CN111479908A - Alkylphenol Cleaner - Google Patents

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 a salt thereof, wherein the polyolefin is derived from having at least 4 A branched chain olefin of carbon atoms, and wherein the polyolefin has a number average molecular weight of 150 to 800. The present invention further relates to a method of lubricating a mechanical device with a lubricant composition.

Description

Alkylphenol Cleaner

technical field

The disclosed technology relates to hydrocarbyl-(eg, alkyl-)phenol cleaners and salts thereof. Specifically, the disclosed technology includes hydroxy-aromatic carboxylic acids. Such compounds and their salts are suitable as lubricant additives.

Background technique

Phenol-based cleaners are known. Among these are phenates based on phenolic monomers, which are linked to sulfur bridges or alkylene bridges (eg, methylene bonds derived from formaldehyde). The phenolic monomers themselves are often substituted with aliphatic hydrocarbon groups to provide a measure of oil solubility. The hydrocarbyl group can be an alkyl group, and dodecylphenol (or propylene tetramer substituted phenol) has been widely used historically. An early reference to basic sulfurized polyvalent metal phenates is US Patent 2,680,96, Walker et al., June 1, 1954; see also US Patent 3,372, 116, Meinhardt, March 6, 1968.

Recently, however, certain alkylphenols and products made from them have come under increased scrutiny due to their association as potential endocrine disruptors. Specifically, alkylphenol cleaners based on phenols alkylated with propylene oligomers (specifically, propylene tetramers (or tetrapropenyl)) may contain residual alkylphenol species. Accordingly, there is interest in developing alkyl-substituted phenolic cleaners for lubricants, fuels and industrial additives that contain reduced or eliminated amounts of the dodecylphenol component and propylene oligomers having 10 to 15 carbon atoms Other substituted phenols of the compound substituent. Nonetheless, it is desirable that the product should have similar oil solubility parameters as phenates prepared from C10-15 propylene oligomers.

Numerous efforts have been made to prepare phenate cleaners that do not contain alkylphenols derived from oligomers of propylene. US Patent 7,435,709, Stonebraker et al., October 14, 2008 discloses a linear alkylphenol-derived cleanser that is substantially free of endocrine disrupting chemicals. It includes salts of the reaction products of (1) olefins having at least 10 carbon atoms, wherein greater than 90 mole percent of the olefins are linear C20-C30 n-alpha olefins, and wherein less than 10 mole percent of the olefins are less than Linear olefins of 20 carbon atoms, and less than 5 mole % of the olefins are branched olefins of 18 carbons or less, and (2) hydroxyaromatic compounds.

US Application 2011/0190185, Sinquin et al., Aug. 4, 2011, discloses an overbased salt of an oligomeric alkylhydroxyaromatic compound. The alkyl group is derived from a mixture of olefins that includes propylene oligomers having an initial boiling point of at least about 195°C and a final boiling point greater than 325°C. The propylene oligomer may contain a distribution of carbon atoms comprising at least about 50% by weight of C14 to C20 carbon atoms.

US Application 2011/0124539, Sinquin et al., May 26, 2011 discloses an overbased sulfide salt of an alkylated hydroxyaromatic compound. Alkyl substituents are residues of at least one isomerized olefin having 15 to about 99 weight percent branches. The hydroxyaromatic compound can be phenol, cresol, xylenol, or a mixture thereof.

US Application 2011/01 18160, Campbell et al., May 19, 2011 discloses an alkylated hydroxyaromatic compound that is substantially free of endocrine disrupting chemicals. Alkylated hydroxyaromatic compounds are prepared by reacting the 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.

US Application 2010/0029529, Campbell et al., Feb. 4, 2010, discloses an overbased salt of an oligomeric alkylhydroxyaromatic compound. The alkyl groups are derived from a mixture of olefins that includes propylene oligomers having an initial boiling point of at least about 195°C and a final boiling point of no more than about 325°C. Suitable hydroxyaromatic compounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, and the like.

US Application 2008/0269351, Campbell et al., Oct. 30, 2008, discloses an alkylated hydroxyaromatic compound substantially free of endocrine disrupting chemicals obtained by combining a hydroxyaromatic compound with a compound having about 20 Prepared by the reaction of branched chain olefin oligomers of up to about 80 carbon atoms.

WO/PCT application 2013/059173, Cook et al. disclose an overbased salt of an oligomeric alkyl hydroxy aromatic compound. Alkyl groups are combinations of very short hydrocarbyl groups (ie, 1 to 8 carbon atoms) and long hydrocarbyl groups (at least about 25 carbon atoms). Suitable compounds include those derived from mixtures of p-cresol and polyisobutylene substituted phenols.

Other general techniques include US Patent 6,310,009, Carrick et al., October 30, 2001, which discloses salts of the following general structure

wherein R can be an alkyl group of 1 to 60 carbon atoms (eg, 9 to 18 carbon atoms). It is to be understood that R1 will generally comprise ^a mixture of various chain lengths, such that the foregoing numbers will generally represent the average number ^of carbon atoms in the R1 group (number average).

SUMMARY OF THE INVENTION

The present invention provides an alkylphenol detergent composition with suitable oil solubility that can 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 potential problems caused by cleaners containing C12 alkylphenol moieties, ie the disclosed invention may be free or substantially free of C12 alkylphenol moieties formed by oligomerization or polymerization.

The present invention provides an alkylphenol-containing cleaning agent comprising a polyolefin-substituted hydroxy-aromatic carboxylic acid or a 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, and wherein the cleaning agent is a neutral or overbased salt of a carboxylic acid. In certain embodiments, the alkylphenol cleaners 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 %) containing propylene oligomer units. In certain embodiments, the alkylphenol cleaners of the present invention are substantially free or substantially free of C12 alkylphenol moieties.

In one embodiment, the alkylphenol-containing cleaning agent may be a polyolefin-substituted hydroxy-aromatic carboxylic acid or a salt thereof, such as a salicylate. Cleaners of this type are ionic cleansers, ie they generally comprise a salt of the cleanser base (phenol-containing material) and a suitable cationic counterion. The cleaning agents of the disclosed technology may be metal-containing salts, amine- or ammonium-containing salts, or mixtures thereof. In one embodiment, the cleaning agent includes one or more alkali metals, one or more alkaline earth metals, or mixtures thereof.

The present invention also encompasses a method of 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 having at least 4 carbon atoms branched chain olefin, and wherein the polyolefin has a number average molecular weight of 150 to 800, and (ii) reacting the substrate with a metal base (such as an alkali or alkaline earth metal oxide or hydroxide) in the presence of carbon dioxide to form an alkane containing Phenol-based cleaner. The reaction conditions for the process are known in the art and comprise the alkylation of phenols in the presence _of known catalysts including _BF3 , AlCl3 or HF. The reaction of substrates with metal bases in the presence of carbon dioxide is a well-known method in the art of preparing detergents.

