Lubricating oil composition for corrosion control

Abstract

The invention discloses a lubricating oil composition. The composition comprises a major amount of an oil of lubricating viscosity, one or more alkylhydroxybenzoate compounds derived from isomerized normal alpha olefins, and an oxidation inhibitor system comprising a molybdenum-containing antioxidant and a diphenylamine. The molybdenum-containing antioxidant is present in an amount to provide at least 120 ppm Mo to the lubricating oil composition. The diphenylamine is present in an amount to provide 0.5 wt% or more to the lubricating oil composition.

Description

Technical Field

[0001] The present disclosure relates to lubricating oil compositions. More particularly, the present disclosure relates to lubricating oil formulations designed for improved corrosion control. Background Art

[0002] Antioxidants are widely used as additives to provide one or more performance benefits to lubricants. These benefits include extending drain intervals, maintaining viscosity, reducing deposits, reducing foam formation, protecting against corrosion, and / or protecting against high temperatures. One potential complication facing lubricant formulators is that antioxidants are not always fully compatible with other ingredients. For example, the combination of an antioxidant and an alkyl hydroxybenzoate (“salicylate”) detergent can negatively impact a lubricant’s ability to protect against corrosion. Summary of the invention

[0003] In one aspect, a lubricating oil composition is provided, comprising: a major amount of an oil of lubricating viscosity; one or more alkylhydroxybenzoate compounds derived from isomerized normal alpha olefins; and an oxidation inhibitor system comprising a molybdenum-containing antioxidant and a diphenylamine; wherein the molybdenum-containing antioxidant is present in an amount to provide at least 120 ppm of Mo to the lubricating oil composition, and wherein the diphenylamine is present in an amount to provide 0.5 wt % or more to the lubricating oil composition.

[0004] In another aspect, a method of reducing copper corrosion in an engine is provided, the method comprising: lubricating the engine with a lubricating oil composition, the lubricating oil composition comprising: a major amount of an oil of lubricating viscosity; one or more alkylhydroxybenzoate compounds derived from isomerized normal alpha olefins; and an oxidation inhibitor system comprising a molybdenum-containing antioxidant and a diphenylamine; wherein the molybdenum-containing antioxidant is present in an amount to provide at least 120 ppm of Mo to the lubricating oil composition, and wherein the diphenylamine is present in an amount to provide 0.5 wt % or more to the lubricating oil composition.

[0005] In another aspect, a lubricating oil composition is provided, comprising: a major amount of an oil of lubricating viscosity; one or more alkylhydroxybenzoate compounds derived from C10-C40 isomerized normal alpha olefins; and an oxidation inhibitor system comprising a molybdenum-containing antioxidant and a diphenylamine; wherein the molybdenum-containing antioxidant is present in an amount to provide at least 120 ppm of Mo to the lubricating oil composition, and wherein the diphenylamine is present in an amount to provide 0.5 wt % or more to the lubricating oil composition. DETAILED DESCRIPTION

[0006] It should be understood that when combinations, subsets, groups, etc. of elements are disclosed (e.g., combinations of components in compositions, or combinations of steps in methods), while specific reference to each of the various individual and collective combinations and arrangements of these elements may not be explicitly disclosed, each is specifically contemplated and described herein.

[0007] The present disclosure relates to a lubricating oil composition for enhancing or improving anti-corrosion properties. The lubricating oil composition of the present disclosure includes an alkylhydroxybenzoate detergent and an oxidation inhibitor system comprising at least two different antioxidants.

[0008] More specifically, it has been unexpectedly discovered that alkyl hydroxybenzoates or alkyl groups thereof comprising or derived from isomerized normal alpha olefins provide improved corrosion resistance when formulated in combination with an antioxidant.

[0009] In some embodiments, the lubricating oil compositions of the present disclosure comprise (a) a major amount of an oil of lubricating viscosity, (b) one or more alkyl hydroxybenzoates or alkyl groups thereof comprising or derived from C10-C40 isomerized normal alpha olefins, and (c) (i) an oxidation inhibitor system comprising a molybdenum compound present in an amount contributing 120 ppm or more of Mo, and (ii) diphenylamine present in an amount of 0.5 wt % or more based on the lubricating oil composition.

[0010] Alkyl Hydroxybenzoate Detergents

[0011] The lubricating oil composition of the present disclosure includes one or more alkylhydroxybenzoate detergents, which contain or are derived from C10-C40 isomerized normal alpha olefins (NAO). In some embodiments, the alkyl group of the alkylhydroxybenzoate contains or is derived from isomerized NAO. In some embodiments, the manufacture of the alkylhydroxybenzoate involves a step of alkylating phenol or another aromatic precursor with isomerized NAO.

[0012] Detergents used in engine oils are typically anionic materials containing a long-chain hydrophobic portion of the molecule and a smaller anionic or oleophobic hydrophilic portion of the molecule. The long-chain hydrophobic portion of the alkyl hydroxybenzoate detergent disclosed herein is isomerized NAO. The anionic portion of the alkyl hydroxybenzoate detergent is derived from a carboxylic acid. The counterion is typically an alkaline earth metal or an alkali metal.

[0013] The alkyl hydroxybenzoate detergents of the present disclosure can be represented by the following general structure:

[0014]

[0015] wherein R" is a C10-C40 alkyl group (ie, having 10 to 40 carbon atoms); n is an integer from 1 to 4; and M is an alkaline earth metal (eg, Ca or Mg).

[0016] In some embodiments, the C10-C40 alkyl group is an isomerized normal alpha olefin (NAO) having an isomerization level (i) of about 0.10 to about 0.40, e.g., 0.10 to 0.35, 0.10 to 0.30, 0.10 to 0.25, 0.10 to 0.20, 0.10 to 0.15, 0.15 to 0.35, 0.15 to 0.30, 0.15 to 0.25, 0.15 to 0.20, 0.20 to 0.40, 0.20 to 0.35, 0.20 to 0.30, 0.20 to 0.25, 0.25 to 0.40, 0.25 to 0.35, 0.25 to 0.30, 0.30 to 0.40, 0.30 to 0.35, or 0.35 to 0.40.

[0017] In some embodiments, the isomerization level is about 0.12 to about 0.30, about 0.12 to about 0.25, about 0.12 to about 0.23, about 0.12 to about 0.22, about 0.12 to about 0.20, about 0.13 to about 0.19, about 0.14 to about 0.18, or about 0.15 to about 0.17.

[0018] The degree of isomerization of olefins (i) can be determined by 1 H-NMR determination. More specifically, the isomerization level (i) represents the relative amount of methyl groups (-CH3) (chemical shift 0.3-1.01 ppm) attached to the methylene backbone groups (-CH2-) (chemical shift 1.01-1.38 ppm). The equation for the isomerization level (i) is as follows:

[0019] Isomerization level = m / (m+n)

[0020] wherein m is the NMR integral of methyl groups with chemical shifts between 0.3±0.03 and 1.01±0.03 ppm, and n is the NMR integral of methylene groups with chemical shifts between 1.01±0.03 and 1.38±0.1 ppm.

