detergent as described herein, and operating the driveline.

[0081] Another aspect is a method of lubricating a transmission, and particularly a transmission in a vehicle with an electric motor, comprising supplying to the transmission a lubricant formulation containing the lubricant additive composition as described herein, and operating the transmission.

[0082] The lubricant should be able to meet the aspects expected of it in normal operation of the driveline power transmitting device.

[0083] The transmissions in which the lubricant formulation may be suitable include automatic transmissions and dual clutch transmissions. The transmission may or may not include a shifting clutch, and, where the transmission includes a shifting clutch, the clutch may be a dry clutch or a wet clutch. In one embodiment, the lubricant may be used on a transmission that does not contain a shifting clutch. In another embodiment, the lubricant additive composition may be employed in a transmission having a wet clutch. In a further embodiment, the lubricant additive composition may be employed on a transmission having a dry clutch.

[0084] The driveline device may be a manual transmission that may or may not contain a synchronizer system, or an axle. In one embodiment the driveline device contains a synchronizer, or axle.

[0085] In one embodiment the driveline device contains a synchronizer. The synchronizer system may have an operating surface comprising brass, carbon, molybdenum, phenolic resin, or a sintered metal (typically bronze), or mixtures thereof.

[0086] As used herein, the term “condensation product” is intended to encompass esters, amides, imides and other such materials that may be prepared by a condensation reaction of an acid or a reactive equivalent of an acid (e.g., an acid halide, anhydride, or ester) with an alcohol or amine, irrespective of whether a condensation reaction is actually performed to lead directly to the product. Thus, for example, a particular ester may be prepared by a transesterification reaction rather than directly by a condensation reaction. The resulting product is still considered a condensation product.

[0087] The technology disclosed may also include a method of lubricating an internal combustion engine comprising supplying to the engine a lubricating formulation comprising an oil of lubricating viscosity, a sulfurized olefin and a metal-containing salixarate detergent.

[0088] The internal combustion engine may be a 2-stroke engine, or a 4-stroke engine. Suitable internal combustion engines include marine diesel engines, aviation piston engines, low-load diesel engines, and automobile and truck engines. The marine diesel engine may be lubricated with a marine diesel cylinder lubricant (typically in a 2-stroke engine), a system oil (typically in a 2-stroke engine), or a crankcase lubricant (typically in a 4-stroke engine).

[0089] The internal combustion engine may be a 4-stroke engine. The internal combustion engine may or may not have an Exhaust Gas Recirculation system. The internal combustion engine may be fitted with an emission control system or a turbocharger. Examples of the emission control system include diesel particulate filters (DPF), or systems employing selective catalytic reduction (SCR).

[0090] The internal combustion engine may be port fuel injected or direct injection. In one embodiment, the internal combustion engine is a gasoline direct injection (GDI) engine.

[0091] The lubricant formulation, in respect of lubricating an internal combustion engine, may have a total sulfated ash content of 1.2 wt % or less. The sulfur content of the lubricant formulation may be 1 wt % or less, or 0.8 wt % or less, or 0.5 wt % or less, or 0.3 wt % or less. In one embodiment the sulfur content may be in the range of 0.001 wt % to 0.5 wt %, or 0.01 wt % to 0.3 wt %. The phosphorus content may be 0.2 wt % or less, or 0.12 wt % or less, or 0.1 wt % or less, or 0.085 wt % or less, or 0.08 wt % or less, or even 0.06 wt % or less, 0.055 wt % or less, or 0.05 wt % or less. In one embodiment the phosphorus content may be 0.04 wt % to 0.12 wt %. In one embodiment the phosphorus content may be 100 ppm to 1000 ppm, or 200 ppm to 600 ppm. The total sulfated ash content may be 0.3 wt % to 1.2 wt %, or 0.5 wt % to 1.1 wt % of the lubricant formulation. In one embodiment the sulfated ash content may be 0.5 wt % to 1.1 wt % of the lubricant formulation.

