CN110770329B

CN110770329B - Lubricating engine oil composition comprising detergent compound

Info

Publication number: CN110770329B
Application number: CN201880041841.3A
Authority: CN
Inventors: A·B·鲍法; W·A·哈特格斯; S·M·霍塞尼; J·D·沃德; C·P·勒德瑞; B·P·米勒; X·H·涂; C·B·卡姆普贝尔; 李月蓉
Original assignee: Chevron Oronite SAS; Chevron Oronite Technology BV; Chevron Oronite Co LLC
Current assignee: Chevron Oronite SAS; Chevron Oronite Technology BV; Chevron Oronite Co LLC
Priority date: 2017-06-30
Filing date: 2018-06-28
Publication date: 2022-07-15
Anticipated expiration: 2038-06-28
Also published as: CA3068664C; CN110770329A; EP3645680A1; JP7315482B2; EP3645680B1; CA3068664A1; WO2019003177A1; JP2020525590A; US20190002789A1

Abstract

The present disclosure relates generally to lubricating oil compositions comprising an oil of lubricating viscosity and an alkyl hydroxybenzoate detergent compound.

Description

Lubricating engine oil compositions containing detergent compounds

This application claims the benefit and priority of U.S. provisional application serial No.62/527,211 filed on 30.6.2017.

Background

It is well known that medium and overbased detergents provide lubricating properties. Such detergent additives are typically compounded with other lubricating additives to provide lubricating oil compositions exhibiting certain desired lubricating properties. Metal-containing detergents function both as detergents to control deposits and as acid neutralizers or rust inhibitors to reduce wear and corrosion and extend engine life. Detergents are used in lubricants to achieve these benefits, but their use also has disadvantages. Detergents are known to be detrimental to friction performance. The increase in friction is associated with a decrease in fuel economy and therefore this can be a disadvantage as improvements in fuel economy are important for environmental and cost-effective reasons.

A major challenge in engine oil formulation is to develop lubricating oil compositions that achieve both wear control and corrosion inhibition while also achieving improved fuel economy. It has been surprisingly found that lubricants formulated with alkylhydroxybenzoate detergents derived from isomerized normal alpha-olefins show improvements in redox, corrosion inhibition and friction properties.

Summary of The Invention

In accordance with one embodiment of the present disclosure, there is provided a lubricating oil composition comprising:

a. a major amount of an oil of lubricating viscosity; and

b. derived from C₁₀-C₄₀The isomerized normal alpha olefin alkylhydroxybenzoate compound of (1), wherein the alkylhydroxybenzoate detergent has a TBN of 10 to 300mgKOH/gm on an oil-free basis.

Also provided is a method of lubricating an engine, the method comprising lubricating the engine with a lubricating oil composition comprising:

a. a major amount of an oil of lubricating viscosity; and

b. derived from C₁₀-C₄₀The alkylhydroxy group of the isomerized normal alpha-olefin of (1)A benzoate compound, wherein said alkylhydroxybenzoate detergent has a TBN of from 10 to 300mgKOH/gm on an oil-free basis.

Detailed Description

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof have been described herein in detail. It should be understood, however, that the description herein of specific embodiments is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.

To facilitate an understanding of the subject matter disclosed herein, a number of terms, abbreviations, or other shorthand used herein are defined below. Any terms, abbreviations or shorthand not defined should be understood to have the ordinary meaning used by the skilled person at the same time as the filing of this application.

Definition of

As used herein, the following terms have the following meanings, unless explicitly indicated to the contrary. In the present specification, the following words and expressions (if used) have the meanings given below.

By "major amount" is meant more than 50% by weight of the composition.

By "minor amount" is meant less than 50% by mass of the composition, expressed as the total mass of the additive and all additives present in the composition, calculated as the active ingredient of the additive.

By "active ingredient" or "active substance" is meant an additive substance that is not a diluent or solvent.

All percentages reported are based on weight of active (i.e., without regard to carrier or diluent oil) unless otherwise indicated.

The abbreviation "ppm" refers to parts per million by weight based on the total weight of the lubricating oil composition.

Total Base Number (TBN) is determined according to ASTM D2896.

High Temperature High Shear (HTHS) viscosity at 150 ℃ is determined according to ASTM D4683.

Kinematic Viscosity (KV) at 100 ℃₁₀₀) Measured according to ASTM D445.

Cold Start simulation (CCS) viscosity at-35 ℃ was determined according to ASTM D5293.

Noack volatility was measured according to ASTM D5800.

Metal-the term "metal" refers to an alkali metal, an alkaline earth metal, or mixtures thereof.

Olefins-the term "olefins" refers to a class of unsaturated aliphatic hydrocarbons having one or more carbon-carbon double bonds obtained by a variety of processes. Those having one double bond are referred to as monoolefins and those having two double bonds are referred to as dienes, alkadienes or diolefins. Alpha-olefins are particularly reactive because the double bond is between the first and second carbons. Examples are 1-octene and 1-octadecene, which are used as starting materials for moderately biodegradable surfactants. Linear and branched olefins are also included in the definition of olefins.

N-alpha-olefin-the term "n-alpha-olefin" refers to a straight, unbranched hydrocarbon chain having a carbon-carbon double bond in the alpha or primary position of the hydrocarbon chain.

Isomerized normal alpha-olefins. As used herein, the term "isomerized normal alpha olefin" refers to an alpha olefin that has been subjected to isomerization conditions that result in a change in the distribution of the olefin species present and/or introduction of branching along the alkyl chain. The isomerized olefin product may be obtained by isomerizing linear alpha olefins containing from about 10 to about 40 carbon atoms, preferably from about 20 to about 28 carbon atoms, preferably from about 20 to about 24 carbon atoms.

All ASTM standards referred to herein are the latest versions up to the filing date of this application.

In one aspect, the present disclosure relates to a lubricating oil composition comprising:

(a) a major amount of an oil of lubricating viscosity; and

(b) derived from C₁₀-C₄₀The isomerized normal alpha olefin alkylhydroxybenzoate compound of (1), wherein the alkylhydroxybenzoate detergent has a TBN of 10 to 300mgKOH/gm on an oil-free basis.

In another aspect, the lubricating oil composition comprises a molybdenum compound.

In another aspect, there is provided a method of lubricating an engine, the method comprising lubricating the engine with a lubricating oil composition comprising:

(a) a major amount of an oil of lubricating viscosity; and (b) is derived from C₁₀-C₄₀The alkylhydroxybenzoate compound of (a), wherein the alkylhydroxybenzoate detergent has a TBN of 10-300mgKOH/gm on an oil-free basis.

In another aspect, the invention is generally a lubricating oil composition suitable for automotive engines, motorcycle engines, natural gas engines, dual fuel engines, railroad locomotive engines, mobile natural gas engines, and as a functional fluid for automotive and industrial applications.

Alkylhydroxybenzoate detergents derived from isomerized Normal Alpha Olefins (NAO)

In one aspect of the disclosure, the alkyl hydroxybenzoate detergent is derived from C₁₀-C₄₀Isomerized NAO, and having a TBN, on actives basis, of from 10 to 300, preferably from 50 to 300, more preferably from 100 to 300, even more preferably from 150 to 300, most preferably from 175 to 250 mgKOH/gram.

In one aspect of the disclosure, derived from C₁₀-C₄₀The alkylhydroxybenzoate detergent of the isomerized NAO is a calcium alkylhydroxybenzoate detergent.

In one aspect of the disclosure, derived from C₁₀-C₄₀The alkylhydroxybenzoate detergent of the isomerized NAO may be an alkylated hydroxybenzoate detergent. In another embodiment, the detergent may be a salicylate detergent. In another embodiment, the detergent may be a carboxylate detergent.

In one aspect of the disclosure, C-derived having from 10 to 300TBN on an oil-free basis₁₀-C₄₀The alkylhydroxybenzoate detergent of the isomerized NAO may be prepared as described in us patent 8,893,499, the entire contents of which are incorporated herein.

