CN110785477A

CN110785477A - Lubricating oil compositions containing detergent compounds

Info

Publication number: CN110785477A
Application number: CN201880041829.2A
Authority: CN
Inventors: A·B·鲍法; W·A·哈特格斯; S·M·霍塞尼; C·B·卡姆普贝尔
Original assignee: Chevron Oronite Technology BV; Chevron Oronite Co LLC
Current assignee: Chevron Oronite Technology BV; Chevron Oronite Co LLC
Priority date: 2017-06-30
Filing date: 2018-06-28
Publication date: 2020-02-11
Also published as: CA3068667C; JP2020525585A; CA3068667A1; JP7348079B2; WO2019003178A1; EP3645681A1; EP3645681B1; US20190002791A1

Abstract

The present disclosure generally relates to a lubricating oil composition comprising: a major amount of an oil of lubricating viscosity, and one or more detergents, wherein at least one detergent is an alkyl hydroxybenzoate compound.

Description

Lubricating oil compositions containing detergent compounds

This application claims the benefit and priority of U.S. provisional application serial No.62/527,089 filed on 30/6/2017.

Background

Overbased detergents are well known to provide lubricating properties. Such detergent additives are typically formulated 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.

The present disclosure relates generally to lubricating oil compositions that achieve both wear control and corrosion inhibition while also achieving improved fuel economy. The lubricating oil composition is suitable for use in automotive engines, motorcycle engines, natural gas engines, dual fuel engines, railroad locomotive engines, mobile natural gas engines, and as functional fluids for automotive and industrial applications.

The present invention is based upon the surprising discovery that, in addition to providing a more economical formulation method than using the overbased hydroxybenzoate detergent technology previously described in the art, lubricating oil compositions comprising a more overbased metal hydroxybenzoate detergent having an active-based TBN of 600mgKOH/g or greater exhibit improved lubricating properties, e.g., superior performance in terms of low temperature, BN retention, oxidation and thermal stability, corrosion resistance, and oxidation and thermal stability.

Disclosure of Invention

According to 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) one or more detergents comprising at least one alkylhydroxybenzoate compound derived from an isomerized NAO having about 10 to about 40 carbon atoms,

wherein the alkylhydroxybenzoate compound has a TBN of at least 600mgKOH/gm, based on the active material.

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;

(b) one or more detergents comprising at least one alkylhydroxybenzoate compound derived from an isomerized NAO having about 10 to 40 carbon atoms,

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 as 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" or "oil-free" is meant an additive material without diluents or solvents.

All percentages reported are by weight of active material (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) was determined according to ASTM D2896.

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

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

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

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

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 methods.those having one double bond are referred to as mono-olefins, and those having two double bonds are referred to as dienes, alkadienes, or diolefins because the double bond is between the first and second carbons, α -olefins are particularly reactive.examples are 1-octene and 1-octadecene, which are used as starting materials for moderate biodegradable surfactants.

N- α -olefin-the term "n- α -olefin" refers to a straight chain, unbranched hydrocarbon having a carbon-carbon double bond at the beginning or end of the hydrocarbon.

As used herein, the term "isomerized n- α -olefin" refers to α -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.

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) one or more detergents comprising at least one alkylhydroxybenzoate compound derived from an isomerized n- α -olefin having about 10 to 40 carbon atoms,

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

The alkyl hydroxybenzoate detergent was derived from C10-C40 isomerized n- α -olefins (NAO).

In one aspect of the disclosure, the alkyl hydroxybenzoate detergent is derived from C ₁₀-C ₄₀An isomerized NAO and a TBN based on active material of at least 600, 600 or greater, 600-800, 600-750, 600-700 mgKOH/g.

In one aspect of the disclosure, a C-derived having a TBN of 600 mgKOH/gram or greater on an oil-free basis ₁₀-C ₄₀The alkylhydroxybenzoate detergent of the isomerized NAO may be prepared as described in us patent 8,993,499, the entire contents of which are incorporated herein.