[0092] In one embodiment in respect of lubricating an internal combustion engine the lubricant formulation may be characterized as having (i) a sulfur content of 0.5 wt % or less, (ii) a phosphorus content of 0.15 wt % or less, and (iii) a sulfated ash content of 0.5 wt % to 1.5 wt % or less.

[0093] The lubricant formulation in respect of lubricating an internal combustion engine may be characterized as having at least one of (i) a sulfur content of 0.2 wt % to 0.4 wt % or less, (ii) a phosphorus content of 0.08 wt % to 0.15 wt %, and (iii) a sulfated ash content of 0.5 wt % to 1.5 wt % or less.

[0094] The lubricant formulation may be characterized as having a sulfated ash content of 0.5 wt % to 1.2 wt %.

[0095] As used herein TBN values are (total base number) measured by the methodology described in D4739 (buffer).

[0096] The lubricant formulation may be characterized as having a total base number (TBN) content of at least 5 mg KOH/g.

[0097] The lubricant formulation may be characterized as having a total base number (TBN) content of 6 to 13 mg KOH/g, or 7 to 12 mg KOH/g. The lubricant may have a SAE viscosity grade of XW-Y, wherein X may be 0, 5, 10, or 15; and Y may be 16, 20, 30, or 40.

[0098] The internal combustion engine disclosed herein may have a steel surface on a cylinder bore, cylinder block, or piston ring.

[0099] The internal combustion engine disclosed herein may be a 2-stroke marine diesel engine, and the disclosed technology may include a method of lubricating a marine diesel cylinder liner of a 2-stroke marine diesel engine.

[0100] The internal combustion engine may have a surface of steel, or an aluminum alloy, or an aluminum composite. The internal combustion engine may be an aluminum block engine where the internal surface of the cylinder bores has been thermally coated with iron, such as by a plasma transferred wire arc (PTWA) thermal spraying process. Thermally coated iron surfaces may be subjected to conditioning to provide ultra-fine surfaces.

[0101] The internal combustion engine may have a laden mass (sometimes referred to as gross vehicle weight rating (GVWR)) of over 2,700 kg (or 6,000 USA pounds) 2,900 kg, or over 3,00 kg, or over 3,300 kg, or over 3,500 kg, or over 3,700 kg, or over 3,900 kg (or 8,500 USA pounds). Typically the upper limit on the laden mass or GVWR is set by national government and may be 10,000 kg, or 9,000 kg, or 8,000 kg, or 7,500 kg.

[0102] Heavy duty diesel engines are noted to be limited to all motor vehicles with a “technically permissible maximum laden mass” over 3,500 kg, equipped with compression ignition engines or positive ignition natural gas (NG) or LPG engines. In contrast, the European Union indicates that for new light duty vehicles (passenger cars and light commercial vehicles) included within the scope of ACEA testing section “C” have a “technically permissible maximum laden mass” not exceeding 2610 kg.

[0103] There is a distinct difference between passenger car, and heavy duty diesel engines. The difference in size from over 3,500 kg to not more than 2610 kg means that engines of both types will experience significantly different operating conditions such as load, oil temperatures, duty cycle and engine speeds. Heavy duty diesel engines are designed to maximize torque for hauling payloads at maximum fuel economy while passenger car diesels are designed for commuting people and acceleration at maximum fuel economy. The designed purpose of the engine hauling versus communing results in different hardware designs and resulting stresses imparted to lubricant designed to protect and lubricate the engine. Another distinct design difference is the operating revolution per minute (RPM) that each engine operates at to haul versus commute. A heavy duty diesel engine such as a typical 12-13 litre truck engine would typically not exceed 2200 rpm while a passenger car engine can go up to 4500 rpm. In one embodiment the internal combustion engine is a heavy duty diesel compression ignited internal combustion engine (or a spark assisted compression ignited) internal combustion engine.