In one aspect of the disclosure, the alkyl hydroxybenzoate detergent is made from an alkylphenol having an alkyl group of 10 to 300TBN derived from an isomerized α -olefin having from about 14 to about 28 carbon atoms, preferably from about 20 to about 24 carbon atoms, or preferably from about 20 to about 28 carbon atoms per molecule.

In one aspect of the disclosure, C-derived having from 10 to 300TBN on an oil-free basis₁₀-C₄₀The alkylhydroxybenzoate salts of the isomerized NAO are made from alkylphenols having alkyl groups derived from the isomerized NAO, which has an isomerization level (i) of from about 0.10 to about 0.40, preferably from about 0.10 to about 0.35, more preferably from about 0.10 to about 0.30, more preferably from about 0.12 to about 0.30.

In one aspect of the disclosure, C-derived having 10 to 300TBN on an oil-free basis₁₀-C₄₀The alkylhydroxybenzoate salt of the isomerized NAO is formed by one or more compounds having a structure derived from C₁₀-C₄₀Alkylphenols having an alkyl group other than C of the isomerized NAO and one or more₁₀-C₄₀An alkylphenol of the alkyl group of the isomerized NAO.

In one aspect of the disclosure, the isomerized NAO of an alkylhydroxybenzoate salt has an isomerization level of about 0.16, and has from about 20 to about 24 carbon atoms.

In one aspect of the disclosure, the isomerized NAO of the alkylhydroxybenzoate salt has an isomerization level of about 0.26, and has from about 20 to about 24 carbon atoms.

In one aspect of the invention, the lubricating oil composition comprises about 0.01 to 2.0 wt.%, based on Ca content, of C derived having a TBN of 10 to 300 on an oil-free basis₁₀-C₄₀The alkylhydroxybenzoate salt of the isomerized NAO is preferably 0.1 to 1.0 wt.%, more preferably 0.05 to 0.5 wt.%, more preferably 0.1 to 0.5 wt.%.

In one aspect of the invention, there are included C-derived compounds having a TBN of from 10 to 300 on an oil-free basis₁₀-C₄₀The lubricating oil composition of the alkyl hydroxybenzoate of the isomerized NAO is an automobile engine oil composition or a fuel gasAn engine oil composition, a dual fuel engine oil composition, a mobile gas engine oil composition, or a locomotive engine oil composition.

In one aspect of the disclosure, a composition comprising C derived from 10 to 300TBN on an oil-free basis₁₀-C₄₀The lubricating oil compositions of the alkylhydroxybenzoate salts of isomerized NAO are functional fluids for automotive and industrial applications, such as transmission oils, hydraulic oils, tractor fluids, gear oils, and the like.

In one aspect of the disclosure, a composition comprising C derived from 10 to 300TBN on an oil-free basis₁₀-C₄₀The lubricating oil composition of the alkylhydroxybenzoate of the isomerized NAO is a multigrade oil or a single-grade oil.

In one aspect of the disclosure, a composition comprising C derived from 10 to 300TBN on an oil-free basis₁₀-C₄₀The lubricating oil composition of alkylhydroxybenzoate salts of isomerized NAO lubricates crankcases, gears and clutches.

Organic molybdenum compound

The organomolybdenum compound contains at least molybdenum, carbon, and hydrogen atoms, but may also contain sulfur, phosphorus, nitrogen, and/or oxygen atoms. Suitable organo-molybdenum compounds include molybdenum dithiocarbamates, molybdenum dithiophosphates, and various organo-molybdenum complexes, such as molybdenum carboxylates, molybdenum esters, molybdenum amines, molybdenum amides, which may be prepared by reacting molybdenum oxide or ammonium molybdate with fats, fatty acid glycerides or fatty acid derivatives (e.g., esters, amines, amides). The term "fat" refers to a carbon chain having from 10 to 22 carbon atoms, typically a straight carbon chain.

In one embodiment, the molybdenum amine is a molybdenum-succinimide complex. Suitable molybdenum-succinimide complexes are described, for example, in U.S. patent No.8,076,275. These complexes are prepared by the following process: reacting an acidic molybdenum compound with an alkyl or alkenyl succinimide of a polyamine of structure (3) or (4) or mixtures thereof:

wherein R is C₂₄To C₃₅₀(e.g. C)₇₀To C₁₂₈) An alkyl or alkenyl group; r' is a linear or branched alkylene group having 2 to 3 carbon atoms; x is 1 to 11; y is 1 to 10.

The molybdenum compound used to prepare the molybdenum-succinimide complex is an acidic molybdenum compound or a salt of an acidic molybdenum compound. By "acidic" is meant a molybdenum compound that will react with a basic nitrogen compound, as specified by ASTM D664 or D2896. Typically, the acidic molybdenum compounds are hexavalent. Representative examples of suitable molybdenum compounds include molybdenum trioxide, molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, such as bisulfates (e.g., sodium hydrogen molybdate), MoOCl₄、MoO₂Br₂、Mo₂O₃Cl₆And the like.

Succinimides useful in the preparation of molybdenum-succinimide complexes are disclosed in a number of references and are well known in the art. U.S. Pat. Nos.3,172,892; 3,219,666; and 3,272,746, the term "succinimide" in the art as taught encompasses certain basic types of succinimides and related materials. The term "succinimide" is understood in the art to include a number of amide, imide, and amidine species that can also be formed. However, the predominant product is succinimide, a term generally recognized as the product of the reaction of an alkyl or alkenyl substituted succinic acid or anhydride with a nitrogen-containing compound. Preferred succinimides are those prepared by reacting polyisobutenyl succinic anhydride of about 70 to 128 carbon atoms with a polyalkylene polyamine selected from the group consisting of triethylene tetramine, tetraethylene pentamine and mixtures thereof.

The molybdenum-succinimide complex may be post-treated with a sulfur source at a suitable pressure and temperature not exceeding 120 ℃ to provide a sulfurized molybdenum-succinimide complex. The vulcanization step may be carried out for a period of about 0.5 to 5 hours (e.g., 0.5 to 2 hours). Suitable sulfur sources include elemental sulfur, hydrogen sulfide, phosphorus pentasulfide, formula R₂S_xWherein R is a hydrocarbon group (e.g., C)₁To C₁₀Alkyl) and x is at least 3, C₁To C₁₀Mercaptans, inorganic sulfides and polysulfides, thioacetamides, and thioureas.

The amount of molybdenum compound used provides at least 50ppm, at least 70ppm, at least 90ppm, at least 110ppm, at least 130ppm, at least 150ppm or at least 200ppm (e.g., 50-1500ppm, 70-1500ppm, 90-1000ppm, 110-1000ppm, 130-1000ppm, 150-1000ppm or 200-1000ppm) relative to the weight of molybdenum in the lubricating oil composition.

Friction modifiers

The lubricating oil compositions disclosed herein contain friction modifiers that can reduce friction between moving parts. Any friction modifier known to those skilled in the art may be used in the lubricating oil composition. Non-limiting examples of suitable friction modifiers include fatty carboxylic acids; derivatives of fatty carboxylic acids (e.g., alcohols, esters, borates, amides, metal salts, etc.); mono-, di-or tri-alkyl substituted phosphoric or phosphonic acids; derivatives (e.g., esters, amides, metal salts, etc.) of mono-, di-or tri-alkyl substituted phosphoric or phosphonic acids; mono-, di-or trialkyl-substituted amines; mono-or di-alkyl substituted amides and combinations thereof. In some embodiments, the friction modifier is selected from the group consisting of aliphatic amines, ethoxylated aliphatic amines, aliphatic carboxylic acid amides, ethoxylated aliphatic ether amines, aliphatic carboxylic acids, glycerol esters, aliphatic carboxylic acid ester-amides, fatty imidazolines, fatty tertiary amines in which the aliphatic or fatty group contains greater than about 8 carbon atoms to impart suitable oil solubility to the compound. In some embodiments, the friction modifier is a fatty acid derivative. In some embodiments, the fatty acid derivative is a fatty acid ester, a borated fatty acid ester, or an amide. In other embodiments, the friction modifier comprises an aliphatic substituted succinimide formed by reacting an aliphatic succinic acid or anhydride with ammonia or a primary amine. The amount of friction modifier may vary within the following ranges: from about 0.01 wt.% to about 10 wt.%, from about 0.05 wt.% to about 5 wt.%, or from about 0.1 wt.% to about 3 wt.%, based on the total weight of the lubricating oil composition.

