Lubricating oil composition

Abstract

A lubricating oil composition is disclosed, comprising a major amount of oil of lubricating viscosity and a salicylate compound derived from isomerized normal alpha olefins (NAO) having from about 10 to about 40 carbon atoms, the salicylate compound having a TBN of at least 600 mg KOH / g, on an active matter basis, the lubricating oil composition containing from about 0.12 to about 0.17 wt. % calcium and being substantially free of magnesium. A method for lubricating an engine with the lubricating oil composition is also provided.

Description

[Background technology]

[0001] Engine downsizing has become a major trend in the automotive industry due to the need to squeeze as much fuel economy out of the engine. However, this can cause problems in certain cases through a phenomenon called low speed pre-ignition (LSPI). In some cases, this can lead to catastrophic failure of engine hardware. Calcium, resulting from calcium detergents present in lubricants, is primarily recognized as a detrimental factor. However, calcium is utilized to provide detergency and rust prevention performance, and must be present in significant amounts (i.e., >1800 ppm Ca) to provide these benefits. Many in the industry have lowered calcium levels and replaced them with magnesium-containing detergents to compensate for the LSPI problem. Magnesium detergents generally have good TBN retention, but are poor at neutralizing acids. In addition, magnesium detergents can sometimes be difficult to handle due to crystal and gel formation. Thus, there is a need for lubricants that are substantially free of magnesium that also provide adequate corrosion control. The inventors of the present application have found such a solution to this problem. Summary of the Invention

[0002] According to one embodiment of the present disclosure, there is provided a lubricating oil composition comprising: (a) a major amount of oil of lubricating viscosity; (b) a salicylate compound derived from isomerized normal alpha olefins (NAO) having from about 10 to about 40 carbon atoms, the salicylate compound having a TBN of at least 600 mg KOH / g on an active matter basis; A lubricating oil composition is provided that contains from about 0.12 to about 0.17 weight percent calcium and is substantially free of magnesium.

[0003] Also provided is a method of lubricating an engine, comprising the steps of: (a) a major amount of oil of lubricating viscosity; (b) a salicylate compound derived from isomerized normal alpha olefins (NAO) having from about 10 to about 40 carbon atoms, the salicylate compound having a TBN of at least 600 mg KOH / g on an active matter basis; A method is provided that includes lubricating the engine with a lubricating oil composition containing from about 0.12 to about 0.17 weight percent calcium and being substantially free of magnesium. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0004] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are described in detail herein. 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.

[0005] To facilitate understanding of the subject matter disclosed herein, numerous terms, abbreviations, or other shorthand forms as used herein are defined below. Any term, abbreviation, or shorthand form not defined will be understood to have the ordinary meaning used by those of ordinary skill in the art at the time of the filing of this application. Note that the following [1] to

[14] are each one embodiment or one aspect of the present invention. [1] 1. A lubricating oil composition comprising: (a) a major amount of oil of lubricating viscosity; (b) a salicylate compound derived from isomerized normal alpha olefins (NAO) having from about 10 to about 40 carbon atoms, the alpha olefin having an isomerization level (I) of from about 0.1 to about 0.4, the salicylate compound having a TBN of at least 600 mg KOH / g on an active matter basis; the lubricating oil composition contains about 0.12 to about 0.17 weight percent calcium and is substantially free of magnesium, and has a total soap content from all detergents of less than 18 mM; The isomerization level (I) represents the relative amount of methyl groups (-CH3) (chemical shifts 0.3 to 1.01 ppm) bonded to methylene backbone groups (-CH2-) (chemical shifts 1.01 to 1.38 ppm), and is represented by the equation (I): I=m / (m+n) Equation (I) wherein m is the NMR integral for the methyl group having a chemical shift of 0.3±0.03 to 1.01±0.03 ppm, and n is the NMR integral for the methylene group having a chemical shift of 1.01±0.03 to 1.38±0.10 ppm. [2] The lubricating oil composition according to [1], further comprising a zinc dithiophosphate compound. [3] The lubricating oil composition according to [1], further comprising a molybdenum dithiocarbamate. [4] [1] The lubricating oil composition according to [1], wherein magnesium is present at less than 50 ppm. [5] The lubricating oil composition according to [1], wherein the lubricating oil composition reduces corrosion in an engine. [6] The lubricating oil composition according to [1], wherein the engine is an internal combustion engine equipped with an EGR system. [7] The lubricating oil composition according to [5], wherein the engine is a hybrid engine or a turbo GDI engine. [8] 1. A method of lubricating an engine comprising: (a) a major amount of oil of lubricating viscosity; (b) a salicylate compound derived from isomerized normal alpha olefins (NAO) having from about 10 to about 40 carbon atoms, the alpha olefin having an isomerization level (I) of from about 0.1 to about 0.4, the salicylate compound having a TBN of at least 600 mg KOH / gm on an active matter basis; the lubricating oil composition contains about 0.12 to about 0.17 weight percent calcium and is substantially free of magnesium, and has a total soap content from all detergents of less than 18 mM; The isomerization level (I) represents the relative amount of methyl groups (-CH3) (chemical shifts 0.3 to 1.01 ppm) bonded to methylene backbone groups (-CH2-) (chemical shifts 1.01 to 1.38 ppm), and is represented by the equation (I): I=m / (m+n) Equation (I) wherein m is the NMR integral for the methyl group having a chemical shift of 0.3±0.03 to 1.01±0.03 ppm, and n is the NMR integral for the methylene group having a chemical shift of 1.01±0.03 to 1.38±0.10 ppm. [9] The method according to [8], wherein the engine is a hybrid engine or a turbo GDI engine.

[10] The method according to [8], wherein the engine is an internal combustion engine equipped with an EGR system.

[11] The method of claim 8, wherein the lubricating oil composition reduces corrosion in the engine.