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

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

Detailed ways

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

The alkylphenol cleaners 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 alkylphenol-containing cleaning agent of the present invention is a polyolefin-substituted hydroxy-aromatic carboxylic acid. Such cleaning agents can be represented by formula (I):

wherein R ¹ is derived from having at least 4 carbon atoms, such as 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 Alkyl groups of branched polyolefin compounds of 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 polyolefin 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. R ² can be hydrogen or a hydrocarbyl group having at least one of 1 to about 40 carbon atoms. In one embodiment, R ² may also be derived from having at least 4 carbon atoms, such as 8 to 50 carbon atoms, or at least 10 carbon atoms, or at least 12 carbon atoms, or at least 14 carbon atoms, or Branched chains of 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 Alkyl groups of polyolefin compounds. The polyolefin 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 can be selected from any carboxylic acid known in the art for such applications. The polyolefin-substituted hydroxy-aromatic carboxylic acid can 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 cleaning agents from carboxylic acids is generally known to those skilled in the art. Methods of forming such cleaners are disclosed, for example, in US Pat. Nos. 4,719,023 and 3,372,116. The present invention may be prepared by any method now known or hereinafter developed.

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

In the polyolefin-substituted hydroxy-aromatic carboxylic acids shown in formulae (I) and (II) above, R or R ¹ represents an alkyl group of an alkylphenol. In the present invention, the alkyl group is derived from having at least 4 carbon atoms, such as 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 atom, 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. Branched polyolefin compounds. The polyolefin 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 with Mn less than 500, eg up to about 400, eg about 300 to 400 are particularly suitable as they allow the compound to provide good detergent properties for deposit control and cleanliness without causing viscosity creep in the oil or undesired thickening.

Examples ^of branched polyolefin groups suitable for use as R or R groups include those derived from branched chains having at least 4 carbon atoms, or up to 12 carbon atoms, or up to 8 carbon atoms, or up to 6 carbon atoms Polyolefin groups of olefins, such as C4-C6 branched olefins. Suitable branched olefins include isobutene (2-methylpropene), 2-methylbutene, 2-ethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene ene, 4-methyl-1-pentene, 2-methyl-1-pentene, 3-methyl-1-pentene, 2-ethyl-1-pentene, 3-ethyl-1-pentene ene, 2-methyl-1-hexene, 3-methyl-1-hexene, 2-ethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene ene, 2-methyl-1-heptene, 3-methyl-1-heptene, 2-methyl-1-octene, 2-methyl-1-nonene, 2-methyl-1-decene alkene, 2-methyl-1-undecene and mixtures thereof. Each polyolefin group is derived from at least two or at least three, or at least four, or up to twenty, or up to eighteen, or up to twelve branched olefin monomer units to form a main chain having A chain of at least two or at least three, or at least four branches. In 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. Branched chain olefins can branch at the alpha or beta positions, or further along the longest chain. In one embodiment, R is derived from a branched olefin that is solely or at least partially isobutylene.

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

In ^one embodiment, R, R1 and R2 consist only of carbon and ^hydrogen .

Polyolefin-substituted hydroxy-aromatic carboxylic acids (eg, alkyl salicylates) may be neutral or nearly neutral salts of carboxylic acids; nearly neutral means that no more than 15 mol% excess base is present, i.e., if The salt is metal-containing, then the metal ratio is 1.15 or less. In one embodiment, the neutral salt of a polyolefin-substituted hydroxy-aromatic carboxylic acid (eg, alkylsalicylic acid) can be an amine or ammonium salt, a metal salt, or a mixture thereof.

Amines suitable for use in the preparation of neutral amine salified polyolefin-substituted hydroxy-aromatic carboxylic acids (eg, alkyl salicylates) are not overly limited and may comprise any alkyl amine, but are typically derived from aliphatic carboxylic acids Acidic fatty acid amines. The alkyl groups present in the amines may contain 10 to 30 carbon atoms, or 12 to 18 carbon atoms, and may be straight or branched chain. In some embodiments, alkyl groups can be straight chain and unsaturated. Typical amines include pentadecylamine, octadecylamine, hexadecylamine, oleylamine, decylamine, dodecylamine, dimethyldodecylamine, tridecylamine, decylamine Heptaalkylamine, octadecylamine, stearylamine, and any combination thereof. In some embodiments, the fatty acid derived amine salt of alkylsalicylic acid can be a salt of oleylamine. In certain embodiments, the amine can be a gamma-aminoester compound; this type of aminoester can be derived from the Michael addition of a primary amine to an alkyl diester of itaconic acid represented by the formula below.

wherein R ¹ and R ² are hydrocarbyl groups containing 2 to 30 carbon atoms, and R ³ is a hydrocarbyl group containing 4 to 50 carbon atoms. In some embodiments, R ³ of the aminoester compound is an alkyl group having at least one hydrocarbyl group substituted at the 1- or 2-position of the alkyl group. In one embodiment, the aminoester is dibutyl 2-(((2-ethylhexyl)-amino)methyl)succinate.

In certain embodiments, the neutral salts of polyolefin-substituted hydroxy-aromatic carboxylic acids (eg, alkylsalicylic acids) can be quaternary ammonium salts, also known as quaternary nitrogen compounds. Quaternary nitrogen compounds are characterized by the tetracoordination of the nitrogen atom; this prevents the release of cationic species that are not protic (ie, acidic protons) under basic conditions. Quaternary nitrogen compounds can be characterized into two broad groups: tetracoordinated tetrahydrocarbylammonium compounds (eg, tetrabutylammonium) and tricoordinated aromatic compounds (eg, N-hydrocarbylpyridinium).

In some embodiments, the quaternary nitrogen salt can include the reaction product of (a) a hydrocarbyl-substituted compound having a tertiary amino group and (b) a quaternization 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 and acids or combinations 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 polyalkane-substituted amine with at least one tertiary amino group and/or a Mannich with a tertiary amino group the Mannich reaction product; and (ii) the quaternizing agent.

The polyolefin-substituted hydroxy-aromatic carboxylic acid cleaners of the present invention may be metal-containing cleaners. Metal-containing cleaners can be neutral, or very nearly neutral, or overbased. Overbased cleaners contain a stoichiometric excess of the metal base for the acidic organic substrate. This is also known as the metal ratio. The term "metal ratio" is the ratio of total equivalents of metals to equivalents of acidic organic compounds. The neutral metal salt has a metal ratio of one. A salt with 4.5 times the metal present in a common salt will have a metal excess of 3.5 equivalents or a ratio of 4.5. The term "Metal ratio".

In one embodiment, the overbased metal-containing polyolefin-substituted hydroxy-aromatic carboxylic acid may be a calcium or magnesium overbased detergent. In one embodiment, the overbased cleaner may include a calcium alkylphenol cleaner with a metal ratio of at least 1.5, at least 3, at least 5, or at least 7. In certain embodiments, the overbased calcium alkylphenol cleaner may have a metal ratio of 1.5 to 25, 2.5 to 20, or 5 to 16.

