CN111479908A

CN111479908A - Alkyl phenol cleaning agent

Info

Publication number: CN111479908A
Application number: CN201880080321.3A
Authority: CN
Inventors: E·E·德尔布里奇; P·E·莫热; P·米亚特
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 2017-12-15
Filing date: 2018-11-14
Publication date: 2020-07-31
Also published as: CA3085881A1; EP3724301A1; SG11202005407TA; US20200369975A1; US20220073836A1; WO2019118117A1

Abstract

The disclosed technology provides a lubricating composition comprising an oil of lubricating viscosity; and a cleaning agent comprising a polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof, wherein the polyolefin is derived from a branched olefin having at least 4 carbon atoms, and wherein the polyolefin has a number average molecular weight of 150 to 800. The invention further relates to a method of lubricating a mechanical device with the lubricant composition.

Description

Alkyl phenol cleaning agent

Technical Field

The disclosed technology relates to hydrocarbyl- (e.g., alkyl-) phenol detergents and salts thereof. Specifically, the disclosed technology comprises hydroxy-aromatic carboxylic acids. Such compounds and salts thereof are useful as lubricant additives.

Background

Phenol-based detergents are known. Among these are phenolates based on phenolic monomers linked to a sulphur bridge or an alkylene bridge, such as a methylene bond derived from formaldehyde. The phenolic monomers themselves are typically substituted with aliphatic hydrocarbyl groups to provide a measure of oil solubility. The hydrocarbyl group may be an alkyl group, and dodecylphenol (or phenol substituted with a propylene tetramer) has historically been widely used. Early references to alkaline sulfurized polyvalent metal phenates are U.S. Pat. Nos. 2,680,96, Walker et al, 6/1/1954; see also U.S. Pat. No. 3,372,116, Meinhardt, 3/6/1968.

Recently, however, certain alkylphenols and products made therefrom have received increased scrutiny due to their association as potential endocrine disrupting substances. Specifically, alkylphenol detergents based on phenols alkylated with propylene oligomers, specifically propylene tetramers (or tetrapropenyl groups), may contain residual alkylphenol species. Accordingly, there is interest in developing alkyl-substituted phenol detergents for lubricants, fuels, and industrial additives that contain reduced or eliminated amounts of dodecylphenol component and other substituted phenols having propylene oligomer substituents of 10 to 15 carbon atoms. Nevertheless, it is desirable that the product should have oil solubility parameters similar to phenates prepared from C10-15 propylene oligomers.

U.S. Pat. No. 7,435,709, Stonebraker et al, 2008, 10.14 discloses a linear alkyl phenol derived detergent substantially free of endocrine disrupting chemicals comprising a salt of the reaction product of (1) an olefin having at least 10 carbon atoms, wherein greater than 90 mole% of the olefin is a linear C20-C30 n- α olefin, and wherein less than 10 mole% of the olefin is a linear olefin having less than 20 carbon atoms, and less than 5 mole% of the olefin is a branched olefin of 18 carbons or less, and (2) a hydroxy aromatic compound.

Us application 2011/0190185, Sinquin et al, 8.2011.4 discloses overbased salts of oligomeric alkyl hydroxyaromatic compounds. The alkyl group is derived from an olefin mixture comprising propylene oligomers having an initial boiling point of at least about 195 ℃ and a final boiling point of greater than 325 ℃. The propylene oligomers may contain a carbon atom distribution comprising at least about 50% by weight of C14 to C20 carbon atoms.

U.S. application No. 2011/0124539, Sinquin et al, 26/5/2011 discloses overbased sulfide salts of alkylated hydroxyaromatic compounds. The alkyl substituent is the residue of at least one isomerized olefin having from 15 to about 99 weight percent branching. The hydroxyaromatic compound may be phenol, cresol, xylenol, or mixtures thereof.

U.S. application No. 2011/0118160, Campbell et al, 2011, 5/19, discloses an alkylated hydroxyaromatic compound substantially free of endocrine disrupting chemicals. Alkylated hydroxyaromatic compounds are prepared by reacting a hydroxyaromatic compound with at least one branched olefin propylene oligomer having from about 20 to about 80 carbon atoms. Suitable hydroxyaromatic compounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, and the like.

U.S. application No. 2010/0029529, Campbell et al, 2.4.2010, discloses overbased salts of oligomeric alkyl hydroxyaromatic compounds. The alkyl group is derived from a mixture of olefins including propylene oligomers having an initial boiling point of at least about 195 ℃ and a final boiling point of no more than about 325 ℃. Suitable hydroxyaromatic compounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, and the like.

U.S. application No. 2008/0269351, Campbell et al, 2008, 10/30 discloses an alkylated hydroxyaromatic compound substantially free of endocrine disrupting chemicals prepared by reacting a hydroxyaromatic compound with a branched olefin oligomer having from about 20 to about 80 carbon atoms.

WO/PCT application 2013/059173, Cook et al discloses overbased salts of oligomeric alkyl hydroxyaromatic compounds. Alkyl groups are combinations of very short hydrocarbyl groups (i.e., 1 to 8 carbon atoms) and long hydrocarbyl groups (at least about 25 carbon atoms). Suitable compounds include those derived from a mixture of p-cresol and polyisobutylene-substituted phenols.

Other common techniques include U.S. Pat. No. 6,310,009 to Carrick et al, 2001, 10/30, which discloses salts of the following general structure

Wherein R can be an alkyl group of 1 to 60 carbon atoms (e.g., 9 to 18 carbon atoms). It is to be understood that R¹Will generally comprise a mixture of various chain lengths such that the foregoing numbers will generally represent R¹Average number (number average) of carbon atoms in the group.

Disclosure of Invention

The present invention provides an alkylphenol detergent composition having suitable oil solubility that may also provide one or more other benefits to the lubricating composition, including antiwear properties, oxidation properties, and/or viscosity properties. In one embodiment, the disclosed technology may provide a solution to the potential problems caused by cleaners containing C12 alkylphenol moieties, i.e., the disclosed invention may be free or substantially free of C12 alkylphenol moieties typically formed by oligomerization or polymerization of propylene.

The present invention provides an alkylphenol-containing detergent comprising a polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof, wherein the polyolefin is derived from a branched olefin having at least 4 carbon atoms, and wherein the polyolefin has a number average molecular weight of from 150 to 800, and wherein the detergent is a neutral or overbased salt of a carboxylic acid. In certain embodiments, the alkylphenol detergents of the present invention are substantially free (or completely free, or contain less than 5 mole% or 3 mole% or 1 mole% or 0.3 mole% or 0.1 mole%) of oligomer units containing propylene. In certain embodiments, the alkylphenol detergents of the present invention are substantially free or substantially free of the C12 alkylphenol moiety.

In one embodiment, the alkylphenol-containing detergent may be a polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof, such as a salicylate. This type of detergent is an ionic detergent, i.e. it typically comprises a salt of a detergent base (phenolic containing material) and a suitable cationic counterion. The detergents of the disclosed technology can be metal-containing salts, amine-or ammonium-containing salts, or mixtures thereof. In one embodiment, the cleaning agent comprises one or more alkali metals, one or more alkaline earth metals, or mixtures thereof.

The invention also encompasses a process for preparing an alkylphenol-containing detergent compound comprising (i) forming a polyolefin-substituted hydroxy-aromatic carboxylic acid to form a matrix, wherein the polyolefin is derived from a branched olefin having at least 4 carbon atoms, and wherein the polyolefin has a number average molecular weight of 150 to 800, and (ii) reacting the matrix with a metal base (such as an alkali or alkaline earth metal oxide or hydroxide) in the presence of carbon dioxide to form an alkylphenol-containing detergent. The reaction conditions of the process are known in the art and include phenol over a known catalyst (including BF)₃、AlCl₃Or HF) is used. The reaction of the substrate with the metal base in the presence of carbon dioxide is a well known method in the art of making detergents.

The disclosed technology also provides a lubricant comprising an oil of lubricating viscosity and the alkylphenol detergent, and a method of lubricating a mechanical device with the lubricant.

The disclosed technology also provides a method of lubricating a mechanical device comprising supplying to the mechanical device a lubricating composition disclosed herein.

The disclosed technology also provides for the use of alkylphenol detergents in lubricating compositions to provide detergency, deposit control and/or oxidative stability to the lubricant.

Detailed Description

The disclosed technology provides alkylphenol detergents, lubricating compositions, methods for lubricating mechanical devices such as internal combustion engines, and uses as disclosed herein.

The alkylphenol detergents of the present invention include polyolefin-substituted hydroxy-aromatic carboxylic acids, wherein the polyolefin is derived from a branched olefin having at least 4 carbon atoms, and wherein the polyolefin has a number average molecular weight of 150 to 800.

The alkyl phenol-containing detergents of the present invention are hydroxy-aromatic carboxylic acids substituted with polyolefins. Such detergents may be represented by formula (I):

wherein R is¹Is an alkyl group derived from a branched polyolefin compound having at least 4 carbon atoms, such as from 8 to 50 carbon atoms, or at least 10 carbon atoms, or at least 12 carbon atoms, or at least 14 carbon atoms, or at least 16 carbon atoms, or at least 18 carbon atoms, or at least 20 carbon atoms, or at least 24 carbon atoms, or up to 40 carbon atoms, or up to 35 carbon atoms, or up to 30 carbon atoms. The polyalkylene group may have a number average molecular weight Mn of at least 150, or at least 200, or at least 300, or at most 800, or at most 600, or at most 500, or at most 400, or at most 360. R²May be hydrogen or a hydrocarbyl group having at least one carbon atom of from 1 to about 40. In one embodiment, R²It may also be an alkyl group derived from a branched polyolefin compound having at least 4 carbon atoms, such as from 8 to 50 carbon atoms, or at least 10 carbon atoms, or at least 12 carbon atoms, or at least 14 carbon atoms, or at least 16 carbon atoms, or at least 18 carbon atoms, or at least 20 carbon atoms, or at least 24 carbon atoms, or up to 40 carbon atoms, or up to 35 carbon atoms, or up to 30 carbon atoms. The polyalkylene group may have a number average molecular weight Mn of at least 150, or at least 200, or at least 300, or at most 800, or at most 600, or at most 500, or at most 400, or at most 360.

