CN114402059A

CN114402059A - Lubricating oil composition

Info

Publication number: CN114402059A
Application number: CN202080065215.5A
Authority: CN
Inventors: C·查姆梅洛克斯; J·R·米勒; S·A·斯克尔顿; M·斯滕德罗维茨; A·布法; 田中勲
Original assignee: Chevron Japan Ltd; Chevron Oronite Co LLC
Current assignee: Chevron Japan Ltd; Chevron Oronite Co LLC
Priority date: 2019-09-05
Filing date: 2020-09-03
Publication date: 2022-04-26
Also published as: US20220213401A1; CA3152975A1; JP2022547073A; EP4025674A1; KR20220057555A; WO2021044326A1

Abstract

The present disclosure generally relates to a lubricating oil composition comprising: a major amount of an oil of lubricating viscosity, one or more detergents comprising at least one alkylhydroxybenzoate compound, and an ashless sulfur compound. A method of lubricating an engine with the lubricating oil composition is also provided.

Description

Lubricating oil composition

Background

To keep pace with modern engine designs, the requirements for engine lubricants are becoming more demanding. One such requirement is the need for greater antioxidant capacity, which has intensified the search for new antioxidants. Oxidation of engine oil adversely affects the performance of the lubricating oil additive and reduces the useful life of the engine oil.

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 from about 10 to about 40 carbon atoms; and

(c) an ashless sulfur compound, wherein the ashless sulfur compound is not a dithiocarbamate.

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; and

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 understanding of the subject matter disclosed herein, a number of terms, abbreviations, or other abbreviations, as used herein, are defined below. Any undefined terms, abbreviations or abbreviations should be understood to have the ordinary meaning as 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 stated to the contrary. In this specification, the following words and expressions, if and when 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 weight of the composition, expressed relative to the stated additives and relative to the total mass of all additives present in the composition, of the active ingredient considered to be one or more additives.

"active ingredient" or "active" or "oil-free" refers to an additive material that is not a diluent or solvent.

Unless otherwise indicated, all reported percentages are based on the weight of the active ingredient (i.e., without regard to the carrier or diluent oil).

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.

The High Temperature High Shear (HTHS) viscosity at 150 ℃ was determined according to ASTM D4863.

Determination of Kinematic Viscosity (KV) at 100 ℃ according to ASTM D445₁₀₀)。

Cold Cranking Simulator (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. Olefins containing one double bond are referred to as monoolefins and olefins containing two double bonds are referred to as dienes, alkadienes or diolefins. Alpha olefins are particularly highly reactive because the double bond is located between the first carbon and the second carbon. Examples are 1-octene and 1-octadecene, which are used as starting points for moderate biodegradable surfactants. Linear and branched olefins are also included in the definition of olefins.

Normal alpha olefins-the term "normal alpha olefins" refers to olefins that are straight, unbranched hydrocarbons with carbon-carbon double bonds present at the beginning and end of the chain.

Isomerizing the normal alpha olefins. The term "isomerize normal alpha olefins" as used herein refers to alpha olefins that have been subjected to isomerization conditions that result in a change in the distribution of the olefinic species present and/or the introduction of branches 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, and preferably from about 20 to about 24 carbon atoms.

All ASTM standards mentioned herein are the latest version up to the date of filing this application.

The present disclosure describes lubricating oil compositions comprising a combination of an alkylhydroxybenzoate detergent and an ashless sulfur compound, wherein the combination synergistically controls oxidation of engine oil.

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 normal alpha olefin having from about 10 to 40 carbon atoms; and

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) one or more detergents comprising at least one alkylhydroxybenzoate compound derived from an isomerized normal alpha olefin having from about 10 to 40 carbon atoms, and

Alkyl hydroxybenzoate detergent compounds derived from C10-C40 isomerized Normal Alpha Olefins (NAO)

In one aspect of the disclosure, derived from C₁₀-C₄₀The TBN of the alkylhydroxybenzoate detergent of the isomerized NAO is about 100 to about 700, such as about 100 to about 650, about 100 to about 600, about 100 to about 500, about 100 to about 400, about 100 to 300, about 150 to 250, about 175 to about 225mg KOH/gram on an oil-free basis.

In one aspect of the disclosure, the alkyl hydroxybenzoate detergent is derived from C₁₀-C₄₀Isomerized NAO and having a TBN of from about 10 to about 300, such as from about 50 to about 300, from about 100 to about 300, from about 150 to about 300, and from about 175 to about 250mg KOH/gram, based on active.

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 invention, 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 one aspect of the disclosure, derived from C₁₀-C₄₀The alkylhydroxybenzoate salts of isomerized NAO may be prepared as described in U.S. patent 8,993,499, which is incorporated herein in its entirety.

In one aspect of the disclosure, the alkyl hydroxybenzoate detergent is made from an alkylphenol having alkyl groups derived from isomerized alpha olefins having about 10 to about 40 carbon atoms per molecule, such as about 14 to about 28 carbon atoms per molecule, about 20 to about 24 carbon atoms per molecule, about 14 to about 18 carbon atoms, and about 20 to about 28 carbon atoms.

In one aspect of the disclosure, derived from C₁₀-C₄₀The alkylhydroxybenzoate salts of the isomerized NAO are made from an alkylphenol having alkyl groups derived from the isomerized NAO, which has an isomerization level (I) of about 0.10 to about 0.40, such as about 0.10 to about 0.35, about 0.10 to about 0.30, about 0.12 to about 0.30, and about 0.12 to about 0.20.

In one aspect of the disclosure, derived from C₁₀-C₄₀The alkylhydroxybenzoate salts of isomerized NAO are formed from one or more compounds having a structure derived from C₁₀-C₄₀An alkylphenol of an alkyl group of an isomerized NAO and one or more of different C₁₀-C₄₀Isomerizing the alkyl group of the NAO.