[0104] Typically the vehicle powered by the compression-ignition internal combustion engine of the disclose technology has a maximum laden mass over 3,500 kg (a heavy duty diesel engine).

[0105] The amount of each chemical component described is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, that is, on an active chemical basis, unless otherwise indicated. However, unless otherwise indicated, each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade. [0106] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include:

• hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);

• substituted hydrocarbon substituents, that is, substituents containing nonhydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);

• hetero substituents, that is, substituents which, while having a predominantly hydrocarbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms and encompass substituents as pyridyl, furyl, thienyl and imidazolyl. Heteroatoms include sulfur, oxygen, and nitrogen. In general, no more than two, or no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; alternatively, there may be no non-hydrocarbon substituents in the hydrocarbyl group.

[0107] It is known that some of the materials described herein may interact in the final formulation, so that the components of the final formulation may be different from those that are initially added. For instance, metal ions (of, e.g., a detergent) can migrate to other acidic or anionic sites of other molecules. The products formed thereby, including the products formed upon employing the composition of the present invention in its intended use, may not be susceptible of easy description. Nevertheless, all such modifications and reaction products are included within the scope of the present invention; the present invention encompasses the composition prepared by admixing the components described above.

[0108] The invention herein may be better understood with reference to the following examples. EXAMPLES

1. All amounts are shown in weight percent and on an oil-free basis unless otherwise noted.

2. Additive package includes at least one viscosity modifier, at least one aminic antioxidant, at least one phenolic antioxidant, at least one anti-foam agent, at least one pour point depressant at least one boronated dispersant, an at least one anti-wear agent, and at least one friction modifier

3. Sulfurized isobutylene (45 wt% sulfur; 35-40 wt% active sulfur, by ASTM D1662)

[0109] The formulations were tested using the wire corrosion test (WCT) according to the method as outlined in the following documents and incorporated herein - Hunt, G., "New Perspectives on the Temperature Dependence of Lubricant Additives on Copper Corrosion," SAE Int. J. Fuels Lubr. 10(2):521-527, 2017; Hunt, G., Gahagan, M, P., Peplow, M, A., “Wire resistance method for measuring the corrosion of copper by lubricating fluids” Lubrication Science, 29,4; and Hunt et al., “Device and testing apparatus for liquid and vapor wire exposure testing,” U.S. Patent No. 12092562, Sep. 17, 2024. Two approximately 1 meter long, 64 pm diameter pure copper (99.99 wt%) wires were used. One was suspended in 400 mL ± 1 mL of test lubricant (solution) and the other fixed above the test lubricant (vapor). A direct current of 1 mA was applied to each wire. The lubricant is held to ± 0.25 °C of 120 °C by means of a thermostatically controlled heating oil bath for a period of 72 hours. The resistance at the start of test is used to normalize the difference in length of the wire, with the calculated value compared to the normalized length. Resistivity changes with temperature and this is accounted for through various equations allowing results to be normalized, the equations for which can be found, for example, in Hunt, G., Choo, L., and Newcomb, T., "100 Years of Corrosion Testing — Is It Time to Move beyond the ASTM D130? The Wire Corrosion and Conductive Deposit Tests," SAE Int. J. Fuels Lubr. 17(1): 17-35, 2024, https://doi.org/10.4271/04-17-01-0002. Comparisons of corrosion reactions at different temperatures can, therefore, be attributed directly to the corrosion process. The change in resistance is used to calculate the apparent change in the wire radius. Results are plotted with radius change on the y-axis, and time in hours along the x-axis. A corrosion rate can then be calculated in Angstroms per hour (A/hr).

[0110] Each of the documents referred to above is incorporated herein by reference, including any prior applications, whether or not specifically listed above, from which priority is claimed. The mention of any document is not an admission that such document qualifies as prior art or constitutes the general knowledge of the skilled person in any jurisdiction. Except in the Examples, or where otherwise explicitly indicated, all numerical quantities in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, and the like, are to be understood as optionally modified by the word "about." It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined. Similarly, the ranges and amounts for each element of the invention can be used together with ranges or amounts for any of the other elements.