Alternatively, polyolefin substituted hydroxy-aromatic carboxylic acid cleaners can be described as having TBN. Overbased carboxylic acid cleaners, such as salicylates, typically have a total base number of 120 to 600 mg KOH/g, or 150 to 550 mg KOH/g, or 180 to 350 mg 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 cleaning agent containing the polyolefin-substituted hydroxy-aromatic carboxylic acid may be present in the lubricant in an amount to deliver 0.5 to 10 TBN to the composition or 1 to 7 TBN or 1.5 to 5 TBN to the composition in the composition.

Overbased detergents can also be defined as the ratio of neutral detergent salts (also known as detergent soaps) to detergent ash. The ash to soap weight ratio of the overbased cleaner can be 3:1 to 1:8, or 1.5:1 to 1:4.1, or 1.3:1 to 1:3.4.

The polyolefin-substituted hydroxy-aromatic carboxylic acid cleaners of the present invention can be advantageously used as additives in lubricants. The amount of polyolefin-substituted hydroxy-aromatic carboxylic acid detergent in the lubricant can be 0.1 to 8 weight percent oil-free, but includes calcium carbonate and other salts present in the overbased composition. When present as an overbased cleaner, the amount may generally range from 0.1 to 25% by weight, or 0.2 to 28, or 0.3 to 20, or 0.5 to 15% by weight. Higher amounts are typical values for marine diesel cylinder lubricants, eg 1% or 3% or 5% to 25%, 20% or 15%. Amounts for gasoline or heavy duty diesel engines (non-marine) will typically 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, eg, 0.1 to 10% or 0.2 to 8% or 0.3 to 6%, for each engine type.

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

The lubricant composition may contain an alkylphenol-containing cleaning agent other than that of the disclosed technology. In one embodiment, the lubricant composition of the disclosed technology includes the polyolefin-substituted polyolefin 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% Hydroxy-aromatic carboxylic acid or salts thereof cleaners, and free or substantially free of alkylphenol-containing cleaners derived from alkylphenols derived from propylene oligomers, especially tetrakis Propylene. In this context, "substantially free" means no more than 0.01% by weight or an amount believed to be due to contamination or other unintentional means.

Oil with lubricating viscosity

The lubricating composition of the present invention includes an oil of lubricating viscosity. Such oils include natural and synthetic oils, oils derived from hydrocracking, hydrogenation and hydrorefining, unrefined, refined, re-refined oils or mixtures thereof. A more detailed description of unrefined, refined and re-refined oils is provided in International Publication WO2008/147704 at paragraphs [0054] to [0056] (similar disclosure is provided in US Patent Application 2010/197536, see [0072] to [0073]). A more detailed description of natural and synthetic lubricating oils is described in WO2008/147704 at paragraphs [0058] to [0059], respectively (similar disclosure is provided in US patent application 2010/197536, see [0075] to [0076] ). Synthetic oils can be prepared by the Fischer-Tropsch reaction, and typically can be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil may be produced by the Fisher-Topsch gas-to-liquid synthesis procedure as well as other gas-to-liquids.

Oils of lubricating viscosity may also be used in accordance with the April 2008 edition of "Appendix E-API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils. Oils)” in Section 1.3, Subheading 1.3. “Base Stock Categories”. US Patent No. 7,285,516 also outlines API guidelines (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, a Group IV synthetic oil, or a Group V naphthenic or ester synthetic oil, or a mixture thereof. In one embodiment, the oil of lubricating viscosity may be an API Group II, Group III mineral oil, or Group IV combination oil, or a mixture thereof.

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

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 that can be combined with additional oils to form, in whole or in part, a finished lubricant, then these additives are compatible with oils of lubricating viscosity and/or Or the ratio to diluent oil comprises the range of 1:99 to 99:1 (by weight) or 80:20 to 10:90 (by weight). Typically, the lubricating compositions of the disclosed technology include 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 Compositions - Other Additives

The engine lubricating compositions 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, antiwear agents, oil soluble titanium compounds, extreme pressure agents, foam inhibitors, viscosity modifiers, corrosion inhibitors, metal passivators, pour point depressants, friction modifiers agents, demulsifiers and seal swelling agents. These additional components are described in more detail below.

The lubricating composition optionally further comprises at least one cleaning agent in addition to the polyolefin-substituted hydroxy-aromatic carboxylic acid or salt thereof as described herein. Exemplary optional cleaners include overbased metal-containing cleaners. The metal of the metal-containing cleaner may be zinc, sodium, calcium, barium or magnesium. The overbased metal-containing cleaner may be selected from the group consisting of sulfonates, non-sulfur-containing phenates, sulfur-containing phenates, salicylate alkoxides, salicylates, and mixtures thereof or borated equivalents thereof. Overbased cleaners can be borated with boric acid agents such as boric acid.

Overbased metal-containing cleaners may also include "hybrid" cleaners formed with mixed surfactant systems comprising phenate and/or sulfonate components, such as phenate/salicylate , sulfonate/phenate, sulfonate/salicylate, sulfonate/phenate/salicylate, as described, for example, in US Pat. Nos. 6,429,178, 6,429,179, 6,153,565, and 6,281,179. Where a mixed sulfonate/phenate cleaner is employed, the mixed cleaner would be considered equivalent to the amount of different phenate and sulfonate cleaners incorporating the same amount of phenate and sulfonate soap, respectively.

Exemplary overbased metal-containing cleaners include zinc sulfonates, sodium sulfonates, calcium sulfonates, and magnesium sulfonates, phenates (including sulfur-containing and sulfur-free phenates), salicylates, and salicylates acid salt. Such overbased sulfonates, salicylate alkoxides, 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 cleaner may be zinc sulfonate, sodium sulfonate, calcium or magnesium sulfonate, phenate, sulfur-containing phenate, salicylate alkoxide, or salicylates. Overbased sulfonates, salicylate alkoxides, phenates, and salicylates typically have a total base number of 120 to 700 TBN. The total base number of the overbased sulfonate is typically 120 to 700, or 250 to 600, or 300 to 500 (on an oil-free basis).

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

In one embodiment, the lubricating composition may be free of linear alkyl benzene sulfonate detergents. In one embodiment, the sulfonate cleaner may be a metal salt of one or more oil-soluble alkyltoluene sulfonate compounds, as disclosed in US Publication No. 20080119378.

The lubricating composition may comprise at least 0.01 wt. % or at least 0.1 wt. % of a cleaning agent 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 cleaner.