[0021] Useful alkylhydroxybenzoate detergents can be neutral, slightly overbased or highly overbased. In some embodiments, the lubricating oil composition may contain alkylhydroxybenzoate detergents with different TBN levels. Salts containing stoichiometric metals are described as neutral salts. Many detergents are overbased, containing a large amount of metal base, which is achieved by reacting an excess of metal compounds (such as metal hydroxides or oxides) rich in acidic gases (such as carbon dioxide). Overbased detergents help neutralize acidic impurities produced by the combustion process and are trapped in the oil. The degree of overbasicity generally depends on the ratio of metal ions to the anionic portion of the detergent on an equivalent basis.

[0022] The alkyl hydroxybenzoate detergents of the present invention have a TBN of 10 mg KOH / g or more, e.g., 15 mg KOH / g or more, 25 mg KOH / g or more, 50 mg KOH / g or more, 75 mg KOH / g or more, 100 mg KOH / g or more, 125 mg KOH / g or more, 150 mg KOH / g or more, 175 mg KOH / g or more, 200 mg KOH / g or more, 225 mg KOH / g or more, 250 mg KOH / g or more, 275 mg KOH / g or more, 300 mg KOH / g or more, 325 mg KOH / g or more, 350 mg KOH / g or more, 375 mg KOH / g or more, 400 mg KOH / g or more, 425 mg KOH / g or more, 450 mg KOH / g or more, 475 mg KOH / g or more, KOH / g or more, 500 mg KOH / g or more, 525 mg KOH / g or more, 550 mg KOH / g or more, 575 mg KOH / g or more, 600 mg KOH / g or more and 650 mg KOH / g or more.

[0023] In some embodiments, the alkyl hydroxybenzoate detergents of the present disclosure have a TBN of 10 to 650 mg KOH / g, e.g., 10 to 600 mg KOH / g, 10 to 550 mg KOH / g, 10 to 500 mg KOH / g, 10 to 450 mg KOH / g, 10 to 400 mg KOH / g, 10 to 350 mg KOH / g, 10 to 300 mg KOH / g, 10 to 250 mg KOH / g, 10 to 200 mg KOH / g, 10 to 150 mg KOH / g, 10 to 100 mg KOH / g, 10 to 50 mg KOH / g, 50 to 650 mg KOH / g, 50 to 600 mg KOH / g, 50 to 550 mg KOH / g, 50 to 500 mg KOH / g. KOH / g, 50 to 450 mg KOH / g, 50 to 400 mg KOH / g, 50 to 350 mg KOH / g, 50 to 300 mg KOH / g, 50 to 250 mg KOH / g, 50 to 200 mg KOH / g, 50 to 150 mg KOH / g, 50 to 100 mg KOH / g, 100 to 650 mg KOH / g, 100 to 600 mg KOH / g, 100 to 550 mg KOH / g, 100 to 500 mg KOH / g, 100 to 450 mg KOH / g, 100 to 400 mg KOH / g, 100 to 350 mg KOH / g, 100 to 300 mg KOH / g, 100 to 250 mg KOH / g, 100 to 200 mg KOH / g, 100 to 150 mg KOH / g, 150 to 650 mg KOH / g, 150 to 600 mg KOH / g, 150 to 550 mg KOH / g, 150 to 500 mg KOH / g, 150 to 450 mg KOH / g, 150 to 400 mg KOH / g, 150 to 350 mg KOH / g, 150 to 300 mg KOH / g, 150 to 250 mg KOH / g, 150 to 200 mg KOH / g, 200 to 650 mg KOH / g, 200 to 600 mg KOH / g, 200 to 550 mg KOH / g, 200 to 500 mg KOH / g, 200 to 450 mg KOH / g, 200 to 400 mg KOH / g, 200 to 350 mg KOH / g, 200 to 300 mg KOH / g, 200 to 250 mg KOH / g, 250 to 650 mg KOH / g, 250 to 600 mg KOH / g, 250 to 550 mg KOH / g, 250 to 500 mg KOH / g, 250 to 450 mg KOH / g, 250 to 400 mg300 to 400 mg KOH / g, 300 to 350 mg KOH / g, 350 to 650 mg KOH / g, 300 to 600 mg KOH / g, 300 to 550 mg KOH / g, 300 to 500 mg KOH / g, 300 to 450 mg KOH / g, 300 to 400 mg KOH / g, 300 to 350 mg KOH / g, 350 to 650 mg KOH / g, 350 to 600 mg KOH / g, 350 to 550 mg KOH / g, 350 to 500 mg KOH / g, 350 to 450 mg KOH / g, 350 to 400 mg KOH / g, 400 to 650 mg KOH / g, 400 to 600 mg KOH / g, 400 to 550 mg or 600 to 650 mg KOH / g.

[0024] In some embodiments, the alkyl hydroxybenzoate detergents of the present disclosure have a TBN of 10 to 150 mg KOH / g, e.g., 10 to 140 mg KOH / g, 10 to 130 mg KOH / g, 10 to 120 mg KOH / g, 10 to 110 mg KOH / g, 10 to 100 mg KOH / g, 10 to 90 mg KOH / g, 10 to 80 mg KOH / g, 10 to 70 mg KOH / g, 10 to 60 mg KOH / g, 10 to 50 mg KOH / g, 10 to 40 mg KOH / g, 10 to 30 mg KOH / g, 10 to 20 mg KOH / g, 20 to 150 mg KOH / g, 20 to 140 mg KOH / g, 20 to 130 mg KOH / g, 20 to 120 mg KOH / g, 20 to 110 mg KOH / g, KOH / g, 20 to 100 mg KOH / g, 20 to 90 mg KOH / g, 20 to 80 mg KOH / g, 20 to 70 mg KOH / g, 20 to 60 mg KOH / g, 20 to 50 mg KOH / g, 20 to 40 mg KOH / g, 20 to 30 mg KOH / g, 30 to 150 mg KOH / g, 30 to 140 mg KOH / g, 30 to 130 mg KOH / g, 30 to 120 mg KOH / g, 30 to 110 mg KOH / g, 30 to 100 mg KOH / g, 30 to 90 mg KOH / g, 30 to 80 mg KOH / g, 30 to 70 mg KOH / g, 30 to 60 mg KOH / g, 30 to 50 mg KOH / g, 30 to 40 mg KOH / g, 40 to 150 mg KOH / g, 40 to 140 mg KOH / g, 40 to 130 mg KOH / g, 40 to 120 mg KOH / g, 40 to 110 mg KOH / g, 40 to 100 mg KOH / g, 40 to 90 mg KOH / g, 40 to 80 mg KOH / g, 40 to 70 mg KOH / g, 40 to 60 mg KOH / g, 40 to 50 mg KOH / g, 50 to 150 mg KOH / g, 50 to 140 mg KOH / g, 50 to 130 mg KOH / g, 50 to 120 mg KOH / g, 50 to 110 mg KOH / g, 50 to 100 mg KOH / g, 50 to 90 mg KOH / g, 50 to 80 mg KOH / g, 50 to 70 mg KOH / g, 50 to 60 mg KOH / g, 60 to 150 mg KOH / g, 60 to 140 mg KOH / g, 60 to 130 mg KOH / g, 60 to 120 mg KOH / g, 60 to 110 mg KOH / g, 60 to 100 mg. KOH / g, 60 to 90 mg KOH / g, 60 to 80 mg KOH / g, 60 to 70 mg KOH / g, 80 to 150 mg KOH / g, 80 to 140 mg KOH / g, 80 to 130 mg KOH / g, 80 to 120 mg KOH / g, 80 to 110 mg KOH / g, 80 to 100 mg KOH / g, 80 to 90 mg KOH / g, 90 to 150 mg KOH / g, 90 to 140 mg KOH / g, 90 to 130 mg KOH / g, 90 to 120 mg KOH / g, 90 to 110 mg KOH / g, 90 to 100 mg KOH / g, 100 to 150 mg KOH / g, 100 to 140 mg KOH / g, 100 to 130 mg KOH / g, 100 to 120 mg or 140 to 150 mg KOH / g.