[12] The method of [8], wherein the lubricating oil composition further comprises a zinc dithiophosphate compound.

[13] The method of claim 8, wherein the lubricating oil composition further comprises a molybdenum dithiocarbamate.

[14] The method of claim 8, wherein magnesium is present at less than 50 ppm of the lubricating oil composition.

[0006] definition As used herein, the following terms have the following meanings, unless expressly stated to the contrary: As used herein, the following words and expressions, if and when used, have the meanings given below.

[0007] By "major amount" is meant greater than 50% by weight of the composition.

[0008] "Minor amount" means less than 50% by weight of the composition, expressed in terms of the stated additive and in terms of the total mass of all additives present in the composition, considered as the active ingredient of the additive(s).

[0009] "Substantially free" means less than 50, less than 40, less than 30, less than 10, less than 50 ppm by weight.

[0010] "Active ingredients" or "actives" or "oil-free" refers to additive materials that are not diluents or solvents.

[0011] All percentages reported are weight percent on an active ingredient basis (ie, without regard to carrier or diluent oil) unless otherwise stated.

[0012] The abbreviation "ppm" means parts per million by weight based on the total weight of the lubricating oil composition.

[0013] Total Base Number (TBN) was determined according to ASTM D2896.

[0014] Metal - The term "metal" refers to an alkali metal, an alkaline earth metal, or a mixture thereof.

[0015] High temperature high shear (HTHS) viscosity at 150° C. was determined according to ASTM D4863.

[0016] Kinematic viscosity at 100℃ (KV 100 ) was determined according to ASTM D445.

[0017] Cold Cranking Simulator (CCS) viscosity at -35°C was determined according to ASTM D5293.

[0018] Olefins - The term "olefins" refers to a class of unsaturated aliphatic hydrocarbons with one or more carbon-carbon double bonds, obtained by a number of processes. Those containing one double bond are called mono-alkenes, those with two double bonds are called dienes, alkyldienes or diolefins. Alpha olefins are particularly reactive because the double bond is between the first and second carbons. Examples are 1-octene and 1-octadecene, which are used as starting points for meso-biodegradable surfactants. Linear and branched chain olefins are also included in the definition of olefins.

[0019] Normal Alpha Olefin - The term "normal alpha olefin" refers to an olefin that is a straight-chain, unbranched hydrocarbon with carbon-carbon double bonds present at the beginning and end of the chain.

[0020] Isomerized normal alpha olefins. As used herein, the term "isomerized normal alpha olefins" refers to alpha olefins that have been subjected to isomerization conditions that result in a change in the distribution of olefin species present and / or the introduction of branching along the alkyl chain. The isomerized olefin products can 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.

[0021] All ASTM standards referred to herein are the most current versions as of the filing date of this application.

[0022] In one aspect, the present disclosure provides a lubricating oil composition comprising: (a) a major amount of oil of lubricating viscosity; (b) a salicylate compound derived from isomerized normal alpha olefins (NAO) having from about 10 to about 40 carbon atoms, the salicylate compound having a TBN of at least 600 mg KOH / g on an active matter basis; The present invention relates to a lubricating oil composition containing about 0.12 to about 0.17 weight percent calcium and being substantially free of magnesium.

[0023] Oil of lubricating viscosity An oil of lubricating viscosity (sometimes referred to as a "base stock" or "base oil") is the primary liquid constituent of a lubricant into which additives and possibly other oils are blended, for example, to produce the final lubricant (or lubricant composition). Base oils are useful for making concentrates and for making lubricant compositions therefrom, and may be selected from natural and synthetic lubricating oils and combinations thereof.

[0024] Natural oils include animal and vegetable oils, liquid petroleum oils, and hydrorefined and 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.

[0025] Synthetic lubricating oils include hydrocarbon oils such as polymerized and copolymerized olefins (e.g., polybutylene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylene, poly(1-hexene), poly(1-octene), poly(1-decene)), 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 their derivatives, analogs and congeners.

[0026] Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., malonic acid, alkyl malonic acids, alkenyl malonic acids, succinic acid, alkyl and alkenyl succinic acids, maleic acid, fumaric acid, azelaic acid, suberic acid, sebacic acid, adipic acid, linoleic acid dimer, phthalic acid) with various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.

[0027] Esters useful as synthetic oils include C5-C 12 Also included are those made from monocarboxylic acids and polyols, as well as polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol.

[0028] Base oils may be derived from Fischer-Tropsch synthesized hydrocarbons. Fischer-Tropsch synthesized hydrocarbons are made from synthesis gas containing H2 and CO using a Fischer-Tropsch catalyst. Such hydrocarbons typically require further processing in order to be useful as base oils. For example, the hydrocarbons may be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed using processes known to those skilled in the art.

[0029] Unrefined, refined and re-refined oils can be used in the lubricating oil composition of the present invention. Unrefined oils are those obtained directly from natural or synthetic sources without further purification treatment. For example, shale oil obtained directly from retort operation, petroleum oil obtained directly from distillation, or ester oil obtained directly from esterification process and used without further treatment are unrefined oils. Refined oils are similar to unrefined oils, except that they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques are known to those skilled in the art, such as distillation, solvent extraction, acid or base extraction, filtration and percolation.

[0030] Re-refined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils already in practical use. Such re-refined oils are also known as reclaimed or reprocessed oils and are often further processed by techniques for the approval of used additives and oil breakdown products.

[0031] Thus, the base oils that may be used to make the lubricating oil compositions of the present invention may be selected from any of the base oils of Groups I through V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines, API Publication 1509. Such base oil groups are summarized in Table 1 below. [Table 1]

[0032] Suitable base oils for use herein are any of the various oils corresponding to API Group II, Group III, Group IV and Group V oils, and combinations thereof, preferably Group III through Group V oils, due to their exceptional volatility, stability, viscosity and detergency characteristics.