The lubricating composition optionally further comprises at least one antioxidant. Exemplary antioxidants suitable for use herein include phenolic antioxidants and amine antioxidants, such as diarylamines, alkylated diarylamines, hindered phenols, and mixtures thereof. The diarylamine or alkylated diarylamine can be phenyl-alpha-naphthylamine (PANA), alkylated diphenylamine or alkylated phenylnaphthylamine or mixtures thereof. Example alkylated diphenylamines include dinonyldiphenylamine, nonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine, didecyldiphenylamine, decyldiphenylamine, and mixtures thereof. Example alkylated diarylamines include octyl, dioctyl, nonyl, dinonyl, decyl, and didecylphenylnaphthylamines. Hindered phenol antioxidants typically contain sec-butyl and/or tert-butyl groups as sterically hindered groups. The phenolic group can be further substituted with a hydrocarbyl group (eg, straight or branched chain alkyl) and/or a bridging group to the second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4 - Propyl-2,6-di-tert-butylphenol, 4-butyl-2,6-di-tert-butylphenol and 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenolic antioxidant can be an ester, such as those described in US Pat. No. 6,559,105. One such hindered phenolic ester is sold as Irganox ^™ L-135, available from Ciba.

When present, the lubricating composition can include at least 0.1 wt%, or at least 0.5 wt%, or at least 1 wt% antioxidant, and in some embodiments, up to 3 wt%, or up to 2.75 wt%, or up to 2.5 wt% Antioxidants.

The lubricating composition optionally further comprises at least one dispersant. Exemplary dispersants include succinimide dispersants, Mannich dispersants, succinamide dispersants and polyolefin succinates, amides and ester-amides and mixtures thereof. When present, the succinimide dispersant can be as described above, as the succinimide is described as being suitable for the cation M.

Succinimide dispersants can be derived from aliphatic polyamines or mixtures thereof. The aliphatic polyamine may be ethylene polyamine, propylene polyamine, butene polyamine or mixtures thereof. In one embodiment, the aliphatic polyamine may be ethylene polyamine. In one embodiment, the aliphatic polyamine may be selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms, and mixtures thereof .

In one embodiment, the dispersant may be a polyolefin succinate, amide, or ester-amide. The polyolefin succinate-amide can be polyisobutylene succinic acid reacted with alcohols (eg, pentaerythritol) and polyamines as described above. Example polyolefin succinates include polyisobutylene succinates 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 US Pat. , 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 0 355 895A.

The succinimide dispersant may include 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 can also be post-treated by conventional methods by reaction with any of a variety of reagents. Among them are boron compounds (such as boric acid), urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids (such as terephthalic acid), hydrocarbon-substituted succinic anhydride, 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 US Publication No. 2009/0054278).

When present, the lubricating composition can include 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 at most 15 wt%, or up to 10 wt%, or up to 6 wt% or up to 3 wt% dispersant.

The lubricating composition optionally further comprises at least one antiwear agent. Examples of suitable antiwear agents suitable for use herein include: titanium compounds, tartrates, tartaramides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, metal dihydrocarbyl dithiophosphates (such as dialkyl dithiophosphates) Zinc thiophosphate), phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds (such as thiocarbamates, thiocarbamate amides, sulfur carbamate ethers, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamoyl)disulfides). In one embodiment, the antiwear agent may comprise a tartrate salt or a tartarimide, as described in US Publication Nos. 2006/0079413, 2006/0183647, and 2010/0081592. The tartrate or tartarimide may contain an alkyl ester group 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 US Publication No. 20050198894.

In one embodiment, the lubricating composition may further comprise a phosphorus-containing antiwear agent. Exemplary phosphorus-containing antiwear 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% of the antiwear agent, and in some embodiments, up to 3 wt%, or up to 1.5 wt%, or up to 0.9 wt% antiwear agent.

The lubricating composition can include one or more oil-soluble titanium compounds that can 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 US Patent No. 7,727,943 and US 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 can be formed from monohydric alcohols, vicinal 1,2-diols, polyhydric alcohols, or mixtures thereof. Monoalkoxides can have 2 to 16 or 3 to 10 carbon atoms. In one embodiment, the titanium compound includes an alkoxide of an vicinal 1,2-diol or polyol. The 1,2-vicinal diols comprise fatty acid monoesters of glycerol, where the fatty acid can 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 the oil-soluble titanium compound is included as part of the antiwear agent.

The lubricating composition may contain extreme pressure agents. Exemplary extreme pressure agents that are soluble in oil include sulfur- and chlorine-sulfur-containing EP agents, dimercaptothiadiazoles or CS ₂ derivatives of dispersants (usually succinimide dispersants), chlorinated hydrocarbons Derivatives of EP agents and phosphorus EP agents. Examples of such EP agents include chlorinated waxes; sulfurized olefins (eg, sulfurized isobutylene), hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazoles and their oligomers, organosulfides, and polymers. Sulfides (such as benzhydryl disulfide), bis-(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkyl phenols, sulfurized dipentene, sulfurized Terpenes and sulfurized Diels-Alder adducts; phosphorus sulfurized hydrocarbons, such as the reaction product of phosphorus sulfide with turpentine or methyl oleate; phosphorus esters, such as dihydrocarbyl phosphites and phosphites Trihydrocarbyl phosphates, such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, amylphenyl phosphite; dipentylphenyl phosphite, tridecyl phosphite esters, distearyl phosphites, and polypropylene-substituted phenolic phosphites; metal thiocarbamates, such as zinc dioctyl dithiocarbamate and barium heptyl phenate; alkyl and dithiocarbamates Amine salts or derivatives of alkylphosphoric acids, comprising, for example, amine salts of the reaction product of dialkyldithiophosphoric acid with propylene oxide and subsequently further reacted with _{P2O5 ;} and mixtures thereof. Some useful extreme pressure agents are described in US Patent 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% extreme pressure agent, and in some embodiments, at most 3 wt%, or at most 1.5 wt%, or at most 0.9 wt% extreme pressure agent.

The lubricating composition may contain a suds suppressor. Foam suppressors useful in lubricant compositions include polysiloxanes, copolymers of ethyl acrylate with 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers including fluorinated polysiloxanes, Trialkyl phosphate, polyethylene glycol, polyethylene oxide, polypropylene oxide and (ethylene oxide-propylene oxide) polymers.

The lubricating composition may contain a viscosity modifier. Viscosity modifiers (sometimes also referred to as viscosity index improvers or viscosity modifiers) useful in lubricant compositions are typically polymers comprising polyisobutylene, polymethacrylate (PMA) and polymethacrylate, dimethacrylate Olefin polymers, polyalkylstyrenes, esterified styrene-maleic anhydride copolymers, hydrogenated alkenyl aromatic hydrocarbons-conjugated diene copolymers, and polyolefins, also known as olefin copolymers or OCPs. PMA is prepared from a mixture of methacrylate monomers with different alkyl groups. Alkyl groups can be straight or branched chain groups containing from 1 to 18 carbon atoms. Most PMAs are viscosity modifiers as well as pour point depressants. In one embodiment, the viscosity modifier is a polyolefin comprising ethylene and one or more higher olefins such as 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. % polymeric viscosity modifier, and in some embodiments, up to 10 wt. %, or at most 5 wt%, or up to 2.5 wt% polymeric viscosity modifier.