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

Derived from C₁₀-C₄₀The alkylhydroxybenzoate detergent of the isomerized NAO may comprise an alkali metal or alkaline earth metal (e.g., barium, sodium, potassium, lithium, calcium, and magnesium). The most commonly used metals are calcium and magnesium, which may all be present in detergents used in lubricants; and mixtures of calcium and/or magnesium with sodium.

In one aspect of the disclosure, the lubricating oil composition comprises about 0.01 to about Ca contentAbout 2.0 wt.%, such as from about 0.1 to about 1.0 wt.%, from about 0.05 to about 0.5 wt.%, and from about 0.1 to about 0.5 wt.% derived from C₁₀-C₄₀Alkylhydroxybenzoate salts of isomerized NAO.

In one aspect of the present disclosure, the lubricating oil composition comprises from about 0.01 to about 2.0 wt.%, such as from about 0.1 to about 1.0 wt.%, from about 0.05 to about 0.5 wt.%, and from about 0.1 to about 0.5 wt.% derived from C, in terms of Mg content₁₀-C₄₀Alkylhydroxybenzoate salts of isomerized NAO.

In one aspect of the disclosure, comprising a compound derived from C₁₀-C₄₀The lubricating oil composition of the isomerized NAO alkylhydroxybenzoate detergent is an automotive engine oil composition, a gas 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, comprising a compound derived from C₁₀-C₄₀The lubricating oil composition of the isomerized NAO alkylhydroxybenzoate detergent is a functional fluid for automotive and industrial applications, such as transmission oil, hydraulic oil, tractor fluid, gear oil, and the like.

In one aspect of the invention, comprising a compound derived from C₁₀-C₄₀The lubricating oil composition of the alkylhydroxybenzoate detergent of isomerized NAO is a multigrade oil or a single-grade oil.

In one aspect of the disclosure, comprising a compound derived from C₁₀-C₄₀The lubricating oil composition of the alkylhydroxybenzoate detergent of isomerized NAO lubricates crankcases, gears and clutches.

Ashless sulfur compounds

Sulfurized fatty acid esters

In one aspect, the ashless sulfur compound is a sulfurized fatty acid ester. Sulfurized fatty acid esters are prepared by reacting sulfur, sulfur monochloride and/or sulfur dichloride with unsaturated fatty acid esters at elevated temperatures. Typical esters include C₈-C₂₄C of unsaturated fatty acids₁-C₂₀Alkyl esters of unsaturated fatty acids, e.g. palmitoleic, oleic, ricinoleic acidPetroselinic acid, vaccenic acid, linoleic acid, linolenic acid, oleostearic acid, licanic acid (licanic acid), stearidonic acid (paraaric acid), tartaric acid, gadoleic acid, arachidonic acid, cetenoic acid, and the like. Particularly good results have been obtained with mixed unsaturated fatty acid esters, such as those obtained from animal fats and vegetable oils (e.g., tall oil, linseed oil, olive oil, castor oil, peanut oil, rape oil, fish oil, whale oil, etc.).

Exemplary fatty esters include lauryl tallate, methyl oleate, ethyl oleate, lauryl oleate, cetyl linoleate, lauryl ricinoleate, oleyl linoleate, oleyl stearate, and alkyl glycerides.

Sulfurized olefins

In one aspect, the ashless sulfur compound is a sulfurized olefin. Cross-sulfurized ester olefins may also be used, such as sulfurized mixtures of a C10 to C25 olefin with a C10 to C25 fatty acid and a fatty acid ester of a C10 to C25 alkyl or alkenyl alcohol, wherein the fatty acid and/or alcohol is unsaturated. Sulfurized olefins are generally derived from alpha olefins, isomerized alpha olefins, cyclic olefins, branched olefins, and polymerized olefins reacted with a sulfur source. Specific examples of olefins include, but are not limited to: 1-butene, isobutene, diisobutylene, 1-pentene, 1-hexene, 1-heptene, 1-octene and more with longer carbon chains up to C60 and beyond to polyolefins. Other examples of non-Normal Alpha Olefins (NAO) include cyclohexene, cyclooctene, pentene (amaryne), isopentene, branched and internal olefin isomers of NAO.

Examples of sulfur sources include sulfur, hydrogen sulfide, sodium sulfide, sulfur chloride, and sulfur dichloride.

Also useful are aromatic and alkyl sulfides such as dibenzyl sulfide, xylyl sulfide, dihexadecyl sulfide, dialkylene wax sulfides and polysulfides, cracked wax-olefin sulfides, and the like. They can be prepared by treating starting materials, for example ethylenically unsaturated compounds, with sulfur, sulfur monochloride and sulfur dichloride. Particularly preferred are the paraffin mercapto polymers described in U.S. patent No. 2,346,156.

Thiadiazole group:

in one aspect, the ashless sulfur compound is a thiadiazole. Thiadiazoles include at least one of the following: 2, 5-dimercapto-1, 3, 4-thiadiazole; 2-mercapto-5-alkylthio-1, 3, 4-thiadiazole; 2-mercapto-5-hydrocarbyl dithio-1, 3, 4-thiadiazole; 2, 5-bis (hydrocarbylthio) and 2, 5-bis (hydrocarbyldithio) -1,3, 4-thiadiazole. Preferred compounds are 1,3, 4-thiadiazoles, especially 2-hydrocarbyl dithio-5-mercapto-1, 3, 4-dithiadiazoles and 2, 5-bis (hydrocarbyl dithio) -1,3, 4-thiadiazoles, some of which are available as commercial articles. Other preferred compounds include polycarboxylate free thiadiazoles containing about 4.0 wt% 2, 5-dimercapto-1, 3, 4-thiadiazole as

4313 available from Afton Chemical (Richmond, Virginia) or as

5955A is available from Lubrizol Corporation (Wycliffe, Ohio).