[0033] The oil of lubricating viscosity for use in the lubricating oil composition of the present disclosure, also referred to as base oil, is typically present in a major amount, for example, greater than 50 wt%, preferably greater than about 70 wt%, more preferably about 80 to about 99.5 wt%, and most preferably about 85 to about 98 wt%, based on the total weight of the composition. As used herein, the expression "base oil" shall be understood to mean a base stock or blend of base stocks that is a lubricant component produced by a single manufacturer to the same specifications (regardless of source or location of manufacturer), meets the same manufacturer's specifications, and is identified by a unique formula, product identification number, or both. The base oil for use herein may be any now known or later discovered oil of lubricating viscosity used in formulating lubricating oil compositions for any and all such applications, such as engine oils, marine cylinder oils, functional fluids (hydraulic fluids, gear oils, transmission fluids, etc.). In addition, the base oils for use herein may optionally contain viscosity index improvers, such as polymeric alkyl methacrylates; olefin-based copolymers, such as ethylene-propylene or styrene-butadiene copolymers; and mixtures thereof.

[0034] As one skilled in the art will readily appreciate, the viscosity of the base oil will depend on the application. Thus, the viscosity of the base oil for use herein will typically range from about 2 to about 2000 centistokes (cSt) at 100 degrees Celsius (C.). Generally, base oils used as engine oils will have a kinematic viscosity range of about 2 cSt to about 30 cSt at 100 degrees C., preferably about 3 cSt to about 16 cSt, and most preferably about 4 cSt to about 12 cSt, respectively, and may be used in a variety of applications, including engine oil grades such as 0W, 0W-8, 0W-12, 0W-16, 0W-20, 0W-26, 0W-30, 0W-40, 0W-50, 0W-60, 0W-80, 0W-90, 0W-100, 0W-110, 0W-120, 0W-130, 0W-140, 0W-150, 0W-160, 0W-170, 0W-180, 0W-190, 0W-200, 0W-210, 0W-220, 0W-230, 0W-240, 0W-250, 0W-260, 0W-270, 0W-280, 0W-290, 0W-310, 0W-320, 0W-330, 0W-340, 0W-350, 0W-360, 0W-370, 0W-380, 0W-390, 0W-400, 0W-410, 0W-420, 0W-430, 0W-440, 0 The lubricating oil compositions may be selected or blended to provide lubricating oil compositions having an SAE viscosity grade of 0, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-30, 10W-40, 10W-50, 15W, 15W-20, 15W-30, 15W-40, 30, 40, etc., depending on the desired end use and additives in the finished oil.

[0035] Salicylate detergent compounds derived from C10-C40 isomerized normal alpha olefins (NAO) In one aspect of the present disclosure, C 10 ~C 40 The salicylate detergent compounds derived from isomerized NAO have a TBN of at least 600, greater than 600, 600-800, 600-750, 600-700 mg KOH / g on an active matter basis.

[0036] In one embodiment of the present disclosure, a C having a TBN of 600 mg KOH / gram or more on an oil-free basis is 10 ~C 40 Salicylate detergents derived from isomerized NAO can be prepared as described in U.S. Pat. No. 8,993,499, which is incorporated herein in its entirety.

[0037] In one aspect of the present disclosure, C 10 ~C 40 The salicylate detergent derived from isomerized NAO is a Ca salicylate detergent.

[0038] In one aspect of the present disclosure, C 10 ~C 40 The salicylate detergent derived from isomerized NAO can be an alkylated hydroxybenzoate detergent. In one embodiment, the detergent can be a salicylate detergent. In another embodiment, the detergent can be a carboxylate detergent. In one aspect of the disclosure, the salicylate detergent having a TBN of 600 mg KOH / g or greater on an oil-free basis is made from an alkylphenol having an alkyl group derived from an isomerized alpha-olefin having from about 14 to about 28, or from about 20 to about 24 carbon atoms per molecule.

[0039] In one embodiment of the present disclosure, a C having a TBN of 600 mg KOH / g or more on an active substance basis. 10 ~C 40 Salicylate detergents derived from isomerized NAO are C 10 ~C 40one or more alkylphenols having an alkyl group derived from isomerized NAO, and C 10 ~C 40 It is made from one or more alkylphenols having alkyl groups different from the isomerized NAO. Preferably, 10 ~C 40 The one or more alkylphenols having an alkyl group different from the isomerized NAO have highly branched alkyl groups of at least 9, 9 to 24, and 10 to 15 carbon atoms. In one embodiment of the present disclosure, the lubricating oil composition comprises a C 2 phenol having a TBN of 600 mg KOH / g or greater on an active matter basis. 10 ~C 40 The salicylate detergent derived from isomerized NAO contains about 0.03 to 0.17% by weight, 0.04 to 0.17% by weight, 0.05 to 0.17% by weight, 0.06 to 0.17% by weight, preferably 0.07 to 0.1% by weight, preferably 0.08 to 0.16% by weight, preferably 0.09 to 0.16% by weight, preferably 0.10 to 0.16% by weight, preferably 0.11 to 0.16% by weight, preferably 0.12 to 0.16% by weight, preferably 0.13 to 0.15% by weight, preferably 0.12 to 0.15% by weight, preferably 0.06 to 0.14, 0.07 to 0.14, 0.07 to 0.12, or 0.08 to 0.14% by weight, in terms of Ca content.

[0040] In one embodiment of the present disclosure, the total amount of calcium in the lubricating oil composition is 0.12 to 0.17 wt%, 0.13 to 0.17 wt%, 0.14 to 0.17 wt%, 0.12 to 0.16 wt%, 0.12 to 0.15 wt%, 0.12 to 0.14 wt%, 0.13 to 0.15 wt%, 0.13 to 0.14 wt%, 0.14 to 0.16 wt%, or 0.14 to 0.15 wt%.