The lubricating composition may contain a corrosion inhibitor. Corrosion inhibitors/metal deactivators that may be suitable for use in the exemplary lubricating compositions include fatty amines, octylamine caprylate, condensation products of dodecenylsuccinic acid or anhydrides, and fatty acids such as oleic acid and polyamines, benzoic Derivatives of triazoles (eg tolyltriazole), 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles and 2-alkyldithiobenzothiazoles.

The lubricating composition may contain a pour point depressant. Pour point depressants that can be used in exemplary lubricating compositions include polyalphaolefins, esters of maleic anhydride-styrene copolymers, polymethacrylates, polyacrylates, or polyacrylamides.

The lubricating composition may contain friction modifiers. Friction modifiers suitable for use in the 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 that generally do not produce any sulfated ash under the conditions of ASTM D 874. An additive is said to be "metal free" if it does not provide metal content to the lubricant composition. As used herein, the term "fatty alkyl" or "fatty" in reference to friction modifiers refers to a carbon chain having from 8 to 30 carbon atoms, typically a straight carbon chain.

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

wherein D and D' are independently selected from -O-, >NH, >NR ²³ , by combining the D and D' groups together and forming R ²¹ -N< between the two >C=O groups The imide group formed by the group; E is selected from -R ²⁴ -OR ²⁵ -, >CH ₂ , >CHR ²⁶ , >CR ²⁶ R ²⁷ , >C(OH)(CO ₂ R ²² ), >C (CO ₂ R ²² ) ₂ and >HOR ²⁸ ; wherein R ²⁴ and R ²⁵ are independently selected from >CH ₂ , >CHR ²⁶ , >CR ²⁶ R ²⁷ , >C(OH)(CO ₂ R ²² ) and >CHOR ²⁸ ; q is 0 to 10, provided that when q=1, E is not > _CH2 , and when n=2, neither Es is >_CH2; p is 0 or 1; ^R21 independently is hydrogen or a hydrocarbyl group, usually containing 1 to 150 carbon atoms, provided that when R ²¹ is hydrogen, p is 0, and q is greater than or equal to 1; R ²² is a hydrocarbyl group usually containing 1 to 150 carbon atoms; R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ are independently hydrocarbyl; and R ²⁸ is hydrogen or hydrocarbyl, typically containing 1 to 150 carbon atoms, or 4 to 32 carbon atoms, or 8 to 24 carbon atoms . In certain embodiments, the hydrocarbyl groups R ²³ , R ²⁴ , and R ²⁵ may be straight chain or predominantly straight chain alkyl groups.

In certain embodiments, the ashless friction modifiers are fatty esters, amides or imides of various hydroxy-carboxylic acids, such as tartaric acid, malolactic acid, glycolic acid, and mandelic acid. Examples of suitable materials include bis(2-ethylhexyl) tartrate (ie, bis(2-ethylhexyl) tartrate), bis(C ₈ -C ₁₀ ) tartrate, bis(C _12-15 ) tartrate , dioleoyl tartrate, oleoyl triamide and oleoyl maleimide.

In certain embodiments, the ashless friction modifier may be selected from long chain fatty acid derivatives of amines, fatty esters, or aliphatic epoxides; fatty imidazolines, such as condensation products of carboxylic acids and polyalkylene-polyamines ; Amine salts of alkyl phosphoric acids; Fatty alkyl tartrates; Fatty alkyl tartarimides; Fatty alkyl tartaramides; Fatty phosphonates; Fatty phosphites; Borated phospholipids, borated aliphatic epoxides ; Glycerides; borated glycerides; fatty amines; alkoxylated fatty amines; borated alkoxylated fatty amines; hydroxy and polyhydroxy fatty amines, including tertiary hydroxy fatty amines; hydroxy alkyl amides; Metal salts of fatty acids; metal salts of alkyl salicylates; fatty oxazolines; fatty ethoxylated alcohols; condensation products of carboxylic acids and polyalkylene polyamines; or fatty carboxylic acids with guanidine, aminoguanidine, urea Or the reaction product of thiourea and its salt.

Friction modifiers may also encompass substances such as sulfurized fatty compounds and olefins, sunflower oil or soybean oil monoesters of 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 0.1 to 3 wt % (or 0.12 to 1.2 or 0.15 to 0.8 wt %). The material may also be present in concentrate form alone or with other additives and minor amounts of oil. In the concentrate, the amount of material can be two to ten times the amount of the above concentrate.

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

The nitrogen-containing molybdenum material includes a molybdenum-amine compound, as described in US Pat. No. 6,329,327, and an organo-molybdenum compound prepared from the reactant of a molybdenum source, a fatty oil, and a diamine, as described in US Pat. No. 6,914,037 . Other molybdenum compounds are disclosed in US Publication No. 20080280795. The molybdenum amine compound can be obtained by reacting a compound containing a hexavalent molybdenum atom with a primary, secondary or tertiary amine represented by the formula NR ²⁹ R ³⁰ R ³¹ , wherein each of R ²⁹ , R ³⁰ and R ³¹ is independently hydrogen or a hydrocarbon group having 1 to 32 carbon atoms, and wherein at least one of R ²⁹ , R ³⁰ and R ³¹ is a hydrocarbon group having 4 or more carbon atoms or represented by the following formula:

wherein R ³² represents a chain hydrocarbon group having 10 or more carbon atoms, s is 0 or 1, and R ³³ and/or R ³⁴ represent a hydrogen atom, a hydrocarbon group, an alkanol or an alkylamino group having 2 to 4 carbon atoms , and when s=0, neither R ³³ nor R ³⁴ is a hydrogen atom or a hydrocarbon group.

Specific examples of suitable amines include monoalkyl (or alkenyl) amines such as tetradecylamine, stearylamine, oleylamine, tallow alkylamine, hardened tallow alkylamine, and soybean oil alkylamine; dioxane (or alkenyl)amines such as N-tetradecylmethylamine, N-pentadecylmethylamine, N-hexadecylmethylamine, N-stearylmethylamine, N-oleylmethylamine , N-docosyl methylamine, N-tallow alkyl methylamine, N-hardened tallow alkyl methylamine, N-soybean oil alkyl methylamine, behenylamine, pentadecylamine , Behenylamine, distearylamine, dioleylamine, behenylamine, bis(2-hexyldecyl)amine, bis(2-octyldodecyl)amine, bis(2-octyldodecyl)amine (2-decyltetradecyl)amine, tallow dialkylamine, hardened tallow dialkylamine and soybean oil dialkylamine, and trialk(en)ylamines such as tetradecyldimethylamine , cetyldimethylamine, octadecyldimethylamine, tallow alkyldimethylamine, hardened tallow alkyldimethylamine, soybean oil alkyldimethylamine, dioleyl methyl amine, tridecylamine, tristearylamine and trioleylamine. Suitable secondary amines have two alkyl (or alkenyl) groups with 14 to 18 carbon atoms.