[0025] In some embodiments, the alkyl hydroxybenzoate detergent has a TBN of 10 to 300 mg KOH / g on an oil-free basis. In some embodiments, the alkyl hydroxybenzoate detergent has a TBN of 600 mg KOH / g or greater on an oil-free basis.

[0026] The synthesis of alkylhydroxybenzoate compounds is well known. For example, one synthetic route for overbased metal alkylhydroxybenzoate detergents begins by reacting an alkylphenol with a metal base. The product is then carboxylated (i.e., reacted with CO 2 The resulting acid product may be neutralized with lime and overbased. Some of these steps (e.g., secondary neutralization and overbased) may be performed simultaneously. A more detailed description of this process may be found in US 8,030,258, which is hereby incorporated by reference.

[0027] The counter ion of the alkylhydroxybenzoate detergent is typically an alkaline earth metal, such as calcium or magnesium. In some embodiments, the lubricating oil composition comprises an alkylhydroxybenzoate containing Ca and Mg.

[0028] In some embodiments, the calcium-containing alkyl hydroxybenzoate may be present in an amount providing about 500 to about 5000 ppm of calcium to the lubricating oil composition, for example, about 500 to about 4500 ppm, 500 to 4000 ppm, 500 to 3500 ppm, 500 to 3000 ppm, 500 to 2500 ppm, 500 to 2000 ppm, 500 to 1500 ppm, 500 to 1000 ppm, 1000 to 5000 ppm, 1000 to 4500 ppm, 1000 to 4000 ppm, 1000 to 3500 ppm, 1000 to 3000 ppm, 1000 to 2500 ppm, 1000 to 2000 ppm, 1000 to 1500 ppm, 1500 to 5000 ppm, 1500 to 5000 ppm, 1500 to 5000 ppm, 1500 to 6000 ppm, 1500 to 7000 ppm, 1500 to 8000 ppm, 1500 to 9000 ppm, 1500 to 10 ... ppm, 3000 to 5000 ppm, 3000 to 4500 ppm, 3000 to 3500 ppm, 3500 to 5000 ppm, 3500 to 4500 ppm, 3500 to 4000 ppm, 4000 to 5000 ppm, 4000 to 4500 ppm or 4500 to 5000 ppm.

[0029] In some embodiments, the magnesium-containing alkyl hydroxybenzoate may be present in an amount providing from about 500 to about 5000 ppm of magnesium to the lubricating oil composition, for example, from about 500 to about 4500 ppm, 500 to 4000 ppm, 500 to 3500 ppm, 500 to 3000 ppm, 500 to 2500 ppm, 500 to 2000 ppm, 500 to 1500 ppm, 500 to 1000 ppm, 1000 to 5000 ppm, 1000 to 4500 ppm, 1000 to 4000 ppm, 1000 to 3500 ppm, 1000 to 3000 ppm, 1000 to 2500 ppm, 1000 to 2000 ppm, 1000 to 1500 ppm, 1500 to 5000 ppm, 1500 to 5000 ppm, 1500 to 5000 ppm, 1500 to 6000 ppm, 1500 to 7000 ppm, 1500 to 8000 ppm, 1500 to 9000 ppm, 1500 to 10 ... ppm, 3000 to 5000 ppm, 3000 to 4500 ppm, 3000 to 3500 ppm, 3500 to 5000 ppm, 3500 to 4500 ppm, 3500 to 4000 ppm, 4000 to 5000 ppm, 4000 to 4500 ppm or 4500 to 5000 ppm.

[0030] In some embodiments, the total amount of calcium-containing alkyl hydroxybenzoate and magnesium-containing alkyl hydroxybenzoate is such that the total amount of calcium and magnesium in the lubricating oil composition is from about 500 to about 5000 ppm, for example, from about 500 to about 4500 ppm, 500 to 4000 ppm, 500 to 3500 ppm, 500 to 3000 ppm, 500 to 2500 ppm, 500 to 2000 ppm, 500 to 1500 ppm, 500 to 1000 ppm, 1000 to 5000 ppm, 1000 to 4500 ppm, 1000 to 4000 ppm, 1000 to 3500 ppm, 1000 to 3000 ppm, 1000 to 2500 ppm, 1000 to 2000 ppm, 1000 to 1500 ppm, 1500 to 5000 ppm. ppm, 1500 to 4500 ppm, 1500 to 4000 ppm, 1500 to 3500 ppm, 1500 to 3000 ppm, 1500 to 2500 ppm, 1500 to 2000 ppm, 2000 to 5000 ppm, 2500 to 4500 ppm, 2500 to 4000 ppm, 2500 to 3500 ppm, 2500 to 3000 ppm, 3000 to 5000 ppm, 3000 to 4500 ppm, 3000 to 4000 ppm, 3000 to 3500 ppm, 3500 to 5000 ppm, 3500 to 4500 ppm, 3500 to 4000 ppm, 4000 to 5000 ppm, 4000 to 4500 ppm or 4500 to 5000 ppm.

[0031] Generally, the total amount of Ca and Mg present in the lubricating oil composition is about 5000 ppm or less. The ppm value is based on the total weight of the lubricating oil composition.

[0032] Oxidation Inhibitor Systems

[0033] The lubricating oil composition of the present disclosure comprises an oxidation inhibitor system comprising at least two antioxidant compounds. The antioxidant compounds include (i) a molybdenum-containing antioxidant and (ii) a diphenylamine antioxidant.

[0034] The molybdenum or molybdenum-containing antioxidant is present in an amount to provide the lubricating oil composition with at least 120 ppm of Mo, e.g., at least 130 ppm, at least 140 ppm, at least 150 ppm, at least 160 ppm, at least 170 ppm, at least 180 ppm, at least 190 ppm, and at least 200 ppm. Examples of molybdenum-containing antioxidants include molybdenum succinimides, molybdenum dithiocarbamates, and trinuclear molybdenum compounds.

[0035] Molybdenum succinimide

[0036] In one embodiment, the molybdenum amine is a molybdenum-succinimide complex. Suitable molybdenum-succinimide complexes are described, for example, in U.S. Pat. No. 8,076,275. These complexes are prepared by a process comprising reacting an acidic molybdenum compound with an alkyl or alkenyl succinimide of a polyamine of the following structure:

[0037]

[0038]

[0039] Where R is C 24 To C 350 (For example, C 70 To C 128 ) alkyl or alkenyl; R' is a straight or branched chain alkylene group having 2 to 3 carbon atoms; x is 1 to 11; and y is 1 to 11.

[0040] The molybdenum compound used to prepare the molybdenum-succinimide complex is an acidic molybdenum compound or a salt of an acidic molybdenum compound. "Acidic" means that the molybdenum compound will react with basic nitrogen compounds as measured by ASTM D664 or D2896. In general, the acidic molybdenum compound is hexavalent. Representative examples of suitable molybdenum compounds include molybdenum trioxide, molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, such as hydrogen salts (e.g., sodium hydrogen molybdate), MoOCl 4 、MoO 2 Br 2 、Mo 2 O 3 Cl 6 wait.