The polyolefin-substituted hydroxy-aromatic carboxylic acid may be selected from any of the carboxylic acids known in the art for such applications. The polyolefin-substituted hydroxy-aromatic carboxylic acid may be a neutral or overbased metal salt of a carboxylic acid. 4-hydroxybenzoic acid, 2-hydroxybenzoic acid (also known as salicylic acid), 3-hydroxybenzoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, and 6-hydroxy-2-naphthoic acid.

The preparation of detergents from carboxylic acids is generally known to those skilled in the art. Methods of forming such cleaners are disclosed in, for example, U.S. patents 4,719,023 and 3,372,116. The present invention may be prepared by any method now known or hereafter developed.

In one embodiment, the polyolefin-substituted hydroxy-aromatic carboxylic acid may be an alkyl salicylate or a salicylate detergent. The salicylate detergents may be neutral or overbased metal salts of alkyl salicylic acids. The alkyl salicylic acid can be represented by formula (II)

In the polyolefin-substituted hydroxy-aromatic carboxylic acids shown above in formulas (I) and (II), R or R¹Represents an alkyl group of an alkylphenol. In the present invention, the alkyl group is derived from a branched polyolefin compound having at least 4 carbon atoms, such as from 8 to 50 carbon atoms, or at least 10 carbon atoms, or at least 12 carbon atoms, or at least 14 carbon atoms, or at least 16 carbon atoms, or at least 18 carbon atoms, or at least 20 carbon atoms, or at least 24 carbon atoms, or up to 40 carbon atoms, or up to 35 carbon atoms, or up to 30 carbon atoms. The polyalkylene group may have a number average molecular weight Mn of at least 150, or at least 200, or at least 300, or at most 800, or at most 600, or at most 500, or at most 400, or at most 360. Polyolefin groups having an Mn of less than 500, such as up to about 400, such as about 300 to 400, are particularly suitable because they allow the compounds to provide good detergent properties for deposit control and cleanliness without causing viscosity creep or undesirable thickening of the oil.

Suitable for use as R or R¹Examples of branched polyolefin groups of groups include polyolefin groups derived from branched olefins having at least 4 carbon atoms, or up to 12 carbon atoms, or up to 8 carbon atoms, or up to 6 carbon atoms, such as C4-C6 branched olefins. Suitable branched olefins include isobutylene (2-methylpropene), 2-methylbutene, 2-ethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-methyl-1-pentene, 3-methyl-1-pentene, 2-ethyl-1-pentene, 3-ethyl-1-pentene, 2-methyl-1-hexene, 3-methyl-1-hexene, 2-ethane-1-hexeneIn one embodiment, the polyolefin comprises chains derived from at least four, or at least five, or at most eighteen, or at most eight, or at most seven, or at most six branched olefin units.

In one embodiment, the compound is free of C8 and higher unbranched alkyl groups.

In one embodiment, R, R¹And R²Consisting only of carbon and hydrogen.

The polyolefin-substituted hydroxy-aromatic carboxylic acid (e.g., alkyl salicylate) can be a neutral or nearly neutral salt of the carboxylic acid; by almost neutral is meant that there is no more than 15 mol% excess base, i.e. if the salt is metal containing, the metal ratio is 1.15 or less. In one embodiment, the neutral salt of a polyolefin-substituted hydroxy-aromatic carboxylic acid (e.g., an alkyl salicylic acid) can be an amine or ammonium salt, a metal salt, or a mixture thereof.

Suitable amines for use in preparing the neutral aminated polyolefin-substituted hydroxy-aromatic carboxylic acid (e.g., alkyl salicylate) are not unduly limited and may comprise any alkyl amine, but are typically fatty acid amines derived from fatty carboxylic acids. The alkyl groups present in the amines may contain from 10 to 30 carbon atoms, or from 12 to 18 carbon atoms, and may be straight chain or branched. In some embodiments, the alkyl group can be linear and unsaturated. Typical amines include pentadecylamine, octadecylamine, hexadecylamine, oleylamine, decylamine, dodecylamine, dimethyldodecylamine, tridecylamine, heptadecylamine, octadecylamine, stearylamine, and any combination thereof. In some embodiments, the fatty acid derived amine salt of an alkyl salicylic acid may be a salt of oleylamine. In certain embodiments, the amine may be a γ -amino ester compound; this type of amino ester can be derived from the Michael addition of a primary amine to an alkyl diester of itaconic acid represented by the following formula.

Wherein R is¹And R²Is a hydrocarbon group containing 2 to 30 carbon atoms, and R³Is a hydrocarbon group containing 4 to 50 carbon atoms. In some embodiments, R of the amino ester compound³Is an alkyl group having at least one hydrocarbyl group substituted at the 1-or 2-position of the alkyl group. In one embodiment, the amino ester is dibutyl 2- (((2-ethylhexyl) -amino) methyl) succinate.

In certain embodiments, the neutral salt of a polyolefin-substituted hydroxy-aromatic carboxylic acid (e.g., an alkyl salicylic acid) may be a quaternary ammonium salt, also known as a quaternary nitrogen compound. Quaternary nitrogen compounds are characterized by a nitrogen atom that is tetracoordinated; this allows the release of cationic species that are not protic (i.e., acidic protons) under basic conditions. Quaternary nitrogen compounds can be characterized as being divided into two major groups: tetra-coordinated tetraalkylammonium compounds (e.g., tetrabutylammonium) and tri-coordinated aromatic compounds (e.g., N-alkylpyridinium).

In some embodiments, the quaternary nitrogen salt may comprise the reaction product of: (a) a hydrocarbyl-substituted compound having a tertiary amino group and (b) a quaternizing agent suitable for converting the tertiary amino group of (a) to a quaternary nitrogen, wherein the quaternizing agent can be selected from the group consisting of dialkyl sulfates, benzyl halides, hydrocarbyl-substituted carbonates, hydrocarbyl epoxides in combination with an acid or mixtures thereof. In one embodiment, the quaternary nitrogen salt comprises the reaction product of: (i) at least one compound selected from the group consisting of: a polyalkyl-substituted amine having at least one tertiary amino group and/or a Mannich reaction product having a tertiary amino group (Mannich reaction product); and (ii) a quaternizing agent.

The polyolefin-substituted hydroxy-aromatic carboxylic acid detergents of the present invention may be metal-containing detergents, which may be neutral, or very near neutral, or overbased.

In one embodiment, the polyolefin-substituted hydroxy-aromatic carboxylic acid containing an overbased metal may be an overbased detergent of calcium or magnesium. In one embodiment, the overbased detergent may comprise a calcium alkyl phenol detergent having a metal ratio of at least 1.5, at least 3, at least 5, or at least 7. In certain embodiments, the metal ratio of the overbased calcium alkyl phenol detergent may be 1.5 to 25, 2.5 to 20, or 5 to 16.

Alternatively, polyolefin-substituted hydroxy-aromatic carboxylic acid detergents may be described as having a TBN. Overbased carboxylic acid detergents, such as salicylates, typically have a total base number of from 120 to 600mg KOH/g, or from 150 to 550mg KOH/g, or from 180 to 350mg KOH/g. The amount of alkylphenol-containing detergent present in the lubricant composition can be defined as the amount necessary to deliver an amount or range of amounts of TBN to the lubricant composition. In certain embodiments, the detergent containing the polyolefin-substituted hydroxy-aromatic carboxylic acid may be present in the lubricant composition in an amount to deliver 0.5 to 10TBN to the composition or 1 to 7TBN or 1.5 to 5TBN to the composition.

An overbased detergent may also be defined as the ratio of neutral detergent salt (also referred to as detergent soap) to detergent ash. The weight ratio of ash to soap of the overbased detergent may be from 3:1 to 1:8, or from 1.5:1 to 1:4.1, or from 1.3:1 to 1: 3.4.

The polyolefin-substituted hydroxy-aromatic carboxylic acid detergents of the present invention may be advantageously used as additives in lubricants. The amount of polyolefin-substituted hydroxy-aromatic carboxylic acid detergent in the lubricant may be 0.1 to 8 weight percent on an oil-free basis, but includes calcium carbonate and other salts present in the overbased composition. When present as an overbased detergent, the amount may typically range from 0.1 to 25 wt.%, or from 0.2 to 28, or from 0.3 to 20, or from 0.5 to 15 wt.%. Higher amounts are typical of marine diesel cylinder lubricants, e.g. 1% or 3% or 5% to 25%, 20% or 15%. The amount used for gasoline or heavy duty diesel engines (non-marine) will generally be in the lower range, such as 0.1 to 10 wt% or 0.5 to 5 or 1 to 3 wt%. When used as a substantially neutral or non-overbased salt, the amount may generally be correspondingly smaller for each engine type, e.g., 0.1 to 10% or 0.2 to 8% or 0.3 to 6%.

In certain embodiments, the amount of polyolefin-substituted hydroxy-aromatic carboxylic acid detergent in the lubricant may be measured as the amount of alkylphenol-containing soap provided to the lubricant composition, regardless of any overbasing. In one embodiment, the lubricant composition may contain 0.05 wt.% to 1.5 wt.% of the alkylphenol-containing soap or 0.1 wt.% to 0.9 wt.% of the alkylphenol-containing soap. In one embodiment, the alkylphenol-containing soap provides 20 wt% to 100 wt% of the total detergent soap in the lubricating composition. In one embodiment, the alkylphenol-containing soap provides from 30 wt% to 80 wt% of the total detergent soap, or from 40 wt% to 75 wt% of the total detergent soap of the lubricating composition.

