Lubricant compositions and methods of using the same

Abstract

The instant disclosure generally relates to lubricating compositions having an oil of lubricating viscosity, an oil of lubricating viscosity, a zinc dialkyl dithiophosphate antiwear agent, a calcium detergent, and a magnesium detergent, wherein the ratio of magnesium provided by the magnesium detergent to calcium provided by the calcium detergent is from 0.16 to 0.3.

Description

Case No. 4850-01- 1 _LUBRICANT COMPOSITIONS AND METHODS OF USING THE SAME SUMMARY

[0001] The instant disclosure relates to a lubricating composition and methods of lubricating an engine with said lubricating composition. The lubricating composition includes an oil of lubricating viscosity, an alkylated alkoxylate, a primary zinc dialkyl dithiophosphate, a calcium detergent in an amount to deliver 800 ppm to 1450 ppm calcium to the lubricating composition, and a magnesium detergent in an amount sufficient to deliver at least 350 ppm magnesium to the lubricating composition. The lubricating composition contains 600 ppm to 800 ppm zinc. In one embodiment, the lubricating composition comprise a mixture of primary zinc dialkyl dithiophosphate and secondary zinc dialkyl dithiophosphate.

[0002] The instant disclosure further relates to methods of lubricating an internal combustion engine by supplying to the engine the lubricating composition as described herein. The invention further provides methods for improving wear performance of a lubricating oil in an engine as well as improving low speed pre-ignition performance.DETAILED DESCRIPTION

[0003] The instant disclosure generally relates to lubricating compositions having an oil of lubricating viscosity, an oil of lubricating viscosity, a zinc dialkyl dithiophosphate antiwear agent, a calcium detergent, and a magnesium detergent, wherein the ratio of magnesium provided by the magnesium detergent to calcium provided by the calcium detergent is from 0.16 to 0.3 or 0.16 to 0.28.Oils of Lubricating Viscosity

[0004] One component of the disclosed compositions is an oil of lubricating viscosity. As used herein, an oil of lubricating viscosity may include natural and synthetic oils, oil derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined, refined, re-refined oils or mixtures thereof, A more detailed description of unrefined, refined and re-refined oils is provided in International Publication W02008 / 147704, paragraphs

[0054] to

[0056] (a similar disclosure is provided in US Patent Application 2010 / 197536, see

[0072] to

[0073] ). A more detailed description of natural and synthetic lubricating oils is described in paragraphs

[0058] to

[0059] respectively of W02008 / 147704 (a similar disclosure is provided in US Patent ApplicationCase No. 4850-01-2- 2010 / 197536, see

[0075] to

[0076] ). The cited portions of both references are incorporated herein. Synthetic oils may also be produced by Fischer-Tropsch reactions and typically may be hydroisomerised Fischer-Tropsch hydrocarbons or waxes. In one embodiment oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to-liquid oils

[0005] Suitable oils may be produced from biological, i.e. natural, sources or by bio-engineered processes. This includes both natural occurring oils, such as vegetable oils and triglyceride oils that may be further refined or purified by standard processes, and those oils that may be derived by biological conversion of a natural chemical into oil directly or by bio-formation of building block pre-cursor molecules capable of being further converted into oil by known processes.

[0006] Oils of lubricating viscosity may also be defined as specified in April 2008 version of " Appendix E - API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils", section 1.3 Sub-heading 1.3. " Base Stock Categories". The API Guidelines are also summarised in US Patent US 7,285,516 (see column 11, line 64 to column 12, line 10), which are incorporated herein by reference.

[0007] In one embodiment the oil of lubricating viscosity may be an API Group I to IV mineral oil, an ester or a synthetic oil, or mixtures thereof. In one embodiment the oil of lubricating viscosity may be an API Group II, Group III, Group IV mineral oil, an ester or a synthetic oil, or mixtures thereof.

[0008] The amount of the oil of lubricating viscosity present is typically the balance remaining after subtracting from 100 wt % the sum of the amount of the additive package according to the instant disclosure and additional, if any, additives. In some embodiments, the oil of lubricating viscosity may be from 80 to 95 wt % of the lubricating compositions. In other embodiments, the oil of lubricating viscosity may be from 80 to 90 wt % of the lubricating composition.