In one aspect of the disclosure, derived from C ₁₀-C ₄₀The alkylhydroxybenzoate detergent of the isomerized NAO is a calcium alkylhydroxybenzoate detergent.

In one aspect of the disclosure, derived from C ₁₀-C ₄₀The alkylhydroxybenzoate detergent of the isomerized NAO may be an alkylated hydroxybenzoate detergent. In one embodiment, the detergent may be a salicylate detergent. In another embodiment, the detergent may be a carboxylate detergent. In one aspect of the invention, inAn alkylhydroxybenzoate detergent having a TBN of 600 mgKOH/gram or greater on an oil basis is made from an alkylphenol having an alkyl group derived from an isomerized α -olefin, the isomerized α -olefin having from about 14 to about 28, or from about 20 to about 24 carbon atoms per molecule.

In one aspect of the disclosure, the C-derived having a TBN of 600 mgKOH/gram or greater on an oil-free basis ₁₀-C ₄₀An alkylhydroxybenzoate detergent of isomerized NAO having a composition derived from C ₁₀-C ₄₀And one or more alkylphenols having an alkyl group other than C of the isomerized NAO of (A) ₁₀-C ₄₀Is prepared from one or more alkylphenols of the alkyl group of the isomerized NAO. Preferably, said has a chemical composition different from C ₁₀-C ₄₀The alkylphenol or alkylphenols of the alkyl group of the isomerized NAO have a highly branched alkyl group of at least 9 carbon atoms, 9-24 and 10-15 carbon atoms. In one aspect of the invention, the lubricating oil composition comprises about 0.01 to 2 wt.%, based on Ca content, of the C-derived having a TBN of 600mgKOH/g or more on an oil-free basis ₁₀-C ₄₀The alkylhydroxybenzoate detergent of the isomerized NAO is preferably 0.1 to 1 wt.%, more preferably 0.05 to 0.5 wt.%, more preferably 0.1 to 0.5 wt.%. In one aspect of the present disclosure, the compositions comprising C derived with a TBN of 600 or greater on an oil-free basis ₁₀-C ₄₀The lubricating oil composition of the alkylhydroxybenzoate of the isomerized NAO is an automotive engine oil, a gasoline engine oil, a motorcycle oil, a dual fuel engine, a mobile gas engine oil, or a locomotive engine oil.

In one aspect of the disclosure, a composition comprising C derived having a TBN of 600 mgKOH/gram or greater on an oil-free basis ₁₀-C ₄₀The lubricating oil composition of the alkylhydroxybenzoate salt of isomerized NAO is a functional fluid for automotive and industrial applications, such as transmission oils, hydraulic oils, tractor fluids, gear oils, and the like. In one aspect of the disclosure, there is included C-derived having a TBN of 600 mgKOH/gram or greater on an oil-free basis ₁₀-C ₄₀The lubricating oil composition of the alkylhydroxybenzoate salt of isomerized NAO is a multigrade oil.

In one aspect of the disclosure, there is included C-derived having a TBN of 600 mgKOH/gram or greater on an oil-free basis ₁₀-C ₄₀The lubricating oil composition of the alkylhydroxybenzoate of the isomerized NAO lubricates the crankcase, gears, and clutches.

Other detergents

The lubricating oil composition of the present invention can further comprise one or more overbased detergents having a TBN of from 10 to 800, 10 to 700, 30 to 690, 100-.

Detergents that may be used include the following salts of metals: oil-soluble overbased sulfonates, sulfur-free phenates, sulfurized phenates, salixarates, salicylates, salicins, complex detergents and naphthenate detergents, as well as other oil-soluble alkylhydroxybenzoate salts, especially alkali or alkaline earth metals, such as barium, sodium, potassium, lithium, calcium and magnesium. The most commonly used metals are calcium and magnesium, both of which may be present in detergents for lubricants, and mixtures of calcium and/or magnesium with sodium.