Antiwear agent

The antiwear agent reduces wear of the metal parts. Suitable antiwear agents include dihydrocarbyl dithiophosphate metal salts, for example Zinc Dihydrocarbyl Dithiophosphate (ZDDP) of the formula (formula 1):

Zn[S–P(＝S)(OR¹)(OR²)]₂in the formula 1, the raw material is shown in the specification,

wherein R is¹And R²Can be the same or different hydrocarbyl group having from 1 to 18 (e.g., 2 to 12) carbon atoms, and includes groups such as alkyl, alkenyl, aryl, arylalkyl, alkylaryl, and cycloaliphatic groups. Particularly preferred as R¹And R²Groups are alkyl groups having 2 to 8 carbon atoms (for example, the alkyl group may be ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl). To obtain oil solubility, the total number of carbon atoms (i.e., R)¹+R²) Will be at least 5. The zinc dihydrocarbyl dithiophosphate may therefore comprise zinc dialkyl dithiophosphates. The zinc dialkyl dithiophosphate is a primary, secondary zinc dialkyl dithiophosphate or a combination thereof.

ZDDP may be present at 3 wt.% or less (e.g., 0.1 to 1.5 wt.% or 0.5 to 1.0 wt.%) of the lubricating oil composition.

In one embodiment, the lubricating oil composition comprising the magnesium salicylate detergents described herein further comprises an antioxidant compound. In one embodiment, the antioxidant is a diphenylamine antioxidant. In another embodiment, the antioxidant is a hindered phenol antioxidant. In another embodiment, the antioxidant is a combination of a diphenylamine antioxidant and a hindered phenol antioxidant.

Antioxidant agent

Antioxidants reduce the tendency of mineral oils to deteriorate during use. Oxidative deterioration is evidenced by sludge in the lubricant, varnish-like deposits on the metal surface, and viscosity increase. Suitable antioxidants include hindered phenols, aromatic amines, and sulfurized alkylphenols, as well as alkali metal and alkaline earth metal salts thereof.

Hindered phenol antioxidants typically contain a secondary and/or tertiary butyl group as a sterically hindering group. The phenolic group may be further substituted with a hydrocarbyl group (usually straight or branched)A catenary alkyl group) and/or a bridging group attached 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. Other useful hindered phenol antioxidants include 2, 6-dialkylphenol propionate derivatives such as those of Ciba

L-135 and bisphenol antioxidants such as 4,4 '-bis (2, 6-di-tert-butylphenol) and 4,4' -methylenebis (2, 6-di-tert-butylphenol).

Typical aromatic amine antioxidants have at least two aromatic groups attached directly to one amine nitrogen. Typical aromatic amine antioxidants have an alkyl substituent of at least 6 carbon atoms. Specific examples of aromatic amine antioxidants useful herein include 4,4 '-dioctyldiphenylamine, 4' -dinonyldiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, and N- (4-octylphenyl) -1-naphthylamine.

The antioxidant may be present at 0.01 to 5 wt.% (e.g., 0.1 to 2 wt.%) of the lubricating oil composition.

Dispersing agent

The dispersant retains suspended matter produced by oxidation during engine operation in the oil, which is insoluble in the oil, thereby preventing flocculation and precipitation or deposition of sludge on metal parts. Dispersants useful in the present invention include nitrogen-containing ashless (metal-free) dispersants known to be effective in reducing deposit formation when used in gasoline and diesel engines.

Suitable dispersants include hydrocarbyl succinimides, hydrocarbyl succinamides, mixed esters/amides of hydrocarbyl-substituted succinic acids, hydroxy esters of hydrocarbyl-substituted succinic acids, and Mannich condensation products of hydrocarbyl-substituted phenols, formaldehyde, and polyamines. Condensation products of polyamines with hydrocarbyl-substituted benzoic acids are also suitable. Mixtures of these dispersants may also be used.

Basic nitrogen-containing ashless dispersants are well known lubricating oil additives and methods for their preparation are extensively described in the patent literature. Preferred dispersants are alkenyl succinimides and succinamides, wherein the alkenyl substituent is a long chain, preferably greater than 40 carbon atoms. These materials can be readily prepared by reacting a hydrocarbyl-substituted dicarboxylic acid material with a molecule containing an amine functional group. Examples of suitable amines are polyamines, such as polyalkylene polyamines, hydroxy-substituted polyamines and polyoxyalkylene polyamines.

Particularly preferred ashless dispersants are polyisobutenyl succinimides formed from polyisobutenyl succinic anhydrides and polyalkylene polyamines such as the polyethylene polyamines of formula 2 below:

NH₂(CH₂CH₂NH)_zh is represented by the formula 2 in the specification,

wherein z is 1 to 11. The polyisobutylene group is derived from polyisobutylene and preferably has a number average molecular weight (Mn) in the range of 700 to 3000 daltons (e.g. 900 to 2500 daltons). For example, the polyisobutenyl succinimide may be a bis-succinimide derived from polyisobutenyl groups having an Mn of 900 to 2500 daltons.

The dispersant may be post-treated (e.g., with a borating agent or a cyclic carbonate) as known in the art.

Nitrogen-containing ashless (metal-free) dispersants are basic and contribute to the TBN of lubricating oil compositions to which they are added without introducing additional sulfated ash.

The dispersant may be present in an amount of 0.1 to 10 wt.% (e.g., 2 to 5 wt.%) of the lubricating oil composition.

Other detergents

The lubricating oil compositions of the present invention may further comprise one or more overbased detergents having a TBN of 10-800, 10-700, 30-690, 100-600, 150-500, 200-450mg KOH/g based on the active material.

In some embodiments, detergents that may be used include oil-soluble overbased sulfonates, non-sulfur containing phenates, sulfurized phenates, salixarates, salicylates, carboxylates, salicins, complex detergents, and naphthenate detergents as well as other oil-soluble metal alkylhydroxybenzoates, particularly alkaline earth metals or alkaline earth metals, such as barium, sodium, potassium, lithium, calcium, and magnesium. The most commonly used metals are calcium and magnesium, which may both be present in detergents for lubricants, and mixtures of calcium and/or magnesium with sodium.

Overbased metal detergents are typically prepared by carbonizing a mixture of hydrocarbons, detergent acids (e.g., sulfonic acids, alkylhydroxybenzoates, etc.), metal oxides or hydroxides (e.g., calcium oxide or calcium hydroxide), and accelerators (e.g., xylene, methanol, and water). For example, to prepare overbased calcium sulfonates, calcium oxide or hydroxide is reacted with gaseous carbon dioxide to form calcium carbonate during carbonation. With excess CaO or Ca (OH)₂Neutralizing the sulfonic acid to form a sulfonate salt.

Overbased detergents may be low overbased, e.g., overbased salts having a TBN of less than 100 based on the active material. In one embodiment, the low overbased salt may have a TBN of from about 30 to about 100. In another embodiment, the low overbased salt may have a TBN of from about 30 to about 80. The overbased detergent may be medium overbased, for example, an overbased salt having a TBN of about 100 to about 250. In one embodiment, the TBN of the medium overbased salt may be from about 100 to about 200. In another embodiment, the TBN of the medium overbased salt may be from about 125 to about 175. Overbased detergents may be highly overbased, e.g., overbased salts having a TBN of greater than 250. In one embodiment, the overbased salt may have a TBN on an actives basis of from about 250 to about 800.