[0009] In the present disclosure, the oil of lubricating viscosity may have a kinematic viscosity measured at 100 °C of 2.4 m2 / s to 6.4 m2 / s. In some embodiments, the kinematic viscosity is from 4.0 m2 / s to 5.0 m2 / s or from 5.2 m2 / s to 5.8 m2 / s or from 6.0 m2 / s to 6.5 m2 / s. In other embodiments, the kinematic viscosity is 6.2 m2 / s or 5.6 m2 / s or 4.6 m2 / s.Case No. 4850-01

[0010] The lubricating composition claimed herein may be in the form of a concentrate and / or a fully formulated lubricant. If the lubricating composition is in the form of a concentrate (which may be combined with additional oil to form, in whole or in part, a finished lubricant), the ratio of the components disclosed herein to the oil of lubricating viscosity and / or to diluent oil include the ranges of 1:99 to 99: 1 by weight, or 80:20 to 10:90 by weight.Zinc Dialkyl Di thiophosphate Anti-Wear Agent

[0011] Zinc dialkyl dithiophosphates may be described as primary zinc dialkyldithiophosphates or as secondary zinc dialkyldithiophosphates, depending on the structure of the alcohol used in its preparation. In some embodiments the compositions of the invention include primary zinc dialkyl dithiophosphates. In some embodiments the compositions of the invention include secondary zinc dialkyldithiophosphates. In some embodiments the compositions of the invention include a mixture of primary and secondary zinc dialkyldithiophosphates. In some embodiments component (b) is a mixture of primary and secondary zinc dialkyldithiophosphates where the ratio of primary zinc dialkyldithiophosphates to secondary zinc dialkyldithiophosphates (one a weight basis) is at least 1:1, or even at least 1:1.2, or even at least 1:1.5 or 1:2, or 1:10. In some embodiments, component (b) is a mixture of primary and secondary zinc dialkyldithiophosphates that is at least 50 percent by weight primary, or even at least 60, 70, 80, or even 90 percent by weight primary.

[0012] Suitable alcohols include those containing up to 30 or to 24, or to 12 carbon atoms, including primary or secondary alcohols. Example of primary alcohols include butyl, amyl, hexyl, octyl, decyl, 2-ethylhexyl and oleyl alcohols as well as any variety of commercial alcohol mixtures having e.g., 8 to 10, 12 to 18, or 18 to 28 carbon atoms. Examples of secondary alcohols include isopropyl, s-amyl, cyclohexyl as well as any variety of commercial alcohol mixtures having e.g., 8 to 10, 12 to 18, or 18 to 28 carbon atoms.

[0013] In one embodiment the ZDDP may be represented by the following structure:S SORCase No. 4850-01-4- wherein each R may be independently a primary or secondary hydrocarbyl group containing from 1 to 24, for example from 2 to 12, carbon atoms. The primary or secondary group is from the alcohol. A ‘"primary ZDDP” is derived from primary alcohol and a “secondary ZDDP” is derived from secondary alcohol.

[0014] In one embodiment of the invention, ZDDP is present in an amount to deliver 600 ppm to 800 ppm zinc to the lubricating composition. In another embodiment of the present invention, the lubricating composition comprises a mixture of primary ZDDP and secondary ZDDP. Where the lubricating composition comprises a mixture of primary ZDDP and secondary ZDDP, the secondary ZDDP is present in an amount sufficient to deliver 200 ppm to 400 ppm, or 200 ppm to 350 ppm, or even 200 ppm to 300 ppm phosphorous to the lubricating composition.Alkaline Earth Metal Detergent

[0015] The lubricating compositions disclosed herein further include an alkaline earth metal detergent. Suitable alkaline earth metal detergents include metal overbased detergents.

[0016] Metal overbased detergents, otherwise referred to as overbased detergents, metalcontaining overbased detergents or superbased salts, are characterized by a metal content in excess of that which would be necessary for neutralization according to the stoichiometry of the metal and the particular acidic organic compound, i.e. the substrate, reacted with the metal. The overbased detergent may comprise one or more of non-sulfur containing phenates, sulfur containing phenates, sulfonates, salicylates, saligenins, salixarates, and mixtures thereof.