Overbased metal detergents are typically prepared by carbonating a mixture of a hydrocarbon, a detergent acid (e.g., sulfonic acid, carboxylate salt, etc.), a metal oxide or hydroxide (e.g., calcium oxide or hydroxide), and a promoter (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. The sulfonic acid being reacted with excess CaO or Ca (OH) ₂And neutralizing to form sulfonate.

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 active-based TBN of the high overbased salt may be from about 250 to about 800.

In one embodiment, the detergent may be one or more alkali metal or alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid. 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 moiety in the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is derived from an α -alkene having from about 10 to about 80 carbon atoms.

In one embodiment, a mixture of linear olefins that may be used is a mixture of n- α -olefins selected from olefins having about 10 to about 40 atoms per molecule in one embodiment, n- α -olefin is 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 detergent (such as the alkyl groups in the alkali metal salt of an alkyl-substituted hydroxybenzoic acid detergent) are C ₂₀Or higher. In another embodiment, the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is an alkali or alkaline earth metal salt of an alkyl-substituted hydroxybenzoic acid, wherein the alkyl-substituted hydroxybenzoic acid is derived from wherein the alkyl group is C ₂₀To about C ₂₈In another embodiment, the alkyl group is derived from at least two alkanesThe alkyl group on at least one of the at least two alkylphenols is derived from an isomerized α -olefin the alkyl group on the second alkylphenol may be derived from a branched or partially branched olefin, a highly isomerized olefin, or mixtures 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 20 to 40 carbon atoms, preferably 20 to 28 carbon atoms, more preferably 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 petroleum fractionation or by 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.

The metal salts of phenol and sulfurized phenol (a sulfurized phenol metal salt is a sulfurized phenate detergent) are prepared by reaction with a suitable metal compound such as an oxide or hydroxide, and neutral or overbased products may be obtained by methods well known in the art. Sulfurized phenols can be prepared by reacting a 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 linked 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 in which 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 C ₂₀To C ₂₄An alkylphenol.

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

In one embodiment, suitable alkylphenol compounds include distilled cashew nutshell liquid (CNSL) or hydrogenated distilled cashew nutshell 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, as well as 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.

In one embodiment, the one or more overbased detergents may be a salicylate having an alkyl group of 20 to 28 carbon atoms, more preferably 20 to 24 carbon atoms. In another embodiment, the one or more overbased detergents may be of a type having a chemical formula derived from C _14-18Salicylate of alkyl of NAO, and less than 0.05 wt.%, preferably less than 0.025 wt.%, more preferably less than 0.01 wt.%, based on Ca content, of the lubricating oil composition.

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.

Antiwear agent

The lubricating oil compositions disclosed herein may comprise one or more antiwear agents. 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)(OR ¹)(OR ²)] ₂in the formula 1, the compound is shown in the specification,

wherein R is ¹And R ²Can be the same or different hydrocarbyl groups having from 1 to 18 (e.g., from 2 to 12) carbon atoms, and include groups such as alkyl, alkenyl, aryl, arylalkyl, alkylaryl, and cycloaliphatic groups. Particularly preferred as R ¹And R ²The radical being an alkyl radical having from 2 to 8 carbon atoms (e.g. an alkane)The 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+R ²) 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

The lubricating oil compositions disclosed herein may comprise one or more antioxidants. Antioxidants reduce the tendency of mineral oils to deteriorate during use. Oxidative deterioration can be 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 (typically a linear or branched alkyl group) and/or a bridging group attached to a 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

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 directly attached 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 lubricating oil compositions disclosed herein may comprise one or more dispersants. The dispersant retains suspended matter produced by oxidation during engine operation in the oil, which is insoluble in the oil, thereby preventing flocculation and settling 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 anhydride and a polyalkylene polyamine such as a polyethylene polyamine of the formula 2:

NH ₂(CH ₂CH ₂NH) _zh is represented by the formula 2 in the specification,

wherein z is 1 to 11. The polyisobutenyl 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 cyclic carbonate, ethylene carbonate, etc.) as is 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.