The lubricant composition may contain an alkylphenol-containing detergent different from the disclosed technology. In one embodiment, the lubricant composition of the disclosed technology comprises a polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof detergent of the disclosed technology in an amount of 0.1 to 25 wt.%, or 0.2 to 28, or 0.3 to 20, or 0.5 to 15 wt.%, and is free or substantially free of alkylphenol-containing detergents derived from alkylphenols derived from propylene oligomers, especially tetrapropenyl. In this context, "substantially free" means no more than 0.01% by weight or an amount that is considered to be due to contamination or other unintended means.

Oil of lubricating viscosity

The lubricating composition of the present invention comprises an oil of lubricating viscosity. Such oils include natural and synthetic oils, oils derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined, refined, re-refined oils, or mixtures thereof. More detailed descriptions of unrefined, refined and re-refined oils are provided in international publication WO2008/147704, paragraphs [0054] to [0056] (similar disclosures are provided in U.S. patent application 2010/197536, see [0072] to [0073 ]). More detailed descriptions of natural and synthetic lubricating oils are described in paragraphs [0058] to [0059] of WO2008/147704, respectively (similar disclosures are provided in U.S. patent application 2010/197536, see [0075] to [0076 ]). Synthetic oils may be produced by the Fischer-Tropsch reaction (Fischer-Tropsch reaction) and may typically be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil may be made by a fischer-tropsch gas-to-oil synthesis procedure, as well as other gas-to-oil.

Oils of lubricating viscosity may also be defined according to the convention section 1.3 of "Base Stock classes (Base Stock Categories)" in section 1.3 of the 2008 < 4.Y edition "Appendix E-API Base Oil Interchangeability guidelines for Passenger Car and Diesel Engine Oils" section 1.3 of the API Base Oil Interchangeability guide for Passenger Car Motor Oils and Diesel Engine Oils ". The API guidelines are also outlined in US 7,285,516 (see column 11, line 64 to column 12, line 10).

In one embodiment, the oil of lubricating viscosity may be an API group I to group III mineral oil, group IV synthetic oil or group V naphthenic or ester synthetic oil or mixtures thereof. In one embodiment, the oil of lubricating viscosity may be an API group II, group III, or group IV synthetic oil, or mixtures thereof.

The amount of oil of lubricating viscosity present is typically the balance remaining after subtracting the sum of the amounts of additives of the disclosed technology and other performance additives from 100 wt.%.

The lubricant composition may be in the form of a concentrate and/or a fully formulated lubricant. If the lubricating compositions of the disclosed technology, including the additives disclosed herein, are in the form of concentrates, which can be combined with additional oils to form, in whole or in part, finished lubricants, the ratio of these additives to the oil of lubricating viscosity and/or to the diluent oil comprises a range of 1:99 to 99:1 (by weight) or 80:20 to 10:90 (by weight). Typically, the lubricating composition of the disclosed technology comprises at least 50 wt.%, or at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.% of an oil of lubricating viscosity.

Engine lubricating composition-other additives

The engine lubricating composition according to the present invention may also contain other additives that provide specific performance benefits to the engine lubricant. These additional additives may include detergents, antioxidants, dispersants, anti-wear agents, oil soluble titanium compounds, extreme pressure agents, foam inhibitors, viscosity modifiers, corrosion inhibitors, metal deactivators, pour point depressants, friction modifiers, demulsifiers, and seal swell agents. These additional components are described in more detail below.

The lubricating composition optionally further comprises at least one detergent in addition to the polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof as described herein. Exemplary optional detergents include overbased metal-containing detergents. The metal of the metal-containing detergent may be zinc, sodium, calcium, barium or magnesium. The overbased metal-containing detergent may be selected from sulfonates, non-sulfurized phenates, salicylates, and mixtures or borated equivalents thereof. The overbased detergent may be borated with a borate agent, such as boric acid.

The overbased metal-containing detergents may also comprise "mixed" detergents formed with mixed surfactant systems comprising phenate and/or sulfonate components, such as phenate/salicylates, sulfonates/phenates, sulfonates/salicylates, sulfonates/phenates/salicylates, as described, for example, in U.S. Pat. nos. 6,429,178, 6,429,179, 6,153,565, and 6,281,179. Where a mixed sulphonate/phenate detergent is employed, the mixed detergent will be considered to correspond to the amount of different phenate and sulphonate detergents introduced into the same amount of phenate and sulphonate soap respectively.

Exemplary overbased metal-containing detergents include zinc, sodium, calcium and magnesium sulfonates, phenates (including sulfur-containing and non-sulfur containing phenates), salicylates, and salicylates. Such overbased sulfonates, salicylates, phenates, and salicylates may have a total base number (on an oil-free basis) of 120 to 700, or 250 to 600, or 300 to 500.

The overbased metal-containing detergent may be zinc sulfonate, sodium sulfonate, calcium sulfonate or magnesium sulfonate, phenate, sulphur-containing phenate, salicylate alkoxide or salicylate. Overbased sulfonates, salicylates, phenates and salicylates typically have a total base number of 120 to 700 TBN. The total base number of the overbased sulfonates is typically from 120 to 700, or from 250 to 600, or from 300 to 500 (on an oil-free basis).

Example sulfonate detergents include linear and branched alkyl benzene sulfonate detergents and mixtures thereof, which may have a metal ratio of at least 8, as described, for example, in U.S. publication No. 2005065045. Linear alkylbenzenes may have a benzene ring attached anywhere on the linear chain (typically in the 2-, 3-, or 4-position) or mixtures thereof. Linear alkylbenzene sulfonate detergents may be particularly useful to help improve fuel economy. In one embodiment, the alkylbenzene sulfonate detergent may be a branched alkylbenzene sulfonate, a linear alkylbenzene sulfonate, or a mixture thereof.

In one embodiment, the lubricating composition may be free of linear alkylbenzene sulfonate detergent. In one embodiment, the sulfonate detergent may be a metal salt of one or more oil-soluble alkyltoluene sulfonate compounds, as disclosed in U.S. publication No. 20080119378.

The lubricating composition may comprise at least 0.01 wt% or at least 0.1 wt% of a detergent other than the polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof, and in some embodiments, at most 2 wt% or at most 1 wt% of another detergent.

Exemplary antioxidants suitable for use herein include phenolic antioxidants and aminic antioxidants such as diarylamines, alkylated diarylamines, hindered phenols, and mixtures thereof diarylamines or alkylated diarylamines can be phenyl- α -naphthylamine (PANA), alkylated diphenylamines, or alkylated phenylnaphthylamine, or mixtures thereof, example alkylated diphenylamines include dinonyldiphenylamine, nonyldiphenylamines, octyldiphenylamine, dioctyldiphenylamines, didecyldiphenylamine, decyldiphenylamines, and mixtures thereof, example alkylated diarylamines include octyl, dioctyl, nonyl, dinonyl, decyl, and didecylphenylnaphthylamine, hindered phenolic antioxidants typically contain sec-butyl and/or tert-butyl as a hindering group the phenolic group can be further substituted with a hydrocarbyl group (e.g., a linear or branched alkyl group) and/or a bridging group that is linked to a second aromatic group examples of suitable hindered phenolic antioxidants include 2, 6-di-tert-butylphenol, 4-methyl-2, 6-di-tert-butylphenol, 4-ethyl-2, 6-di-butyl-2, 6-di-tert-butylphenol, 4-butyl-6, 6-di-tert-butylphenol, 4-di-butyl-6, 6-di-tert-butylphenol, and one such as those hindered phenol esters described in the U.S. Pat. No. 5,559^TML-135, commercially available from Ciba (Ciba).

When present, the lubricating composition may comprise at least 0.1 wt.%, or at least 0.5 wt.%, or at least 1 wt.% antioxidant, and in some embodiments, at most 3 wt.%, or at most 2.75 wt.%, or at most 2.5 wt.% antioxidant.

The lubricating composition optionally further comprises at least one dispersant. Exemplary dispersants include succinimide dispersants, mannich dispersants, succinimide dispersants, and polyolefin succinate, amide, and ester-amide dispersants, and mixtures thereof. When present, the succinimide dispersant may be as described above, as the succinimide is described as suitable for use with the cation M.

The succinimide dispersant may be derived from an aliphatic polyamine or mixtures thereof. The aliphatic polyamine can be an ethylene polyamine, a propylene polyamine, a butylene polyamine, or mixtures thereof. In one embodiment, the aliphatic polyamine can be an ethylene polyamine. In one embodiment, the aliphatic polyamine can be selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms (still bottoms), and mixtures thereof.

In one embodiment, the dispersant may be a polyolefin succinate, amide, or ester-amide. The polyolefin succinate-amide may be polyisobutylene succinic acid reacted with an alcohol (e.g., pentaerythritol) and a polyamine as described above. Example polyolefin succinates include polyisobutylene succinate of pentaerythritol and mixtures thereof.

The dispersant may be an N-substituted long chain alkenyl succinimide. An example of an N-substituted long chain alkenyl succinimide is polyisobutylene succinimide. Typically, the polyisobutylene derived from polyisobutylene succinic anhydride has a number average molecular weight of 350 to 5000, or 550 to 3000 or 750 to 2500. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Pat. nos. 3,172,892, 3,219,666, 3,316,177, 3,340,281, 3,351,552, 3,381,022, 3,433,744, 3,444,170, 3,467,668, 3,501,405, 3,542,680, 3,576,743, 3,632,511, 4,234,435, Re 26,433 and 6,165,235 and 7,238,650 and european patent application 0355895A.

The succinimide dispersant may include a polyisobutylene succinimide, wherein the polyisobutylene from which the polyisobutylene succinimide is derived has a number average molecular weight of 350 to 5000, or 750 to 2500.