[0017] The amount of excess metal is commonly expressed in terms of substrate to metal ratio. The terminology “metal ratio” is used in the prior art and herein to define the ratio of the total chemical equivalents of the metal in the overbased salt to the chemical equivalents of the metal in the salt which would be expected to result from the reaction between the hydrocarbyl substituted organic acid, the hydrocarbyl-substituted phenol or mixtures thereof to be overbased, and the basic metal compound according to the known chemical reactivity and the stoichiometry of the two reactants Thus, in a normal or neutral salt (i.e soap) the metal ratio is one and, in an overbased salt, the metal ratio is greater than one, especially greater than 1.3. The overbased detergent of the invention may have a metal ratio of 5 to 30, or a metal ratio of 7 to 22, or a metal ratio of at least 11.Case No. 4850-01-5-

[0018] The metal-containing detergent may also include "hybrid" detergents formed with mixed surfactant systems including phenate and / or sulfonate components, e.g., phenate / salicylates, sulfonate / phenates, sulfonate / salicylates, sulfonates / phenates / salicylates, as described, for example, in US Patents 6,429,178; 6,429,179; 6,153,565; and 6,281,179. Where, for example, a hybrid sulfonate / phenate detergent is employed, the hybrid detergent would be considered equivalent to amounts of distinct phenate and sulfonate detergents introducing like amounts of phenate and sulfonate soaps, respectively. Overbased phenates and salicylates typically have a total base number of 180 to 450 TBN. Overbased sulfonates typically have a total base number of 250 to 600, or 300 to 500. Overbased detergents are known in the art

[0019] Alkylphenols are often used as constituents in and / or building blocks for overbased detergents. Alkylphenols may be used to prepare phenate, salicylate, salixarate, or saligenin detergents or mixtures thereof. Suitable alkylphenols may include para-substitued hydrocarbyl phenols. The hydrocarbyl group may be linear or branched aliphatic groups of 1 to 60 carbon atoms, 8 to 40 carbon atoms, 10 to 24 carbon atoms, 12 to 20 carbon atoms, or 16 to 24 carbon atoms. In one embodiment, the alkylphenol overbased detergent is prepared from an alkylphenol or mixture thereof that is free of or substantially free of (i.e. contains less than 0.1 weight percent) p-dodecylphenol. In one embodiment, the lubricating composition of the invention contains less than 0.3 weight percent of alkylphenol, less than 0.1 weight percent of alkylphenol, or less than 0.05 weight percent of alkylphenol.

[0020] The overbased metal -containing detergent may be alkali metal or alkaline earth metal salts. In one embodiment, the overbased detergent may be sodium salts, calcium salts, magnesium salts, or mixtures thereof of the phenates, sulfur-containing phenates, sulfonates, salixarates and salicylates.

[0021] In one embodiment, the sulfonate detergent may be predominantly a linear alkylbenzene sulfonate detergent having a metal ratio of at least 8 as is described in paragraphs

[0026] to

[0037] of US Patent Publication 2005 / 065045 (and granted as US 7,407,919). The linear alkylbenzene sulfonate detergent may be particularly useful for assisting in improving fuel economy. The linear alkyl group may be attached to the benzene ring anywhere along the linear chain of the alkyl group, but often in the 2, 3 or 4 position of the linear chain, and in some instances, predominantly in the 2 position, resulting in the linear alkylbenzene sulfonate detergentCase No. 4850-01-6-

[0022] Salicylate detergents and overbased salicylate detergents may be prepared in at least two different manners. Carbonylation (also referred to as carboxylation) of a p-alkylphenol is described in many references including US Patent 8,399,388. Carbonylation may be followed by overbasing to form overbased salicylate detergent. Suitable p-alkylphenols include those with linear and / or branched hydrocarbyl groups of 1 to 60 carbon atoms. Salicylate detergents may also be prepared by alkylation of salicylic acid, followed by overbasing, as described in US Patent 7,009,072. Salicylate detergents prepared in this manner, may be prepared from linear and / or branched alkylating agents (usually 1 -olefins) containing 6 to 50 carbon atoms, 10 to 30 carbon atoms, or 14 to 24 carbon atoms. In one embodiment, the overbased detergent of the invention is a salicylate detergent. In one embodiment, the salicylate detergent of the invention is free of unreacted p-alkylphenol (i.e., contains less than 0.1 weight percent). In one embodiment, the salicylate detergent of the invention is prepared by alkylation of salicylic acid.

[0023] In some embodiments, the metal of the alkaline earth metal detergent is selected from calcium, magnesium, or mixtures thereof In one embodiment, the alkaline earth metal detergent is a calcium sulfonate detergent. In another embodiment, the alkaline earth metal detergent is a calcium salicylate detergent. In another embodiment, the alkaline earth metal detergent is a magnesium sulfonate detergent. In one embodiment, the alkaline earth metal detergent is a mixture of two or more alkaline earth metal detergents. In embodiments where the alkaline earth metal detergent is a mixture, the mixture may include a calcium sulfonate detergent, a calcium salicylate detergent, and a magnesium sulfonate detergent.