Foam inhibitor

The lubricating oil compositions disclosed herein may comprise one or more foam inhibitors that can disrupt foam in the oil. Non-limiting examples of suitable foam or anti-foam inhibitors include silicone oils or polydimethylsiloxanes, fluorosilicones, alkoxylated aliphatic acids, polyethers (e.g., polyethylene glycol), branched polyvinyl ethers, alkyl acrylate polymers, alkyl methacrylate polymers, polyalkoxyamines, and combinations thereof.

Other co-additives

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. Further, 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 various alcohols (e.g., butanol, hexanol, dodecanol, 2-ethylhexanol, 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 prepared from C5-C12 monocarboxylic 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 hydrocarbons synthesized by Fischer-Tropsch synthesis are obtained by using a Fischer-Tropsch catalyst containing H ₂And 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 are typically additionally processed by techniques for removing 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)According to ASTM D2622, ASTM D3120, ASTM D4294 or ASTM D4927 measurement.

^(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 depending on the desired end use and finished oil to provide the desired grade of engine oil, e.g., 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.

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 content of the lubricating oil composition of the present invention is less than or equal to about 0.12 wt.%, based on the total weight of the lubricating oil composition, e.g., the phosphorus content is from about 0.01 wt.% to about 0.12 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 content of the lubricating oil composition of the present invention is less than or equal to about 0.10 wt.%, based on the total weight of the lubricating oil composition, e.g., the phosphorus content is from about 0.01 wt.% to about 0.10 wt.%. In one embodiment, the phosphorus content of the lubricating oil composition of the present invention is less than or equal to about 0.09 wt.%, based on the total weight of the lubricating oil composition, e.g., the phosphorus content is from about 0.01 wt.% to about 0.09 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 from 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 present in an amount of less than or equal to about 0.80 wt.%, as determined by ASTM D874, for example in an amount of from about 0.10 to about 0.80 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 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.

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 the TopSpin 3.2 spectral processing software.

The level of isomerization (I) represents the linkage to the methylene backbone group (-CH) ₂- (. chemically shifted 1.01-1.38ppm) of a methyl group (-CH) ₃) (chemical shift 0.3-1.01ppm) and is defined by the following equation (1),

i ═ m/(m + n) formula (I)

Wherein m is the NMR integral of methyl groups having chemical shifts in the range of 0.3. + -. 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.

α -olefin has an isomerization level (I) of from about 0.1 to about 0.4, preferably from about 0.1 to about 0.3, more preferably from about 0.12 to about 0.3.

In one embodiment, the NAO has an isomerization level of about 0.16 and has from about 20 to about 24 carbon atoms.

In another embodiment, the NAO has an isomerization level of about 0.26 and has from about 20 to about 24 carbon atoms.

Baseline formulation 1

A 5W-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) zinc dialkyldithiophosphates;

(3) a mixture of antioxidants;

(4) a foam inhibitor.

Example A

Use of C _20-24Isomerized n- α -olefin, produced alkylated phenol and calcium alkylhydroxybenzoate in essentially the same manner as in U.S. Pat. No.8,993,499. α -olefin had an isomerization level of about 0.16. the resulting alkylhydroxybenzoate component had a TBN of about 630 and a Ca content of about 22.4 wt.% on an oil-free basis.

Example B

Use of C _20-24Isomerized normal α -olefins in substantially the same manner as in U.S. Pat. No.8,993,499Preparation of alkylated phenols and calcium alkylhydroxybenzoate α -the level of isomerization of the olefin was about 0.16 the resulting alkylhydroxybenzoate component had a TBN of about 225 and a Ca content of about 8 wt.% on an oil-free basis.

Comparative example A

From compounds having a structure derived from C ₁₄-C ₁₈The alkylated phenols of the alkyl group of the NAO produced alkylhydroxybenzoate salts with a TBN of about 300 and Ca content of about 10.6 wt.% on an oil-free basis.

Comparative example B

Using C available from CP Chem _20-28NAO, prepared in substantially the same manner as in U.S. patent No.8,030,258. The resulting alkylhydroxybenzoate composition had a TBN of about 520 and a Ca content of about 18.7 wt.% on an oil-free basis.