Ashless dithiophosphates:

in one aspect, the ashless sulfur compound is an ashless dithiophosphate. One class of suitable ashless dithiophosphates for use herein includes those represented by formula (I):

wherein R is¹¹And R¹²Independently an alkyl group having 3 to 8 carbon atoms. Suitable ashless dithiophosphates include those commercially available from r.t. vanderbilt co

7611M。

Another suitable class of ashless dithiophosphates for use herein includes dithiophosphoric acid esters of carboxylic acids, such as are commercially available from BASF

63。

Another suitable class of ashless dithiophosphates for use herein includes triphenyl phosphorothioates, such as are commercially available from BASF

TPPT。

Sulfurized hindered phenol:

in one aspect, the ashless sulfur compound is a sulfurized hindered phenol. Sulfurized hindered phenols suitable for use in the present invention can be prepared by a number of known methods. Sulfurized hindered phenols are characterized by the type of hindered phenol used in their production and their final sulfur content. Hindered tertiary butyl phenols are preferred. The sulfurized hindered phenols may be chlorine-free, prepared from chlorine-free sulfur sources such as elemental sulfur, sodium sulfide or sodium polysulfide, or they may contain chlorine, prepared from sulfur chloride sources such as sulfur monochloride and sulfur dichloride. Preferred sulfurized hindered phenols include those represented by formula (II).

Wherein R is an alkyl group, R₁Is an alkyl radical or hydrogen, Z or Z₁One of which is an-OH group and the other is hydrogen, Z₂Or Z₃One is an-OH group and the other is hydrogen, x is in the range of 1 to 6, and y is in the range of 0 to 2.

Suitable chlorine-free sulfurized hindered phenols may be prepared by the method taught in U.S. Pat. No. 3,929,654, or may be obtained by: (a) preparing a mixture of (i) at least one non-chlorine containing hindered phenol, (ii) a non-chlorine containing sulfur source, and (iii) at least one alkali metal hydroxide promoter in a polar solvent, and (b) reacting components (i), (ii), and (iii) at a sufficient temperature and for a sufficient time to form at least one non-chlorine containing sulfurized hindered phenol as taught in co-pending application 08/657,141 filed 6/3/1996 and co-pending application 08/877,533 filed 2/19/1997.

Suitable sulfurized hindered phenol products prepared from a sulfur chloride source include those taught in U.S. Pat. Nos. 3,250,712 and 4,946,610, both of which are hereby incorporated by reference.

Examples of sulfurized hindered phenols useful in the present invention include 4,4' -thiobis (2, 6-di-t-butylphenol), 4' -dithiobis (2, 6-di-t-butylphenol), 4' -thiobis (2-t-butyl-6-methylphenol), 4' -dithiobis (2-t-butyl-6-methylphenol), 4' -thiobis (2-t-butyl-5-methylphenol), and mixtures of these.

Preferably the sulfurized hindered phenol is a substantially liquid product. As used herein, substantially liquid refers to a composition that is primarily liquid. In this regard, aged samples of sulfurized hindered phenols may form small amounts of crystallization, usually around the sides of the container and the glass container surfaces where the product comes into contact with air. It is further preferred that the sulfurized hindered phenol be chlorine-free, have low corrosivity, and have a high content of monosulfide, as described in co-pending application 08/657,141 filed on 3.6.1996 and co-pending application 08/877,533 filed on 19.2.1997. It is also preferred that the sulfur content of the sulfurized hindered phenol be in the range of from about 4.0 wt.% to about 12.0 wt.%.

Phenothiazines:

in one aspect, the ashless sulfur compound is phenothiazine. Phenothiazines useful in the practice of the present invention include alkylated phenothiazine compounds represented by formula (III):

wherein R is¹Is a straight or branched chain group having from 4 to 24 carbon atoms, such as from 4 to 10 carbon atoms, and being an alkyl or alkylaryl group; and R is²Independently of R¹Is a straight or branched chain group having from 4 to 24 carbon atoms, such as from 4 to 10 carbon atoms, and being an alkyl or alkylene group, or is a hydrogen atom.

As an example of the above formula (III), R¹Is a nonyl radical, and R²Is a hydrogen atom or a nonyl group.

In one aspect of the alkylated phenothiazine, R¹Preferably an alkyl group having 4 to 10 carbon atoms, and R²Is a hydrogen atom or an alkyl group having 4 to 10 carbon atoms.

The alkylated phenothiazine preferably comprises a mixture of monoalkylated and dialkylated phenothiazines, for example, wherein about 15 to about 85 mass% of the mixture is monoalkylated.

Alkylated phenothiazines are known in the art and may be prepared by methods known in the art. For example, phenothiazine may be reacted with C in the presence of an acid catalyst₁To C₁₀Olefins or mixtures thereof are reacted to alkylate, and suitable such olefins include alpha olefins and internal olefins such as isobutylene, diisobutylene, nonene, and 1-decene.

Additional detergents

The lubricating oil compositions of the present invention may also contain one or more overbased detergents having a TBN of about 10 to about 800, such as about 10 to about 700, about 30 to about 690, about 100 to about 600, about 150 to about 500, and about 200 to about 450mg KOH/g, based on actives.