In one embodiment, the detergent may be an alkali metal or alkaline earth metal salt of one or more alkyl-substituted hydroxyaromatic carboxylic acids. Suitable hydroxyaromatic compounds include mononuclear monohydroxy and polyhydroxy aromatic hydrocarbons having from 1 to 4, preferably from 1 to 3, hydroxyl groups. Suitable hydroxyaromatic compounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, and the like. The preferred hydroxyaromatic compound is phenol.

The alkyl-substituted portion of the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is derived from an alpha-olefin having from about 10 to about 80 carbon atoms. The olefin may be a linear olefin, an isomerized linear olefin, a branched or partially branched linear olefin. The olefin may be a mixture of linear olefins, a mixture of isomerized linear olefins, a mixture of branched olefins, a mixture of partially branched linear olefins, or a mixture of any of the foregoing.

In one embodiment, mixtures of linear olefins that may be used are mixtures of normal alpha olefins selected from olefins having from about 10 to about 40 carbon atoms per molecule. In one embodiment, the n-alpha olefins are isomerized using at least one of a solid or liquid catalyst.

In one embodiment, at least about 50 mole%, at least about 75 mole%, at least about 80 mole%, at least about 85 mole%, at least about 90 mole%, at least about 95 mole% of the alkyl groups contained in the alkali metal or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid, such as the alkyl groups contained in the alkaline earth metal salt of an alkyl-substituted hydroxybenzoic acid detergent, are C₂₀Or higher. In another embodiment, the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is derived from an alkyl group C₂₀To about C₂₈Alkali metal or alkaline earth metal salts of alkyl-substituted hydroxybenzoic acids of n-alpha-olefin. In another embodiment, the alkyl group is derived from at least two alkylated phenols. The alkyl group on at least one of the at least two alkylphenols is derived from an isomerized alpha olefin. The alkyl group on the second alkyl phenol can be derived from a branched or partially branched olefin, a highly isomerized olefin, or a mixture thereof.

In another embodiment, the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is a salicylate derived from an alkyl group having from 20 to 40 carbon atoms, preferably from 20 to 28 carbon atoms, more preferably an isomerized 20 to 24 NAO.

Sulfonates can be prepared from sulfonic acids, which are typically obtained by sulfonation of alkyl-substituted aromatic hydrocarbons (such as those obtained from the fractionation of petroleum or by the alkylation of aromatic hydrocarbons). Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, biphenyl, or halogen derivatives thereof. The alkylation may be carried out with an alkylating agent having from about 3 to more than 70 carbon atoms in the presence of a catalyst. The alkylaryl sulfonates typically contain from about 9 to about 80 or more carbon atoms, preferably from about 16 to about 60 carbon atoms, preferably from about 16 to 30 carbon atoms, and more preferably from 20 to 24 carbon atoms per alkyl-substituted aromatic moiety.

Metal salts of phenols and sulfurized phenols are sulfurized phenate detergents prepared by reaction with an appropriate metal compound such as an oxide or hydroxide and neutral or overbased products may be obtained by methods well known in the art. Can be prepared by reacting phenol with sulfur or a sulfur-containing compound, such as hydrogen sulfide, sulfur monohalide or sulfur dihalide, to form a product which is typically a mixture of compounds in which 2 or more phenols are bridged by sulfur-containing bridges.

Additional details regarding the general preparation of sulfurized phenates can be found in, for example, U.S. Pat. nos.2,680,096; 3,178,368,3,801,507 and 8,580,717, the contents of which are incorporated herein by reference.

Considering now in detail the reactants and reagents used in the present process, it is first possible to use all allotropic forms of sulfur. The sulfur may be used either as molten sulfur or as a solid (e.g., powder or granules) or as a solid suspension in a compatible hydrocarbon liquid.

It is desirable to use calcium hydroxide as the calcium base because it is convenient to handle compared to, for example, calcium oxide, and also because it provides excellent results. Other calcium bases, such as calcium alkoxides, may also be used.

Suitable alkylphenols which can be used are those wherein the alkyl substituent contains a sufficient number of carbon atoms to render the resulting overbased calcium sulfurized alkylphenate composition oil soluble. Oil solubility may be provided by a single long chain alkyl substituent or a combination of alkyl substituents. In general, the alkylphenol used will be a mixture of different alkylphenols, for example C₂₀To C₂₄An alkyl phenol.

In one embodiment, a suitable alkylphenol compound will be derived from an isomerized α -olefin alkyl group having from about 10 to about 40 carbon atoms per molecule at a level (I) of isomerization of about 0.1 to about 0.4. In one embodiment, a suitable alkylphenol compound will be derived from an alkyl group that is a branched olefin propylene oligomer having from about 9 to about 80 carbon atoms, or a mixture thereof. In one embodiment, the branched olefin propylene oligomer or mixture thereof has from about 9 to about 40 carbon atoms. In one embodiment, the branched olefin propylene oligomer or mixture thereof has from about 9 to about 18 carbon atoms. In one embodiment, the branched olefin propylene oligomers or mixtures thereof have from about 9 to about 12 carbon atoms.

In one embodiment, suitable alkylphenol compounds include distilled Cashew Nut Shell Liquid (CNSL) or hydrogenated distilled cashew nut shell liquid. Distilled CNSL is a mixture of biodegradable meta-hydrocarbyl substituted phenols, wherein the hydrocarbyl groups are linear and unsaturated, including cardanol. The catalytic hydrogenation of the distilled CNSL produces a mixture of meta-hydrocarbyl substituted phenols that are predominantly rich in 3-pentadecylphenol.

The alkylphenol may be para-alkylphenol, meta-alkylphenol, or ortho-alkylphenol. Since it is believed that para-alkylphenols are helpful in producing a highly overbased calcium sulfurized alkylphenol, when an overbased product is desired, the alkylphenols are preferably predominantly para-alkylphenols in which the ortho-alkylphenol content of the alkylphenol is not more than about 45 mole percent, and more preferably not more than about 35 mole percent of the alkylphenols are ortho-alkylphenols. Alkyl-hydroxytoluenes or xylenes and also other alkylphenols having one or more alkyl substituents in addition to at least one long-chain alkyl substituent may also be used. In the case of distilling cashew nutshell liquid, catalytic hydrogenation of the distilled CNSL produces a mixture of m-hydrocarbyl substituted phenols.

In one embodiment, the one or more overbased detergents may be a complex or hybrid detergent known in the art to comprise a surfactant system derived from at least two of the above surfactants.

Typically, the amount of detergent may be about 0.001 wt.% to about 50 wt.%, or about 0.05 wt.% to about 25 wt.%, or about 0.1 wt.% to about 20 wt.%, or about 0.01 to 15 wt.%, based on the total weight of the lubricating oil composition.

Other coadditives

The lubricating oil compositions of the present invention may also contain other conventional additives which may impart or improve any desired properties of the lubricating oil composition in which these additives are dispersed or dissolved. Any additive known to one of ordinary skill in the art may be used in the lubricating oil compositions disclosed herein. Mortier et al in "Chemistry and Technology of Lubricants", 2nd Edition, London, Springer, (1996); and Leslie R.Rudnick, "scientific Additives: Chemistry and Applications", New York, Marcel Dekker (2003), both of which are incorporated herein by reference. For example, the lubricating oil composition may be mixed with antioxidants, anti-wear agents, detergents such as metal detergents, rust inhibitors, dehazing agents, demulsifying agents, metal deactivating agents, friction modifiers, pour point depressants, antifoaming agents, co-solvents, corrosion-inhibitors, ashless dispersants, multi-functional agents, dyes, extreme pressure agents, and the like, and mixtures thereof. Various additives are known and commercially available. These additives or their analogous compounds can be used to prepare the lubricating oil compositions of the present invention by conventional blending methods.

In the preparation of lubricating oil formulations, it is common practice to introduce additives in the form of 10 to 100 wt.% active ingredient concentrates into hydrocarbon oils, for example, mineral lubricating oils or other suitable solvents.