[0111] 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, un-recited elements or method steps. However, in each recitation of “comprising” herein, it is intended that the term also encompass, 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 un-recited elements or steps that do not materially affect the essential or basic and novel characteristics of the composition or method under consideration. The expression “consisting of’ or “consisting essentially of,” when applied to an element of a claim, is intended to restrict all species of the type represented by that element, notwithstanding the presence of “comprising” elsewhere in the claim.

Clause 1 A lubricant formulation comprising a) an oil of lubricating viscosity; b) a sulfurized olefin; and c) a metal-containing salixarate detergent.

Clause 2 The lubricant formulation of Clause 1, wherein the sulfurized olefin comprises a mixture of sulfurized olefins of formula RI-SX-R-2 where Ri and R2 separately are derived from 2 to 6 carbon atom containing olefins and x is an integer of between 1 and 10, with the proviso that the sulfurized olefin will have a sulfur content of from about 10 to about 75 wt%, or from 10 to 60 wt.% or even from 10 to 50 wt%.

Clause 3 The lubricant formulation of any previous Clause wherein the oil of lubricating viscosity comprises a group I oil.

Clause 4 The lubricant formulation of any previous Clause wherein the oil of lubricating viscosity comprises a group II oil.

Clause 5 The lubricant formulation of any previous Clause wherein the oil of lubricating viscosity comprises a group III oil.

Clause 6 The lubricant formulation of any previous Clause wherein the oil of lubricating viscosity comprises a group III+ oil.

Clause 7 The lubricant formulation of any previous Clause wherein the oil of lubricating viscosity comprises a group IV oil.

Clause 8 The lubricant formulation of any previous Clause wherein the oil of lubricating viscosity comprises a group V oil.

Clause 9 The lubricant formulation of any previous Clause wherein the oil of lubricating viscosity has a kinematic viscosity at 100 °C by ASTM D445 of 1.5 to 7.5 mm²/s. Clause 10 The lubricant formulation of any previous Clause wherein the oil of lubricating viscosity has a kinematic viscosity at 100 °C by ASTM D445 of 2 to 7 mm²/s.

Clause 11 The lubricant formulation of any previous Clause wherein the oil of lubricating viscosity has a kinematic viscosity at 100 °C by ASTM D445 of 2.5 to 6.5 mm²/s. Clause 12 The lubricant formulation of any previous Clause wherein the oil of lubricating viscosity has a kinematic viscosity at 100 °C by ASTM D445 of 3 to 6 mm²/s.

Clause 13 The lubricant formulation of any previous Clause wherein the oil of lubricating viscosity comprises a polyalphaolefin.

Clause 14 The lubricant formulation of any previous Clause, wherein Ri and R2 of the sulfurized olefin separately are derived from 3 to 5 carbon atom containing olefins.

Clause 15 The lubricant formulation of any previous Clause, wherein at least one of Ri and R2 of the sulfurized olefin separately are derived from butylene.

Clause 16 The lubricant formulation of any previous Clause, wherein at least one of Ri and R2 of the sulfurized olefin separately are derived from isobutylene.

Clause 17 The lubricant formulation of any previous Clause, wherein at least one of Ri and R2 of the sulfurized olefin separately are derived from amylene.

Clause 18 The lubricant formulation of any previous Clause, wherein at least one of Ri and R2 of the sulfurized olefin separately are derived from isoamylene.

Clause 19 The lubricant formulation of any previous Clause, wherein at least one of Ri and R2 of the sulfurized olefin separately are derived from diisobutylene.

Clause 20 The lubricant formulation of any previous Clause, wherein at least one of Ri and R2 of the sulfurized olefin separately are derived from mixtures of any of the foregoing olefins.