[0024] The alkaline earth metal detergent may be present in the lubricating composition in an amount sufficient to deliver at least 500 ppm, or at least 800 ppm, or even at least 1000 ppm alkaline earth metal to the lubricating composition. In another embodiment, where a mixture of detergents is used, calcium detergents may be present in an amount to deliver 400 ppm to 3000 ppm, or 800 ppm to 2500 ppm calcium, or even 800 ppm to 1500 ppm, or even 800 ppm to 1450 ppm calcium, or even 1200 ppm to 1400 ppm to the lubricating composition and a magnesium detergent may be present in an amount sufficient to deliver 50 ppm to 500 ppm or even at least 200 ppm, or even 100 ppm to 400 ppm or 200 ppm to 400 ppm magnesium to the lubricating composition. In one embodiment, the magnesium detergent / s) and the calcium detergent(s) are present in an amount to deliver a magnesium to calcium ratio of from 0.16 to 0.3 or 0.16 to 0.28.Case No. 4850-01-1- Corrosion Inhibitors

[0025] In one embodiment, the lubricating composition contains an alkylated alkoxylate as a corrosion inhibitor.

[0026] In one embodiment, the alkylated alkoxylate corrosion inhibitor is a polyhydric alcohol. In one embodiment, the corrosion inhibitor comprises a polyhydric alcohol with oxyalkylene groups. In one embodiment the corrosion inhibitor comprises a polyhydric alcohol comprising monomeric units of oxyalkylene groups. The polyhydric alcohol is often aliphatic, cycloaliphatic, aromatic, or heterocyclic. The polyhydric alcohol may be selected from the group consisting of aliphatic-substituted cycloaliphatic alcohols, aliphatic-substituted aromatic alcohols, aliphatic-substituted heterocyclic alcohols, cycloaliphatic-substituted aliphatic alcohols, cycloaliphatic-substituted aromatic alcohols, cycloaliphatic-substituted heterocyclic alcohols, heterocyclic-substituted aliphatic alcohols, heterocyclic-substituted cycloaliphatic alcohols, heterocyclic-substituted aromatic alcohols or mixtures thereof.

[0027] The polyhydric alcohol typically contains 2 to 10, 2 to 6 or 2 to 4 hydroxy groups The polyhydric alcohol may be derived from a polyglycol contain up to 150, up to 100, up to 75 or up to 50 oxyalkylene groups. The oxyalkylene group may be present in repeat units present from 2 to 150 repeat units, or 2 to 125 repeat units, 4 to 90 repeat units, or 6 to 45 repeat units. Each oxyalkylene group may independently contain a number of carbon atoms present from 2 to 8, 2 to 5 or 3 to 4. In one embodiment the oxyalkylene group contains 3 or 4 carbon atoms.

[0028] Other examples of polyhydric alcohols include glycols such as ethylene glycol, propylene glycol, butylene glycol, pentaerthyritol, mannitol, sorbitol, glycerol, di-glycerol, triglycerol, tetra-glycerol, erythritol, 2-hydroxymethyl-2-methyl- 1,3-propanediol (trimethylolethane), 2-ethyl-2-(hydroxymethyl)-l,3-propanediol (trimethylolpropane), 1,2,4-hexanetriol and mixtures thereof.

[0029] Exemplary alkylated alkoxylates include the reaction product of an Cl 2-14 alcohol mix with propylene oxide having between 23 - 25 oxypropylene repeat units as described in US6348075B1 and the reaction product of butyl alcohol with propylene oxide having a weight average molecular weight of 2300 g / mol as described in EP3374606B1. Other examples of suitable polyhydric alcohol corrosion inhibitor include a polyalkylene glycol called Pluriol® commercially available from BASF, or Synalox® 100-20B, Synalox® 100-30B, Synalox® 100-50B, Synalox®Case No. 4850-01-8- 100-85B, Synalox® 100-120B or Synalox® 100-150B (all commercially available from Dow). The Synalox® corrosion inhibitors are polyhydric alcohol with oxyalkylene groups that is, poly or oligo-oxyalkylene groups, with very low pour points and high viscosity indices. Typically, the Synalox® corrosion inhibitor comprises a homopolymer or copolymer of propylene oxide. The Synalox® corrosion inhibitor is described in more detail in a product brochure with Form No. 118-01453-0702 AMS, published by The Dow Chemical Company. The product brochure is entitled “SYNALOX Lubricants, High-Performance Polyglycols for Demanding Applications.”