Typically, these concentrates may be diluted with 3 to 100, e.g., 5 to 40 parts by weight of lubricating oil per part by weight of the additive package in forming a finished lubricant, e.g., crankcase motor oil. The purpose of the concentrate is, of course, to make handling of the various materials less difficult and awkward and to facilitate dissolution or dispersion in the final blend.

When each of the foregoing additives is used, it is used in a functionally effective amount to impart the desired properties to the lubricant. Thus, for example, if the additive is a friction modifier, a functionally effective amount of the friction modifier will be an amount sufficient to impart the desired friction modifying properties to the lubricant.

Typically, when each additive in the lubricating oil composition is used, its concentration may be from about 0.001 wt.% to about 20 wt.%, from about 0.01 wt.% to about 15 wt.%, or from about 0.1 wt.% to about 10 wt.%, from about 0.005 wt.% to about 5 wt.%, or from about 0.1 wt.% to about 2.5 wt.%, based on the total weight of the lubricating oil composition. In addition, the total amount of additives in the lubricating oil composition can be about 0.001 wt.% to about 20 wt.%, about 0.01 wt.% to about 10 wt.%, or about 0.1 wt.% to about 5 wt.%, based on the total weight of the lubricating oil composition.

Oil of lubricating viscosity

The oil of lubricating viscosity (sometimes referred to as a "base stock" or "base oil") is the main liquid component of the lubricant, into which additives and possibly other oils are incorporated, for example, to make the final lubricant (or lubricant composition). The base oil may be used in the manufacture of concentrates and in the manufacture of lubricating oil compositions therefrom, and may be selected from natural and synthetic lubricating oils and combinations thereof.

Synthetic lubricating oils include hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly (1-hexenes), poly (1-octenes), poly (1-decenes)); alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di (2-ethylhexyl) benzene); polyphenols (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof.

Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., malonic acid, alkylmalonic acids, alkenylmalonic acids, succinic acid, alkylsuccinic acids and alkenylsuccinic acids, maleic acid, fumaric acid, azelaic acid, suberic acid, sebacic acid, adipic acid, linoleic acid dimer, phthalic acid) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and a complex ester formed by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid.

Esters useful as synthetic oils also include those derived from C₅-C₁₂Monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.

The base oil may be derived from fischer-tropsch derived hydrocarbons. The Fischer-Tropsch synthesized hydrocarbon is prepared from H-containing gas by using Fischer-Tropsch catalyst₂And CO. Such hydrocarbons typically require further processing to be used as base oils. For example, hydrocarbons may be hydroisomerized; hydrocracking and hydroisomerization; dewaxing or hydroisomerisation and dewaxing; methods known to those skilled in the art are used.

Unrefined, refined and rerefined oils are useful in the lubricating oil compositions of the present invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process and used without further treatment is an unrefined oil. Refined oils are similar to unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and diafiltration, are known to those skilled in the art.

Rerefined oils are obtained by application to refined oils that have been used in service in processes similar to those used to obtain the refined oils. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for the removal of spent additives and oil breakdown products.

Thus, the Base oils useful in preparing the lubricating Oil compositions of the present invention may be selected from any of the Base oils in groups I-V as specified in the American Petroleum Institute (API) Base Oil interconvertibility Guidelines (API publication 1509). Table 1 below summarizes these base oils:

TABLE 1

^(a)Group I-III are mineral oil base oils

^(b)Measured according to ASTM D2007.

^(c)Measured according to ASTM D2622, ASTM D3120, ASTM D4294 or ASTM D4927.

^(d)Measured according to ASTM D2270.

Base oils suitable for use in the present invention are any variety corresponding to API group II, group III, group IV and group V oils and combinations thereof, with group III to group V oils being preferred due to their superior volatility, stability, viscosity and cleanliness characteristics.

The oil of lubricating viscosity, also referred to as a base oil, used in the lubricating oil compositions of the present disclosure is typically present in a major amount, for example, in an amount greater than 50 wt.%, preferably greater than about 70 wt.%, more preferably from about 80 to about 99.5 wt.%, most preferably from about 85 to about 98 wt.%, based on the total weight of the composition. As used herein, the phrase "base oil" is understood to mean a base stock or mixture of base stocks that is a lubricant component produced by a single manufacturer to the same specifications (independent of feed source or manufacturer's location); meet the specifications of the same manufacturer; and is identified by the unique recipe, the product identification code, or both. The base oil for use herein can be any currently known or later-discovered oil of lubricating viscosity for use in lubricating oil compositions formulated for any and all such applications, e.g., engine oils, marine cylinder oils, functional fluids such as hydraulic oils, gear oils, transmission fluids, and the like. In addition, the base oils used herein may optionally include viscosity index improvers, e.g., polymerized alkyl methacrylates; olefin copolymers such as ethylene-propylene copolymers or styrene-butadiene copolymers; and the like and mixtures thereof.

As will be readily understood by those skilled in the art, the viscosity of the base oil depends on the application. Thus, the viscosity of the base oils for use herein will typically range from about 2 to about 2000 centistokes (cSt) at 100 ℃ (C). Typically, base oils used as engine oils will have kinematic viscosities at 100 ℃ in the range of from about 2cSt to about 30cSt, preferably from about 3cSt to about 16cSt, and most preferably from about 4cSt to about 12cSt, respectively. The additives will be selected or blended to provide the desired grade of engine oil, for example, a lubricating oil composition having an SAE viscosity grade of 0W, 0W-8, 0W-12, 0W-16, 0W-20, 0W-26, 0W-30, 0W-40, 0W-50, 0W-60, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W-20, 10W-30, 10W-40, 10W-50, 15W-20, 15W-30, 15W-40, 30, 40, etc., depending on the desired end use and the finished oil.

Lubricating oil composition

Typically, the sulfur content in the lubricating oil compositions of the present invention is less than or equal to about 0.7 wt.%, based on the total weight of the lubricating oil composition, for example, sulfur content levels of about 0.01 wt.% to about 0.70 wt.%, 0.01 to 0.6 wt.%, 0.01 to 0.5 wt.%, 0.01 to 0.4 wt.%, 0.01 to 0.3 wt.%, 0.01 to 0.2 wt.%, 0.01 wt.% to 0.10 wt.%. In one embodiment, the sulfur content of the lubricating oil composition of the present invention is less than or equal to about 0.60 wt.%, less than or equal to about 0.50 wt.%, less than or equal to about 0.40 wt.%, less than or equal to about 0.30 wt.%, less than or equal to about 0.20 wt.%, less than or equal to about 0.10 wt.%, based on the total weight of the lubricating oil composition.

In one embodiment, the phosphorus is present in the lubricating oil composition of the present invention in an amount less than or equal to about 0.12 wt.%, based on the total weight of the lubricating oil composition, e.g., in an amount of from about 0.01 wt.% to about 0.12 wt.%. In one embodiment, the phosphorus content of the lubricating oil composition of the present invention is less than or equal to about 0.11 wt.%, based on the total weight of the lubricating oil composition, e.g., the phosphorus content is from about 0.01 wt.% to about 0.11 wt.%. In one embodiment, the phosphorus is present in the lubricating oil composition of the present invention in an amount less than or equal to about 0.10 wt.%, based on the total weight of the lubricating oil composition, e.g., in an amount of from about 0.01 wt.% to about 0.10 wt.%. In one embodiment, the phosphorus is present in the lubricating oil composition of the present invention in an amount less than or equal to about 0.09 wt.%, based on the total weight of the lubricating oil composition, e.g., in an amount of from about 0.01 wt.% to about 0.09 wt.%. In one embodiment, the phosphorus content of the lubricating oil composition of the present invention is less than or equal to about 0.08 wt.%, based on the total weight of the lubricating oil composition, e.g., the phosphorus content is from about 0.01 wt.% to about 0.08 wt.%. In one embodiment, the phosphorus content of the lubricating oil composition of the present invention is less than or equal to about 0.07 wt.%, based on the total weight of the lubricating oil composition, e.g., the phosphorus content is about 0.01 wt.% to about 0.07 wt.%. In one embodiment, the phosphorus content of the lubricating oil composition of the present invention is less than or equal to about 0.05 wt.%, based on the total weight of the lubricating oil composition, e.g., the phosphorus content is from about 0.01 wt.% to about 0.05 wt.%.