Clause 21 The lubricant formulation of any previous Clause, wherein the amounts of sulfur and hydrogen sulfide per mole of olefinic compound in the sulfurized olefin are, respectively, about 0.3-2.0 gram-atoms and about 0.1-1.5 moles.

Clause 22 The lubricant formulation of any previous Clause, wherein the amounts of sulfur and hydrogen sulfide per mole of olefinic compound in the sulfurized olefin are, respectively, about 0.5-1.5 gram-atoms and about 0.4-1.25 moles.

Clause 23 The lubricant formulation of any previous Clause, wherein the amounts of sulfur and hydrogen sulfide per mole of olefinic compound in the sulfurized olefin are, respectively, about 0.7-1.2 gram-atoms and about 0.4-0.8 mole.

Clause 24 The lubricant formulation of any previous Clause, wherein the sulfurized olefin is present at 0.01 to 10 wt%.

Clause 25 The lubricant formulation of any previous Clause, wherein the sulfurized olefin is present at 0.1 to 8 wt%.

Clause 26 The lubricant formulation of any previous Clause, wherein the sulfurized olefin is present at 0.2 to 6 wt%. Clause 27 The lubricant formulation of any previous Clause, wherein the sulfurized olefin is present at 0.5 to 5 wt%.

Clause 28 The lubricant formulation of any previous Clause, wherein the sulfurized olefin provides 0.5 to 3 wt% sulfur to the lubricant formulation.

Clause 29 The lubricant formulation of any previous Clause, wherein the sulfurized olefin provides 0.75 to 2.75 wt% sulfur to the lubricant formulation.

Clause 30 The lubricant formulation of any previous Clause, wherein the sulfurized olefin provides 1 to 2.5 wt% sulfur to the lubricant formulation.

Clause 31 The lubricant formulation of any previous Clause, wherein the metal-containing salixarate detergent comprises or consists of calcium salixarate.

Clause 32 The lubricant formulation of any previous Clause, wherein the metal-containing salixarate detergent comprises or consists of sodium salixarate.

Clause 33 The lubricant formulation of any previous Clause, wherein the metal-containing salixarate detergent comprises or consists of potassium salixarate.

Clause 34 The lubricant formulation of any previous Clause, wherein the metal-containing salixarate detergent comprises or consists of magnesium salixarate.

Clause 35 The lubricant formulation of any previous Clause, wherein the metal-containing salixarate detergent is a neutral detergent.

Clause 36 The lubricant formulation of any previous Clause, wherein the metal-containing salixarate detergent has a TBN of 20 to less than 200 mg KOH/g.

Clause 37 The lubricant formulation of any previous Clause, wherein the metal-containing salixarate detergent has a TBN of 30 to 100 mg KOH/g.

Clause 38 The lubricant formulation of any previous Clause, wherein the metal-containing salixarate detergent has a TBN of 35 to 50 mg KOH/g.

Clause 39 The lubricant formulation of any previous Clause, wherein the metal-containing salixarate detergent has a TBN of 20 to 175 mg KOH/g.

Clause 40 The lubricant formulation of any previous Clause, wherein the metal-containing salixarate detergent has a TBN of 30 to 100 mg KOH/g.

Clause 41 The lubricant formulation of any previous Clause, wherein the metal-containing salixarate detergent is an overbased detergent.

Clause 42 The lubricant formulation of any previous Clause, wherein the metal-containing salixarate detergent has a TBN of greater than 200 mg KOH/g.

Clause 43 The lubricant formulation of any previous Clause, wherein the metal-containing salixarate detergent has a TBN of 250 to 600 mg KOH/g. Clause 44 The lubricant formulation of any previous Clause, wherein the metal-containing salixarate detergent has a TBN of 300 to 500 mg KOH/g.