[0041] Succinimides useful for preparing molybdenum-succinimide complexes are disclosed in many references and are well known in the art. Certain basic types of succinimides and related materials covered by the special term "succinimide" are taught in U.S. Patents Nos. 3,172,892; 3,219,666; and 3,272,746. The term "succinimide" is understood in the art to include many amide, imide and amidine species that may also be formed. However, the major product is succinimide, and this term has been recognized to mean the product of the reaction of an alkyl or alkenyl substituted succinic acid or anhydride with a nitrogen-containing compound. A preferred succinimide is a succinimide prepared by reacting a polyisobutenyl succinic anhydride having about 70 to 128 carbon atoms with a polyamine.

[0042] Preferred polyamines may have 2 to 60 carbon atoms and 2 to 12 nitrogen atoms per molecule. Particularly preferred amines include polyalkylene amines represented by the formula:

[0043] NH2 (CH 2 ) n —(NH(CH 2 ) n ) m —NH 2

[0044] wherein n is 2 to 3 and m is 0 to 10. Illustrative examples include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, and the like, as well as commercially available mixtures of such polyamines.

[0045] The molybdenum-succinimide complex can be post-treated with a sulfur source at a suitable pressure and a temperature not exceeding 120° C. to provide a sulfided molybdenum-succinimide complex. The sulfurization step can be performed for a period of about 0.5 to 5 hours (e.g., 0.5 to 2 hours). Suitable sulfur sources include elemental sulfur, hydrogen sulfide, phosphorus pentasulfide, a molybdenum sulfide having the formula R 2 S x An organic polysulfide (wherein R is a hydrocarbon group (e.g., C 1 To C 10 alkyl) and x is at least 3), C 1 To C 10 Mercaptans, inorganic sulfides and polysulfides, thioacetamide and thiourea.

[0046] Molybdenum dithiocarbamate

[0047] Suitable molybdenum dithiocarbamates include any molybdenum dithiocarbamate that can be used as an additive to lubricating oils. One class of molybdenum dithiocarbamates used herein is represented by the following structure:

[0048]

[0049] Where R 3 , R 4 , R 5 and R 6 are each independently hydrogen or a hydrocarbon group, including, for example, alkyl, alkenyl, aryl, cycloalkyl, and cycloalkenyl, and X 1 , X 2 , X 3 and X 4 Each is independently sulfur or oxygen.

[0050] Suitable alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, neopentyl, tert-pentyl, hexyl, sec-hexyl, heptyl, sec-heptyl, octyl, 2-ethylhexyl, sec-octyl, nonyl, sec-nonyl, decyl, sec-decyl, undecyl, sec-undecyl, dodecyl, sec-dodecyl, tridecyl, isotridecyl, sec-tridecyl, tetradecyl, sec-tetradecyl, hexadecyl, sec-hexadecyl, stearyl, eicosyl, docosyl, tetracosyl, triacontyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl, 2-octyldodecyl, 2-decyltetradecyl, 2-dodecylhexadecyl, 2-hexadecyloctadecyl, 2-tetradecyloctadecyl, monomethyl branched isostearyl, and the like.

[0051] Suitable alkenyl groups include, but are not limited to, vinyl, allyl, propenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl, and the like.

[0052] Suitable aryl groups include, but are not limited to, phenyl, tolyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, diphenylmethyl, triphenylmethyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, biphenyl, benzylphenyl, styrenated phenyl, p-cumylphenyl, α-naphthyl, β-naphthyl, and the like.

[0053] Suitable cycloalkyl and cycloalkenyl groups include, but are not limited to, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, methylcycloheptenyl, and the like.

[0054] In one embodiment, X 1 To X 4 are independently selected from sulfur or oxygen atoms, and X 1 To X 4 All may be sulfur atoms or oxygen atoms, or a mixture of sulfur atoms and oxygen atoms. Considering the balance between friction reduction effect and corrosiveness, the molar ratio (quantity ratio) of sulfur atoms / oxygen atoms should particularly preferably be in the range of about 1 / 3 to about 3 / 1.

[0055] Some of the oil-soluble or oil-dispersible molybdenum compounds are commercially available. For example, wherein X 1 and X 2 O, X 3 and X4 is S and where R 3 To R 6 C 13 H 27 Products with an aliphatic hydrocarbon radical and in which the molybdenum is in the oxidation state V are marketed by RT Vanderbilt Company Inc. (Norwalk, Conn. USA) under the trademark 807 and 822 is sold as an antioxidant and friction reducing additive. These molybdenum compounds can be prepared by the process described in U.S. Pat. No. 3,356,702, wherein MoO 3 It is converted into a soluble molybdate by dissolving it in an alkali metal hydroxide solution and neutralized by adding an acid followed by a secondary amine and carbon disulfide. 1 To X 4 is O or S and can be prepared by various methods known in the art, such as, for example, US Pat. Nos. 4,098,705 and 5,631,213.

[0056] In general, molybdenum oxysulfide dithiocarbamates can be prepared by reacting molybdenum trioxide or molybdate with an alkali metal sulfide or alkali metal hydrosulfide, and then adding carbon disulfide and a secondary amine to the reaction mixture and reacting the resulting mixture at an appropriate temperature. In order to prepare asymmetric molybdenum oxysulfide dithiocarbamates, it is sufficient to use secondary amines having different hydrocarbon groups or to use two or more different secondary amines in the above process. Symmetric molybdenum oxysulfide dithiocarbamates can also be prepared in a similar manner, but using only one secondary amine.

[0057] Examples of suitable molybdenum dithiocarbamate compounds include, but are not limited to, diethyl molybdenum dithiocarbamate sulfide, dipropyl molybdenum dithiocarbamate sulfide, dibutyl molybdenum dithiocarbamate sulfide, diamyl molybdenum dithiocarbamate sulfide, dihexyl molybdenum dithiocarbamate sulfide, dioctyl molybdenum dithiocarbamate sulfide, didecyl molybdenum dithiocarbamate sulfide, didodecyl molybdenum dithiocarbamate sulfide, ditridecyl molybdenum dithiocarbamate sulfide, di(butylphenyl) molybdenum dithiocarbamate sulfide, di(nonylphenyl) molybdenum dithiocarbamate sulfide, diethyl molybdenum dithiocarbamate sulfide, dioct ... dioctyl molybdenum dithiocarbamate sulfide, dioctyl molybdenum dithiocarbamate sulfide, dioctyl molybdenum dithiocarbamate sulfide, dioctyl molybdenum dithiocarbamate sulfide, dioctyl molybdenum dithiocarbamate sulfide, dioctyl molybdenum dithiocarbamate sulfide, dioctyl molybdenum dithiocarbamate sulfide, molybdenum oxysulfide for carbamate, dipropyl molybdenum oxysulfide for dithiocarbamate, dibutyl molybdenum oxysulfide for dithiocarbamate, dipentyl molybdenum oxysulfide for dithiocarbamate, dihexyl molybdenum oxysulfide for dithiocarbamate, dioctyl molybdenum oxysulfide for dithiocarbamate, didecyl molybdenum oxysulfide for dithiocarbamate, didodecyl molybdenum oxysulfide for dithiocarbamate, ditridecyl molybdenum oxysulfide for dithiocarbamate, di(butylphenyl) molybdenum oxysulfide for dithiocarbamate, di(nonylphenyl) molybdenum oxysulfide for dithiocarbamate, wherein all alkyl groups may be linear or branched, and the like, and mixtures thereof.