Example 1

To baseline formulation 1, 0.13 wt.% of the calcium alkylhydroxybenzoate detergent of example a, based on the Ca content, and 0.05 wt.% of the calcium alkylhydroxybenzoate detergent of example B, based on the Ca content, were added.

Example 2

To baseline formulation 1, 0.13 wt.% of the calcium alkylhydroxybenzoate detergent of example a, based on the Ca content, and 0.02 wt.% of the overbased calcium sulfurized phenate detergent, based on the Ca content, were added.

Example 3

To baseline formulation 1 was added (9.83mmol soap) the calcium alkylhydroxybenzoate detergent of example a.

Comparative example 1

To baseline formulation 1, 0.13 wt.% of the calcium alkylhydroxybenzoate detergent of comparative example B, based on the Ca content, and 0.02 wt.% of the overbased calcium sulfurized phenate detergent, based on the Ca content, were added.

Comparative example 2

To baseline formulation 1 was added (9.83mmol soap) the calcium alkylhydroxybenzoate detergent of comparative example B.

HTCBT test

ASTM D6594 HTCBT testing is used to test diesel lubricants to determine their tendency to corrode various metals, particularly alloys of lead and copper, which are 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 were reported. The lead concentration should not exceed 120ppm and the copper concentration should not exceed 20ppm to pass the test.

TABLE 2 HTCBT

TABLE 3 HTCBT (comparison of soap identity)

Baseline formulation 2

A heavy duty automotive lubricating oil composition is prepared comprising a major amount of a base oil of lubricating viscosity and the following additives to provide an SAE 15W-40 finished oil:

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

(2) 990ppm based on phosphorus of a mixture of primary and secondary zinc dialkyldithiophosphates;

(3) providing 50ppm of molybdenum succinimide complex of molybdenum,

(4) an alkylated diphenylamine antioxidant;

(5) 5ppm of foam inhibitor based on the silicon content;

(6)9.5 wt% non-dispersant OCP VII (additive) and 0.3 wt% PPD; and

(7) the balance group II base oil (Chevron 220R).

Example 4

To baseline formulation 2 was added 0.2290 wt.% calcium alkylhydroxybenzoate of example A, based on calcium contentDetergent and 0.078 wt.% C based on magnesium content ₂₀-C ₂₄Magnesium alkylhydroxybenzoate detergent, said C ₂₀-C ₂₄The magnesium alkylhydroxybenzoate detergent was prepared from an isomerized NAO having an isomerization level of 0.16. The properties are as follows: 35 wt.% TBN (mgKOH/g) 199 in Diluent oil

Comparative example 3

To baseline formulation 2, 0.2290 wt.%, based on calcium content, of the calcium alkylhydroxybenzoate detergent of example a and 0.075 wt.%, based on magnesium content, of C were added ₁₄-C ₁₈Magnesium alkylhydroxybenzoate detergent, said C ₁₄-C ₁₈The alkyl hydroxyl benzoic acid detergent is prepared from α -olefin, and has the properties of TBN (mgKOH/g) ═ 236 and Mg (weight percent) ═ 5.34.

Oxidation Bx test

A 25g sample was weighed into a special glass oxidation cell. The catalyst was added and then inserted into a glass stirrer. The cell was then sealed and placed in an oil bath maintained at 340 ° F and connected to a source of oxygen. One liter of oxygen was injected into the cell while the stirrer agitated the oil sample. The test was conducted until the sample consumed 1 liter of oxygen and the total time (in hours) the sample was run was recorded. The higher the number of hours to reach 1 liter, the better the oxidation performance. The results are given in table 4 below.

TABLE 4

Example C

Use of C _20-24Isomerized n- α -olefin, produced alkylated phenol and calcium alkylhydroxybenzoate in essentially the same manner as in U.S. Pat. No.8,993,499. α -olefin had an isomerization level of about 0.16. the resulting alkylhydroxybenzoate component had a TBN of about 120 and a Ca content of 4.2 wt.% on an oil-free basis.