[0030] When the corrosion inhibitor comprises the polyhydric alcohol with poly- or oligo- oxyalkylene groups, typically, the monomeric oxyalkylene groups contain at least 50 wt % or at least 65 wt % or at least 80 wt % or at least 95 wt %, groups of 3 to 8 carbon atoms. In some instances, a number of oxyalkylene groups may be ethylene oxide, provided the corrosion inhibitor is oil soluble.

[0031] In the present invention, the alkylated alkoxylate corrosion inhibitor may be present in amounts of from 0.01 wt% to 0.25 wt° / o or 0.05 wt% to 0.15 wt%, or 0.08 to 0.12 wt% or 0 1 wt%.Other Additives

[0032] The lubricating compositions of the instant disclosure may optionally comprise one or more additional performance additives These additional performance additives may include one or more dispersants, antioxidants, metal deactivators, viscosity modifiers, friction modifiers, corrosion inhibitors, dispersant viscosity modifiers, extreme pressure agents, foam inhibitors, demulsifiers, pour point depressants, seal swelling agents, and any combination or mixture thereof. Typically, fully-formulated lubricating oil will contain one or more of these performance additives, and often a package of multiple performance additives.

[0033] The lubricating compositions of the present invention may also comprise an ashless polyolefin dispersant. The dispersant may be a succinimide dispersant, a polyolefin succinic acid ester, amide, or ester-amide, or mixtures thereof. In one embodiment, the dispersant may be borated. In one embodiment, the dispersant may be present, as a single dispersant. In one embodiment, the dispersant may be present as a mixture of two or three different dispersants, wherein at least one may be a succinimide dispersant.Case No. 4850-01-9-

[0034] The succinimide dispersant may be a derivative of an aliphatic polyamine, or mixtures thereof. The aliphatic polyamine may be aliphatic polyamine such as an ethylenepolyamine, a propylenepolyamine, a butylenepolyamine, or mixtures thereof. In one embodiment, the aliphatic polyamine may be ethylenepolyamine. In one embodiment, the aliphatic polyamine may be selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethyl enepentamine, pentaethylenehexamine, polyamine still bottoms, and mixtures thereof.

[0035] The succinimide dispersant may be a derivative of an aromatic amine, an aromatic polyamine, or mixtures thereof. The aromatic amine may be 4-aminodiphenylamine (ADPA) (also known as N-phenylphenylenediamine), derivatives of ADPA (as described in United States Patent Publications 2011 / 0306528 and 2010 / 0298185), a nitroaniline, an aminocarbazole, an amino-indazolinone, an aminopyrimidine, 4-(4-nitrophenylazo)aniline, or combinations thereof. In one embodiment, the dispersant is derivative of an aromatic amine wherein the aromatic amine has at least three non-continuous aromatic rings.

[0036] The succinimide dispersant may be a derivative of a polyether amine or polyether polyamine. Typical polyether amine compounds contain at least one ether unit and will be chain terminated with at least one amine moiety. The poly ether polyamines can be based on polymers derived from C2-C6 epoxides such as ethylene oxide, propylene oxide, and butylene oxide. Examples of polyether polyamines are sold under the Jeffamine® brand and are commercially available from Hunstman Corporation located in Houston, Texas.

[0037] The dispersant may be a N-substituted long chain alkenyl succinimide. Examples of N-substituted long chain alkenyl succinimide include polyisobutylene succinimide. Typically, the polyisobutylene from which polyisobutylene succinic anhydride is derived has a number average molecular weight of 350 to 5000, or 550 to 3000 or 750 to 2500. Succinimide dispersants and their preparation are disclosed, for instance in U. S. Pat. Nos. 3,172,892, 3,219,666, 3,316,177, 3,340,281, 3,351,552, 3,381,022, 3,433,744, 3,444,170, 3,467,668, 3,501,405, 3,542,680, 3,576,743, 3,632,511, 4,234,435, Re 26,433, and 6,165,235, 7,238,650 and EP Patent 0 355 895B1.

[0038] The dispersant may also be post-treated by conventional methods by a reaction with any of a variety of agents. Among these are boron compounds, urea, thiourea.Case No. 4850-01-10- dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds.

[0039] The dispersant may be borated using one or more of a variety of agents selected from the group consi sting of the various forms of boric acid (including metaboric acid, HBO2, orthoboric acid, H3BO3, and tetraboric acid, H2B4O7), boric oxide, boron trioxide, and alkyl borates. In one embodiment the borating agent is boric acid which may be used alone or in combination with other borating agents. Methods of preparing borated dispersants are known in the art. The borated dispersant may be prepared in such a way that they contain 0.1 weight % to 3.5 weight % boron, or 1.0 weight % to 3.0 weight %, or 0.1 weight % to 2.5 weight % boron or 0.2 to 1.5 weight % boron or 0.3 to 1.0 weight % boron.