[0058] Trinuclear molybdenum compounds

[0059] Suitable molybdenum-containing antioxidants also include trinuclear molybdenum compounds known in the art, such as trinuclear molybdenum dialkyldithiocarbamates, as taught in US Pat. Nos. 5,888,945 and 6,010,987, which are incorporated herein by reference.

[0060] In some embodiments, the trinuclear molybdenum compound may be of the formula Mo 3 S 4 (dtc) 4 、Mo 3 S 5 (dtc) 4 、Mo 3 S 4 (dtc) 6 and Mo 3 S 7 (dtc) 4 and mixtures thereof, wherein dtc represents independently selected diorganodithiocarbamate ligands containing independently selected organic groups, and wherein the ligands have a sufficient number of carbon atoms in all organic groups of the ligands of the compound to render the compound soluble or dispersible in a lubricating oil.

[0061] Diphenylamine

[0062] Diphenylamine is an aromatic amine antioxidant and may have one or more carbon-based substituents. Diphenylamine-type oxidation inhibitors include, but are not limited to, alkylated diphenylamine, phenyl-α-naphthylamine and alkyl or aralkyl substituted phenyl-α-naphthylamine, alkylated p-phenylenediamine, and tetramethyldiaminodiphenylamine.

[0063] Specific examples of the diphenylamine antioxidants include bis-nonylated diphenylamine, bis-octylated diphenylamine and octylated / butylated diphenylamine, 4,4'-dioctyldiphenylamine, 4,4'-dinonyldiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine and N-(4-octylphenyl)-1-naphthylamine.

[0064] The diphenylamine antioxidant may be present at 0.01 to 5 wt %, for example, 0.01 to 4.5 wt %, 0.01 to 4.0 wt %, 0.01 to 3.5 wt %, 0.01 to 3.0 wt %, 0.01 to 2.5 wt %, 0.01 to 2.0 wt %, 0.01 to 1.5 wt %, 0.01 to 1.0 wt %, 0.01 to 0.5 wt %, 0.5 to 5.0 wt %, 0.5 to 4.5 wt %. %, 0.5 to 4.0 wt %, 0.5 to 3.5 wt %, 0.5 to 3.0 wt %, 0.5 to 2.5 wt %, 0.5 to 2.0 wt %, 0.5 to 1.5 wt %, 0.5 to 1.0 wt %, 1.0 to 5.0 wt %, 1.0 to 4.5 wt %, 1.0 to 4.0 wt %, 1.0 to 3.5 wt %, 1.0 to 3.0 wt %, 1.0 to 2.5 wt %, 1.0 to 2.0 wt %, 1.0 %, 1.5 to 5.0 wt %, 1.5 to 4.5 wt %, 1.5 to 4.0 wt %, 1.5 to 3.5 wt %, 1.5 to 3.0 wt %, 1.5 to 2.5 wt %, 1.5 to 2.0 wt %, 2.0 to 5.0 wt %, 2.0 to 4.5 wt %, 2.0 to 4.0 wt %, 2.0 to 3.5 wt %, 2.0 to 3.0 wt %, 2.0 to 2.5 wt %, 2.5 to 5.0 %, 2.5 to 4.5 wt %, 2.5 to 4.0 wt %, 2.5 to 3.5 wt %, 2.5 to 3.0 wt %, 3.0 to 5.0 wt %, 3.0 to 4.5 wt %, 3.0 to 4.0 wt %, 3.0 to 3.5 wt %, 3.5 to 5.0 wt %, 3.5 to 4.5 wt %, 3.5 to 4.0 wt %, 4.0 to 5.0 wt %, 4.0 to 4.5 wt %, or 4.5 to 5.0 wt %.

[0065] Optional additives

[0066] Optionally, the lubricating oil composition may contain a hindered phenol antioxidant. Examples of hindered phenol antioxidants include 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-4-(2-octyl-3-propionic acid)phenol.

[0067] The hindered phenol antioxidant may be present in the lubricating oil composition at 0.01 to 5 wt %, for example, 0.01 to 4.5 wt %, 0.01 to 4.0 wt %, 0.01 to 3.5 wt %, 0.01 to 3.0 wt %, 0.01 to 2.5 wt %, 0.01 to 2.0 wt %, 0.01 to 1.5 wt %, 0.01 to 1.0 wt %, 0.01 to 0.5 wt %, 0.5 to 5.0 wt %, 0.5 to 4.5 wt %. %, 0.5 to 4.0 wt %, 0.5 to 3.5 wt %, 0.5 to 3.0 wt %, 0.5 to 2.5 wt %, 0.5 to 2.0 wt %, 0.5 to 1.5 wt %, 0.5 to 1.0 wt %, 1.0 to 5.0 wt %, 1.0 to 4.5 wt %, 1.0 to 4.0 wt %, 1.0 to 3.5 wt %, 1.0 to 3.0 wt %, 1.0 to 2.5 wt %, 1.0 to 2.0 wt %, 1.0 %, 1.5 to 5.0 wt %, 1.5 to 4.5 wt %, 1.5 to 4.0 wt %, 1.5 to 3.5 wt %, 1.5 to 3.0 wt %, 1.5 to 2.5 wt %, 1.5 to 2.0 wt %, 2.0 to 5.0 wt %, 2.0 to 4.5 wt %, 2.0 to 4.0 wt %, 2.0 to 3.5 wt %, 2.0 to 3.0 wt %, 2.0 to 2.5 wt %, 2.5 to 5.0 %, 2.5 to 4.5 wt %, 2.5 to 4.0 wt %, 2.5 to 3.5 wt %, 2.5 to 3.0 wt %, 3.0 to 5.0 wt %, 3.0 to 4.5 wt %, 3.0 to 4.0 wt %, 3.0 to 3.5 wt %, 3.5 to 5.0 wt %, 3.5 to 4.5 wt %, 3.5 to 4.0 wt %, 4.0 to 5.0 wt %, 4.0 to 4.5 wt %, or 4.5 to 5.0 wt %.

[0068] Succinimide

[0069] Optionally, the lubricating oil composition may include a polyalkenyl succinimide dispersant, such as those described herein. Generally, the nitrogen content of the nitrogen-containing dispersant is from about 0.010 wt % to about 0.30 wt %, such as from about 0.050 wt % to about 0.25 wt %, from about 0.050 wt % to about 0.20 wt %, and from about 0.050 wt % to about 0.15 wt %, based on the lubricating oil composition.

[0070] In one embodiment, the polyalkenyl bissuccinimide can be prepared by reacting a polyalkenyl substituted succinic anhydride of the structure

[0071]

[0072] (wherein R is a polyalkenyl substituent derived from a polyolefin group having a number average molecular weight of about 500 to about 3000) and a polyamine. In one embodiment, R is a polyalkenyl substituent derived from a polyolefin group having a number average molecular weight of about 1000 to about 2500. In one embodiment, R is a polyisobutylene substituent derived from a polyisobutylene having a number average molecular weight of about 500 to about 3000. In another embodiment, R is a polyisobutylene substituent derived from a polyisobutylene having a number average molecular weight of about 1000 to about 2500.