Baseline formulation 3

A passenger car lubricating oil composition is prepared comprising a major amount of a base oil of lubricating viscosity and the following additives to provide an SAE 5W-30 finished oil:

(1) ethylene carbonate post-treated bis-succinimide dispersants and boronated dispersants;

(2) 770ppm calculated as phosphorus of a mixture of a primary and a secondary zinc dialkyl dithiophosphate;

(3) providing 180ppm of a molybdenum succinimide complex of molybdenum,

(4) an alkylated diphenylamine antioxidant;

(5) a boronated friction modifier;

(5) 5ppm of foam inhibitor based on the silicon content;

(6)9.5 wt% non-dispersant OCP VII (additive) and 0.3 wt% PPD; and

(7) the balance group III base oils.

Example 5

To baseline formulation 3 was added a total of 0.2230 wt% of a mixture of calcium alkylhydroxybenzoate from example a (32.3mMol) and example C (23.3 mMol).

Example 6

To formulation baseline 3 was added a total of 0.2300 wt% of the calcium alkylhydroxybenzoate from example C (23.3mMol) and the calcium alkylhydroxybenzoate derived from C _20-24A mixture of HOB sulfonates (31.7mMol) of NAO.

Comparative example 4

To baseline formulation 3 was added a total of 0.2230 wt.% of C-derived having a TBN of 135 on an oil-free basis _20-28Calcium alkylhydroxybenzoate of NAO (24.1mMol) and comparative example B (31.6 mMol).

Comparative example 5

To baseline formulation 3 was added a total of 0.2300 wt.% of C-derived having a TBN of 135 on an oil-free basis _20-28Calcium alkylhydroxybenzoate of NAO (27.7mMol) and derived from C _20-24A mixture of HOB sulfonates (29.6mMol) of NAO.

Baseline formulation 4

A passenger car lubricating oil composition is prepared comprising a major amount of a base oil of lubricating viscosity and the following additives to provide an SAE5W-40 finished oil:

(2) 740ppm, based on the phosphorus content, of a secondary zinc dialkyldithiophosphate;

(3) a mixture of boronated borates, LOB sulfonates, and MOB phenates;

(4) providing 90ppm of molybdenum succinimide complex of molybdenum,

(5) alkylated diphenylamines and hindered phenol antioxidants;

(6) 5ppm of foam inhibitor based on the silicon content;

(7) 13.5% by weight of non-dispersant OCP VII (additive) and 0.3% by weight PPD; and

(8) the balance group III base oils.

Example 7

To baseline formulation 4 was added the calcium alkylhydroxybenzoate of example a (27 mMol).

Comparative example 6

To baseline formulation 4 was added the calcium alkylhydroxybenzoate of comparative example B (27 mMol).

ASTM D4684 Mini rotary viscometer test (MRV)

In this test, the test oil is first heated and then cooled to the test temperature, in this case-40 ℃, in a miniature rotational viscometer bath (cell). Each slot contains a calibrated rotor-stator arrangement (set) in which the rotor is rotated by a chord (string) which rotates about the rotor axis and is connected (weight) to a weight. A series of incremental weights were applied to the string starting with a 10g weight until rotation occurred to determine the yield stress. The results are reported as the yield stress (in pascals) of the applied force. A 150g weight was then applied to determine the apparent viscosity of the oil. The greater the apparent viscosity, the less likely it will be that the oil will be continuously and adequately fed to the oil pump inlet. Results are reported in viscosity in centipoise.

The results of the MRV testing of the various lubricating oil compositions are given in table 4 below.

TABLE 4

TABLE 5

	Comparative example 6	Example 7
			Yield stress (-40 ℃ C.) Pa	>35	<35
Viscosity (-40 ℃ C.) (cP)<60,000)	27,000	20,900

It is clear from these examples that the performance of lubricating oils formulated with the alkylhydroxybenzoate detergents of the present invention is better or superior to formulations containing alkylhydroxybenzoate salts that are not derived from isomerized NAO having from about 10 to about 40 carbon atoms.