[0041] In one embodiment of the present disclosure, a C having a TBN of 600 or more on an active substance basis is provided. 10 ~C 40 The lubricating oil composition comprising the salicylates derived from isomerized NAO is an automobile engine oil, a gas engine oil, a motorcycle oil, a dual fuel engine oil, a mobile gas engine oil or a locomotive engine oil.

[0042] In another embodiment of the present disclosure, the lubricating oil composition is for use in internal combustion engines equipped with EGR control systems, naturally aspirated engines, hybrid engine oils, supercharged gasoline direct injection (GDI) engine oils.

[0043] In internal combustion engines equipped with EGR control systems, the EGR gases are highly corrosive.

[0044] In the situation where the engine oil temperature is low, water accumulates in the oil and contacts the highly corrosive EGR gas, which causes corrosion of the engine parts. In one aspect of the present disclosure, the lubricating oil composition inhibits or reduces corrosion in an internal combustion engine equipped with an EGR control system. In another aspect of the present disclosure, the lubricating oil composition inhibits or reduces corrosion in an internal combustion engine equipped with an EGR control system, where low engine oil temperatures lead to the accumulation of water that contacts the highly corrosive EGR gas, which causes corrosion of the engine parts. In particular, in the case of a hybrid vehicle, the vehicle can be driven by the driving force from the motor with the internal combustion engine being turned off. It is difficult to warm up the engine in a short time when EV driving is frequently used, and water with dissolved EGR gas is likely to collect and accumulate. The metal-containing detergent in the lubricating oil composition of the present invention is generally available in the form of an oil-based dispersion containing a metal salt of an organic acid (generally referred to as a "soap component") and particles of a basic inorganic salt (e.g., calcium carbonate particles) that collect around the metal salt of an organic acid in the base oil. The soap content is based on 1 Kg of oil.

[0045] 1) Measurement of organic acid metal salt content (soap content): The mineral oil portion and low molecular weight compounds in the metal-containing detergent are removed by a conventional rubber membrane dialysis method. The residue (A) remaining in the membrane is weighed. Separately, the content of carbon dioxide derived from carbonate in the metal-containing detergent is measured, and a quantitative analysis of the metal elements is carried out. From the carbon dioxide content and metal content, the amount (B) of the overbase component such as calcium carbonate or magnesium carbonate is calculated. The soap content (i.e., the organic acid metal salt content) is calculated by estimating (B) from (A). In one embodiment, the lubricating oil composition has a total soap content of less than 18 mM. In one embodiment, the lubricating oil composition has a total soap content of from 2 mM to 18 mM. In another embodiment, the lubricating oil composition has a total soap content of from 2 mM to 17 mM, from 2 mM to 16 mM, or from 3 mM to 16 mM.

[0046] Additional cleaning agents Additional calcium detergents may be present so that the total calcium in the finished oil does not exceed 0.17% by weight.

[0047] The lubricating oil composition of the present invention may further contain one or more overbased detergents having a TBN of 10-800, 10-700, 30-690, 30-600, 50-600, 100-600, 150-600, 50-500, 150-500, 50-450, 200-450 mg KOH / g on an active matter basis.

[0048] Detergents that may be used include oil-soluble overbased sulfonates, non-sulfur containing phenates, sulfurized phenates, salixarates, salicylates, saligenins, complex detergents and naphthenate detergents, as well as other oil-soluble salicylates of metals, particularly 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 used in lubricants, as well as mixtures of calcium and / or magnesium with sodium.

[0049] Overbased metal detergents are generally produced by carbonating a mixture of a hydrocarbon, a detergent acid such as sulfonic acid, salicylate, etc., a metal oxide or hydroxide (e.g., calcium oxide or hydroxide), and promoters such as xylene, methanol, and water. For example, to prepare overbased calcium sulfonate, in carbonation, calcium oxide or hydroxide reacts with gaseous carbon dioxide to form calcium carbonate. The sulfonic acid is neutralized with excess CaO or Ca(OH)2 to form a sulfonate.

[0050] The overbased detergent may be an overbased salt with low overbasing, e.g., a TBN below 100, on an actives basis. In one embodiment, the TBN of the low overbased salt may be from about 30 to about 100. In another embodiment, the TBN of the low overbased salt may be from about 30 to about 80. The overbased detergent may be an overbased salt with medium overbasing, e.g., a TBN of from 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. The overbased detergent may be an overbased salt with high overbasing, e.g., a TBN above 250. In one embodiment, the TBN of the high overbased salt may be from about 250 to about 800, on an actives basis.

[0051] In one embodiment, the detergent may be one or more alkali or alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids. Suitable hydroxyaromatic compounds include mononuclear monohydroxy and polyhydroxyaromatic hydrocarbons having 1 to 4 and preferably 1 to 3 hydroxyl groups. Suitable hydroxyaromatic compounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, and the like. A preferred hydroxyaromatic compound is phenol.

[0052] 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 linear, isomerized linear, branched or partially branched linear. 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 or a mixture of any of the foregoing.

[0053] In one embodiment, the mixture of linear olefins that may 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, the normal alpha olefins are isomerized using at least one of a solid catalyst or a liquid catalyst.

[0054] In one embodiment, at least about 50 mol%, at least about 75 mol%, at least about 80 mol%, at least about 85 mol%, at least about 90 mol%, at least about 95 mol% of the alkyl groups contained in the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid, such as the alkyl groups of the alkaline earth metal salt of an alkyl-substituted hydroxybenzoic acid detergent, are selected from the group consisting of C 20 In another embodiment, the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is 20 ~About C 28 The alkyl substituted hydroxybenzoic acid is an alkali or alkaline earth metal salt derived from an alkyl substituted hydroxybenzoic acid that is a normal alpha olefin. In another embodiment, the alkyl group is derived from at least two alkylated phenols. The alkyl group on at least one of the at least two alkyl phenols is derived from an isomerized alpha olefin. The alkyl group on the second alkyl phenol can be derived from a branched or partially branched olefin, a highly isomerized olefin, or a mixture thereof.