Detergents that may be used include oil-soluble overbased sulfonates, non-sulfur containing phenates, sulfurized phenates, salicylate, salixarates, complex detergents and naphthenate detergents, as well as other oil-soluble alkylhydroxybenzoate salts (of metals, particularly alkali or alkaline earth metals (e.g., barium, sodium, potassium, lithium, calcium, and magnesium)). The most commonly used metals are calcium and magnesium, which may all be present in detergents used in 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, alkylhydroxybenzoate, or the like), a metal oxide or hydroxide (e.g., calcium oxide or calcium 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 is used in excess of 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 about 100 based on the active. 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.

In some embodiments, the overbased detergent may be moderately overbased, e.g., an overbased salt having a TBN of about 100 to about 250. In one embodiment, the moderately overbased salt may have a TBN of from about 100 to about 200. In another embodiment, the moderately overbased salt may have a TBN of from about 125 to about 175.

In some embodiments, the overbased detergent may be highly overbased, e.g., an overbased salt having a TBN of greater than about 250. In one embodiment, the TBN of the highly overbased salt may be from about 250 to about 800 based on the active material.

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 and 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 employed may be a linear olefin, an isomerized linear olefin, a branched olefin or a 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, the mixture of linear olefins that can be used is a mixture of normal alpha olefins selected from olefins having from about 10 to about 40 carbon atoms per molecule. In one embodiment, normal 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 or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid, such as the alkyl group of 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 an alkali or alkaline earth metal salt of an alkyl-substituted hydroxybenzoic acid derived from an alkyl-substituted hydroxybenzoic acid in which the alkyl group is C₂₀To about C₂₈Normal alpha-olefins. 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 alkylphenol can 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 isomerized NAO having from about 20 to about 40 carbon atoms, preferably from about 20 to about 28 carbon atoms, more preferably from about 20 to about 40 carbon atoms.

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 alkyl group of the alkylaryl sulfonates usually contains from about 9 to about 80 or more carbon atoms, preferably from about 16 to about 60 carbon atoms, preferably from about 16 to about 30 carbon atoms, and more preferably from about 20 to about 24 carbon atoms.

The phenol and the metal salt of the sulfurized phenol as sulfurized phenate detergent are prepared by reacting with an appropriate metal compound such as an oxide or hydroxide. Neutral or overbased detergent 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 two or more phenols are bridged by a sulfur-containing bridge.

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

The reactants and reagents used in the process of the invention may utilize all allotrope forms of sulfur. The sulfur may be used as molten sulfur or as a solid (e.g., powder or particulate) or as a suspension of a solid in a compatible hydrocarbon liquid.

In some cases, it may be desirable to use calcium hydroxide as the calcium base because of its superior properties. Calcium hydroxide is believed to be more convenient to handle than, for example, calcium oxide. Other compatible calcium bases include, for example, calcium alkoxides.

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. Typically, the alkylphenols used will be different alkylphenols (e.g., C)₂₀To C₂₄Alkylphenol).

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

In one embodiment, suitable alkylphenol compounds may be derived from distilled cashew nut shell oil (CNSL) or hydrogenated distilled cashew nut shell oil. Distilled CNSL is a mixture of biodegradable meta-hydrocarbyl substituted phenols in which the hydrocarbyl group is linear and unsaturated, including cardanol. Catalytic hydrogenation of distilled CNSL produces a mixture of m-hydrocarbyl substituted phenols that are predominantly rich in 3-pentadecylphenol.

The alkylphenol may be para-alkylphenol, meta-alkylphenol, or ortho-alkylphenol. Because it is believed that para-alkylphenols help produce the highly overbased calcium sulfurized alkylphenols which require an overbased product, the alkylphenols are preferably predominantly para-alkylphenols, with no more than about 45 mole% of the alkylphenols being ortho-alkylphenols; and more preferably no more than about 35 mole% 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, can also be used. In the case of distilling cashew nut shell oil, 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 comprising 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 comprising an alkyl group having from about 20 to about 28 carbon atoms, more preferably from about 20 to about 24 carbon atoms. In another embodiment, one or more overbased detergents may be one having a chemical formula derived from C_14-18Salicylate of alkyl group of NAO and contribute to the lubricating oil by less than about 0.05 wt%, preferably less than about 0.025 wt%, more preferably less than about 0.01 wt%, in terms of Ca content.

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, Zinc Dihydrocarbyl Dithiophosphates (ZDDP) of formula (IV):

Zn[S-p(＝S)(OR¹)(OR²)]₂formula (IV)

Wherein R is¹And R²Can be the same or different hydrocarbyl groups having from 1 to 18 (e.g., 2 to 12) carbon atoms. Suitable hydrocarbyl groups include, but are not limited to, alkyl, alkenyl, aryl, aralkyl, alkaryl, and cycloaliphatic groups. Particularly preferred R¹And R²Groups include alkyl groups having 2 to 8 carbon atoms (e.g., 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) Should be at least 5. The zinc dihydrocarbyl dithiophosphate may therefore comprise zinc dialkyl dithiophosphates. The zinc dialkyldithiophosphate is a primary, secondary zinc dialkyldithiophosphate or a combination thereof. The ZDDP may be present in the lubricating oil composition at about 3 wt.% or less (e.g., about 0.1 to about 1.5 wt.%, or about 0.5 to about 1.0 wt.%). In one embodiment, the lubricating oil composition containing 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 yet 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 may be evidenced by sludge in the lubricant, varnish-like deposits on the metal surface, and/or viscosity growth. Suitable antioxidants include hindered phenols, aromatic amines, and sulfurized alkylphenols, as well as their alkali metal and alkaline earth metal salts.

Hindered phenol antioxidants typically contain a sec-butyl and/or tert-butyl group as a sterically hindering group. The phenolic group may be further substituted by a hydrocarbyl group (typically straight or branched chain)Alkyl) 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 from 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 group 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 in about 0.01 to about 5 wt.% (e.g., about 0.1 to about 2 wt.%) of the lubricating oil composition.