[0073] Suitable polyamines for preparing the bis-succinimide dispersant include polyalkylene polyamines. Such polyalkylene polyamines typically contain from about 2 to about 12 nitrogen atoms and from about 2 to 24 carbon atoms. Particularly suitable polyalkylene polyamines are those having the formula: H2N—(R′NH)x—H, wherein R′ is a linear or branched alkylene group having 2 or 3 carbon atoms, and x is from 1 to 9. Representative examples of suitable polyalkylene polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and heavy polyamines (e.g., ethyleneamine E-100, available from Huntsman Company).

[0074] In general, the polyalkenyl-substituted succinic anhydride is reacted with the polyamine at a temperature of about 130° C. to about 220° C. (e.g., 145° C. to 175° C.). The reaction can be carried out under an inert atmosphere, such as nitrogen or argon. In general, a suitable molar charge of the polyamine to the polyalkenyl-substituted succinic anhydride is about 0.35:1 to about 0.6:1 (e.g., 0.4:1 to 0.5:1). As used herein, "molar charge of polyamine to polyalkenyl-substituted succinic anhydride" means the ratio of the number of moles of polyamine to the number of succinic acid groups in the succinic anhydride reactant.

[0075] One class of suitable polyalkenyl succinimides can be represented by the following structure:

[0076]

[0077] wherein R and R' are as described herein above and y is 1 to 11.

[0078] Post-treatment of polyalkenyl succinimide

[0079] In some embodiments, the succinimide dispersant may be post-treated with a reactive boron compound or an organic carbonate.

[0080] Suitable boron compounds that can be used as boron sources include, for example, boric acid, borates, boric esters, and the like. Representative examples of boric acid include orthoboric acid, metaboric acid, secondary boric acid, and the like. Representative examples of borates include ammonium borates, such as ammonium metaborate, ammonium tetraborate, ammonium pentaborate, ammonium octaborate, and the like. Representative examples of boric esters include monomethyl borate, dimethyl borate, trimethyl borate, monoethyl borate, diethyl borate, triethyl borate, monopropyl borate, dipropyl borate, tripropyl borate, monobutyl borate, dibutyl borate, tributyl borate, and the like.

[0081] In some embodiments, the lubricating oil composition comprises boronated and unborated succinimide. In some embodiments, the mass ratio of boronated to unborated succinimide is less than 1, such as less than 0.95, less than 0.90, less than 0.85, and less than 0.80.

[0082] lubricating oil

[0083] The oil of lubricating viscosity (sometimes referred to as "base stock" or "base oil") is the major 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 oils useful for preparing the concentrates and for preparing the lubricating oil compositions therefrom may be selected from natural (vegetable, animal or mineral) lubricating oils and synthetic lubricating oils and mixtures thereof.

[0084] The oil used as base oil will be selected or blended according to the additive in the desired end use and finished oil to obtain the engine oil of the desired grade. In one embodiment, the lubricating oil composition is a multigrade oil for heavy-duty vehicles or passenger cars. The multigrade oil can have the following SAE viscosity grades: 0W-8, 0W-12, 0W-16, 0W-20, 0W-30, 0W-40, 0W-50, 0W-60, 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, 20W-40 or 20W-50.

[0085] The definitions of base stocks and base oils in this disclosure are the same as those in Appendix E of the American Petroleum Institute (API) Publication 1509 ("API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils", February 2022). Using the test methods specified in Table E-1, Group I base stocks contain less than 90% saturated hydrocarbons and / or greater than 0.03% sulfur, and have a viscosity index greater than or equal to 80 and less than 120. Using the test methods specified in Table E-1, Group II base stocks contain greater than or equal to 90% saturated hydrocarbons and less than or equal to 0.03% sulfur, and have a viscosity index greater than or equal to 80 and less than 120. Using the test methods specified in Table E-1, Group III base stocks contain greater than or equal to 90% saturated hydrocarbons and less than or equal to 0.03% sulfur, and have a viscosity index greater than or equal to 120. Group IV base stocks are polyalphaolefins (PAOs). Group V base stocks include all other base stocks not included in Group I, Group II, Group III or Group IV.

[0086] Natural oils include animal oils, vegetable oils (e.g., castor oil and lard) and mineral oils. Animal oils and vegetable oils with good thermal oxidation stability can be used. Among natural oils, mineral oils are preferred. Mineral oils vary greatly in their crude oil sources (e.g., whether they are paraffinic, cycloparaffinic or mixed paraffinic-cycloparaffinic). Oils derived from coal or shale are also useful. Natural oils also vary in their production and purification methods (e.g., their distillation ranges) and whether they are straight run or cracked, hydrofined or solvent extracted.

[0087] Synthetic oils include hydrocarbon oils. Hydrocarbon oils include oils such as polymerized and interpolymerized olefins (e.g., polybutene, polypropylene, propylene isobutylene copolymers, ethylene-olefin copolymers, and ethylene-α-olefin copolymers). Polyalphaolefin (PAO) oil base stocks are commonly used synthetic hydrocarbon oils. For example, a base stock derived from C 8 To C 14 Olefins, such as C 8 , C 10 , C 12 , C 14 PAO of olefins or mixtures thereof.

[0088] Other useful fluids for use as base oils include non-conventional or unconventional base stocks which have been processed (preferably catalytically processed) or synthesized to provide high performance properties.

[0089] Unconventional or extra-conventional base stocks / base oils include one or more of the following: mixtures of base stocks derived from one or more natural gas to liquids (GTL) materials, and isomerate / isodewaxate base stocks derived from natural waxes or waxy feeds, mineral and or non-mineral oil waxy feeds such as slack wax, natural waxes and waxy feeds such as gas oils, waxy fuel hydrocracker bottoms, waxy raffinates, hydrocracked products, thermal cracked products or other mineral, mineral oil or even non-petroleum derived waxy materials such as waxy materials obtained from coal liquefaction or shale oil, and mixtures of such base stocks. Other base oils include coal to liquids (CTL) products and alkylated naphthalenes.

[0090] The base oil used in the lubricating oil composition of the present disclosure is any kind of oil corresponding to API Group I, Group II, Group III, Group IV and Group V oils and mixtures thereof, preferably API Group II, Group III, Group IV and Group V oils and mixtures thereof, more preferably Group III to Group V base oils, due to their superior volatility, stability, viscosity and cleanliness characteristics.

[0091] The lubricating oil composition may have a high temperature shear (HTHS) viscosity at 150° C. of 5.2 cP or less, e.g., 5.1 cP or less, 5.0 cP or less, 4.5 cP or less, 4.0 cP or less, 3.9 cP or less, 3.8 cP or less, 3.7 cP or less, 3.6 cP or less, 3.5 cP or less, 3.4 cP or less, 3.3 cP or less, 3.2 cP or less, 3.1 cP or less, 3.0 cP or less, 2.9 cP or less , 2.8cP or lower, 2.7cP or lower, 2.6cP or lower, 2.5cP or lower, 2.4cP or lower, 2.3cP or lower, 2.2cP or lower, 2.1cP or lower, 2.0cP or lower, 1.9cP or lower, 1.8cP or lower, 1.7cP or lower, 1.6cP or lower, 1.5cP or lower, 1.4cP or lower, 1.3cP or lower, 1.2cP or lower, 1.1cP or lower, or 1.0cP or lower. In some embodiments, the lubricating oil composition may have a HTHS at 150°C of 1.0 to 5.2 cP, e.g., 1.0 to 4.5 cP, 1.0 to 4.0 cP, 1.0 to 2.9 cP, 1.3 to 2.9 cP, 1.0 to 2.6 cP, 1.3 to 2.6 cP, 1.0 cP to 2.3 cP, 1.3 cP to 2.3 cP, 1.0 cP to 2.0 cP, 1.3 cP to 2.3 cP, 1.0 cP to 1.7 cP, or 1.3 cP to 1.7 cP. The viscosity index of the lubricating oil composition may be at least 135 (e.g., 135 to 400 or 135 to 250), at least 150 (e.g., 150 to 400, 150 to 250), at least 165 (e.g., 165 to 400 or 165 to 250), at least 190 (e.g., 190 to 400 or 190 to 250), or at least 200 (e.g., 200 to 400 or 200 to 250). If the viscosity index of the lubricating oil composition is lower than 135, it may be difficult to improve fuel efficiency while maintaining the HTHS viscosity at 150° C. If the viscosity index of the lubricating oil composition exceeds 400, evaporation characteristics may be reduced, and defects may be caused due to insufficient solubility of additives and matching characteristics with sealing materials.