Exemplary dispersants may also be post-treated by conventional methods by reaction with any of a variety of reagents. Among these are boron compounds (e.g., boric acid), urea, thiourea, thiodiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids (e.g., terephthalic acid), hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds. In one embodiment, the post-treatment dispersant is borated. In one embodiment, the post-treatment dispersant is reacted with dimercaptothiadiazole. In one embodiment, the post-treatment dispersant is reacted with phosphoric acid or phosphorous acid. In one embodiment, the post-treatment dispersant is reacted with terephthalic acid and boric acid (as described in U.S. publication No. 2009/0054278).

When present, the lubricating composition may comprise at least 0.01 wt.%, or at least 0.1 wt.%, or at least 0.5 wt.%, or at least 1 wt.% of other dispersants, and in some embodiments, up to 20 wt.%, or up to 15 wt.%, or up to 10 wt.%, or up to 6 wt.%, or up to 3 wt.% of dispersants.

The lubricating composition optionally further comprises at least one antiwear agent. Examples of suitable antiwear agents for use herein include: titanium compounds, tartrates, tartramides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, metal dihydrocarbyl dithiophosphates (e.g., zinc dialkyldithiophosphate), phosphites (e.g., dibutyl phosphite), phosphonates, thiocarbamate-containing compounds (e.g., thiocarbamates, thiocarbamate amides, thiocarbamate ethers, alkylene-coupled thiocarbamates, and bis (S-alkyldithiocarbamoyl) disulfides). In one embodiment, the antiwear agent may comprise a tartrate or a tartrimide, as described in U.S. publication nos. 2006/0079413, 2006/0183647, and 2010/0081592. The tartrate or tartrimide may contain alkyl ester groups in which the sum of the carbon atoms in the alkyl group is at least 8. In one embodiment, the antiwear agent may comprise citrate, as described in U.S. publication No. 20050198894.

In one embodiment, the lubricating composition may further comprise a phosphorus-containing antiwear agent. Exemplary phosphorus-containing anti-wear agents include zinc dialkyldithiophosphates, phosphites, phosphates, phosphonates, and ammonium phosphates, and mixtures thereof.

When present, the lubricating composition may comprise at least 0.01 wt.%, or at least 0.1 wt.%, or at least 0.5 wt.% antiwear agent, and in some embodiments, at most 3 wt.%, or at most 1.5 wt.%, or at most 0.9 wt.% antiwear agent.

The lubricating composition may include one or more oil soluble titanium compounds that may act as antiwear agents, friction modifiers, antioxidants, deposit control additives, or have more than one of these functions. Exemplary oil-soluble titanium compounds are disclosed in U.S. patent No. 7,727,943 and U.S. publication No. 2006/0014651. Exemplary oil-soluble titanium compounds include titanium (IV) alkoxides, such as titanium (IV) isopropoxide and titanium (IV) 2-ethylhexaoxide. Such alkoxides may be formed from monohydric alcohols, vicinal 1, 2-diols, polyols or mixtures thereof. The monoalkoxides may have 2 to 16 or 3 to 10 carbon atoms. In one embodiment, the titanium compound comprises an alkoxide of a vicinal 1, 2-diol or polyol. The 1, 2-vicinal diol comprises a fatty acid monoester of glycerol, wherein the fatty acid may be, for example, oleic acid. Other exemplary titanium compounds include titanium carboxylates, such as titanium neodecanoate.

When present in the lubricating composition, the amount of oil soluble titanium compound is included as part of the antiwear agent.

The lubricating composition may comprise an extreme pressure agent. Exemplary extreme pressure agents that are soluble in oil comprise a CS of a sulfur-and chlorothiogen-containing EP agent, dimercaptothiadiazole, or dispersant (typically a succinimide dispersant)₂Derivatives, chlorinated hydrocarbon EP agents, and derivatives of phosphorus EP agents. Examples of such EP agents include chlorinated waxes; sulfurized olefins (such as sulfurized isobutylene), hydrocarbyl-substituted 2, 5-dimercapto-1, 3, 4-thiadiazoles and oligomers thereof, organosulfurs and polysulfides (such as benzhydryl disulfide), bis- (chlorophenylmethyl) disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenols, sulfurized dipentene, sulfurized terpenes, and sulfurized Diels-Alder adducts (Diels-Alder adducts); phosphorus sulfurized hydrocarbons, such as the reaction product of phosphorus sulfide with turpentine or methyl oleate; phosphorus esters, such as dialkyl and trialkyl phosphites, for example dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite; dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite and polypropylene-substituted phenol phosphites; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol dicarboxylate; amine salts or derivatives of alkyl and dialkyl phosphoric acids, containing, for example, diAmine salts of reaction products of alkyl dithiophosphoric acids with propylene oxide and subsequently with P₂O₅Further reaction; and mixtures thereof. Some useful extreme pressure agents are described in U.S. Pat. No. 3,197,405.

When present, the lubricating composition may comprise at least 0.01 wt.%, or at least 0.1 wt.%, or at least 0.5 wt.% of the extreme pressure agent, and in some embodiments, at most 3 wt.%, or at most 1.5 wt.%, or at most 0.9 wt.% of the extreme pressure agent.

The lubricating composition may comprise a foam inhibitor. Foam inhibitors useful in the lubricant composition comprise a polysiloxane, a copolymer of ethyl acrylate and 2-ethylhexyl acrylate, and optionally vinyl acetate; a demulsifier comprising a fluorinated polysiloxane, a trialkyl phosphate, a polyethylene glycol, a polyethylene oxide, a polypropylene oxide and a (ethylene oxide-propylene oxide) polymer.

The lubricating composition may comprise a viscosity modifier. Viscosity modifiers (also sometimes referred to as viscosity index improvers or viscosity modifiers) useful in lubricant compositions are typically polymers comprising polyisobutylene, Polymethacrylate (PMA) and polymethacrylate, diene polymers, polyalkylstyrene, esterified styrene-maleic anhydride copolymers, hydrogenated alkenyl arene-conjugated diene copolymers, and polyolefins, also referred to as olefin copolymers or OCP. PMA is prepared from a mixture of methacrylate monomers having different alkyl groups. The alkyl group may be a straight or branched chain group containing 1 to 18 carbon atoms. Most PMAs are viscosity modifiers and pour point depressants. In one embodiment, the viscosity modifier is a polyolefin comprising ethylene and one or more higher olefins (e.g., propylene).

When present, the lubricating composition may comprise at least 0.01 wt.%, or at least 0.1 wt.%, or at least 0.3 wt.%, or at least 0.5 wt.% of the polymeric viscosity modifier, and in some embodiments, up to 10 wt.%, or up to 5 wt.%, or up to 2.5 wt.% of the polymeric viscosity modifier.

The lubricating composition may comprise a corrosion inhibitor. Corrosion inhibitors/metal passivators suitable for use in exemplary lubricating compositions include fatty amines, octylamine octanoate, condensation products of dodecenylsuccinic acid or anhydride and fatty acids (such as oleic acid with polyamines), derivatives of benzotriazole (e.g., tolyltriazole), 1,2, 4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, and 2-alkyldithiobenzothiazole.

Pour point depressants useful in exemplary lubricating compositions include poly α -olefins, esters of maleic anhydride-styrene copolymers, polymethacrylates, polyacrylates, or polyacrylamides.

The lubricating composition may comprise a friction modifier. Friction modifiers that may be suitable for use in exemplary lubricating compositions include fatty acid derivatives, such as amines, esters, epoxides, fatty imidazolines, condensation products of carboxylic acids and polyalkylene-polyamines, and amine salts of alkylphosphoric acids. The friction modifier may be an ashless friction modifier. Such friction modifiers are those which do not normally produce any sulfated ash under the conditions of ASTM D874. If the additive does not provide metal content to the lubricant composition, it is referred to as "metal free". As used herein, the term "fatty alkyl" or "fatty" with respect to friction modifiers refers to carbon chains having from 8 to 30 carbon atoms, typically straight carbon chains.

In one embodiment, the ashless friction modifier may be represented by the formula:

wherein D and D' are independently selected from-O-, (I),>NH、>NR²³By combining the D and D' groups together and in both>R is formed between C ═ O groups²¹-N<An imide group formed by radicals; e is selected from-R²⁴-OR²⁵-、>CH₂、>CHR²⁶、>CR²⁶R²⁷、>C(OH)(CO₂R²²)、>C(CO₂R²²)₂And>HOR²⁸(ii) a Wherein R is²⁴And R²⁵Is independently selected from>CH₂、>CHR²⁶、>CR²⁶R²⁷、>C(OH)(CO₂R²²) And>CHOR²⁸(ii) a q is 0 to 10, with the proviso that when q is 1, E is not>CH₂And when n is 2, neither Es is>CH₂(ii) a p is 0 or 1; r²¹Independently hydrogen or a hydrocarbyl group, typically containing from 1 to 150 carbon atoms, with the proviso that when R is²¹When is hydrogen, p is 0 and q is greater than or equal to 1; r²²Is a hydrocarbyl group typically containing 1 to 150 carbon atoms; r²³、R²⁴、R²⁵、R²⁶And R²⁷Independently a hydrocarbyl group; and R is²⁸Is hydrogen or a hydrocarbyl group, typically containing from 1 to 150 carbon atoms, or from 4 to 32 carbon atoms, or from 8 to 24 carbon atoms. In certain embodiments, hydrocarbyl groups R²³、R²⁴And R²⁵And may be straight chain or predominantly straight chain.

In certain embodiments, the ashless friction modifier is a fatty ester, amide or imide of various hydroxy-carboxylic acids, such as tartaric acid, malic acid, lactic acid, glycolic acid, and mandelic acid. Examples of suitable materials include di (2-ethylhexyl) tartrate (i.e., di (2-ethylhexyl) tartrate), di (C) tartrate₈-C₁₀) Di (C) ester, tartrate_12-15) Esters, dilinoleoyl tartrate, oleoyl triamides, and oleoyl maleimides.