[0055] 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 20 to 24 NAO isomerization.

[0056] Sulfonates can typically be prepared from sulfonic acids 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, diphenyl, or their halogen derivatives. The alkylation can be carried out in the presence of a catalyst with an alkylating agent having from about 3 to more than 70 carbon atoms. Alkaryl sulfonates usually 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 about 30 carbon atoms, and more preferably from 20 to 24 carbon atoms per alkyl-substituted aromatic moiety.

[0057] The metal salts of phenols and sulfurized phenols that are sulfurized phenate detergents are prepared by reaction with appropriate metal compounds such as oxides or hydroxides, and neutral or overbased products can be obtained by methods well known in the art. Sulfurized phenols can be prepared by reacting phenols with sulfur or sulfur-containing compounds such as hydrogen sulfide, sulfur monohalides or sulfur dihalides to form products that are generally mixtures of compounds in which two or more phenols are crosslinked by sulfur-containing bridges.

[0058] Additional details regarding the general preparation of sulfurized phenates can be found, for example, in 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.

[0059] Considering now in detail the reactants and reagents used in the process of the present invention, for the first time, all allotropic forms of sulfur can be used. The sulfur can be employed either as molten sulfur, or as a solid (e.g., powder or particulate), or as a solid suspension in a compatible hydrocarbon liquid.

[0060] For example, it is desirable to use calcium hydroxide as the calcium base because it is easier to handle and gives superior results compared to calcium oxide. Other calcium bases, such as calcium alkoxides, can also be used.

[0061] Suitable alkylphenols that may be used are those in which the alkyl substituent contains a sufficient number of carbon atoms to render the resulting overbased sulfurized calcium alkylphenate composition oil soluble. Oil solubility may be provided by a single long chain alkyl substitution or by a combination of alkyl substituents. Typically, the alkylphenol used is a mixture of different alkylphenols, e.g., C 20 ~C 24 It is a mixture of alkylphenols.

[0062] In one embodiment, suitable alkylphenolic compounds are derived from isomerized alpha olefinic alkyl groups having from about 10 to about 40 carbon atoms per molecule with an alpha olefin isomerization level (I) of from about 0.1 to about 0.4. In one embodiment, suitable alkylphenolic compounds are derived from alkyl groups that are branched olefinic propylene oligomers or mixtures thereof having from about 9 to about 80 carbon atoms. In one embodiment, the branched olefinic propylene oligomers or mixtures thereof have from about 9 to about 40 carbon atoms. In one embodiment, the branched olefinic propylene oligomers or mixtures thereof have from about 9 to about 18 carbon atoms. In one embodiment, the branched olefinic propylene oligomers or mixtures thereof have from about 9 to about 12 carbon atoms.

[0063] In one embodiment, suitable alkylphenolic compounds include distilled cashew nut shell liquid (CNSL) or hydrogenated distilled cashew nut shell liquid. Distilled CNSL is a mixture of biodegradable meta-hydrocarbyl-substituted phenols in which the hydrocarbyl groups are linear and unsaturated, including cardanol. Catalytic hydrogenation of distilled CNSL produces a mixture of meta-hydrocarbyl-substituted phenols that are primarily enriched in 3-pentadecylphenol.

[0064] The alkylphenol may be para-alkylphenol, meta-alkylphenol or ortho-alkylphenol. When an overbased product is desired, the alkylphenol is preferably predominantly para-alkylphenol with no more than about 45 mole percent of the alkylphenol being ortho-alkylphenol, and more preferably no more than about 35 mole percent of the alkylphenol being ortho-alkylphenol, since it is believed that para-alkylphenol facilitates the preparation of highly overbased calcium sulfurized alkylphenates. Alkyl-hydroxytoluenes or xylenes and 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 distilled cashew nut shell liquid, catalytic hydrogenation of the distilled CNSL produces a mixture of meta-hydrocarbyl substituted phenols.

[0065] In one embodiment, the one or more overbased detergents may be a complex or hybrid detergent known in the art as comprising a surfactant system derived from at least two of the surfactants described above.

[0066] In one embodiment, the one or more overbased detergents may be salicylates having an alkyl group having from 20 to 28 carbon atoms, more preferably from 20 to 24 carbon atoms. 14~18 It may be a salicylate having an alkyl group derived from NAO, which contributes less than 0.05 wt %, preferably less than 0.025 wt %, and more preferably less than 0.01 wt %, calculated as the Ca content of the lubricating oil.

[0067] Generally, the amount of detergent can be from about 0.001% to about 50% by weight, or from about 0.05% to about 25% by weight, or from about 0.1% to about 20% by weight, or from about 0.01 to 15% by weight, based on the total weight of the lubricating oil composition.

[0068] Anti-wear Agent The lubricating oil compositions disclosed herein may contain one or more antiwear agents. Antiwear agents reduce wear of metal parts. Suitable antiwear agents include those represented by the formula (Formula 1): Zn[SP(=S)(OR 1 )(OR 2 )]2 formula 1 [In the formula, R 1 and R 2 and dihydrocarbyl dithiophosphate metal salts such as zinc dihydrocarbyl dithiophosphate (ZDDP) in which R has 1 to 18 (e.g., 2 to 12) carbon atoms and can be the same with different hydrocarbyl radicals, including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl, and alicyclic radicals. 1 and R 2 Particularly preferred as groups are alkyl groups having 2 to 8 carbon atoms (e.g., the alkyl radical can 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 ) is at least 5. Thus, the zinc dihydrocarbyl dithiophosphate may include a zinc dialkyl dithiophosphate. The zinc dialkyl dithiophosphate may be primary, secondary zinc dialkyl dithiophosphate, or a combination thereof. The ZDDP may be present at 3 wt % or less (e.g., 0.1-1.5 wt % or 0.5-1.0 wt %) of the lubricating oil composition. In one embodiment, the lubricating oil composition containing the magnesium salicylate detergent 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.