In one embodiment, the sulfated ash produced by the lubricating oil composition of the present invention is present in an amount of less than or equal to about 1.60 wt.%, as determined according to ASTM D874, for example, in an amount of from about 0.10 to about 1.60 wt.%. In one embodiment, the sulfated ash produced by the lubricating oil composition of the invention is present in an amount of less than or equal to about 1.00 wt.%, as determined by ASTM D874, for example in an amount of from about 0.10 to about 1.00 wt.%. In one embodiment, the sulfated ash produced by the lubricating oil composition of the invention is less than or equal to about 0.80 wt.%, for example from about 0.10 to about 0.80 wt.%, as determined according to ASTM D874. In one embodiment, the sulfated ash produced by the lubricating oil composition of the present invention is present in an amount of less than or equal to about 0.60 wt.%, as determined according to ASTM D874, for example in an amount of from about 0.10 to about 0.60 wt.%.

The following examples are provided to illustrate embodiments of the present disclosure, but are not intended to limit the disclosure to the specific embodiments set forth. Unless indicated to the contrary, all parts and percentages are by weight. All numerical values are approximate. When numerical ranges are given, it should be understood that embodiments outside the stated ranges may still fall within the scope of the invention. The specific details described in each embodiment should not be construed as essential features of the invention.

Examples

The following examples are for illustrative purposes only and do not limit the scope of the present disclosure in any way.

The degree of isomerization was determined by NMR method.

Isomerization level (I) and NMR method

The level of olefin isomerization (I) was determined by hydrogen-1 (1H) NMR. NMR spectra were obtained on Bruker Ultrashield Plus 400 in chloroform-d 1 at 400MHz using TopSpin3.2 Spectroscopy processing software.

The isomerization level (I) represents the group (-CH) attached to the methylene backbone₂- (. chemically shifted 1.01-1.38ppm) of a methyl group (-CH)₃) (chemical shift 0.30-1.01ppm) and is defined by the following equation (1),

i ═ m/(m + n) formula (1)

Wherein m is the NMR integral of methyl groups having chemical shifts in the range of 0.30. + -. 0.03 to 1.01. + -. 0.03ppm, and n is the NMR integral of methylene groups having chemical shifts in the range of 1.01. + -. 0.03 to 1.38. + -. 0.10 ppm.

Baseline formulation 1

A 15W-40 lubricating oil composition is prepared comprising a major amount of a base oil of lubricating viscosity and the following additives:

(1) ethylene carbonate post-treated bis-succinimide;

(2) a mixture of a primary zinc dialkyl dithiophosphate and a secondary zinc dialkyl dithiophosphate;

(3) a diphenylamine antioxidant;

(4) 45ppm, based on the molybdenum content, of sulfur-containing molybdenum succinimide; and

(5) a foam suppressor.

Baseline formulation 2

(1) ethylene carbonate post-treated bis-succinimide;

(2) zinc secondary dialkyldithiophosphates;

(3) a diphenylamine antioxidant;

(4) 380ppm, based on the molybdenum content, of sulfur-containing molybdenum succinimide; and;

(5) a foam suppressor.

Baseline formulation 3

(1) ethylene carbonate post-treated bis-succinimide;

(2) zinc secondary dialkyldithiophosphates;

(3) a diphenylamine antioxidant;

(5) a foam suppressor.

Example A

Using C available from CP Chem_20-24Isomerized normal alpha olefins produce alkylated phenols and alkylated calcium alkylhydroxybenzoates in substantially the same manner as in U.S. patent No.8,993,499. The isomerization level of the alpha-olefins was about 0.16. The resulting alkylated alkylhydroxybenzoate component had a TBN of about 225mgKOH/gm and a Ca content of 8 wt.% on an oil-free basis.

Example B

Using C available from CP Chem_20-24Isomerized normal alpha olefins produce alkylated phenols and alkylated calcium alkylhydroxybenzoates in substantially the same manner as in U.S. patent No.8,993,499. The isomerization level of the alpha-olefins was about 0.16. The resulting alkylated alkylolThe benzoate component had a TBN of about 120mgKOH/gm and a Ca content of 4.2 wt.% on an oil free basis.

Comparative example A

Using C available from CP Chem_20-28N-alpha-olefins, alkylated phenols and alkylated calcium alkylhydroxybenzoates were prepared in substantially the same manner as in U.S. patent No.8,030,258. The resulting alkylated alkylhydroxybenzoate component had a TBN of about 230 and Ca content of about 8 wt.% on an oil-free basis.

Comparative example B

From a compound having a structure derived from C₁₄-C₁₈Alkylated phenols of the alkyl group of the n-alpha-olefin produced alkylated calcium alkylhydroxybenzoate with a TBN of about 300mgKOH/gm and a Ca content of about 10.6 wt.% on an oil-free basis.

Comparative example C

From a compound having a structure derived from C₂₀–C₂₈Alkylated phenols of the alkyl group of the n-alpha-olefin produced alkylated calcium alkylhydroxybenzoate with a TBN of about 115mgKOH/gm and a Ca content of about 4 wt.% on an oil-free basis.

Comparative example D

A overbased calcium sulfonate having a TBN of about 700mgKOH/gm and a Ca content of about 26 weight percent on an oil-free basis.

Example 1

To baseline formulation 1, 0.35 wt.% of the calcium alkylhydroxybenzoate detergent of example a, based on Ca content, was added. The lubricating oil composition had 0.21 wt.% S, 0.1 wt.% P, and 1.3 wt.% ash.

Comparative example 1

To baseline formulation 1 was added 0.35 wt% of the calcium alkylhydroxybenzoate detergent of comparative example a, calculated as Ca content. The lubricating oil composition had 0.22 wt.% S, 0.1 wt.% P, and 1.3 wt.% ash.

Comparative example 2

To baseline formulation 1, 0.35 wt.% of the calcium alkylhydroxybenzoate detergent of comparative example B, calculated as Ca content, was added. The lubricating oil composition had 0.22 wt.% S, 0.1 wt.% P, and 1.3 wt.% ash.

Example 2

To baseline formulation 2, 0.35 wt.% of the calcium alkylhydroxybenzoate detergent of example a, calculated on the Ca content, was added. The lubricating oil composition had 0.17 wt.% S, 0.07 wt.% P, and 1.3 wt.% ash.

Comparative example 3

To baseline formulation 2, 0.35 wt.% of the calcium alkylhydroxybenzoate detergent of comparative example B, calculated as Ca content, was added. The lubricating oil composition had 0.16 wt.% S, 0.07 wt.% P, and 1.3 wt.% ash.

Example 3

To baseline formulation 3 was added 0.35 wt% based on Ca content of the calcium alkylhydroxybenzoate detergent of example a. The lubricating oil composition had 0.17 wt.% S, 0.07 wt.% P, and 1.3 wt.% ash.

Comparative example 4

To baseline formulation 3 was added 0.35 wt% of the calcium alkylhydroxybenzoate detergent of comparative example B, calculated on the Ca content. The lubricating oil composition had 0.16 wt.% S, 0.07 wt.% P, and 1.3 wt.% ash.

Examples 1 to 3 and comparative examples 1 to 4 were evaluated in the TEOST MHT4 and HTCBT tests described below. The results are in table 2.