Dispersing agent

The lubricating oil compositions disclosed herein may comprise one or more dispersants. The dispersant is retained in an oil insoluble suspension material produced by oxidation during engine operation, thereby preventing sludge flocculation and precipitation or deposition on metal parts. Dispersants useful herein 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. Also suitable are condensation products of polyamines and hydrocarbyl-substituted phenyl acids. Mixtures of these dispersants may also be used. Basic nitrogen-containing ashless dispersants are well known lubricating oil additives and their preparation methods are widely described in the patent literature. Preferred dispersants are alkenyl succinimides and succinamides, wherein the alkenyl substituent is a long chain, preferably greater than about 40 carbon atoms. These materials are 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 the polyethylene polyamine of formula (V):

NH₂(CH₂CH₂NH)_zh type (V)

Wherein z is 1 to 11. The polyisobutylene group is derived from polyisobutylene and preferably has a number average molecular weight (M) in the range of about 700 to about 3000 daltons (e.g., about 900 to about 2500 daltons)_n). For example, the polyisobutenyl succinimide may be derived from a compound having an M of from about 900 to about 2500 daltons_nThe bis-succinimide of a polyisobutenyl group of (a). 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 can be present in about 0.1 to about 10 wt.% (e.g., about 2 to about 5 wt.%) of the lubricating oil composition.

Suds suppressor

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

Additional co-additives

The lubricating oil compositions of the present disclosure may also contain other conventional additives that 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. Some suitable additives are described in Mortier et al, "Chemistry and Technology of Lubricants", 2 nd 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 blended 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 disclosure by conventional blending procedures.

In the preparation of lubricating oil formulations, it is common practice to incorporate additives in the form of about 10 to about 100 wt.% active ingredient concentrates in hydrocarbon oils (e.g., mineral lubricating oils or other suitable solvents).

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

Each of the foregoing additives is used in a functionally effective amount at the time of use to impart the desired properties to the lubricant. Thus, for example, if the additive is a friction modifier, a functionally effective amount of such friction modifier will be an amount sufficient to impart the desired friction modifying properties to the lubricant.

Generally, when used, the concentration of each additive in the lubricating oil composition can range from 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 range from about 0.001 wt.% to about 20 wt.%, from about 0.01 wt.% to about 10 wt.%, or from about 0.1 wt.% to about 5 wt.%, based on the total weight of the lubricating oil composition.

Oil of lubricating viscosity

An 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 blended, for example to produce the final lubricant (or lubricant composition). The base oil may be used to prepare concentrates and lubricating oil compositions therefrom, and may be selected from natural and synthetic lubricating oils and combinations thereof.

Natural oils include animal and vegetable oils, liquid petroleum oils, and hydrorefined, solvent-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.

Synthetic lubricating oils include hydrocarbon oils such as polymeric and interpolyolefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly (1-hexenes), poly (1-octenes), poly (1-decenes), alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di (2-ethylhexyl) benzenes), polyphenols (e.g., biphenyls, terphenyls, alkylated polyphenols), and alkylated diphenyl ethers and sulfides and their derivatives, analogs and homologs.

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., 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 dimer of linoleic acid, and the 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 made from C₅To 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 by using Fischer-Tropsch catalyst containing H₂And CO. Such hydrocarbons typically require further processing to be used as base oils. For example, hydrocarbons may undergo hydroisomerization; hydrocracking and hydroisomerization; dewaxing; or hydroisomerization 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 would be 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 processes similar to those used to obtain refined oils that have been put to use. Such rerefined oils are also known as reclaimed or reprocessed oils and are typically additionally processed by techniques for approving spent additives and oil breakdown products.

Thus, the base oils useful in preparing the present lubricating oil compositions may be selected from any of the base oils in groups I-V as specified in the American Petroleum Institute (API) base oil interchangeability guide (API publication 1509). Such base oil groups are summarized in table 1 below:

TABLE 1

^(a)Groups I-III are mineral oil base stocks.

^(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.

Suitable base oils for use herein are any variety corresponding to API group II, group III, group IV and group V oils and combinations thereof, preferably group III to group V oils because of their excellent volatility, stability, viscosity and cleanliness characteristics.

The oil of lubricating viscosity (also referred to as base oil) used in the lubricating oil compositions of the present disclosure is typically present in a major amount, for example, in an amount of greater than about 50 wt.%, preferably greater than about 70 wt.%, more preferably from about 80 to about 99.5 wt.%, and most preferably from about 85 to about 98 wt.%, based on the total weight of the composition. The expression "base oil" as used herein is understood to mean a base stock or blend of base stocks, which is a lubricant component produced by a single manufacturer to the same specifications (regardless of the source of the feedstock or the location of the manufacturer); the specifications of the same manufacturer are met; and is identified by a unique formula, a product identification number, or both. The base oil for use herein can be any presently known or later-discovered oil of lubricating viscosity used to formulate lubricating oil compositions 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 for use herein may optionally contain viscosity index improvers, such as 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). Generally, base oils used as engine oils, alone, will have a kinematic viscosity range of from about 2cSt to about 30cSt, preferably from about 3cSt to about 16cSt, and most preferably from about 4cSt to about 12cSt, at 100 deg.C, and will be selected or blended depending on the desired end use and additives in the finished oil to provide the desired grade of engine oil, e.g., SAE viscosity grades 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, 10W-40, 10W-50, 15W, 15W-30, 15W-40, 30, 40, etc.