[0069] Antioxidants The lubricating oil composition disclosed herein may contain 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 metal surfaces, and by viscosity growth. Suitable antioxidants include hindered phenols, aromatic amines, and sulfurized alkylphenols, as well as their alkali and alkaline earth metal salts.

[0070] Hindered phenol antioxidants often contain secondary butyl and / or tertiary butyl groups as steric hindrance groups.Phenol group can be further substituted with hydrocarbyl group (typically linear or branched alkyl) and / or bridging group that connects with 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-di-alkyl-phenolic propionic acid ester derivatives such as IRGANOX® L-135 from Ciba, and bis-phenolic antioxidants such as 4,4'-bis(2,6-di-tert-butylphenol) and 4,4'-methylenebis(2,6-di-tert-butylphenol).Other useful hindered phenol antioxidants include hindered phenols with sulfur antioxidants such as thio-ethylene-bis-('3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (IRGANOX® L-115 from Ciba). Typical aromatic amine antioxidants have at least two aromatic groups attached directly to one amine nitrogen. Typical aromatic amine antioxidants have alkyl substituents of at least six carbon atoms. Specific examples of aromatic amine antioxidants useful herein include 4,4'-dioctyldiphenylamine, 4,4'-dinonyldiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octyphenyl)-1-naphthylamine, and N-(4-octylphenyl)-1-naphthylamine. The antioxidant may be present at 0.01 to 5 weight percent (e.g., 0.1 to 2 weight percent) of the lubricating oil composition.

[0071] Dispersants The lubricating oil composition disclosed herein may contain one or more dispersants. Dispersants maintain in suspension materials that are insoluble in oil and result from 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 that are known to be effective in reducing deposit formation when used in gasoline and diesel engines.

[0072] Suitable dispersants include hydrocarbyl succinimides, hydrocarbyl succinamides, mixed esters / amides of hydrocarbyl-substituted succinic acids, hydroxyesters of hydrocarbyl-substituted succinic acids, and Mannich condensation products of hydrocarbyl-substituted phenols, formaldehyde, and polyamines. Also suitable are condensation products of polyamines with hydrocarbyl-substituted phenyl acids. Mixtures of these dispersants can 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 alkenyl succinamides, where the alkenyl substituent is preferably a long chain of more than 40 carbon atoms. These materials are easily made by reacting hydrocarbyl-substituted dicarboxylic acid materials with molecules containing amine functionality. Examples of suitable amines are polyamines, such as polyalkylene polyamines, hydroxy-substituted polyamines, and polyoxyalkylene polyamines.

[0073] Particularly preferred ashless dispersants are those comprising polyisobutenyl succinic anhydride and a compound of formula 2: NH2(CH2CH2NH) z H formula 2 and polyisobutenyl succinimides formed from polyalkylene polyamines such as polyethylene polyamines of the formula: where z is 1 to 11. The polyisobutenyl group is derived from polyisobutene and preferably has a number average molecular weight (M) in the range of 700 to 3000 Daltons (e.g., 900 to 2500 Daltons). n For example, polyisobutenyl succinimide has an M of 900 to 2500 daltons. n The dispersant may be a bis-succinimide derived from a polyisobutenyl group having the formula: As is known in the art, the dispersant may be post-treated (e.g., with a boronating agent or a cyclic carbonate, ethylene carbonate, etc.).

[0074] Nitrogen-containing ashless (metal-free) dispersants are basic and contribute to the TBN of the lubricating oil composition to which they are added without introducing additional sulfated ash. Dispersants may be present at 0.1 to 10 wt % (e.g., 2 to 5 wt %) of the lubricating oil composition.

[0075] Foam suppressor The lubricating oil compositions disclosed herein may include one or more foam suppressors that may destroy foam in the oil. Non-limiting examples of suitable foam suppressors or antifoam inhibitors include silicone oils or polydimethylsiloxanes, fluorosilicones, alkoxylated aliphatic acids, polyethers (e.g., polyethylene glycols), branched polyvinyl ethers, alkyl acrylate polymers, alkyl methacrylate polymers, polyalkoxyamines, and combinations thereof.

[0076] Additional co-additives The lubricating oil compositions of the present disclosure may also contain other conventional additives that can impart or improve any desirable properties of the lubricating oil composition in which these additives are dispersed or dissolved. Any additive known to those skilled 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", 2nd Edition, London, Springer, (1996), and Leslie R. Rudnick, "Lubricant Additives: Chemistry and Applications", New York, Marcel Dekker (2003), both of which are incorporated herein by reference. For example, the lubricating oil compositions may be blended with antioxidants, antiwear agents, detergents such as metal detergents, rust inhibitors, anti-tarnish agents, demulsifiers, metal deactivators, friction modifiers, pour point depressants, antifoam agents, co-solvents, corrosion inhibitors, ashless dispersants, multifunctional agents, dyes, extreme pressure agents, and the like, and mixtures thereof. A variety of additives are known and commercially available. These additives, or similar compounds thereof, can be employed for preparing the lubricating oil compositions of this disclosure by conventional blending procedures.

[0077] In preparing lubricating oil formulations, it is common practice to incorporate the additives in a hydrocarbon oil, such as a mineral lubricating oil or other suitable solvent, in the form of a 10 to 100% by weight concentrate of the active ingredient.

[0078] Typically, these concentrates may be diluted with 3 to 100, say 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, of course, is to make the various materials easier and more convenient to handle and to facilitate dissolution or dispersion in the final blend.

[0079] Each of the foregoing additives, when used, is used in a functionally effective amount to impart a desired characteristic to the lubricant. Thus, for example, if an additive is a friction modifier, a functionally effective amount of the friction modifier would be an amount sufficient to impart the desired friction modifying characteristic to the lubricant.