[0040] Suitable polyisobutylenes for use in the succinimide dispersant, may include those formed from polyisobutylene or highly reactive polyisobutylene having at least about 50 mol %, such as about 60 mol %, and particularly from about 70 mol % to about 90 mol % or greater than 90 mol %, terminal vinylidene content. Suitable polyisobutenes may include those prepared using BF3 catalysts. In one embodiment the dispersant is prepared from a polyolefin having number average molecular weight (calculated based on total weight of polymer divided by the total number of molecules) of 350 to 3000 Daltons, or 500 to 1500 Daltons, or 800 to 1200 Daltons, and a vinylidene content of at least 50 mol %, or at least 70 mol %, or at least 90 mol %.

[0041] The dispersant may be prepared / obtained / obtainable from reaction of succinic anhydride by an “ene” or “thermal” reaction, by what is referred to as a “direct alkylation process.” The “ene” reaction mechanism and general reaction conditions are summarized in “Maleic Anhydride”, pages, 147-149, Edited by B. C. Trivedi and B. C. Culbertson and Published by Plenum Press in 1982. The dispersant prepared by a process that includes an “ene” reaction maybe a polyisobutylene succinimide having a carbocyclic ring present on less than 50 mole %, or 0 to less than 30 mole %, or 0 to less than 20 mole %, or 0 mole % of the dispersant molecules. The “ene” reaction may have a reaction temperature of 1800C. to less than 300cC., or 200 ° C. to 2500C,, or 2000C. to 2200C.

[0042] The dispersant may also be obtained / obtainable from a chlorine-assisted process, often involving Diels-Alder chemistry, leading to formation of carbocyclic linkages. The process is known to a person skilled in the art. The chlorine-assisted process may produce a dispersant thatCase No. 4850-01-11- is a polyisobutylene succinimide having a carbocyclic ring present on 50 mole % or more, or 60 to 100 mole % of the dispersant molecules. Both the thermal and chlorine-assisted processes are described in greater detail in U. S. Pat. No. 7,615,521, columns 4-5 and preparative examples A and B.

[0043] The dispersant may be used alone or as part of a mixture of non-borated and borated dispersants If a mixture of dispersants is used, there may be two to five, or two to three or two dispersants.

[0044] The lubricating composition of the present invention may contain the dispersant in amounts of at least 1 wt %, or at least 2 wt%, or at least 2.5 wt%, or up to 5 wt% or up to 6 wt% or up to 7 wt% or up to 8 wt% of the lubricating composition. In one embodiment, the dispersant is present in an amount to deliver up to 0.1 wt% or up to 0.11 wt% nitrogen to the lubricating composition.

[0045] In one embodiment, the lubricant composition of the present invention includes an one or more antioxidants In one embodiment, the antioxidant may include an aryl amine antioxidant, such as arylamines, diarylamines, alkylated arylamines, or alkylated diaryl amines. In one embodiment of the present invention, the aryl amine antioxidant comprises or consists of a hydrocarbyl substituted diphenylamine. The hydrocarbyl substituted diphenylamine may include mono- or di- C4 to C 16-, or C6 to C 12-, or C9- alkyl diphenylamine. For example, the hydrocarbyl substituted diphenylamine may be octyl diphenylamine, or di-octyl diphenylamine, dinonyl diphenylamine, typically dinonyl di phenyl amine.

[0046] The diarylamine or alkylated diarylamine may be a phenyl -a-naphthylamine (PANA), an alkylated diphenylamine, or an alkylated phenylnapthylamine, or mixtures thereof. The alkylated diphenylamine may include di-nonyl ated di phenyl amine, nonyl diphenylamine, octyl diphenylamine, di-octylated diphenylamine, di-decylated diphenylamine, decyl diphenylamine and mixtures thereof. In one embodiment, the diphenylamine may include nonyl diphenylamine, dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine, or mixtures thereof. In one embodiment the alkylated diphenylamine may include nonyl diphenylamine, or dinonyl diphenylamine. The alkylated diarylamine may include octyl, di-octyl, nonyl, di-nonyl, decyl or di-decyl phenylnapthylamines.Case No. 4850-01-12-