Lubricating oil composition

Generally, the sulfur content in the lubricating oil composition of the present invention is less than or equal to about 0.7 wt.%, e.g., from about 0.01 wt.% to about 0.70 wt.%, from about 0.01 to about 0.6 wt.%, from about 0.01 to about 0.5 wt.%, from about 0.01 to about 0.4 wt.%, from about 0.01 to about 0.3 wt.%, from about 0.01 to about 0.2 wt.%, from about 0.01 to about 0.10 wt.% sulfur content, based on the total weight of the lubricating oil composition. In one embodiment, the sulfur content in 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 in the lubricating oil composition of the present invention is less than or equal to about 0.12 wt.%, for example from about 0.01 wt.% to about 0.12 wt.% phosphorus content, based on the total weight of the lubricating oil composition. In one embodiment, the phosphorus content in the lubricating oil composition of the present invention is less than or equal to about 0.11 wt.%, for example from about 0.01 wt.% to about 0.11 wt.%, phosphorus content based on the total weight of the lubricating oil composition. In one embodiment, the phosphorus content in the lubricating oil composition of the present invention is less than or equal to about 0.10 wt.%, for example from about 0.01 wt.% to about 0.10 wt.%, phosphorus content based on the total weight of the lubricating oil composition. In one embodiment, the phosphorus content in the lubricating oil composition of the present invention is less than or equal to about 0.09 wt.%, for example from about 0.01 wt.% to about 0.09 wt.%, phosphorus content based on the total weight of the lubricating oil composition. In one embodiment, the phosphorus content in the lubricating oil composition of the present invention is less than or equal to about 0.08 wt.%, for example from about 0.01 wt.% to about 0.08 wt.%, phosphorus content based on the total weight of the lubricating oil composition. In one embodiment, the phosphorus content in the lubricating oil composition of the present invention is less than or equal to about 0.07 wt.%, for example from about 0.01 wt.% to about 0.07 wt.%, phosphorus content based on the total weight of the lubricating oil composition. In one embodiment, the phosphorus content in the lubricating oil composition of the present invention is less than or equal to about 0.05 wt.%, for example from about 0.01 wt.% to about 0.05 wt.%, phosphorus content based on the total weight of the lubricating oil composition.

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

In certain embodiments, the present disclosure provides lubricating oil compositions suitable for reducing friction in passenger car internal combustion engines, particularly spark-ignited, direct-injection, and/or port fuel-injected engines. In certain embodiments, the engine may be coupled to a motor/battery system in a hybrid vehicle (e.g., a port fuel injection spark ignition engine coupled to the motor/battery system in the hybrid vehicle). In certain embodiments, the present disclosure provides lubricating oil compositions suitable for reducing friction in heavy duty diesel internal combustion engines.

The following examples are presented to illustrate embodiments of the invention, but are not intended to limit the invention to the specific embodiments set forth. All parts and percentages are by weight unless indicated to the contrary. 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. Specific details described in each embodiment should not be construed as essential features of the invention.

Examples

The following examples are intended 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 at 400MHz on Bruker Ultrashield Plus 400 using TopSpin 3.2 spectral processing software. NMR samples were dissolved in chloroform-d 1.

The isomerization level (I) represents the relative amount of a methyl group (-CH3) (chemical shift 0.3-1.01ppm) attached to a methylene backbone group (-CH2-) (chemical shift 1.01-1.38ppm) and is defined by equation (1) as shown below,

1 ═ m/(m + n) formula (I)

Wherein m is the NMR integral of methyl groups with chemical shifts between 0.3. + -. 0.03 to 1.01. + -. 0.03ppm and n is the NMR integral of methylene groups with chemical shifts between 1.01. + -. 0.03 to 1.38. + -. 0.10 ppm.

The level of isomerization (I) of the alpha olefin is between about 0.1 to about 0.4, preferably about 0.1 to about 0.3, more preferably about 0.12 to about 0.3.

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

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

Example A

Use of C_20-24The isomerized normal alpha olefin produces alkylated phenols and calcium alkylhydroxybenzoates in substantially the same manner as in U.S. patent No. 8,993,499. The isomerization level of the alpha olefin was about 0.16. The resulting alkylhydroxybenzoate composition had a TBN of about 225 and a Ca content of about 8 wt.% on an oil-free basis.

Comparative example B

The alkyl hydroxy benzoate is derived from_14-18Alkylphenol of the alkyl group of NAO and TBN on an oil free basis is about 300 and Ca content is about 10.6 wt.%.

Example C

Example C is a sulfurized olefin, i.e., sulfurized isobutylene.

Example D

Example D is a sulfurized fatty ester which is the reaction product of (9-octadecenoic acid (Z) -, isooctyl ester, with triolein and sulfur).

Example E

Example E is an ashless dithiocarbamate, namely methylenebis (dibutyldithiocarbamate).

Example F

Example F is a thiadiazole under the trade name Hitec 4313.

Example G

Example G is an ashless dithiophosphate sold under the trade name Irgalube TPPT.

Example H

Example H is a sulfurized phenol having a sulfur content of 15.8 wt.%.

Baseline formulation 1

A 15W-40 lubricating oil composition was prepared containing a major amount of a group II base oil of lubricating viscosity and the following additives:

(1) mixture of three dispersants

(2) A secondary zinc dialkyldithiophosphate in an amount of 0.077 wt.% phosphorus;

(3) an olefin copolymer viscosity index improver;

(4) a polymethacrylate pour point depressant; and

(5) suds suppressor

Example 1

Between 30 and 36mM of example a was added to baseline 1, providing a lubricant containing between 1200 and 1400ppm Ca. Example C was also added at 0.29 wt.%, providing a finished oil containing approximately 1300ppm of sulfur.

Example 2

Between 30 and 36mM of example a was added to baseline 1, providing a lubricant containing between 1200 and 1400ppm Ca. Example D was also added at 1.35 wt.%, providing a finished oil containing approximately 1300ppm of sulfur.