In certain embodiments, the ashless friction modifier may be selected from a long chain fatty acid derivative of an amine, a fatty ester, or a fatty epoxide; fatty imidazolines, such as condensation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; a fatty alkyl tartrimide; a fatty alkyl tartaric amide; a fatty phosphonate ester; a fatty phosphite; borated phospholipids, borated fatty epoxides; a glyceride; a borated glyceride; a fatty amine; alkoxylated fatty amines; a borated alkoxylated fatty amine; hydroxyl and polyhydroxy fatty amines, including tertiary hydroxyl fatty amines; a hydroxyalkylamide; metal salts of fatty acids; metal salts of alkyl salicylates; an aliphatic oxazoline; a fatty ethoxylated alcohol; condensation products of carboxylic acids and polyalkylene polyamines; or reaction products of fatty carboxylic acids with guanidines, aminoguanidines, ureas or thioureas and salts thereof.

Friction modifiers may also encompass materials such as: sulfurized fatty compounds and soy monoesters of olefins, sunflower oil or polyols and aliphatic carboxylic acids.

In another embodiment, the friction modifier may be a long chain fatty acid ester. In another embodiment, the long chain fatty acid ester can be a monoester, and in another embodiment the long chain fatty acid ester can be a triglyceride.

The amount of ashless friction modifier in the lubricant may be from 0.1 to 3 wt.% (or from 0.12 to 1.2 or from 0.15 to 0.8 wt.%). The material may also be present in the form of a concentrate, alone or together with other additives and smaller amounts of oil. In the concentrate, the amount of material may be two to ten times the amount of the above concentration.

Molybdenum compounds are also known as friction modifiers. Exemplary molybdenum compounds do not contain dithiocarbamate moieties or ligands.

The nitrogen-containing molybdenum material comprises a molybdenum-amine compound, as described in U.S. Pat. No. 6,329,327, and an organomolybdenum compound made from reactants of a molybdenum source, a fatty oil, and a diamine, as described in U.S. Pat. No. 6,914,037. Other molybdenum compounds are disclosed in U.S. publication No. 20080280795. The molybdenum amine compound can be prepared by reacting a compound containing hexavalent molybdenum atoms with a compound represented by the formula NR²⁹R³⁰R³¹A primary, secondary or tertiary amine represented by wherein R²⁹、R³⁰And R³¹Each of which is independently hydrogen or a hydrocarbyl group having 1 to 32 carbon atoms, and wherein R is²⁹、R³⁰And R³¹Is a hydrocarbon group having 4 or more carbon atoms or represented by the formula:

wherein R is³²Represents a chain hydrocarbon group having 10 or more carbon atoms, s is 0 or 1, R³³And/or R³⁴Represents a hydrogen atom, a hydrocarbon group, an alkanol or an alkylamino group having 2 to 4 carbon atoms, and when s ═ 0,R³³and R³⁴Are not hydrogen atoms or hydrocarbon groups.

Specific examples of suitable amines include monoalkyl (or alkenyl) amines such as tetradecylamine, stearylamine, oleylamine, tallow alkylamine, hardened tallow alkylamine, and soybean oil alkylamine; dialkyl (or alkenyl) amines, for example N-tetradecylmethylamine, N-pentadecylmethylamine, N-hexadecylmethylamine, N-stearylmethylamine, N-oleylmethylamine, N-docosylmethylamine, N-tallow alkylmethylamine, N-hardened tallow alkylmethylamine, N-soya oleylmethylamine, lignoceryl-amine, pentacosyl-amine, hexacosyl-amine, distearyl-amine, dioleylamine, docosyl-amine, bis (2-hexyldecyl) amine, bis (2-octyldodecyl) amine, bis (2-decyltetradecyl) amine, tallow dialkyl amine, hardened tallow dialkyl amine and soya oleyl dialkyl amine, and trialkyl (alkenyl) amines, for example tetradecyldimethylamine, hexadecyldimethylamine, octadecyldimethylamine, tallowalkyldimethylamine, hardened tallow alkyl dimethyl amine, soybean oil alkyl dimethyl amine, dioleyl methyl amine, tridecyl amine, tristearyl amine, and triolyl amine. Suitable secondary amines have two alkyl (or alkenyl) groups having from 14 to 18 carbon atoms.

Examples of the compound containing a hexavalent molybdenum atom include molybdenum trioxide or a hydrate (MoO) thereof₃ ^.nH₂O), molybdic acid (H)₂MoO₄) Alkali metal molybdate (Q)₂MoO₄) Wherein Q represents an alkali metal such as sodium and potassium, ammonium molybdate { (NH)₄)₂MoO₄Or heptamolybdate (NH)₄)₆[Mo₇O₂₄].4H₂O}、MoOCl₄、MoO₂Cl₂、MoO2Br2、Mo₂O₃Cl₆And so on. Molybdenum trioxide or its hydrates, molybdic acid, alkali metal molybdates and ammonium molybdate are generally suitable due to their availability. In one embodiment, the lubricating composition includes a molybendum amine compound.

Other organomolybdenum compounds of the invention may be the reaction product of a fatty oil, a monoalkylated alkylene diamine, and a molybdenum source. Such materials are generally prepared in two steps, a first step involving the preparation of the aminoamide/glyceride mixture at elevated temperature, and a second step involving the incorporation of molybdenum.

Examples of fatty oils that may be used include cottonseed oil, peanut oil, coconut oil, linseed oil, palm kernel oil, olive oil, corn oil, palm oil, castor oil, rapeseed oil (low or high erucic acid), soybean oil, sunflower oil, herring oil, sardine oil, and tallow. These fatty oils are commonly referred to as glycerides, triacylglycerols, or triglycerides of fatty acids.

Some examples of monoalkylated alkylene diamines that may be used include methylaminopropylamine, methylaminoethylamine, butylaminopropylamine, butylaminoethylamine, octylaminopropylamine, octylaminoethylamine, dodecylaminopropylamine, dodecylaminoethylamine, hexadecylaminopropylamine, hexadecylaminoethylamine, octadecylaminopropylamine, octadecylaminoethylamine, isopropyloxypropyl-1, 3-diaminopropane and octyloxypropyl-1, 3-diaminopropane. Monoalkylated alkylene diamines derived from fatty acids may also be used. Examples include N-cocoalkyl-1, 3-propanediamine (C)

C) N-tall oil alkyl-1, 3-propanediamine (A)

T) and N-oleyl-1, 3-propanediamine (

O), all available from Akzo Nobel (Akzo Nobel).

The source of molybdenum for incorporation into the fatty oil/diamine complex is typically an oxygen-containing molybdenum compound, similar to those above, comprising ammonium molybdate, sodium molybdate, molybdenum oxide, and mixtures thereof. One suitable molybdenum source includes molybdenum trioxide (MoO)₃)。

Commercially available nitrogen-containing molybdenum compounds include, for example, those available from Adeka

710, and available from r.t. van der bilt (Vanderbilt)

855。

The nitrogen-containing molybdenum compound may be present in the lubricant composition at 0.005 to 2 weight percent of the composition or 0.01 to 1.3 weight percent of the composition or 0.02 to 1.0 weight percent of the composition. The molybdenum compound may provide 0 to 1000ppm, or 5 to 1000ppm, or 10 to 750ppm, 5ppm to 300ppm, or 20ppm to 250ppm molybdenum to the lubricant composition.

Suitable demulsifiers for use herein include trialkyl phosphates, as well as various polymers and copolymers of ethylene glycol, ethylene oxide, propylene oxide, and mixtures thereof.

Seal swell agents useful herein include sulfolene derivatives, such as Exxon Necton-37^TM(FN 1380) and Exxon Mineral Seal Oil^TM(FN 3200)。

The lubricating composition may be prepared by adding the product of the process described herein to an oil of lubricating viscosity, optionally in the presence of other performance additives (as described below).

In various embodiments, the engine lubricant may have a composition as illustrated in table 1. All additives are expressed on an oil-free basis.

Table 1:engine lubricating composition

Use of engine lubricating compositions

End uses for the engine lubricating compositions described herein include use as cylinder lubricants for internal combustion engines (e.g., 2-stroke marine diesel engines), as engine oils for two-or 4-stroke engines in passenger cars, heavy duty, medium and light duty diesel engines, small engines (e.g., motorcycles and 2-stroke oil engines), as transmission lubricants (including gear and automatic transmission oils), and as other industrial oils (e.g., hydraulic lubricants).

An exemplary method of lubricating a mechanical device, such as a cylinder of an internal combustion engine, comprises supplying an exemplary lubricating composition to the device.

Generally, a lubricating composition is added to a lubricating system of an internal combustion engine, which subsequently delivers the lubricating composition to the cylinders of the engine during operation thereof, wherein the lubricating composition can be ignited with a fuel.

The internal combustion engine may be a diesel fueled engine (e.g., a 2-stroke marine diesel engine), or a gasoline fueled engine, a natural gas fueled engine, a mixed gasoline/alcohol fueled engine, or a biodiesel fueled engine. The internal combustion engine may be a 2-stroke or a 4-stroke engine.

The lubricating composition may be suitable for use as a cylinder lubricant, regardless of the sulfur, phosphorus or sulfated ash (ASTM D-874) content of the fuel. The lubricating composition may have a sulfur content (which is particularly suitable for use as an engine oil lubricant) of 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 range from 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, 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 100ppm to 1000ppm, or 200ppm to 600 ppm. The total sulfated ash content may be 2 wt.% or less, or 1.5 wt.% or less, or 1.1 wt.% or less, or 1 wt.% or less, or 0.8 wt.% or less, or 0.5 wt.% or less, or 0.4 wt.% or less. In one embodiment, the sulfated ash content may be from 0.05 wt.% to 0.9 wt.%, or from 0.1 wt.% to 0.2 wt.%, or to 0.45 wt.%.