Clause 45 The lubricant formulation of any previous Clause, wherein the metal-containing salixarate detergent is present in an amount sufficient to deliver up to 2000 ppm of metal to the lubricant formulation.

Clause 46 The lubricant formulation of any previous Clause, wherein the metal-containing salixarate detergent is present in an amount sufficient to deliver 100 ppm to 1000 ppm of metal to the lubricant formulation.

Clause 47 The lubricant formulation of any previous Clause, wherein the metal-containing salixarate detergent is present in an amount sufficient to deliver 100 ppm to 600 ppm of metal to the lubricant formulation.

Clause 48 The lubricant formulation of any previous Clause, wherein the metal-containing salixarate detergent is present in an amount sufficient to deliver 100 ppm to 250 ppm of metal to the lubricant formulation.

Clause 49 The lubricant formulation of any previous Clause, wherein the metal-containing salixarate detergent is present in an amount sufficient to deliver 400 ppm to 750 ppm of metal to the lubricant formulation.

Clause 50 The lubricant formulation of any previous Clause, wherein the metal-containing salixarate detergent is present in an amount sufficient to deliver 500 ppm to 5000 ppm of metal to the lubricant formulation.

Clause 51 The lubricant formulation of any previous Clause, further comprising a corrosion inhibitor.

Clause 52 The lubricant formulation of any previous Clause, wherein the corrosion inhibitor comprises or consists of triazoles.

Clause 53 The lubricant formulation of any previous Clause, wherein the corrosion inhibitor comprises or consists of Benzotriazoles.

Clause 54 The lubricant formulation of any previous Clause, wherein the corrosion inhibitor comprises or consists of 1,2,4-triazoles.

Clause 55 The lubricant formulation of any previous Clause, wherein the corrosion inhibitor comprises or consists of N,N-bis(2-ethylhexyl)-triazol emethylamine

Clause 56 The lubricant formulation of any previous Clause, wherein the corrosion inhibitor comprises or consists of tolytriazole. Clause 57 The lubricant formulation of any previous Clause, wherein a triazole corrosion inhibitor is present at from about 0.005 or 0.01 wt % of the lubricant additive composition.

Clause 58 The lubricant formulation of any previous Clause, wherein a triazole corrosion inhibitor is present at from about 0.1 wt %, or about 0.08 wt % of the lubricant additive composition.

Clause 59 The lubricant formulation of any previous Clause, wherein a triazole corrosion inhibitor is present at from about 0.04 wt % to about 0.068 wt % of the lubricant additive composition.

Clause 60 The lubricant formulation of any previous Clause, wherein a triazole corrosion inhibitor is present at from about 0.045 wt % to about 0.057 wt % of the lubricant additive composition.

Clause 61 The lubricant formulation of any previous Clause, wherein the corrosion inhibitor comprises or consists of benzimidazoles.

Clause 62 The lubricant formulation of any previous Clause, wherein the corrosion inhibitor comprises or consists of 2-alkyldithiobenzimidazoles.

Clause 63 The lubricant formulation of any previous Clause, wherein the corrosion inhibitor comprises or consists of 2-alkyldithiobenzothiazoles.

Clause 64 The lubricant formulation of any previous Clause, wherein the corrosion inhibitor comprises or consists of 2-(N,N-dialkyldithiocarbamoyl)benzothiazoles.

Clause 65 The lubricant formulation of any previous Clause, wherein the corrosion inhibitor comprises or consists of 2,5-bis(alkyl-dithio)-l,3,4-thiadiazoles.

Clause 66 The lubricant formulation of any previous Clause, wherein the corrosion inhibitor comprises or consists of 2,5-bis(N,N-dialkyldithiocarbamoyl)-l,3,4-thiadia- zoles.

Clause 67 The lubricant formulation of any previous Clause, wherein the corrosion inhibitor comprises or consists of 2-alkyldithio-5-mercapto thiadiazoles

Clause 68 The lubricant formulation of any previous Clause, wherein a thiadiazole corrosion inhibitor is present at from about 0.01 wt % to about 1 wt % of the lubricant additive composition.