[0080] Generally, the concentration of each of the additives in the lubricating oil composition, when used, may range from about 0.001% to about 20% by weight, about 0.01% to about 15% by weight, or about 0.1% to about 10% by weight, about 0.005% to about 5% by weight, or about 0.1% to about 2.5% by weight, based on the total weight of the lubricating oil composition. Additionally, the total amount of additives in the lubricating oil composition may range from about 0.001% to about 20% by weight, about 0.01% to about 10% by weight, or about 0.1% to about 5% by weight, based on the total weight of the lubricating oil composition.

[0081] The following examples are presented to illustrate embodiments of the present invention, but are not intended to limit the present invention to the specific embodiments specified. Unless otherwise stated, 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 present invention. The specific details described in each example should not be construed as essential features of the present invention. EXAMPLES

[0082] The following examples are intended for illustrative purposes only and are not intended to limit the scope of the disclosure in any way.

[0083] Isomerization Level (I) and NMR Method The isomerization level of olefins (I) was determined by hydrogen-1 (1H) NMR. NMR spectra were obtained on a Bruker Ultrashield Plus 400 in chloroform-d1 at 400 MHz using TopSpin3.2 spectrum processing software.

[0084] The isomerization level (I) represents the relative amount of methyl groups (-CH3) (chemical shifts 0.30-1.01 ppm) attached to the methylene backbone group (-CH2-) (chemical shifts 1.01-1.38 ppm) and is represented by the following equation (I): I=m / (m+n) Equation (I) [wherein m is the NMR integral for the methyl group with a chemical shift of 0.3±0.03 to 1.01±0.03 ppm, and n is the NMR integral for the methylene group with a chemical shift of 1.01±0.03 to 1.38±0.10 ppm].

[0085] The isomerization level (I) of the alpha olefin is about 0.1 to about 0.4, preferably about 0.1 to about 0.3, and more preferably about 0.12 to about 0.3.

[0086] In one embodiment, the NAO has an isomerization level of about 0.16 and has from about 20 to about 24 carbon atoms.

[0087] In another embodiment, the NAO has an isomerization level of about 0.26 and has from about 20 to about 24 carbon atoms.

[0088] Baseline Formulation 1 A 0W-16 lubricating oil composition was prepared containing a major amount of a base oil of lubricating viscosity and the following additives: (1) Ethylene carbonate post-treated bis-succinimide, (2) borated bis-succinimide, (3) A mixture of a primary zinc dialkyldithiophosphate and a secondary zinc dialkyldithiophosphate having 0.077% by weight phosphorus, the molar ratio of primary to secondary being 9:1; (4) diphenylamine antioxidants, (5) PMA comb polymer, (6) MoDTC compound in 0.085 wt.% molybdenum; (7) Foam suppressors, and (8) The remaining Group III base oils were included.

[0089] Cleaning agent 1 Alkylated phenols and Ca salicylates, C 20~24 The salicylate composition was prepared in substantially the same manner as in U.S. Patent No. 8,993,499, using isomerized normal alpha olefins. The isomerization level of the alpha olefins is about 0.16. The resulting salicylate composition has a TBN of about 630 and a Ca content of about 22.4 wt.% on an oil-free basis.

[0090] Cleaning agent 2 An overbased calcium sulfonate having an alkyl group derived from C20-24 NAO, with a TBN of 690 and a Ca content of about 26% by weight, on an active matter basis.

[0091] Cleaning agent 3 Salicylate, C 14~18 It was prepared with an alkyl group derived from NAO, and a TBN of about 300 and a Ca content of about 10.6 wt% on an oil-free basis.

[0092] Cleaning agent 4 Alkylated phenols and alkylated Ca salicylates were prepared using C 20~24Prepared in substantially the same manner as in U.S. Patent No. 8,993,499 using isomerized normal alpha olefins. The isomerization level of the alpha olefins is about 0.16. The resulting alkylated salicylate composition has a TBN of about 225 mg KOH / gm and a Ca content of 8 wt. % on an oil-free basis.

[0093] Cleaning agent 5 Alkylated phenols and alkylated Ca salicylates were prepared using C 20~24 Prepared in substantially the same manner as in U.S. Patent No. 8,993,499 using isomerized normal alpha olefins. The isomerization level of the alpha olefins is about 0.16. The resulting alkylated salicylate composition has a TBN of about 120 mg KOH / gm and a Ca content of 4.2 wt. % on an oil-free basis.

[0094] Cleaning agent 6 Salicylate, C 14~18 It was prepared with an alkyl group derived from NAO, and a TBN of about 520 and a Ca content of about 18.7 wt.% on an oil-free basis.

[0095] Example 1 Detergent 1 (35 mM) was added at 0.14 wt % Ca content to baseline formulation 1. The total soap from the detergent mixture is shown in Table 2 below.

[0096] Example 2 To the baseline formulation 1 was added a mixture of detergent 1 (15.0 mM), detergent 4 (10.0 mM) and detergent 5 (10.0 mM) in an approximate 1.5:1:1 mixture based on mM of detergents, with 0.14 wt% Ca content. The total soap from the detergent mixture is shown in Table 2 below.

[0097] Example 3 To the baseline formulation 1 was added a mixture of Detergent 1 (23.0 mM), Detergent 4 (6.0 mM) and Detergent 5 (6.0 mM) in an approximate 3.83:1:1 mixture based on mM of detergents, with 0.14 wt % Ca content. The total soap from the detergent mixture is shown in Table 2 below.

[0098] Example 4 To the baseline formulation 1 was added a mixture of Detergent 1 (19.8 mM), Detergent 4 (5.10 mM) and Detergent 5 (5.10 mM) in an approximate 3.88:1:1 mixture based on mM of detergents, with 0.12 wt % Ca content. The total soap from the detergent mixture is shown in Table 3 below.