Other lubricating compositions may also be formulated using the polyolefin-substituted hydroxy-aromatic carboxylic acid detergents of the present invention, along with additional additives. Exemplary other lubricating compositions are described below.

Driveline lubricating composition

In one embodiment, the lubricating composition according to the present invention is used in a driveline device. The lubricating composition for a driveline device may comprise a polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof as described herein in an oil with a lubricating viscosity increasing agent, which may comprise a dispersant, an antiwear agent, a dispersant viscosity modifier, a friction modifier, a viscosity modifier, an antioxidant, an overbased detergent (in addition to the polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof as described above), a foam inhibitor, a demulsifier or a pour point depressant or mixtures thereof, optionally in the presence of other performance additives. In one embodiment, the present disclosure provides a lubricant composition comprising at least one of the following in addition to a polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof: polyisobutylene succinimide dispersants, antiwear agents, corrosion inhibitors, dispersant viscosity modifiers, friction modifiers, viscosity modifiers (typically polymethacrylates having a linear, comb or star architecture), antioxidants (including phenolic and aminic antioxidants), overbased detergents (including overbased sulfonates, phenates and salicylates described above in addition to polyolefin-substituted hydroxy-aromatic carboxylic acids or salts thereof), or mixtures thereof.

The amount of each other performance additive and the chemistry of the other performance additives will depend on the type of driveline device being lubricated. When present, common additives for each driveline lubricant include viscosity modifiers, dispersants, foam inhibitors, corrosion inhibitors, pour point depressants, demulsifiers, and seal swell agents.

The driveline lubricating composition is described below. All additives are expressed on an oil-free basis.

Manual transmission lubricant

In one embodiment, the present invention provides a manual transmission lubricant composition comprising:

an oil of lubricating viscosity, which oil has,

thiadiazoles (typically present at 0.05 wt.% to 1 wt.%, or 0.07 wt.% to 0.7 wt.%, or 0.1 wt.% to 0.3 wt.%, or 0.15 wt.% to 0.25 wt%),

a dispersant (typically present at 0.1 wt% to 5 wt%, or 0.3 wt% to 4 wt%, or 1 wt% to 3 wt%, or 0.1 wt% to 3 wt%),

a phosphorus-containing antiwear agent selected from (i) a nonionic phosphorus compound, which may be a hydrocarbyl phosphite; or (ii) an amine salt of a phosphorus compound,

about 0.1 to about 2 wt% detergent, typically present in an amount to deliver 110 to 700ppm, 130 to 600ppm, 150 to 500ppm, or 160 to 400ppm calcium; and wherein about 0.01 to about 2 wt.%, or about 0.1 to about 1.75 wt.%, or about 0.2 to about 1.5 wt.% of the cleaning agent comprises a polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof described herein.

The manual transmission may have synchromesh, or in another embodiment, the manual transmission does not have synchromesh. The synchromesh may be composed of aluminum, steel, bronze, molybdenum, brass (sintered or non-sintered), carbon in fibrous form, graphite material (optionally in combination with cellulosic material), or cellulosic material or phenolic resin.

In one embodiment, the lubricant may include 0.03 to 1.0 wt.%, or 0.1 to 0.6 wt.%, or 0.2 to 0.5 wt.% calcium.

The lubricant may have 100 to 2000ppm, 150 to 1500ppm, 200 to 1000 or 250 to 800ppm or 500 to 875ppm phosphorus delivered by the antiwear agent, i.e., by the zinc dialkyldithiophosphate or another phosphorus containing antiwear agent.

In one embodiment, the present invention provides a method of lubricating a manual transmission comprising supplying to the manual transmission a lubricant composition comprising:

an oil of lubricating viscosity, which oil has,

about 0.1 to about 5 wt% detergent, typically present in an amount to deliver 110 to 700ppm, 130 to 600ppm, 150 to 500ppm, or 160 to 400ppm calcium; and wherein about 0.01 to about 2 wt.%, or about 0.1 to about 1.75 wt.%, or about 0.2 to about 1.5 wt.% of the cleaning agent comprises a polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof as described herein.

The thiadiazole compound may comprise a 2, 5-dimercapto-1, 3, 4-thiadiazole compound substituted with a mono or dialkyl group. Examples of thiadiazoles include 2, 5-dimercapto-1, 3, 4-thiadiazole or oligomers thereof, hydrocarbyl substituted 2, 5-dimercapto-1, 3, 4-thiadiazole, hydrocarbyl thio substituted 2, 5-dimercapto-1, 3, 4-thiadiazole or oligomers thereof. Oligomers of hydrocarbyl-substituted 2, 5-dimercapto-1, 3, 4-thiadiazoles are typically formed by forming a thio-thio bond between 2, 5-dimercapto-1, 3, 4-thiadiazole units to form oligomers having two or more of said thiadiazole units. These thiadiazole compounds may also be used for post-treatment of dispersants as mentioned below for formation of dimercaptothiadiazole derivatives of polyisobutylene succinimide.

Examples of suitable thiadiazole compounds include at least one of the following: dimercaptothiadiazole, 2, 5-dimercapto- [1,3,4] -thiadiazole, 3, 5-dimercapto- [1,2,4] -thiadiazole, 3, 4-dimercapto- [1,2,5] -thiadiazole or 4-5-dimercapto- [1,2,3] -thiadiazole. Generally, readily available materials are typically utilized, such as 2, 5-dimercapto-1, 3, 4-thiadiazole or hydrocarbyl substituted 2, 5-dimercapto-1, 3, 4-thiadiazole.

Other additives for manual transmission fluids may be selected from those described herein or known to those skilled in the art, or those developed below.

Automatic transmission lubricant

In one embodiment, the present invention provides an automatic transmission lubricant composition comprising:

an oil of lubricating viscosity, which oil has,

a dispersant typically present at 0.01 wt% to 5 wt%, or 0.05 wt% to 3 wt%, or 0.1 wt% to 2 wt%,

from about 0.1 to about 1, typically present in an amount to deliver from 40 to 1000ppm, 50 to 700ppm, 60 to 600ppm, or 70 to 250ppm calcium; and wherein about 0.01 to about 0.8 wt.%, or about 0.1 to about 0.5 wt.%, or about 0.2 to about 0.15 wt.% of the cleaning agent comprises a polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof, described herein, and

friction modifiers are typically present at 0 to 4 wt.%, or 0.1 to 4 wt.%, 0.2 to 3 wt.%, 0.3 to 3 wt.%, 0.25 to 2.5 wt.%. In one embodiment, a friction modifier is present, and in an alternative embodiment, no friction modifier is present.

In one embodiment, the present invention provides a method of lubricating an automatic transmission comprising supplying to the automatic transmission a lubricant composition comprising:

an oil of lubricating viscosity, which oil has,

a dispersant typically present at 0.5 wt% to 3 wt%, or 1 wt% to 2.5 wt%, or 1.5 wt% to 4 wt%, or 1.5 wt% to 3 wt%,

the thiadiazole is typically present at 0.1 wt% to 0.5 wt%, or 0.2 wt% to 0.4 wt%, or 0.25 wt% to 0.35 wt%.

About 0.1 to about 5 wt% detergent, typically present in an amount to deliver 40 to 700ppm, 50 to 600ppm, 60 to 500ppm, or 70 to 250ppm calcium; and wherein about 0.01 to about 2 wt.%, or about 0.1 to about 1.75 wt.%, or about 0.2 to about 1.5 wt.% of the cleaning agent comprises a polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof, and

Automatic transmissions include Continuously Variable Transmissions (CVTs), continuously variable transmissions (IVTs), toroidal transmissions, continuously slipping torque transfer clutches (CSTCCs), step-variable automatic transmissions, and Dual Clutch Transmissions (DCTs).

Other additives for automatic transmission fluids may be selected from those described herein or known to those skilled in the art, or those developed below.

The automatic transmission lubricant compositions described herein may contain calcium-containing detergents in addition to the polyolefin-substituted hydroxy-aromatic carboxylic acids of the present invention. The optional additional cleaning agent can be an overbased cleaning agent, a non-overbased cleaning agent, or mixtures thereof. Typically, the detergent is overbased.

Off-highway vehicle

The polyolefin-substituted hydroxy-aromatic carboxylic acids or salts thereof described herein are useful in lubricating compositions for off-highway vehicles, such as agricultural tractors and construction vehicles. Such vehicles typically have a common oil sump that lubricates not only the transmission but also the gears, axles and hydraulics in the vehicle. In one embodiment, the present invention comprises a lubricant composition comprising:

an oil of lubricating viscosity, which oil has,

a dispersant typically present at 0.1 wt% to 3 wt%, or 0.1 wt% to 2.5 wt%, or 0.2 wt% to 2 wt%,

from about 0.1 to about 5 wt% detergent, typically present in an amount to deliver 100 to 5000ppm, 500 to 4500ppm, 500 to 4250ppm, 650 to 4200ppm calcium; and wherein about 0.01 to about 2 wt.%, or about 0.1 to about 1.75 wt.%, or about 0.2 to about 1.5 wt.% of the cleaning agent comprises a polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof described herein.

In one embodiment, the invention comprises a method of lubricating an off-highway vehicle comprising supplying to the vehicle a lubricant composition comprising:

an oil of lubricating viscosity, which oil has,

phosphorus-containing antiwear agents selected from (i) nonionic phosphorus compounds, which may be hydrocarbyl phosphites, such as zinc dialkyldithiophosphates; or (ii) an amine salt of a phosphorus compound,

from about 0.1 to about 5 wt% detergent, typically present in an amount to deliver 10 to 5000ppm, 500 to 4500ppm, 500 to 4250ppm, 650 to 4200ppm calcium; and wherein about 0.01 to about 2 wt.%, or about 0.1 to about 1.75 wt.%, or about 0.2 to about 1.5 wt.% of the cleaning agent comprises a polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof described herein.