[0047] Substituted diphenylamines are defined as phenyl amines having a substituent on one or more of the carbon atoms of the phenyl rings. The substituent(s) can be hydrocarbyl substituent(s) selected from aliphatic substituents (including cycloaliphatic), aromatic substituents, substituents with alkyl and aryl moi eties, and mixtures thereof. Substituted diphenylamines of this type include mono-, di-, tri-, and poly- alkyl, alkenyl, alkynyl, alkoxyalkyl, alkylamino, aryl, alkylaryl, and / or alkoxyaryl-substituted diphenylamines, e.g., C1-C24, particularly C6 and higher, alkyl-substituted diphenylamines, such as mono-octyl diphenylamine, di-octyl diphenylamine, mono-butyl-mono-octyl diphenylamine, nonyl diphenylamine, di-nonyl diphenylamine, tri-nonyl diphenylamine, decyl diphenylamine, and di-decyl di phenyl amine, as described, for example, in U. S. Pat. Nos. 2,943,112; 4,824,601; 5,672,752; 6,204,412; 6,315,925; 6,355,839, and U. S. Pub. Nos. 2015 / 0307803 and 2016 / 0017252, as well as polymers of such monomers, as described, for example, in U. S. Pub. No. 20190127526A1. Aryl-substituted diphenylamines include phenyl-a-naphthyl amine (PANA) and alkylated phenyl naphthylamines.

[0048] In the present invention, aryl amine antioxidants may be present in amounts of less than or equal to 3.0 wt %, less than or equal to 2.5 wt %, less than or equal to 2.0 wt%, less than or equal to 1.5 wt%, or less than equal to 1.0 wt %, of the lubricant additive composition. In one embodiment, hydrocarbyl substituted diphenylamine antioxidant is present from 0.1 to 3.0 wt %, or from 0.3 to 2.0 wt %, or from 0.1 to 2.0 wt %, or from 0.1 to 1.5 wt %.

[0049] The lubricating composition of the present invention may also contain a phenolic antioxidant. Exemplary phenolic antioxidants include hindered phenols, including hindered phenol esters, such as phenol alkyl esters, hindered phenol acetates, hindered phenol alkoxides, bis- and polyphenols, condensates of phenols with formic acid and mixtures thereof. Hindered phenol antioxidants often contain a secondary butyl and / or a tertiary butyl group as a sterically hindering group. The phenol group may be further substituted with a hydrocarbyl group (typically linear or branched alkyl) and / or a bridging group linking to a second aromatic group.

[0050] Example phenolic antioxidants that may be used include:• Hindered phenols, such as 2-tert-butyl phenol, 2-tert-butyl-4-methylphenol, 2-tert- butyl-5-methylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, 2,4- dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl -4- methoxyphenol, 3-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,Case No. 4850-01-13- 2,6-di-tert-butyl-4-ethylphenol; 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;• Hindered alkyl phenol esters, such as C7-C9 branched alkyl esters of 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-benzenepropanoic acid, alkyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionates such as n-octadecyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate, n-butyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate and 2'-ethylhexyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate;• Hindered alkoxy phenols, such as 2,6-di-tert-butyl-4-alkoxyphenols, e.g., 2,6-di- tert-butyl-4-methoxyphenol and 2,6-di-tert-butyl-4-ethoxyphenol;• Hindered phenol acetates, such as 3,5-di-tert-butyl-4- hydroxybenzylmercaptooctyl acetate;• Hindered bisphenols, such as 2,2'-methylene-bis(4-alkyl-di-tert-butylphenol)s, e.g., 2,2'-methylenebis(4-methyl-di-tert-butylphenol, and 2,2-methylenebis(4-ethyl-di- tert-butylphenol), bisphenols, such as 4,4'-butylidenebis(3-methyl-6-tert- butylphenol, 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-bis(2,6-di-tert- butylphenol), 2,2-(di-p-hydroxyphenyl)propane, 2,2-bis(3,5-di-tert-butyl-4- hydroxyphenyl)propane, 4,4'-cyclohexylidenebis(2,6-tert-butylphenol), hexamethyleneglycol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], triethyleneglycolbis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], 2,2'-thio-[diethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis{1,1- di methyl -2- [3 -(3 -tert-butyl -4-hy droxy - 5 -m ethyl - phenyl)propionyloxy]ethyl}2,4,8,10-tetraoxaspiro-[5,5]undecane, 4,4'-thiobis(3- methyl-6-tert-butylphenol) and 2,2'-thiobis(4,6-di-tert-butylresorcinol);• Polyphenols such as tetrakis[methylene-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate]methane, 1, 1,3-tris(2-methyl-4-hydroxy-5-tert- butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4- hydroxybenzyl)benzene, bis-[3,3'-bis(4'-hydroxy-3'-tert-butylphenyl)butyric acid]glycol ester, 2-(3',5'-di-tert-butyl-4-hydroxyphenyl)methyl-4-(2",4"-di-tert-Case No. 4850-01-14- butyl-3”-hydroxyphenyl)methyl-6-tert-butylphenol and 2,6-bis(2'-hydroxy-3'-tert- butyl-5'-methylbenzyl)-4-methylphenol;• 4-tert-butylphenol-formaldehyde condensates and 4-tert-butylphenol-acetaldehyde condensates;• and mixtures thereof.