TEOST MHT4

The ASTM D7097 TEOST MHT4 test is designed to predict deposit formation tendencies of engine oil in the piston ring belt and upper piston crown areas. The correlation between the TEOST MHT program and the TU3MH Peugeot engine test for deposit formation has been shown. The test determines the amount of deposit formed on a specially constructed test bar, over which 8.5g of engine oil was passed repeatedly as a thin film under oxidative and catalytic conditions at 285 ℃. The oxidation conditions were determined by recycling an oil catalyst mixture containing a small sample (8.4g) of oil and a very small amount (0.1g) of organometallic catalyst. The mixture was circulated over a special wire-wound deposition rod on a TEOST MHT instrument for 24 hours, which was heated by electric current to a controlled temperature of 285 ℃ at the hottest position on the rod. The bars were weighed before and after the test. A deposit weight of 35mg was considered as pass/fail criterion.

HTCBT

The ASTM D6594 HTCBT test is used to test diesel lubricants to determine their tendency to corrode various metals, particularly alloys of lead and copper commonly used in cam followers and bearings. Four metal coupons of copper, lead, tin and phosphor bronze were immersed in a quantity of motor oil. The oil was blown at high temperature (170 ℃ C.) with air (5l/h) for a period of time (168 h). After the test is complete, the copper coupon and the pressurized oil will be inspected to detect corrosion and corrosion products, respectively. The concentrations of copper, lead and tin and the corresponding changes in metal concentrations in the new and pressure oils are reported. The lead concentration should not exceed 120ppm and the copper concentration should not exceed 20ppm to pass the test.

TABLE 2 HTCBT and TEOST MHT4

	HTCBT (lead in ppm)	TEOST MHT4
			Example 1	6	25.7
Comparative example 1	32	25.2
			Comparative example 2	68	74.6
Example 2	14	11.8
			Comparative example 3	104	33.4
Example 3	17	14.8
			Comparative example 4	110	24.9

Derived from C at the same Ca level₂₀-C₂₄The calcium alkylhydroxybenzoate of the isomerized NAO has surprisingly better corrosion inhibition and deposit control properties than calcium alkylhydroxybenzoate derived from non-isomerized NAO. This effect is enhanced in the presence of effective levels of molybdenum compounds.

Baseline formulation 4

A 5W-20 lubricating oil composition is prepared comprising a major amount of a base oil of lubricating viscosity and the following additives:

(1) ethylene carbonate post-treated bis-succinimide;

(2) a boronated disuccinimide dispersant;

(3) a mixture of a primary and a secondary zinc dialkyl dithiophosphate;

(4) a mixture of molybdenum succinimide and diphenylamine antioxidants; and

(5) a foam inhibitor.

Example 4

To baseline formulation 4, 0.18 wt.% of the calcium alkylhydroxybenzoate detergent of example a, based on Ca content, was added. The lubricating oil composition had 0.16 wt.% S, 0.077 wt.% P, and 0.75 wt.% ash.

Example 5

To baseline formulation 4, 0.18 wt.% of the calcium alkylhydroxybenzoate detergent of example a, based on Ca content, and 68ppm of a boronated glycerol monooleate (Glymo) friction modifier, based on boron content, were added. The lubricating oil composition had 0.16 wt.% S, 0.077 wt.% P, and 0.76 wt.% ash.

Comparative example 8

To baseline formulation 4, 0.18 wt.% high overbased calcium sulfonate detergent, based on Ca content, and 68ppm boronated glycerol monooleate (Glymo) friction modifier, based on boron content, were added. The lubricating oil composition had 0.18 wt.% S, 0.077 wt.% P, and 0.75 wt.% ash.

Comparative example 9

To baseline formulation 4, 0.18 wt% of example D, based on Ca content, was added. The lubricating oil composition had 0.18 wt.% S, 0.077 wt.% P, and 0.76 wt.% ash.

MTM test

The friction performance of examples 4-5 and comparative examples 8 and 9 were tested in a small tractor (MTM) bench test. The MTM was manufactured by PCS Instruments and operated with balls (0.75 inch 8620 steel balls) loaded onto a rotating disk (52100 steel). These conditions employ a load of about 10-30 newtons, a velocity of about 10-2000mm/s and a temperature of about 125-150 ℃. In this bench test, the boundary friction performance of the formulation under rolling/sliding contact was measured by the low speed traction coefficient. The low speed traction coefficient is the average traction coefficient of the second Stribeck, between 15 and 20mm/s. A lower low speed traction coefficient corresponds to better boundary friction performance of the oil. The results are in table 3.

TABLE 3 MTM test

	Coefficient of low speed traction
		Example 4	0.1268
Example 5	0.0885
		Comparative example 8	0.1150
Comparative example 9	0.1269

Derived from C₂₀-C₂₄The calcium alkylhydroxybenzoate of the isomerized NAO has similar boundary friction properties to the highly overbased calcium sulfonate at the same Ca level. However, from C₂₀-C₂₄The combination of isomerized NAO-derived alkylhydroxybenzoate and friction modifier had significantly better boundary friction performance than the overbased calcium sulfonate and friction modifier combination or alkylhydroxybenzoate alone, indicating synergy between the alkylhydroxybenzoate and the friction modifier.

Baseline formulation 5

A railroad lubricating oil composition is prepared comprising a major amount of a base oil of lubricating viscosity and the following additives:

(1) ethylene carbonate post-treated bis-succinimide;

(2) a mixture of phenate detergents;

(3) a mixture of molybdenum succinimide and a diphenylamine antioxidant;

(4) friction modifiers

(5) Foam inhibitor

(6) Viscosity improver

Example 6

To baseline formulation 5, 0.05 wt.% of the calcium alkylhydroxybenzoate detergent of example a, based on Ca content, was added.

Comparative example 10

To baseline formulation 5 was added 0.04 wt.% of the calcium alkylhydroxybenzoate detergent of comparative example a, calculated as Ca content.

Example 6 and comparative example 10 were evaluated in the B2-7 oxidation test and the B72-2 Ali silver lubricity test, as described below.

B2-7 test

The B2-7 test is an oxidation test performed under the following conditions:

the oils to be tested were heated under bubbling oxygen at 300 ° F for 96 hours according to the B2-7 test. Copper, iron and lead coupons were suspended in oil. Samples of 50 ml were taken at 48, 72 and 96 hours. Fresh oil was replenished on the 48 and 72 hour samples. The oil test samples were evaluated for base number, acid number, pH and lead.

The decrease in the Total Base Number (TBN) of comparative example 10 and example 6 of the present invention was evaluated. The results are in table 4.

TABLE 4-B2-7 testing

TBN D4739	Comparative example 10	Example 6
			0hr	9.70	9.64
48hr	6.50	6.76
			72hr	6.21	6.49
96hr	5.98	6.22
			TBN reduction	3.72	3.42

Higher TBN reduces greater consumption of base in the oil and is considered disadvantageous. The widely used engine oils in locomotive diesel engines will ideally retain TBN.

The results show that detergents derived from C and calcium alkylhydroxybenzoate derived from non-isomerized NAO₂₀-C₂₄The isomerized NAO calcium alkylhydroxybenzoate detergent of (a) provides better BN retention, which means better protection of the engine.

Baseline formulation 6

A 5W-30 lubricating oil composition is prepared comprising a major amount of a base oil of lubricating viscosity and the following additives:

(1) boronated disuccinimides;

(2) ethylene carbonate-treated bissuccinimide;

(3) a overbased calcium sulfonate detergent;

(4) a mixture of a primary and a secondary zinc dialkyl dithiophosphate;

(5) a mixture of molybdenum succinimide and diphenylamine antioxidants;

(6) a friction modifier;

(7) a suds suppressor;

(8) a pour point depressant;

(9) a viscosity modifier.

Example 7

To baseline formulation 6 was added 0.1 wt% calcium alkylhydroxybenzoate detergent of comparative example B, calculated as Ca content.

Comparative example 11

To baseline formulation 6, 0.1 wt.% of the calcium alkylhydroxybenzoate detergent of comparative example C, calculated as Ca content, was added.

Example 7 and comparative example 11 were evaluated in the MRV test as described below.