Lubricated off-highway vehicles typically have wet brakes, transmissions, hydraulics, final drives, and power take-off systems. These components are typically lubricated by a single lubricant supplied from a common oil sump. The transmission may be a manual transmission or an automatic transmission.

Other additives for off-highway vehicles may be selected from those described herein or known to those skilled in the art, or those developed below.

Hydraulic oil, turbine oil or circulating oil

In one embodiment, the lubricating composition according to the present invention is used in a hydraulic system, a turbine system or a circulating oil system. Hydraulic systems are generally devices or apparatuses in which a fluid (typically an oil-based fluid) delivers energy to different parts of the system by hydraulic application of force. Turbine lubricants are commonly used to lubricate gears or other moving parts of a turbine (or turbine system), such as a steam turbine or a gas turbine. Circulating oil is typically used in equipment or devices to distribute heat to or through which it is circulated.

In one embodiment, the lubricant composition contains a polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof as described herein in an amount of 0.001 wt.%, or 0.005 wt.% to 5 wt.%, or 0.01 wt.%, or 0.05 wt.% to 1.5 wt.%, 0.05 wt.% to 1 wt.%, 0.01 wt.% to 0.5 wt.% of the total composition.

The hydraulic, turbine or circulating lubricant composition may also contain one or more additional additives. In some embodiments, the additional additive may comprise, in addition to the polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof or metal salt thereof of the present invention, an antioxidant, an antiwear agent, a corrosion inhibitor, a rust inhibitor, a foam inhibitor, a dispersant, a demulsifier, a metal deactivator, a friction modifier, a detergent, an emulsifier, an extreme pressure agent, a pour point depressant, a viscosity modifier, or any combination thereof.

Thus, the lubricant may comprise an antioxidant or a mixture thereof. The antioxidant may be present at 0 wt% to 4.0 wt%, or 0.02 wt% to 3.0 wt%, or 0.03 wt% to 1.5 wt% of the lubricant.

The lubricant composition may further comprise a dispersant or a mixture thereof. Suitable dispersants comprise: (i) a polyetheramine; (ii) borated succinimide dispersants; (iii) a non-borated succinimide dispersant; (iv) a Mannich reaction product of a dialkylamine, an aldehyde, and a hydrocarbyl-substituted phenol (Mannich reaction product); or any combination thereof. In some embodiments, the dispersant may be present at 0 wt% or 0.01 wt% to 2.0 wt%, 0.05 wt% to 1.5 wt%, or 0.005 wt% to 1 wt%, or 0.05 wt% to 0.5 wt% of the total composition.

Defoamers, also known as foam inhibitors, are known in the art and include organopolysiloxanes and non-silicon foam inhibitors. Examples of the organopolysiloxane include dimethyl polysiloxane and polysiloxane. Examples of non-silicon foam inhibitors include copolymers of ethyl acrylate and 2-ethylhexyl acrylate, terpolymers of ethyl acrylate, 2-ethylhexyl acrylate and vinyl acetate, polyethers, polyacrylates and mixtures thereof. In some embodiments, the defoamer is a polyacrylate. The anti-foaming agent may be present in the composition at 0.001 wt% to 0.012 wt%, or 0.004 wt%, or even 0.001 wt% to 0.003 wt%.

Demulsifiers are known in the art and comprise derivatives of propylene oxide, ethylene oxide, polyoxyalkylene alcohols, alkyl amines, amino alcohols, diamines or polyamines which are continuously reacted with ethylene oxide or substituted ethylene oxides or mixtures thereof. Examples of demulsifiers include polyethylene glycol, polyethylene oxide, polypropylene oxide, (ethylene oxide-propylene oxide) polymers, and mixtures thereof. In some embodiments, the demulsifier is a polyether. The demulsifier may be present in the composition from 0.002% to 0.012% by weight.

Pour point depressants are known in the art and include maleic anhydride-styrene copolymers, esters of polymethacrylates; a polyacrylate; polyacrylamide; condensation products of halogenated paraffins and aromatic compounds; a vinyl carboxylate polymer; and terpolymers of dialkyl fumarates, vinyl esters of fatty acids, ethylene-vinyl acetate copolymers, alkylphenol formaldehyde condensation resins, alkyl vinyl ethers, and mixtures thereof.

The lubricant composition may further comprise a rust inhibitor. Suitable rust inhibitors include hydrocarbyl amine salts of alkyl phosphoric acids, hydrocarbyl amine salts of dialkyl dithiophosphoric acids, hydrocarbyl amine salts of hydrocarbyl aryl sulfonic acids, aliphatic carboxylic acids or esters thereof, esters of nitrogen containing carboxylic acids, ammonium sulfonates, imidazolines, alkylated succinic acid derivatives reacted with an alcohol or ether, or any combination thereof; or mixtures thereof.

The rust inhibitor may be present in the range of 0 or 0.02 wt.% to 0.2 wt.%, 0.03 wt.% to 0.15 wt.%, 0.04 wt.% to 0.12 wt.%, or 0.05 wt.% to 0.1 wt.% of the lubricating oil composition. The rust inhibitors may be used alone or in the form of a mixture thereof.

The lubricant may contain a metal deactivator or a mixture thereof. The metal deactivator may be selected from the following derivatives: benzotriazoles (typically tolyltriazole), 1,2, 4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles or 2-alkyldithiobenzthiazoles, 1-amino-2-propanol, derivatives of dimercaptothiadiazoles, octylamine octanoates, condensation products of dodecenylsuccinic acid or anhydrides and/or fatty acids such as oleic acid with polyamines. Metal deactivators may also be described as corrosion inhibitors.

The metal deactivator may be present in the range of 0 or 0.001 wt.% to 0.1 wt.%, 0.01 wt.% to 0.04 wt.%, or 0.015 wt.% to 0.03 wt.% of the lubricating oil composition. The metal deactivator may also be present in the composition at 0.002 wt% or 0.004 wt% to 0.02 wt%. The metal deactivators may be used individually or as mixtures thereof.

In one embodiment, the present invention provides a lubricant composition further comprising a metal-containing detergent other than the polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof as described herein. The additional metal-containing detergent may be present at 0 wt% to 5 wt%, or 0.001 wt% to 1.5 wt%, or 0.005 wt% to 1 wt%, or 0.01 wt% to 0.5 wt% of the hydraulic composition.

The lubricant may include an extreme pressure agent. The extreme pressure agent may be a sulfur and/or phosphorus containing compound. Examples of extreme pressure agents include polysulfides, sulfurized olefins, thiadiazoles, or mixtures thereof.

The extreme pressure agent may be present in the hydraulic composition at 0 wt% to 3 wt%, 0.005 wt% to 2 wt%, 0.01 wt% to 1.0 wt%.

The lubricant may further comprise a viscosity modifier or a mixture thereof. Viscosity modifiers (commonly referred to as visco-viscosity index modifiers) suitable for use in the present invention comprise polymeric materials comprising styrene-butadiene rubber, olefin copolymers, hydrogenated styrene-isoprene polymers, hydrogenated free radical isoprene polymers, poly (meth) acrylates, polyalkylstyrenes, hydrogenated alkenyl aryl conjugated diene copolymers, esters of maleic anhydride-styrene copolymers, or mixtures thereof. In some embodiments, the viscosity modifier is a poly (meth) acrylate, an olefin copolymer, or a mixture thereof. The viscosity modifier may be present at 0 wt% to 10 wt%, 0.5 wt% to 8 wt%, 1 wt% to 6 wt% of the lubricant.

In one embodiment, the lubricant disclosed herein may contain at least one friction modifier. The friction modifier may be present at 0 wt% to 3 wt%, or 0.02 wt% to 2 wt%, or 0.05 wt% to 1 wt% of the lubricant composition.

In one embodiment, the lubricant composition further comprises an antiwear agent. Typically, the antiwear agent may be a phosphorus antiwear agent or a mixture thereof. The antiwear agent is present at 0 wt.% to 5 wt.%, 0.001 wt.% to 2 wt.%, 0.01 wt.% to 1.0 wt.% of the lubricant.

Thus, the hydraulic lubricant may comprise:

0.01 to 2% by weight of a polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof as described herein,

0.0001 to 0.15% by weight of a corrosion inhibitor selected from 2, 5-bis (tert-dodecyl-disulfide) -1,3, 4-thiadiazole, tolyltriazole or mixtures thereof,

an oil of lubricating viscosity, which oil has,

0.02 to 3% by weight of an antioxidant selected from aminic antioxidants or phenolic antioxidants or mixtures thereof,

0 wt% to 1.5 wt% dispersant, e.g., a borated succinimide or non-borated succinimide dispersant or a substantially nitrogen-free dispersant as described herein,

0.001 to 1.5% by weight of a neutral or slightly overbased calcium sulfonate, and

0.001 to 2 or 0.01 to 1 weight percent of an antiwear agent selected from the group consisting of zinc dialkyldithiophosphates, zinc dialkylphosphates, amine salts of phosphorus esters, or mixtures thereof.

Thus, the hydraulic lubricant may comprise:

0.01 to 1.5% by weight of a polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof as described herein,

an oil of lubricating viscosity, which oil has,

from 0.005 wt% to 1.5 wt% of a dispersant, for example, a borated succinimide or non-borated succinimide dispersant or a substantially nitrogen-free dispersant as described herein,

0.001 to 1.5% by weight of a neutral or slightly overbased calcium sulfonate,

The hydraulic lubricant may also include a formulation defined in the following table:

table 2:hydraulic lubricant composition

Specific examples of hydraulic lubricants include those summarized in the following table:

table 3:hydraulic lubricant composition

Other additives for hydraulic lubricants may be selected from those described herein or known to those skilled in the art, or those developed below.