Claims

1. A lubricating oil composition comprising:

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

(b) one or more detergents comprising at least one alkylhydroxybenzoate compound derived from an isomerized n- α -olefin (NAO) having from about 10 to about 40 carbon atoms,

2. The lubricating oil composition of claim 1, wherein the alkyl hydroxybenzoate compound has an active-material-based TBN of 600-800 mgKOH/gm.

3. The lubricating oil composition of claim 1, further comprising one or more detergents derived from an alkyl group having 20 to 40 carbon atoms, the detergent being selected from an alkali or alkaline earth metal sulfonate, phenate or salixarate, salicin or complex detergent, carboxylate or salicylate, and the detergent being different from the alkylhydroxybenzoate detergent compound of claim 1.

4. The lubricating oil composition of claim 3, wherein the further detergent is an alkali or alkaline earth metal sulfonate having a TBN of from 10 to 700 mgKOH/gm.

5. The lubricating oil composition of claim 3, wherein the further detergent is an alkali or alkaline earth metal sulfonate having a TBN of from 10 to 600 mgKOH/gm.

6. The lubricating oil composition of claim 3, wherein the further detergent is an alkylhydroxybenzoate derived from an alkali or alkaline earth metal having an alkyl group with 20-28 carbon atoms and a TBN of 10-590 mgKOH/gm.

7. The lubricating oil composition of claim 1, wherein the isomerized n- α -olefin has a n- α -olefin isomerization degree (I) of from about 0.1 to about 0.4.

8. The lubricating oil composition of claim 1, further comprising an additional detergent.

9. The lubricating oil composition of claim 8, wherein the additional detergent is an alkyl hydroxybenzoate, phenate, sulfonate, or a combination thereof.

10. The lubricating oil composition of claim 9, wherein the detergent is derived from a NAO, an isomerized NAO, or a combination thereof.

11. The lubricating oil composition of claim 10, wherein the detergent is a magnesium alkylhydroxybenzoate derived from an isomerized NAO.

12. The lubricating oil composition of claim 9, wherein the sulfonate salt is a calcium sulfonate salt or a magnesium sulfonate salt.

13. 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;

14. The method as claimed in claim 13, wherein the alkyl hydroxybenzoate compound has an active-material-based TBN of 600-800 mgKOH/gm.

15. The method of claim 13, wherein the lubricating oil composition further comprises one or more detergents derived from an alkyl group having 20 to 40 carbon atoms selected from an alkali or alkaline earth metal sulfonate, phenate, or salixarate, salicin or complex detergent, carboxylate, or salicylate, and the detergent is different from the alkylhydroxybenzoate detergent compound of claim 1.

16. The method of claim 15, wherein the further detergent is an alkali or alkaline earth metal sulfonate having a TBN of 10 to 700 mgKOH/gm.

17. The method of claim 15 wherein the further detergent is an alkali or alkaline earth metal sulfonate having a TBN of 100-600 mgKOH/gm.

18. The method of claim 15, wherein the further detergent is an alkylhydroxybenzoate derived from an alkali or alkaline earth metal having an alkyl group with 20-28 carbon atoms and a TBN of 10-590 mgKOH/gm.

19. The process of claim 13 wherein the isomerized n- α -olefin has a n- α -olefin isomerization degree (I) of from about 0.1 to about 0.4.

20. The method of claim 13, wherein the lubricating oil composition further comprises an additional detergent.

21. The method of claim 20, wherein the additional detergent is an alkyl hydroxybenzoate, phenate, sulfonate, or a combination thereof.

22. The method of claim 21, wherein the detergent is derived from a NAO, an isomerized NAO, or a combination thereof.

23. The method of claim 22, wherein the detergent is a magnesium alkylhydroxybenzoate derived from an isomerized NAO.

24. The method of claim 21, wherein the sulfonate salt is a calcium sulfonate salt or a magnesium sulfonate salt.