MRV(Mini rotary viscometer)

ASTM D4684 MRV testing covers the yield stress (0) of engine oils cooled to final test temperatures of-10 and-40 ℃ at a controlled rate in a period of no more than 45 hours<Y<35max) and viscosity (60,000cp max). In the MRV test, the engine oil sample was maintained at 80 ℃, and then cooled at a set cooling rate to the final test temperature. A low torque is applied to the rotor shaft to measure the yield stress. A higher torque was then applied to determine the apparent viscosity of the sample. In the range of 0.4 to 15s^-1At a shear rate of (2), the viscosity measurement is carried out at a shear stress of 525 Pa.

TABLE 5 MRV test @ -35C (ASTM D-4684)

	Apparent viscosity (cP)	Yield stress (Pa)
			Example 7	43100	<175
Comparative example 11	Freezing and freezing	>350

Derived from C, in comparison with calcium alkylhydroxybenzoate derived from non-isomerized NAO at equivalent Ca levels₂₀-C₂₄The calcium alkylhydroxybenzoate of the isomerized NAO has better low temperature properties.

Baseline formulation 7

(1) boronated disuccinimides;

(2) ethylene carbonate-treated bissuccinimide;

(3) a mixture of a primary and a secondary zinc dialkyl dithiophosphate;

(4) a mixture of molybdenum succinimide and a diphenylamine antioxidant;

(5) a friction modifier;

(6) a foam inhibitor;

(7) a pour point depressant;

(8) a viscosity modifier.

Example 8

To baseline formulation 7, 0.06 wt% of the calcium alkylhydroxybenzoate of example a, based on the Ca content, and 0.12 wt% of comparative example D, based on the Ca content, were added.

Example 9

To baseline formulation 7, 0.12 wt% of the calcium alkylhydroxybenzoate of example a, based on Ca content, and 0.06 wt% of comparative example D, based on Ca content, were added.

Comparative example 12

To baseline formulation 7 was added 0.18 wt% of the calcium alkylhydroxybenzoate of example a, calculated as Ca content.

Comparative example 13

To baseline formulation 7 was added 0.18 wt.% of comparative example D based on Ca content.

Examples 8,9 and comparative examples 12 and 13 were evaluated in the TE 77 test as follows.

Plint TE 77 high-frequency friction machine

Boundary coefficient of friction measurements for examples 8 and 9 and comparative examples 12 and 13 were obtained using a Plint TE-77 high frequency friction machine (commercially available from Phoenix Tribology).

For each test, a 5mL sample of the test oil was placed into the apparatus. The TE-77 was run at 100 ℃ with a 56N load placed on the test sample. The reciprocation rate was swept from 10Hz to 1Hz and coefficient of friction data was collected throughout the test. The measured values of the friction coefficient are shown in table 6.

TABLE 6 Plint TE 77

	Example 8	Example 9	Comparative example 12	Comparative example 13
					1Hz	0.01	0.01	0.06	0.02
2Hz	0.01	0.01	0.06	0.02
					3Hz	0.01	0.01	0.07	0.02
4Hz	0.01	0.02	0.07	0.04
					5Hz	0.01	0.03	0.07	0.06
6Hz	0.02	0.05	0.08	0.08
					7Hz	0.05	0.07	0.08	0.10
8Hz	0.07	0.08	0.08	0.12
					9Hz	0.09	0.09	0.09	0.13
10Hz	0.10	0.08	0.08	0.14

The friction coefficient data collected for these oils is in a boundary friction state with a reciprocating speed of 1 to 2 Hz.

Boundary friction conditions are an important consideration in low viscosity engine oil design. Boundary friction occurs when the fluid film separating the two surfaces becomes thinner than the asperity height on the surfaces. The resulting surface contact can produce undesirably high friction in the engine and poor fuel economy. Boundary friction of the engine may occur at high load, low engine speed, and low oil viscosity. Low viscosity motor oils are more susceptible to engine damage due to thinner, less durable films. Since additives other than base oils affect the coefficient of friction under boundary conditions, additives that exhibit lower coefficients of friction in TE-77 under boundary conditions will provide excellent fuel economy in low viscosity engine oils for engines.

Based on the boundary friction conditions of examples 8 and 9, it is clear that there is a synergy when alkylhydroxybenzoate derived from isomerized n-alpha-olefin is used with overbased calcium sulfonate.

Baseline formulation 8

(1) ethylene carbonate-treated bis-succinimide;

(2) a overbased calcium sulfonate detergent;

(3) zinc secondary dialkyldithiophosphates;

(4) a diphenylamine antioxidant;

(5) a foam inhibitor;

(6) a pour point depressant;

(7) a viscosity modifier;

example 10

To baseline formulation 8 was added 0.2 wt% of the calcium alkylhydroxybenzoate of example a, calculated as Ca content.

Comparative example 13

To baseline formulation 8 was added 0.2 wt.% of the calcium alkylhydroxybenzoate of comparative example B, calculated as Ca content.

Procedure IVA test

The lubricating oil compositions of example 10 and comparative example 13 were evaluated for wear of valve mechanisms in gasoline engines: procedure IVA, ASTM D6891, average cam wear (7 position average, μm). The passing limit of the test is at most 90 μm.

Table 7 procedure IVA test

Example 10	Comparative example 13
		Camshaft wear (μm)	67	96

Derived from C, in contrast to calcium alkylhydroxybenzoate derived from non-isomerized NAO at equivalent Ca levels₂₀-C₂₄The calcium alkylhydroxybenzoate of the isomerized NAO has surprisingly better valve wear properties.

Claims

1. Derived from C₁₀-C₄₀Wherein the alkylhydroxybenzoate detergent has a TBN of from 10 to 300mgKOH/gm on an oil-free basis as determined according to ASTM D2896 and wherein the alkylhydroxybenzoate detergent is calcium alkylhydroxybenzoate, the lubricating oil comprises a major amount of oil of lubricating viscosity, wherein the "major amount" means more than 50 wt% of the composition, and the lubricating oil comprises from 0.01 wt% to 2.0 wt% of the alkylhydroxybenzoate, based on the calcium content, with molar equivalents thereofRub performance was determined according to the MTM bench test described herein or obtained using the Plint TE 77 high frequency friction machine described herein.

2. Use according to claim 1, wherein the lubricating oil composition further comprises a molybdenum compound.

3. The use according to claim 2, wherein the molybdenum compound is molybdenum succinimide.

4. The use according to claim 1, wherein the lubricating oil composition further comprises a friction modifier.

5. The use of claim 4, wherein the friction modifier is a fatty acid derivative.

6. The use of claim 5, wherein the fatty acid derivative is a fatty acid ester, a boronated fatty acid ester, or an amide.

7. The use of claim 1, wherein the lubricating oil composition further comprises a detergent selected from the group consisting of phenates, sulfonates, salicylates, salixarates, salicins, complex detergents, and naphthenate detergents.

8. Use according to claim 7, wherein the detergent is an overbased sulphonate.

9. The use of claim 1, wherein the isomerized normal alpha olefin has an isomerization level (I) of normal alpha olefin of 0.1 to 0.4, wherein the isomerization level (I) is determined by hydrogen-1 (1H) NMR using TopSpin3.2 spectroscopy processing software to obtain NMR spectra at 400MHz on Bruker Ultrashield Plus 400 in chloroform-d 1, wherein the isomerization level (I) is:

I＝m/(m+n)

10. The use according to claim 1, wherein the isomerized normal alpha olefin has from 14 to 28 carbon atoms per molecule.

11. The use of claim 1, wherein the isomerized normal alpha olefin has from 18 to 24 carbon atoms per molecule.

12. The use of claim 1, wherein the isomerized normal alpha olefin has from 20 to 24 carbon atoms per molecule.

13. The use of claim 1, wherein the alkyl hydroxybenzoate detergent is an alkylated hydroxybenzoate detergent.

14. The use of claim 1, wherein the lubricating oil composition further comprises a metal dithiophosphate, wherein the metal dithiophosphate contains secondary alkyl groups.