Example 3

Between 30 and 36mM of example a was added to baseline 1, providing a lubricant containing between 1200 and 1400ppm Ca. Example F was also added at 0.375 wt.%, providing a finished oil containing approximately 1300ppm of sulfur.

Example 4

Between 30 and 36mM of example a was added to baseline 1, providing a lubricant containing between 1200 and 1400ppm Ca. Example G was also added at 1.452 wt.%, providing a finished oil containing approximately 1300ppm sulfur.

Example 5

Between 30 and 36mM of example a was added to baseline 1, providing a lubricant containing between 1200 and 1400ppm Ca. Example H was also added at 0.854 wt.%, providing a finished oil containing approximately 1300ppm of sulfur.

Comparative example 1

Comparative example B was added to baseline 1 between 30 and 36mM, providing a lubricant containing between 1200 and 1400ppm Ca. Example C was also added at 0.29 wt.%, providing a finished oil containing approximately 1300ppm of sulfur.

Comparative example 2

Comparative example B was added to baseline 1 between 30 and 36mM, providing a lubricant containing between 1200 and 1400ppm Ca. Example D was also added at 1.35 wt.%, providing a finished oil containing approximately 1300ppm of sulfur.

Comparative example 3

Between 30 and 36mM of example a was added to baseline 1, providing a lubricant containing between 1200 and 1400ppm Ca. Example E was also added at 0.45 wt.%, providing a finished oil containing approximately 1300ppm of sulfur.

Comparative example 4

Comparative example B was added to baseline 1 between 30 and 36mM, providing a lubricant containing between 1200 and 1400ppm Ca. Example E was also added at 0.45 wt.%, providing a finished oil containing approximately 1300ppm of sulfur.

Example I

Example I was prepared by slurrying MgO (82 g) in MeOH (81.4 g) and xylene (500 g) was prepared and introduced into the reactor. Hydroxybenzoic acid made from isomerized alpha olefin (C20-24, 0.16 isomerization level) (1774 grams, 43% active in xylene) was then loaded into the reactor and the temperature was maintained at 40 ℃ for 15 minutes. Dodecene anhydride (DDSA, 7.6 g), then AcOH (37.3 g), then H were then added over 30 minutes₂O (69 g) was introduced into the reactor while the temperature was increased to 50 ℃. Then CO is stirred vigorously₂Was introduced into the reactor (96 g). A slurry consisting of MgO in xylene (28 g) was then introduced into the reactor, and an additional amount of CO was added₂Bubbling through the mixture. In CO₂At the end of the introduction, the distillation of the solvent was completed by heating to 132 ℃. 500 grams of base oil was then introduced into the reactor. The mixture was then centrifuged in a laboratory centrifuge to remove unreacted magnesium oxide and other solids. Finally, the mixture was heated under vacuum (15 mbar) at 170 ℃ to remove the xylene and yield as C₂₀-C₂₄Magnesium alkylhydroxybenzoate detergent (made from isomerized NAO with an isomerization level of 0.16) was a final product containing 4.3% magnesium. The properties are as follows: TBN (mgKOH/g) 199 in 35 wt% dilution oil.

Comparative example J

ComparisonExample J is C made from alpha olefins₁₄-C₁₈A magnesium alkylhydroxybenzoate detergent. The properties are as follows: TBN (mgKOH/g) ═ 236; mg (wt.%) 5.34.

Comparative example 5

Example I was added to baseline 1 between 38 and 46mM, providing a lubricant containing between 900 and 1200ppm Mg. Example E was also added at 0.45 wt.%, providing a finished oil containing approximately 1300ppm of sulfur.

Comparative example 6

Comparative example J, between 38 and 46mM, was added to baseline 1, providing a lubricant containing between 900 and 1100ppm Mg. Example E was also added at 0.45 wt.%, providing a finished oil containing approximately 1300ppm of sulfur.

Comparative example 7

Comparative example B was added to baseline 1 between 30 and 36mM, providing a lubricant containing between 1200 and 1400ppm Ca. Example F was also added at 0.375 wt.%, providing a finished oil containing approximately 1300ppm of sulfur.

Comparative example 8

Comparative example B was added to baseline 1 between 30 and 36mM, providing a lubricant containing between 1200 and 1400ppm Ca. Example G was also added at 1.452 wt.%, providing a finished oil containing approximately 1300ppm sulfur.

Comparative example 9

Comparative example B was added to baseline 1 between 30 and 36mM, providing a lubricant containing between 1200 and 1400ppm Ca. Example H was also added at 0.854 wt.%, providing a finished oil containing approximately 1300ppm of sulfur.

Example K

Use of C_20-24The isomerized normal alpha olefin produces alkylated phenols and calcium alkylhydroxybenzoates in substantially the same manner as in U.S. patent No. 8,993,499. The isomerization level of the alpha olefin was about 0.15. The resulting alkylhydroxybenzoate composition had a TBN of about 225 and a Ca content of about 8 wt.% on an oil-free basis.

Example L

Use of C_20-24The isomerized normal alpha olefin produces alkylated phenols and calcium alkylhydroxybenzoates in substantially the same manner as in U.S. patent No. 8,993,499. The isomerization level of the alpha olefin was about 0.219. The resulting alkylhydroxybenzoate composition had a TBN of about 225 and a Ca content of about 8 wt.% on an oil-free basis.

Example M

Use of C_20-24The isomerized normal alpha olefin produces alkylated phenols and calcium alkylhydroxybenzoates in substantially the same manner as in U.S. patent No. 8,993,499. The isomerization level of the alpha olefin was about 0.23. The resulting alkylhydroxybenzoate composition had a TBN of about 225 and a Ca content of about 8 wt.% on an oil-free basis.