Clause 69 The lubricant formulation of any previous Clause, wherein a thiadiazole corrosion inhibitor is present at from about 0.05 wt % to about 0.9 wt % of the lubricant additive composition. Clause 70 The lubricant formulation of any previous Clause, wherein a thiadiazole corrosion inhibitor is present at from about 0.1 wt % to about 0.8 wt % of the lubricant additive composition.

Clause 71 The lubricant formulation of any previous Clause, wherein a thiadiazole corrosion inhibitor is present at from about 0.2 wt % to about 0.7 wt % of the lubricant additive composition.

Clause 72 The lubricant formulation of any previous Clause, wherein a thiadiazole corrosion inhibitor is present at from about 0.2 wt % to about 0.5 wt % of the lubricant additive composition.

Clause 73 The lubricant formulation of any previous Clause, wherein a thiadiazole corrosion inhibitor is present at from about 0.25 wt % to about 0.35 wt % of the lubricant additive composition.

Clause 74 The lubricant formulation of any previous Clause, wherein the lubricant comprises a total sulfur level of about 0.75 to about 5 wt%.

Clause 75 The lubricant formulation of any previous Clause, wherein the lubricant comprises a total phosphorus level of about 0.01 to about 0.5 wt%.

Clause 76 A method of minimizing corrosion in automotive or industrial device comprising providing to the automobile or industrial device the lubricant formulation of any previous Clause, and operating the automobile or industrial device.

Clause 77 The method of Clause 87 wherein the automobile or industrial device comprises a driveline power transmitting device.

Clause 78 The method of any of Clause 87 to Clause 88, wherein the driveline power transmitting device comprises a bearing, a gear or an axle.

Clause 79 The method of any of Clause 87 to Clause 89, wherein the automobile or industrial device comprises an engine.

[0112] While certain representative embodiments and details have been shown for the purpose of illustrating the subject invention, it will be apparent to those skilled in this art that various changes and modifications can be made therein without departing from the scope of the subject invention. In this regard, the scope of the invention is to be limited only by the following claims.

Claims

What is claimed is:

1. A lubricant formulation comprising

(a) an oil of lubricating viscosity;

(b) sulfurized olefin, and

(c) metal-containing salixarate detergent.

2. The lubricant formulation of claim 1, wherein the sulfurized olefin comprises a mixture of sulfurized olefins of formula RI-SX-R-2 where Ri and R2 separately are derived from 2 to 8 carbon atom containing olefins and x is an integer of between 1 and 10, with the proviso that the sulfurized olefin will have a sulfur content of from about 10 to about 75 wt%, or from 10 to 60 wt.% or even from 10 to 50 wt%.

3. The lubricant formulation of any previous claim, wherein the sulfurized olefin is present from 0.01 to 10 wt%.

4. The lubricant formulation of any preceding claim, wherein the metal-containing salixarate detergent comprises or consists of calcium salixarate.

5. The lubricant formulation of any previous claim, wherein the metal-containing salixarate detergent is present in an amount sufficient to deliver up to 2000 ppm, or 100 ppm to 1000 ppm, or 100 ppm to 600 ppm, or 100 ppm to 250 ppm, or 400 ppm to 750 ppm of metal to the lubricant formulation.

6. The lubricant formulation of any of previous claim, wherein the lubricant comprises a total sulfur level of about 0.2 to about 5 wt%.

7. The lubricant formulation of any of previous claim, wherein the lubricant comprises a total phosphorus level of about 0.01 to about 0.5 wt%.

8. A method of lubricating an automotive or industrial device by supplying thereto the lubricant composition as claimed in any previous claim, and operating the automotive or industrial device.

9. The use of a combination of a sulfurized olefin and a metal-containing salixarate detergent in a lubricant formulation to minimize copper corrosion.