[0092] The kinematic viscosity of the base oil at 100°C (ASTM D445) can be between 1.4 and 20 mm 2 / s range, for example 3 to 12 mm 2 / s, e.g. 3 to 11 mm 2 / s, 3 to 10 mm 2 / s, 3 to 9 mm 2 / s, 3 to 8 mm 2 / s, 3 to 7 mm 2 / s, 3 to 6 mm 2 / s, 3 to 5 mm 2 / s, 3 to 4 mm 2 / s, 4 to 12 mm 2 / s, 4 to 11 mm 2 / s, 4 to 10 mm 2 / s, 4 to 9 mm 2 / s, 4 to 8 mm 2 / s, 4 to 7 mm 2 / s, 4 to 6 mm 2 / s, 4 to 5 mm 2 / s, 5 to 12 mm 2 / s, 5 to 11 mm 2 / s, 5 to 10 mm 2 / s, 5 to 9 mm 2 / s, 5 to 8 mm 2 / s, 5 to 7 mm 2 / s, 5 to 6 mm 2 / s, 6 to 12 mm 2 / s, 6 to 11 mm 2 / s, 6 to 10 mm 2 / s, 6 to 9 mm 2 / s, 6 to 8 mm 2 / s, 6 to 7 mm 2 / s, 7 to 12 mm 2 / s, 7 to 11 mm 2 / s, 7 to 10 mm 2 / s, 7 to 9 mm 2 / s, 7 to 10 mm 2 / s, 7 to 9 mm 2 / s, 7 to 8 mm 2 / s, 8 to 12 mm 2 / s, 8 to 11 mm 2 / s, 8 to 10 mm 2 / s, 8 to 9 mm 2 / s, 9 to 12 mm 2 / s, 9 to 11 mm 2 / s, 9 to 10 mm 2 / s, 10 to 12 mm 2 / s, 10 to 11 mm 2 / s or 11 to 12 mm 2 / s.

[0093] Other additives

[0094] The lubricating oil composition of the present invention may also contain conventional lubricant additives for imparting auxiliary functions to obtain a finished lubricating oil composition in which these additives are dispersed or dissolved. For example, the lubricating oil composition may be blended with antioxidants, ashless dispersants, antiwear agents, rust inhibitors, demisters, demulsifiers, friction modifiers, metal deactivators, pour point depressants, viscosity modifiers, defoamers, cosolvents, packaging extenders, corrosion inhibitors, dyes, extreme pressure agents, etc. and mixtures thereof. Various additives are known and commercially available. These additives or their analogous compounds may be employed to prepare the lubricating oil composition of the present invention by conventional blending procedures.

[0095] When used, each of the aforementioned additives is used in a functionally effective amount to impart the desired properties to the lubricant. Thus, for example, if the additive is an ashless dispersant, the functionally effective amount of such ashless dispersant will be an amount sufficient to impart the desired dispersion characteristics to the lubricant. Generally speaking, unless otherwise indicated, when used, the concentration of each of these additives may be in the range of about 0.001 wt % to about 20 wt %, such as about 0.01 wt % to about 10 wt %.

[0096] The following non-limiting examples are illustrative of the present invention. A brief description of how the examples were prepared is provided.

[0097] Example

[0098] Each of the samples described herein contained a dispersant inhibitor package containing one or more of the following:

[0099] Dispersant Inhibitor Package

[0100] 1) Dispersant

[0101] 2) Anti-wear agent

[0102] 3) Detergent

[0103] 4) Antioxidants

[0104] 5) Optional friction modifier

[0105] 6) Optional corrosion inhibitor

[0106] The fully formulated lubricating oil composition comprises a dispersant inhibitor package and a base oil. The composition may also include a viscosity index improver and a pour point depressant.

[0107] The specific detergent components used are described below. Salicylate detergents (A, B, D) were synthesized as or substantially as described in U.S. Pat. No. 8,993,499. Salicylate detergent C was synthesized as or substantially as described in U.S. Pat. No. 8,030,258. Isomerized normal alpha olefins were commercially available from CP Chem.

[0108] Salicylate A

[0109] Salicylate A is prepared by alkylation with C20-24 isomerized normal-alpha olefins. The isomerization level of the alpha olefin is about 0.16. The resulting alkyl hydroxybenzoate composition has a TBN of about 225 mg KOH / g on an oil-free basis and a Ca content of 8 wt%.

[0110] Salicylate B

[0111] Salicylate B is prepared by alkylation with C20-24 isomerized normal-alpha olefins. The isomerization level of the alpha olefin is about 0.16. The resulting alkyl hydroxybenzoate composition has a TBN of about 630 mg KOH / g on an oil-free basis and a Ca content of 22 wt%.

[0112] Salicylate C

[0113] Salicylate C is prepared by alkylation with C20-28 normal-alpha olefins. The resulting alkyl hydroxybenzoate composition has a TBN of about 520 mg KOH / g on an oil-free basis and a Ca content of 19 wt%.

[0114] Salicylate D

[0115] Salicylate D is prepared by alkylation with C14-C18 normal-alpha olefins. The resulting alkyl hydroxybenzoate composition has a TBN of about 300 mg KOH / g on an oil-free basis and a Ca content of about 10.6 wt%.

[0116] Calcium Sulfonate 1

[0117] Calcium Sulfonate 1 is a low overbased calcium sulfonate having a TBN of about 35 mg KOH / g on an oil-free basis and a Ca content of about 4.4 wt%.

[0118] Calcium Sulfonate 2

[0119] Calcium Sulfonate 2 is a highly overbased calcium sulfonate having a TBN of about 700 mg KOH / g on an oil-free basis and a Ca content of about 26 wt%.

[0120] Magnesium sulfonate

[0121] Magnesium sulfonate is a moderately overbased sulfonate having a TBN of about 656 mg KOH / g on an oil-free basis and a Mg content of about 15.4 wt%.

[0122] Phenol salt

[0123] Phenate is a highly overbased calcium phenate having a TBN of about 383 mg KOH / g on an oil-free basis and a Ca content of about 14 wt%.

[0124] HTCBT Test

[0125] Diesel engine lubricating oils were tested using the ASTM D6594 HTCBT protocol to determine their tendency to corrode various metals. Four metal specimens of copper, lead, tin and phosphor bronze were immersed in a measured amount of engine oil. The oil was blown with air (5 l / h) at high temperature (170°C) for a period of time (168h). The copper coupons and the pressurized oil were then examined to detect corrosion and corrosion products, respectively.