Example 6

Example K was added to baseline 1 between 30 and 36mM, providing a lubricant containing between 1200 and 1400ppm Ca. Example C was also added at 0.29 wt.%, providing a finished oil containing approximately 1300ppm of sulfur.

Example 7

Example L was added to baseline 1 between 30 and 36mM, providing a lubricant containing between 1200 and 1400ppm Ca. Example C was also added at 0.29 wt.%, providing a finished oil containing approximately 1300ppm of sulfur.

Example 8

Example M was added to baseline 1 between 30 and 36mM, providing a lubricant containing between 1200 and 1400ppm Ca. Example C was also added at 0.29 wt.%, providing a finished oil containing approximately 1300ppm of sulfur.

Oxidation-nitration test

Oxidation-nitration bench tests demonstrate the ability of lubricating oils to resist oxidation and nitration. This test is an additional tool to help determine oil performance as they are relevant to the actual service of lubricated engines using natural gas as a fuel source. The lower the oxidation and nitration values at the end of the test, the better the product performance. The oxidation-nitration bench test was designed to simulate Caterpillar 3500 series engine conditions that correlate to the actual field performance of the Caterpillar 3516 model. Examples 1 to 8 and comparative examples 1 to 9 were subjected to oxidation-nitration tests. The lubricating oil compositions from these examples were placed in a heated glassware bath and subjected to a calibrated level of nitrous oxide gas over a specified period of time. The tests were run in duplicate for each sample and the results were the average of two runs. The samples were evaluated using differential infrared spectroscopy to determine a baseline for each sample prior to placing the sample in a heated glass bath. The samples were re-evaluated at the end of the test period. The difference between the baseline data (absorbance units at 5.8 and 6.1 microns) and the data acquired at the end of the test period provides an indication of the oxidation-nitrification resistance of the sample.

Differential infrared spectroscopy measures the amount of light absorbed by an oil sample and provides units of measurement called absorbance units. DIR (differential infrared) spectra were determined by subtracting the fresh oil spectrum from the used oil spectrum to observe changes due to oxidation, nitration, fuel dilution, soot accumulation and or contamination. 0.1 millimeter (mm) batteries are typically used; however, after determining its associated path length, an ATR crystal setup may be used. If the instrument does not have software to determine path length, the path length can be back-calculated by measuring oxidation using a calibrated 0.1mm cell. If limited to a narrow area of oxygenation and nitrification (about 1725 to 1630 cm)^-1) The difference between ATR and vertical cell measurements is small.

From about 1715. + -.5 cm^-1The peak maxima at (d) to the spectral baseline (in absorbance) measure DIR oxidation.

From about 1630 + -1 cm^-1The DIR nitration was measured from the peak maximum at to the baseline peak (in absorbance).

An oxidation level of 5.8 microns and a nitrification level of 6.1 microns were used as peak height comparisons.

The examples containing ashless sulfur compounds and isomerized NAO detergents performed better with respect to oxidation than their corresponding comparative examples containing the same ashless sulfur compounds and non-isomerized detergents. This test, which quantifies the oxidation resistance of the lubricating oil, is used to determine whether a sample is a good candidate for extending the useful life of the lubricating oil. Oxidation is undesirable for lubricating oils.

Examples 1 to 8 and comparative examples 1 to 9 were each tested by using each as a lubricant in a bench test.

The samples were analyzed for oxidation performance using differential IR as described above.

The following table shows the oxidation performance.

TABLE 2 evaluation of Oxidation Properties

Claims

1. 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 Normal Alpha Olefin (NAO) having from about 10 to 40 carbon atoms; and

(c) an ashless sulfur compound, wherein the ashless sulfur compound is not a dithiocarbamate; and is

Wherein the TBN of the alkylhydroxybenzoate compound is at least 600mg KOH/gm, on an active basis.

2. The lubricating oil composition of claim 1, wherein the TBN of the alkyl hydroxybenzoate compound is 600-800mg KOH/gm on an active matter basis.

3. The lubricating oil composition of claim 1, wherein one or more detergents are alkali or alkaline earth metal alkylhydroxybenzoate salts derived from alkyl groups having 20-28 carbon atoms.

4. The lubricating oil composition of claim 1, wherein the isomerized normal alpha olefin has an isomerization level (I) of normal alpha olefin of from about 0.1 to about 0.4.

5. The lubricating oil composition of claim 1, wherein the alkylhydroxybenzoate detergent is calcium alkylhydroxybenzoate derived from an isomerized NAO.

6. The lubricating oil composition of claim 1, wherein the ashless sulfur compound is selected from the group consisting of sulfurized fatty esters, sulfurized olefins, thiadiazoles, sulfurized olefins, ashless dithiophosphates, sulfurized phenols, and phenothiazines.

7. 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

8. The method of claim 7 wherein the TBN of the alkylhydroxybenzoate compound is 600-800mgKOH/gm based on active.

9. The method of claim 7, wherein the ashless sulfur compound is a sulfurized fatty ester, sulfurized olefin, thiadiazole, sulfurized olefin, ashless dithiophosphate, sulfurized phenol, and phenothiazine, or a combination thereof.

10. The method of claim 7, wherein one or more detergents are alkali or alkaline earth metal alkylhydroxybenzoate salts derived from an alkyl group having 20-28 carbon atoms.

11. The process of claim 7 wherein the isomerized normal alpha olefin has an isomerization level (I) of normal alpha olefin of from about 0.1 to about 0.4.

12. The method of claim 7, wherein the alkylhydroxybenzoate detergent is calcium alkylhydroxybenzoate derived from isomerized NAO.

13. The method of claim 7, wherein oxidation of the lubricating oil in an engine is reduced.