Examples of the compound containing a hexavalent molybdenum atom include molybdenum trioxide or its hydrate (MoO ₃ .nH ₂ O) ^, molybdic acid (H ₂ MoO ₄ ), alkali metal molybdate (Q ₂ MoO ₄ ), wherein Q represents Alkali metals such as sodium and potassium, ammonium molybdate {(NH ₄ ) ₂ MoO ₄ or heptamolybdate (NH ₄ ) ₆ [Mo ₇ O ₂₄ ].4H ₂ O}, MoOCl ₄ , MoO ₂ Cl ₂ , MoO2Br2 , Mo ₂ O ₃ Cl ₆ and 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 molybdenum amine compound.

Other organo-molybdenum compounds of the present 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 can be used include cottonseed oil, peanut oil, coconut oil, linseed oil, palm kernel oil, olive oil, corn oil, palm oil, castor oil, canola 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.

C)、N-妥尔油烷基-1,3-丙二胺(

T)和N-油基-1,3-丙二胺(

O)，所有均可购自阿克苏贝尔(Akzo Nobel)。Examples of some monoalkylated alkylene diamines that can be used include methylaminopropylamine, methylaminoethylamine, butylaminopropylamine, butylaminoethylamine, octylaminopropylamine, octylaminoethylamine, ten Dialkylaminopropylamine, dodecylaminoethylamine, hexadecylaminopropylamine, hexadecylaminoethylamine, octadecylaminopropylamine, octadecylaminoethylamine, isopropyloxy propylpropyl-1,3-diaminopropane and octyloxypropyl-1,3-diaminopropane. Monoalkylated alkylene diamines derived from fatty acids can also be used. Examples include N-cocoalkyl-1,3-propanediamine (

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

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

O), all available from Akzo Nobel.

Sources of molybdenum for incorporation into fatty oil/diamine complexes are generally oxygen-containing molybdenum compounds, similar to those above, including ammonium molybdate, sodium molybdate, molybdenum oxide, and mixtures thereof. A suitable source of molybdenum includes molybdenum trioxide (MoO ₃ ).

710，和可购自R.T.范德比尔特(Vanderbilt)的

855。Commercially available nitrogen-containing molybdenum compounds include, for example, Adeka®

710, and available from RT Vanderbilt

855.

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

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

Seal swelling agents suitable for use herein include sulfolane derivatives such as Exxon Necton-37 ^™ (FN 1380) and Exxon Mineral Seal Oil ^™ (FN 3200).

Lubricating compositions can be prepared by adding the product of the methods 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 described in Table 1. All additives are expressed on an oil-free basis.

Table 1: Engine Lubricating Compositions

Use of engine lubricating compositions

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

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

Generally, a lubricating composition is added to the lubricating system of an internal combustion engine, which then during its operation delivers the lubricating composition to the engine's cylinders, where the lubricating composition can be ignited with fuel.

The internal combustion engine can be a diesel-fueled engine (such as 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 can be a 2-stroke or 4-stroke engine.

The lubricating composition is suitable for use as a cylinder lubricant regardless of the sulfur, phosphorus or sulfated ash (ASTM D-874) content of the fuel. The sulfur content of the lubricating composition, which is particularly suitable for use as an engine oil lubricant, 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 range from 0.001 to 0.5 wt%, or 0.01 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 100 ppm to 1000 ppm, or 200 ppm to 600 ppm. The total sulfated ash content can 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% by weight or less. In one embodiment, the sulfated ash content may be from 0.05% to 0.9% by weight, or from 0.1% to 0.2% by weight, or to 0.45% by weight.

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

Transmission system lubricating composition

In one embodiment, the lubricating composition according to the present invention is used in a driveline device. Lubricating compositions for powertrain devices may comprise a polyolefin-substituted hydroxy-aromatic carboxylic acid or a salt thereof, as described herein, in an oil with a lubricating tackifier, optionally in other properties. In the presence of additives, which may include dispersants, antiwear agents, dispersant viscosity modifiers, friction modifiers, viscosity modifiers, antioxidants, overbased detergents (other than polyolefin substituted hydroxy- aromatic carboxylic acids or their salts or their salts), suds suppressors, demulsifiers or pour point depressants or mixtures thereof. In one embodiment, the present invention provides a lubricant composition comprising at least one of the following in addition to a polyolefin-substituted hydroxy-aromatic carboxylic acid or a salt thereof: a polyisobutylene succinimide dispersion additives, antiwear agents, corrosion inhibitors, dispersants, viscosity modifiers, friction modifiers, viscosity modifiers (usually polymethacrylates with linear, comb or star architecture), antioxidants (including phenols and amines) Antioxidants), overbased cleaners (comprising the overbased sulfonates, phenates and salicylates described above other than polyolefin-substituted hydroxy-aromatic carboxylic acids or salts or salts thereof) ) or a mixture thereof.

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

The driveline lubricating compositions are 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:

oils of lubricating viscosity,

thiadiazoles (usually present at 0.05% to 1%, or 0.07% to 0.7%, or 0.1% to 0.3%, or 0.15% to 0.25% by weight),

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

A phosphorus-containing antiwear agent selected from (i) a non-ionic 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 delivering 110 to 700 ppm, 130 to 600 ppm, 150 to 500 ppm, or 160 to 400 ppm calcium; and wherein about 0.01 to about 2 wt%, or about 0.1 to about 1.75 The wt %, or from about 0.2 to about 1.5 wt %, of the cleaning agent includes the polyolefin-substituted hydroxy-aromatic carboxylic acids or salts thereof described herein.

The manual transmission may have synchromesh, or in another embodiment, the manual transmission may not have synchromesh. The synchromesh may be constructed of aluminum, steel, bronze, molybdenum, brass (sintered or non-sintered), carbon in the form of fibers, graphite materials (optionally combined with cellulosic materials) or cellulosic materials or phenolic resins.

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 2000 ppm, 150 to 1500 ppm, 200 to 1000 or 250 to 800 ppm or 500 to 875 ppm phosphorus delivered by an antiwear agent, ie by zinc dialkyldithiophosphate or another phosphorus containing antiwear agent deliver.

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

oils of lubricating viscosity,

thiadiazoles (usually present at 0.05% to 1%, or 0.07% to 0.7%, or 0.1% to 0.3%, or 0.15% to 0.25% by weight),

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

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

about 0.1 to about 5% by weight detergent, typically present in an amount to deliver 110 to 700 ppm, 130 to 600 ppm, 150 to 500 ppm, or 160 to 400 ppm calcium; and of about 0.01 to about 2 wt%, or about 0.1 to about 1.75 The wt %, or from about 0.2 to about 1.5 wt %, of the cleaning agent includes the polyolefin-substituted hydroxy-aromatic carboxylic acids or salts thereof described herein.