[0099] Example 5 To the baseline formulation 1 was added a mixture of Detergent 1 (12.9 mM), Detergent 4 (8.55 mM) and Detergent 5 (8.55 mM) in an approximate 1.5:1:1 mix based on mM of detergents, with 0.12 wt % Ca content. The total soap from the detergent mixture is shown in Table 3 below.

[0100] Example 6 To the baseline formulation 1 was added a mixture of detergent 1 (4.2 mM), detergent 4 (12.9 mM) and detergent 5 (12.9 mM) in an approximate 0.33:1:1 mixture based on mM of detergents, with 0.12 wt % Ca content. The total soap from the detergent mixture is shown in Table 3 below.

[0101] Example 7 Detergent 1 (40 mM) was added at 0.16 wt % Ca content to baseline formulation 1. The total soap from the detergent mixture is shown in Table 4 below.

[0102] Comparative example A Detergent 2 (35 mM) was added at 0.14 wt % Ca content to baseline formulation 1. The total soap from the detergent mixture is shown in Table 2 below.

[0103] Comparative example B Detergent 3 (35 mM) was added at 0.14 wt % Ca content to baseline formulation 1. The total soap from the detergent mixture is shown in Table 2 below.

[0104] Comparative example C To the baseline formulation 1 was added a mixture of Detergent 1 (5 mM), Detergent 4 (15 mM), and Detergent 5 (15 mM) in a 0.33:1:1 mix based on mM of detergents, with 0.14 wt % Ca content. The total soap from the detergent mixture is shown in Table 2 below.

[0105] Comparative example D Detergent 6 (35 mM) was added at 0.14 wt % Ca content to baseline formulation 1. The total soap from the detergent mixture is shown in Table 2 below.

[0106] Ball Rust Test (BRT)-ASTM D6557 The ball rust test referred to herein is performed using the method of ASTM-D-6557. The ball rust test (BRT) is a procedure for evaluating the corrosion resistance capabilities of fluid lubricants. According to ASTM D6557, ball bearings are immersed in oil. Air saturated with acidic contaminants is bubbled through the oil for 18 hours at 49°C. After the 18-hour reaction period, the balls are removed from the test oil and the amount of corrosion on the balls is quantified using light reflectance techniques. The amount of reflected light is reported as average gray value (AGV). The AGV for a new, uncorroded ball is approximately 140. A completely corroded ball has an AGV result of less than 20. A lubricant composition that exhibits an AGV of at least 100 passes the BRT. A lubricant composition that exhibits an AGV of less than 100 fails the BRT. [Table 2] [Table 3] [Table 4]

Claims

1. 1. A lubricating oil composition comprising: (a) a major amount of oil of lubricating viscosity; (b) a calcium salicylate compound derived from isomerized normal alpha olefins (NAO) having from 10 to 40 carbon atoms, the alpha olefins having an isomerization level (I) of from 0.1 to 0.4, the calcium salicylate compound having a TBN of at least 600 mg KOH / g, on an active matter basis; the lubricating oil composition contains 0.12 to 0.17 wt. % calcium and is substantially free of magnesium, and has a total soap content from all detergents of less than 18 mM; The isomerization level (I) represents the relative amount of methyl groups (-CH3) (chemical shift 0.3-1.01 ppm) attached to the methylene backbone group (-CH2-) (chemical shift 1.01-1.38 ppm), and is represented by the equation (I): I=m / (m+n) Equation (I) wherein m is the NMR integral for the methyl groups having a chemical shift from 0.3±0.03 to 1.01±0.03 ppm, and n is the NMR integral for the methylene groups having a chemical shift from 1.01±0.03 to 1.38±0.10 ppm.

2. 10. The lubricating oil composition of claim 1, further comprising a zinc dithiophosphate compound.

3. 10. The lubricating oil composition of claim 1, further comprising a molybdenum dithiocarbamate.

4. 10. The lubricating oil composition of claim 1, wherein the lubricating oil composition reduces corrosion in an engine.

5. 5. The lubricating oil composition of claim 4, wherein the engine is an internal combustion engine equipped with an EGR system.

6. 5. The lubricating oil composition of claim 4, wherein the engine is a hybrid engine or a turbo GDI engine.

7. 1. A method of lubricating an engine comprising: (a) a major amount of oil of lubricating viscosity; (b) a calcium salicylate compound derived from isomerized normal alpha olefins (NAO) having from 10 to 40 carbon atoms, the alpha olefins having an isomerization level (I) of from 0.1 to 0.4, the calcium salicylate compound having a TBN of at least 600 mg KOH / gm on an active matter basis; the lubricating oil composition contains 0.12 to 0.17 wt. % calcium and is substantially free of magnesium, and has a total soap content from all detergents of less than 18 mM; The isomerization level (I) represents the relative amount of methyl groups (-CH3) (chemical shift 0.3-1.01 ppm) attached to the methylene backbone group (-CH2-) (chemical shift 1.01-1.38 ppm), and is represented by the equation (I): I=m / (m+n) Equation (I) wherein m is the NMR integral for methyl groups having chemical shifts from 0.3±0.03 to 1.01±0.03 ppm, and n is the NMR integral for methylene groups having chemical shifts from 1.01±0.03 to 1.38±0.10 ppm.

8. The method of claim 7, wherein the engine is a hybrid engine or a turbo GDI engine.

9. The method of claim 7 , wherein the engine is an internal combustion engine equipped with an EGR system.

10. 8. The method of claim 7, wherein the lubricating oil composition reduces corrosion in the engine.

11. The method of claim 7, wherein the lubricating oil composition further comprises a zinc dithiophosphate compound.

12. The method of claim 7, wherein the lubricating oil composition further comprises a molybdenum dithiocarbamate.

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