[0126] The concentrations of copper, lead, and tin in fresh and pressurized oils and the corresponding changes in metal concentrations are reported below.

[0127]

[0128]

[0129] For the sake of brevity, only some ranges are clearly disclosed herein. However, the range from any lower limit can be combined with any upper limit to list the range that is not clearly listed, and the range from any lower limit can be combined with any other lower limit to list the range that is not clearly listed, in the same way, the range from any upper limit can be combined with any other upper limit to list the range that is not clearly listed. In addition, each point or single value between the endpoints of the scope is included in the scope, even if it is not clearly listed. Therefore, each point or single value can serve as its own lower limit or upper limit to be combined with any other point or single value or any other lower limit or upper limit to list the range that is not clearly listed.

[0130] Likewise, the term "comprising" is considered synonymous with the term "including." Likewise, whenever a composition, an element, or a group of elements is preceded by the transitional phrase "comprising," it should be understood that we also contemplate the same composition or group of elements having the transitional phrases "consisting essentially of," "consisting of," "selected from the group consisting of," or "being" preceding the recitation of the composition, an element, or a plurality of elements, and vice versa.

[0131] As used herein, the terms "a", "an" and "the" should be construed to cover the plural as well as the singular.

[0132] Various terms have been defined above. If a term used in a claim is not defined above, it should be given the broadest definition that persons in the relevant art have given that term as reflected in at least one printed publication or issued patent. In addition, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.

[0133] The foregoing description of the present disclosure illustrates and describes the present disclosure. In addition, the present disclosure shows and describes only preferred embodiments, but as mentioned above, it should be understood that the present disclosure can be used in various other combinations, modifications and environments, and can be changed or modified within the scope of the concepts expressed herein commensurate with the above teachings and / or the technology or knowledge of the relevant field. Although the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the present disclosure can be designed without departing from the basic scope of the present disclosure, and the scope of the present disclosure is determined by the appended claims.

[0134] It should be understood that when combinations, subsets, groups, etc. of elements are disclosed (e.g., combinations of components in compositions, or combinations of steps in methods), while specific reference to each of the various individual and collective combinations and arrangements of these elements may not be explicitly disclosed, each is specifically contemplated and described herein.

[0135] The embodiments described above are further intended to explain the best known modes of practicing it and to enable others skilled in the art to utilize the present disclosure in such or other embodiments and with various modifications required for a particular application or use. Therefore, this specification is not intended to be limited to the forms disclosed herein. In addition, the appended claims are intended to be interpreted as including alternative embodiments.

Claims

1. A lubricating oil composition comprising: a major amount of oil of lubricating viscosity; one or more alkylhydroxybenzoate compounds derived from isomerized normal alpha olefins; and An oxidation inhibitor system comprising a molybdenum-containing antioxidant and diphenylamine; wherein the molybdenum-containing antioxidant is present in an amount to provide at least 120 ppm of Mo to the lubricating oil composition, and wherein the diphenylamine is present in an amount to provide 0.5 wt. % or more to the lubricating oil composition.

2. The lubricating oil composition according to claim 1, wherein the alkylhydroxybenzoate compound has a TBN of 10 to 300 mg KOH / g on an oil-free basis.

3. The lubricating oil composition of claim 1, wherein the one or more alkylhydroxybenzoate compounds have a TBN of 600 mg KOH / g or greater on an oil-free basis.

4. The lubricating oil composition of claim 1, wherein the one or more alkylhydroxybenzoate compounds are a mixture of an alkylhydroxybenzoate compound having a TBN of 10 to 300 mg KOH / g on an oil-free basis and an alkylhydroxybenzoate compound having a TBN of 600 mg KOH / g or more on an oil-free basis.

5. The lubricating oil composition of claim 1, wherein the molybdenum-containing antioxidant is molybdenum succinimide, molybdenum dithiocarbamate or a trinuclear molybdenum compound.

6. The lubricating oil composition of claim 1, further comprising a friction modifier, a viscosity index improver, a corrosion inhibitor or a pour point depressant.

7. The lubricating oil composition of claim 1, wherein the isomerized normal alpha olefin contains 10 to 40 carbon atoms.

8. A method for reducing copper corrosion in an engine, the method comprising: The engine is lubricated with a lubricating oil composition, the lubricating oil composition comprising: a major amount of oil of lubricating viscosity; one or more alkylhydroxybenzoate compounds derived from isomerized normal alpha olefins; and An oxidation inhibitor system comprising a molybdenum-containing antioxidant and diphenylamine; wherein the molybdenum-containing antioxidant is present in an amount to provide at least 120 ppm of Mo to the lubricating oil composition, and wherein the diphenylamine is present in an amount to provide 0.5 wt. % or more to the lubricating oil composition.

9. The method of claim 8, wherein the alkyl hydroxybenzoate compound has a TBN of 10 to 300 mg KOH / g on an oil-free basis.

10. The method of claim 8, wherein the one or more alkyl hydroxybenzoate compounds have a TBN of 600 mg KOH / g or greater on an oil-free basis.

11. The method of claim 8, wherein the one or more alkylhydroxybenzoate compounds are a mixture of an alkylhydroxybenzoate compound having a TBN of 10 to 300 mg KOH / g on an oil-free basis and an alkylhydroxybenzoate compound having a TBN of 600 mg KOH / g or more on an oil-free basis.

12. The method of claim 8, wherein the molybdenum-containing antioxidant is molybdenum succinimide, molybdenum dithiocarbamate or a trinuclear molybdenum compound.

13. The method of claim 1, wherein the lubricating oil composition further comprises a friction modifier, a viscosity index improver, a corrosion inhibitor, or a pour point depressant.

14. The process of claim 8 wherein the isomerized normal alpha olefins contain from 10 to 40 carbon atoms.

15. A lubricating oil composition comprising: a major amount of oil of lubricating viscosity; One or more alkylhydroxybenzoate compounds derived from C10-C40 isomerized normal alpha olefins; and An oxidation inhibitor system comprising a molybdenum-containing antioxidant and diphenylamine; wherein the molybdenum-containing antioxidant is present in an amount to provide at least 120 ppm of Mo to the lubricating oil composition, and wherein the diphenylamine is present in an amount to provide 0.5 wt. % or more to the lubricating oil composition.

16. The lubricating oil composition of claim 15, wherein the alkylhydroxybenzoate compound has a TBN of 10 to 300 mg KOH / g on an oil-free basis.

17. The lubricating oil composition of claim 15, wherein the one or more alkylhydroxybenzoate compounds have a TBN of 600 mg KOH / g or greater on an oil-free basis.

18. The lubricating oil composition of claim 15, wherein the one or more alkylhydroxybenzoate compounds are a mixture of an alkylhydroxybenzoate compound having a TBN of 10 to 300 mg KOH / g on an oil-free basis and an alkylhydroxybenzoate compound having a TBN of 600 mg KOH / g or more on an oil-free basis.

19. The lubricating oil composition of claim 15, wherein the molybdenum-containing antioxidant is molybdenum succinimide, molybdenum dithiocarbamate or a trinuclear molybdenum compound.

20. The lubricating oil composition of claim 15, further comprising a friction modifier, a viscosity index improver, a corrosion inhibitor, or a pour point depressant.

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