The thiadiazole compound may comprise a mono- or dihydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole compound. Examples of thiadiazoles include 2,5-dimercapto-1,3,4-thiadiazole or oligomers thereof, hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole, Hydrocarbylthio-substituted 2,5-dimercapto-1,3,4-thiadiazoles or oligomers thereof. Oligomers of hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazoles are typically formed by sulfur-sulfur formation between 2,5-dimercapto-1,3,4-thiadiazole units bonds to form oligomers having two or more of said thiadiazole units. These thiadiazole compounds can also be used in the post-treatment of dispersants as mentioned below for the 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. Typically, readily available materials such as 2,5-dimercapto-1,3,4-thiadiazole or hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole or Hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazoles.

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:

oils of lubricating viscosity,

dispersants typically present at 0.01% to 5% by weight, or 0.05% to 3% by weight, or 0.1% to 3% by weight, or 0.1% to 2% by weight,

about 0.1 to about 1, typically present in an amount to deliver 40 to 1000 ppm, 50 to 700 ppm, 60 to 600 ppm, or 70 to 250 ppm 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% by weight of a cleaning agent comprising a polyolefin-substituted hydroxy-aromatic carboxylic acid or a 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 alternate 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:

oils of lubricating viscosity,

dispersing agent 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%,

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

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% by weight detergent, typically present in an amount to deliver 40 to 700 ppm, 50 to 600 ppm, 60 to 500 ppm, or 70 to 250 ppm calcium; and of about 0.01 to about 2 wt%, or about 0.1 to about 1.75 % by weight, or from about 0.2 to about 1.5 % by weight, of the cleaning agent comprising the polyolefin-substituted hydroxy-aromatic carboxylic acids described herein, or a salt thereof, or a salt thereof, 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 alternate embodiment, no friction modifier is present.

Automatic transmissions include continuously variable transmissions (CVT), continuously variable transmissions (IVT), toroidal transmissions, continuous slip torque conversion clutches (CSTCC), stepped automatic transmissions and dual clutch transmissions (DCT).

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 other than the polyolefin-substituted hydroxy-aromatic carboxylic acids of the present invention. The optional additional cleaning agent may be an overbased cleaner, a non-overbased cleaner, or a mixture thereof. Typically, cleaning agents are highly alkaline.

Off-Highway Vehicles

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 usually have a common oil sump which lubricates not only the transmission in the vehicle but also the gears, axles and hydraulics in the vehicle. In one embodiment, the present invention comprises a lubricant composition comprising:

oils of lubricating viscosity,

Dispersants are typically present at 0.1 to 3 wt%, or 0.1 to 2.5 wt%, or 0.2 to 2 wt%,

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

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

oils of lubricating viscosity,

Dispersants are typically present at 0.1 to 3 wt%, or 0.1 to 2.5 wt%, or 0.2 to 2 wt%,

Phosphorus-containing antiwear agents selected from (i) non-ionic phosphorus compounds, which may be hydrocarbyl phosphites, such as zinc dialkyldithiophosphates; or (ii) amine salts of phosphorus compounds,

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

Lubricated off-highway vehicles typically have wet brakes, transmission, hydraulics, final drive, power take-off. These parts are usually lubricated by a single lubricant supplied from a common oil sump. The transmission can 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, turbine 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. A hydraulic system is generally a device or device in which a fluid, typically an oil-based fluid, delivers energy to different parts of the system by applying hydraulic force. Turbine lubricants are commonly used to lubricate the gears or other moving parts of turbines (or turbine systems), such as steam or gas turbines. Circulating oil is typically used to distribute heat to or through equipment or devices that circulate it.

In one embodiment, the lubricant composition is at 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 % of the total composition % to 1 wt %, 0.01 wt % to 0.5 wt % contains the polyolefin-substituted hydroxy-aromatic carboxylic acid or salt or salt thereof as described herein.

The hydraulic, turbine or circulating lubricant composition may also contain one or more additional additives. In some embodiments, additional additives may include antioxidants, antiwear agents, corrosion inhibitors, rust inhibitors, foams, in addition to the polyolefin-substituted hydroxy-aromatic carboxylic acids of the present invention or salts thereof or metal salts thereof Inhibitors, dispersants, demulsifiers, metal deactivators, friction modifiers, detergents, emulsifiers, extreme pressure agents, pour point depressants, viscosity modifiers, or any combination thereof.

Thus, the lubricant may include antioxidants or mixtures thereof. Antioxidants may be present from 0 to 4.0%, or from 0.02 to 3.0%, or from 0.03 to 1.5% by weight of the lubricant.

The lubricant composition may also contain dispersants or mixtures thereof. Suitable dispersants include: (i) polyetheramines; (ii) borated succinimide dispersants; (iii) non-borated succinimide dispersants; (iv) dialkylamines, aldehydes and A Mannich reaction product of a hydrocarbyl-substituted phenol; or any combination thereof. In some embodiments, the dispersant may be present at 0 or 0.01 to 2.0, 0.05 to 1.5, or 0.005 to 1, or 0.05 to 0.5 wt% of the total composition.

Defoamers, also known as foam suppressors, are known in the art and include organopolysiloxanes and non-silicon foam suppressors. Examples of organopolysiloxanes include dimethylpolysiloxane 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 its mixture. In some embodiments, the antifoaming agent is a polyacrylate. The antifoaming agent may be present in the composition from 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 include propylene oxide, ethylene oxide, polyoxyalkylene alcohols, alkylamines, aminoalcohols continuously reacted with ethylene oxide or substituted ethylene oxide or mixtures thereof , diamine or polyamine derivatives. 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 at 0.002% to 0.012% by weight.

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

The lubricant composition may also contain a rust inhibitor. Suitable rust inhibitors include hydrocarbylamine salts of alkylphosphoric acids, hydrocarbylamine salts of dialkyldithiophosphoric acids, hydrocarbylamine salts of hydrocarbylarylsulfonic acids, aliphatic carboxylic acids or esters thereof, esters of nitrogen-containing carboxylic acids , ammonium sulfonate, imidazoline, alkylated succinic acid derivatives reacted with alcohols or ethers, or any combination thereof; or mixtures thereof.

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

The lubricant may contain metal deactivators or mixtures thereof. The metal deactivator can be selected from derivatives of benzotriazole (usually tolyltriazole), 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole or 2 - alkyldithiobenthiazoles, 1-amino-2-propanols, derivatives of dimercaptothiadiazoles, condensation products of octylamine caprylate, dodecenylsuccinic acid or anhydrides and/or Fatty acids and polyamines such as oleic acid. Metal passivators can also be described as corrosion inhibitors.