Examples of the invention

The detergent according to the invention was prepared as follows:

PIB phenol was prepared by reacting high vinylidene 550Mn polyisobutylene with phenol using BF3 as a catalyst, then reacting PIB phenol with KOH to give potassium phenolate, which was then heated to 150 ℃ and vacuum stripped (25mmHg/5h) to remove water and then the mixture was exposed to CO 25 hours the final material was found to have a ratio of PIB salicylate to PIB phenol (determined by 13C NMR),% K3.31%, TBN 56.41, 50% active in diluent oil (dil oil). then, at 60 ℃, treated with 90g CaCl2 in MAO L (360g) for 1h, potassium phenolate/methyl salicylate was converted to overbased calcium salicylate, slaked lime (55g), acetic acid (50% aqueous solution) and isobutanol and pentanol and mixture (100g) were added and CO2 was bubbled through mixture at 60 ℃ for 40 minutes (0.6cfh) to DBN for 11. the final product was obtained by distillation under vacuum filtration of 150, 4925% solvent with 15 g, 15% volatile solvent, and the final product was found to have a brown color of SA 38, 15 g, C, b, 3, 15, 3

The Total Base Number (TBN) can be determined using the method of ASTM D2896.

Lubricating compositions incorporating the polyolefin-substituted hydroxy-aromatic carboxylic acids of the present invention may be prepared as described herein and evaluated for cleanliness, i.e., the ability to prevent or reduce deposit formation; sludge treatment; treating the ash; oxidation resistance and reduced wear, abrasion resistance, deposit control and oxidation control, etc.

The sludge handling properties of each lubricant can be evaluated according to ASTM D4310-10 (Standard test method for determining sludge and Corrosion tendencies of inhibited mineral oils). Performance was judged by the total amount of sludge formed during oxidation of lubricants and mineral oil-based fluids at high temperatures in the presence of oxygen, water and copper and iron metals and the ability of these oils to corrode copper catalyst metals.

The wear resistance was measured in a programmed temperature High Frequency Reciprocating Rig (HFRR) available from PCS instruments. The HFRR conditions used for the evaluation were 200g loading, 75 min duration, 1000 micron stroke, 20 hz frequency and temperature profile at 40 ℃ for 15 min, followed by increasing the temperature to 160 ℃ at a rate of 2 ℃/min. The wear marks in microns and film formation rate in percent film thickness were then measured at lower wear mark values and higher film formation values, indicating improved wear performance.

Deposit control was performed by a Komatsu Hot Tube (KHT) test using a heated glass Tube through which sample lubricant was pumped, approximately 5 ml of the total sample, typically used at 0.31 ml/hr for a long period of time (e.g., 16 hours), with an air flow of 10m L/min.

In the panel coker deposition test, the samples were left to splash on an aluminum plate held at 325 ℃ for 4 hours at a temperature of 105 ℃. The aluminum panels were analyzed using image analysis techniques to obtain a universal grade. The rating score is based on "100" being a clean plate and "0" being a plate completely covering the deposit.

The oxidation control was evaluated using differential pressure scanning calorimetry (PDSC), which determines the Oxidation Induction Time (OIT) of the lubricating composition, a standard test procedure in the lubricating oil industry based on CEC L-85T-99 in this test, the lubricating composition was heated to an elevated temperature, typically about 25℃ below the average decomposition temperature of the tested sample (215℃ at 690kPa in this case), and the time at which the composition began to decompose was measured.

The friction performance and ductility of a driveline lubricating composition (e.g., a transmission oil) may be evaluated using tests such as a variable speed friction test, a coefficient of friction test based on Falex L FW-1 or JASO M358, a VT20 durability test, a JASO M349 anti-shudder durability test, and the like, or using

The rig was tested.

It is known that some of the above materials may interact in the final formulation and therefore the components of the final formulation may be different from those initially added. The products formed thereby, including products formed using the lubricant compositions of the present invention in their intended use, may not be readily described. Nevertheless, all such modifications and reaction products are included within the scope of the present invention, which encompasses lubricant compositions prepared by incorporating the components described above.

Each of the documents mentioned above is incorporated herein by reference. Except in the examples, or where otherwise explicitly indicated, all numerical quantities in this description specifying amounts of material, reaction conditions, molecular weight, number of carbon atoms, and the like, are to be understood as modified by the word "about". Unless otherwise indicated, each chemical species or composition referred to herein is to be construed as a commercial grade material which may contain the isomers, by-products, derivatives and other such materials which are generally understood to exist in commercial grade form. However, unless otherwise indicated, the amount of each chemical component does not include any solvent or diluent oil, which may be typically present in commercial materials. It is to be understood that the amounts, ranges, and ratio limitations of the upper and lower limits described herein may be independently combined. Similarly, the ranges and amounts for each element of the invention can be used with ranges or amounts for any of the other elements.

While the invention has been described with respect to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. It is, therefore, to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

Claims

1. A lubricating composition, comprising:

(a) an oil of lubricating viscosity; and

(b) a cleaning agent comprising a polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof, wherein the polyolefin is derived from a branched olefin having at least 4 carbon atoms, and wherein the polyolefin has a number average molecular weight of 150 to 800.

2. The lubricating composition of claim 1, wherein the polyolefin-substituted hydroxy-aromatic carboxylic acid is represented by the following structure:

wherein R is¹Represents said polyolefin and R²Selected from hydrogen or a hydrocarbon group of 1 to 40 carbon atoms.

3. The lubricating composition of claim 2, wherein R²A second polyolefin derived from a branched olefin having at least 4 carbon atoms, and wherein the polyolefin has a number average molecular weight of from 150 to 800.

4. The lubricating composition of any one of claims 1 to 3, wherein the carboxylic acid is a hydroxybenzoic acid.

5. The lubricating composition of any one of claims 1 to 4, wherein the polyolefin-substituted hydroxy-aromatic carboxylic acid is an alkyl salicylic acid represented by the structure

Wherein R represents the polyolefin.

6. The lubricating composition of any of claims 1 to 5, wherein the branched olefin comprises isobutylene.

7. The lubricating composition of any one of claims 1 to 6, wherein said polyolefin comprises a chain derived from at least 4, or at least 5, or up to 6, or up to 7, or up to 8, or up to 18 branched olefin units.

8. Lubricating composition according to any of claims 1 to 7 wherein the polyolefin has a number average molecular weight of from 150 to 400.

9. The lubricating composition of any one of claims 1 to 8, wherein the detergent is a metal salt.

10. The lubricating composition of claim 9, wherein the metal in the salt comprises calcium.

11. The lubricating composition of claim 9 or 10, wherein the metal is overbased.

12. The lubricating composition of any one of claims 1 to 11, wherein the detergent is free of C8 and higher unbranched alkyl chains.

13. Lubricating composition according to any of claims 1 to 12 wherein the polyolefin contains from 8 to 50 carbon atoms, or at least 10 carbon atoms, or at least 12 carbon atoms, or at least 14 carbon atoms, or at least 16 carbon atoms, or at least 18 carbon atoms, or at least 20 carbon atoms, or at least 24 carbon atoms, or up to 40 carbon atoms, or up to 35 carbon atoms, or up to 30 carbon atoms.

14. The lubricating composition of any one of claims 1 to 13, wherein the polyolefin is polyisobutylene.

15. The lubricating composition of claim 14, wherein the polyisobutylene has a number average molecular weight of up to 600.

16. The lubricating composition of claim 15, wherein the polyisobutylene has a number average molecular weight of up to 500.

17. The lubricating composition of claim 16, wherein the polyisobutylene has a number average molecular weight of 300 to 400.

18. The lubricating composition of any one of claims 1 to 17, wherein the polyolefin-substituted hydroxy-aromatic carboxylic acid is at least 0.01 wt% of the lubricating composition.

19. The lubricating composition of claim 18, wherein the polyolefin-substituted hydroxy-aromatic carboxylic acid is at least 0.1 wt.%, or at least 0.5 wt.%, or at least 1 wt.%, or at least 2 wt.% of the lubricating composition.

20. The lubricating composition of claim 18 or 19, wherein the polyolefin-substituted hydroxy-aromatic carboxylic acid is at most 20 wt.%, or at most 10 wt.%, or at most 5 wt.%, or at most 3 wt.%, or at most 2.5 wt.% of the lubricating composition.

21. The lubricating composition of any one of claims 1 to 20, wherein the oil of lubricating viscosity comprises at least one of API group I, group II, group III, group IV and group V base oils.

22. The lubricating composition of any one of claims 1 to 21, wherein the oil of lubricating viscosity is at least 10 wt% of the lubricating composition.

23. The lubricating composition of claim 22, wherein the oil of lubricating viscosity is at least 30 wt% of the lubricating composition.

24. The lubricating composition of any one of claims 1 to 23, wherein the oil of lubricating viscosity is at most 95 wt% of the lubricating composition.

25. The lubricating composition of any one of claims 1 to 24, further comprising at least one of the group consisting of: detergents, antioxidants, dispersants, antiwear agents, friction modifiers, corrosion inhibitors, and combinations thereof.

26. A method of lubricating a mechanical device comprising supplying to the device a lubricating composition of any of claims 1 to 25.

27. The method of claim 26, wherein the mechanical device comprises an engine or a transmission system device.

28. The method of claim 26 or 27, wherein the mechanical device comprises a heavy duty diesel or marine diesel engine.

29. The method of claim 26, wherein the mechanical device is a hydraulic system, a turbine system, or a circulating oil system.

30. The method of claim 27, wherein the mechanical device is a transmission.

31. Use of the lubricating composition of any one of claims 1 to 25 for lubricating a mechanical device.

32. A method of forming a lubricating composition comprising:

(i) forming a polyolefin-substituted hydroxy-aromatic carboxylic acid to form a matrix, wherein the polyolefin is derived from a branched olefin having at least 4 carbon atoms, and wherein the polyolefin has a number average molecular weight of 150 to 800;

(ii) optionally, reacting the substrate with a metal base in the presence of carbon dioxide to form a metal salt; and

(iii) a polyolefin-substituted hydroxy-aromatic carboxylate thereof is combined with an oil of lubricating viscosity.