The metal deactivator may be present in the range of 0 or 0.001% to 0.1%, 0.01% to 0.04%, or 0.015% to 0.03% by weight of the lubricating oil composition. The metal passivator may also be present in the composition at 0.002 wt% or from 0.004 wt% to 0.02 wt%. The metal passivators can be used alone or in mixtures thereof.

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

Lubricants may include extreme pressure agents. 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 from 0 to 3 wt%, 0.005 to 2 wt%, 0.01 to 1.0 wt% of the hydraulic composition.

The lubricant may further include viscosity modifiers or mixtures thereof. Viscosity modifiers (commonly referred to as viscosity index improvers) suitable for use in the present invention comprise polymeric materials comprising styrene-butadiene rubber, olefin copolymers, hydrogenated styrene-isoprene polymers, Hydrogenated 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 to 10, 0.5 to 8, 1 to 6 wt% of the lubricant.

In one embodiment, the lubricants disclosed herein may contain at least one friction modifier. The friction modifier may be present from 0% to 3%, or from 0.02% to 2%, or from 0.05% to 1% by weight 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 to 5, 0.001 to 2, 0.01 to 1.0 wt% of the lubricant.

Therefore, hydraulic lubricants can include:

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

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

oils of lubricating viscosity,

0.02% to 3% by weight of antioxidants selected from amine antioxidants or phenolic antioxidants or mixtures thereof,

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

0.001 wt% to 1.5 wt% neutral or slightly overbased calcium sulfonate, and

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

Therefore, hydraulic lubricants can include:

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

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

oils of lubricating viscosity,

0.02% to 3% by weight of antioxidants selected from amine antioxidants or phenolic antioxidants or mixtures thereof,

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

0.001 wt% to 1.5 wt% neutral or slightly overbased calcium sulfonate,

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

Hydraulic lubricants may also include the formulations defined in the table below:

Table 2: Hydraulic Lubricant Compositions

Specific examples of hydraulic lubricants include those outlined in the table below:

Table 3: Hydraulic Lubricant Compositions

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

example

The cleaning agent according to the invention is prepared as follows:

PIB phenol was prepared by reacting high vinylidene 550Mn polyisobutene with phenol using BF3 as a catalyst. The PIB phenol was then reacted with KOH to give potassium phenate, which was then heated to 150°C and vacuum stripped (25mmHg/5h) to remove water and then the mixture was exposed to CO2 for 5 hours. The final material was found to have a ratio of pib salicylate to pib phenol (determined by 13C NMR) of 66% to 34%, %K = 3.31%, TBN = 56.41, 50% active in dil oil. Then, potassium phenate/methyl salicylate was converted to overbased calcium salicylate by treatment with 90 g of CaCl2 in MAOL (360 g) for 1 h at 60 °C. Hydrated lime (55 g), acetic acid (50% in water) and isobutanol and amyl alcohol and mixture (100 g) were added and CO2 was bubbled through the mixture at 60°C for 40 minutes (0.6 cfh) to a DBN of 11. Volatile solvents were removed by vacuum distillation (150°C, 25mmHg, 30 minutes). The reaction mixture was then filtered and a clear brown liquid was obtained. By NN_29C, the final product was found to have 115TBN, %K=4.71 for D4951, SA=15.665% for D874

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 can be prepared as described herein and evaluated for cleanliness, ie, ability to prevent or reduce deposit formation; sludge treatment; soot treatment; Antioxidant and wear reduction, antiwear properties, deposit control and oxidation control, etc.

The sludge handling performance of each lubricant can be evaluated according to ASTM D4310-10 (Standard Test Method for Determining Sludge and Corrosion Propensity of Inhibited Mineral Oils). Performance was judged by the total amount of sludge formed during the oxidation of lubricants and mineral oil-based fluids at elevated temperatures in the presence of oxygen, water, and copper and iron metals, and the ability of these oils to corrode copper catalyst metals.

Wear resistance was measured in a programmed temperature high frequency reciprocating drilling rig (HFRR) available from PCS Instruments. The HFRR conditions used for the evaluation were 200 g loading, 75 min duration, 1000 micron stroke, 20 Hz frequency, and a temperature profile at 40 °C for 15 min followed by increasing the temperature to 160 °C at a rate of 2 °C/min. The wear trace in microns and the film formation rate in percent of film thickness were then measured at lower wear trace values and higher film formation values, indicating improved wear performance.

Deposit control is performed by the Komatsu Hot Tube (KHT) test using a heated glass tube through which the sample lubricant is pumped, approximately 5 ml of total sample, typically at 0.31 ml/hour long Time (eg 16 hours) use, the air flow is 10mL/min. At the end of the test, the glass tubes had a deposit rating of 0 (very heavy varnish) to 10 (no varnish).

In the panel coker deposition test, the samples were kept splashed on an aluminum panel at 325°C at a temperature of 105°C for 4 hours. Aluminum panels were analyzed using image analysis techniques to obtain generic grades. The rating score is based on "100" being a clean board and "0" being a board completely covered with sediment.

Oxidative control was assessed using differential pressure scanning calorimetry (PDSC), which determines the oxidation induction time (OIT) of lubricating compositions. This is the standard test procedure in the lubricant industry based on CEC L-85T-99. In this test, the lubricating composition is heated to an elevated temperature, typically about 25°C below the average decomposition temperature of the samples tested (in this case, 215°C at 690 kPa), and the time at which the composition begins to decompose is measured. The longer the test time, reported in minutes, the better the oxidative stability of the composition and additives present therein.

钻机进行测试。Tests such as Variable Speed Friction Test, Coefficient of Friction Test based on Falex LFW-1 or JASO M358, VT20 Durability Test, JASO M349 Anti-Shake Durability Test, etc. can be used to evaluate the friction performance of driveline lubricating compositions such as transmission oils and malleability, or use

Rig for testing.

Some of the above-mentioned materials are known to interact in the final formulation and thus the components of the final formulation may differ from those initially added. Products thus formed, including products formed using the lubricant compositions of the present invention in their intended use, may not be readily described. Nonetheless, all such modifications and reaction products are included within the scope of the present invention, which encompasses lubricant compositions prepared by admixing the components described above.

Each of the documents mentioned above is incorporated herein by reference. All numerical amounts in this specification specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, etc., are understood to be modified by the word "about", except where in the examples or otherwise expressly indicated otherwise. Unless otherwise indicated, each chemical substance or composition referred to herein should be construed as a commercial grade material that may contain isomers, by-products, derivatives, and other such materials 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 normally be present in commercial materials. It should be understood that the upper and lower limits of the amount, range, and ratio limits described herein can be independently combined. Similarly, the ranges and amounts for each element of the invention can be used together with ranges or amounts for any other element.

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

Claims (32)

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.