[0051] The hindered phenol antioxidant often contains a secondary butyl and / or a tertian' butyl group as a sterically hindering group. The phenol group may be further substituted with a hydrocarbyl group (typically linear or branched alkyl) and / or a bridging group linking to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butyl phenol, 4-butyl-2,6-di-tert-butvlphenol, and 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment the hindered phenol antioxidant is an ester and may include, e.g., Irganox™ L 135 or L 115 from BASF. Irganox™ L 135 is a phenolic antioxidant, specifically, a mixture of C7-C9 branched alkyl esters of 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-benzenepropanoic acid. Irganox™ L 115 is a higher molecular weight phenolic antioxidant, more specifically, 2,2'-thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] A more detailed description of suitable ester-containing hindered phenol antioxidant chemistry is found in U. S. Pat. No. 6,559,105. In another embodiment, the hindered alkyl phenol is a C4 alkyl ester of 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-benzenepropanoic acid.

[0052] Coupled phenols useful herein may contain two alkylphenols coupled with alkylene groups to form bisphenol compounds. Examples of suitable coupled phenol compounds include 4,4'-methylene bis(2,6-di-tert-butyl phenol); 4-methyl-2,6-di-tert-butylphenol; 2,2'-bis(6-tert-butyl-4-heptylphenol); 4,4'-bis(2,6-di-tert-butyl phenol); 2,2'-methylene bis(4-methyl-6-tert-butylphenol), and 2,2'-methylene bis(4-ethyl-6-tert-butylphenol).

[0053] Other phenolic antioxidants may include polyhydric aromatic compounds and their derivatives. Examples of suitable polyhydric aromatic compounds include esters and amides of gallic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, l,4-dihydroxy-2-naphthoic acid, 3,5-dihydroxynaphthoic acid, 3,7-dihydroxy naphthoic acid, and mixtures thereof. In one embodiment, the phenolic antioxidant comprises a hindered phenol. In another embodiment the hindered phenol is derived from 2,6-di-tert-butyl phenol.Case No. 4850-01-15-

[0054] The phenolic antioxidant may be present in the lubricating composition at a total concentration of at least 0.1 wt. %, or at least 0.5 wt. %, or at least 1 wt. %, or at least 1.5 wt, %, or at least 2 wt. %, or up to 8 wt. %, or up to 6 wt. %, or up to 5 wt. %, or up to 4 wt. %, or up to 3 wt. % of the lubricating composition

[0055] In one embodiment, the lubricating composition contains a sulfurized organic compound. The exemplary sulfurized organic compound helps to control wear in a lubricated device, such as an engine, particularly for extreme pressure conditions in automobile, truck and industrial engines. They can also have very' good thermal oxidation stability and rust inhibition properties.

[0056] The term “active sulfur’’ of a sulfur-containing compound refers to the relative ability of a sulfur-containing compound to react chemically with a metal surface to form a metal sulfide. As used herein, active sulfur is the weight percent of sulfur which is available for a reaction at 150°C, as determined by ASTM D1662-19, “Standard Test Method for Active Sulfur in Cutting Oils,” hereinafter, ASTM D1662. It is to be noted that the active sulfur of a sulfur-containing compound is not merely a function of the mole percent of sulfur that it contains and that two sulfur-containing compounds may have very similar mole % (or weight %) of sulfur but distinctly different weight % of active sulfur. The balance of the sulfur is referred to as inactive sulfur.

[0057] The sulfurized organic compound is generally one which is low in active sulfur, A sulfurized organic compound which is low in active sulfur has either a low weight percent of active sulfur or a low weight % active sulfur in the total sulfur in the sulfurized organic compound, or both.

[0058] Sulfurized organic compounds include those that are substantially nitrogen-free, that is, they do not contain nitrogen functionality. They may be formed by sulfurizing an organic compound containing at least one olefinic double bond (a non-aromatic double bond), that is, one connecting two aliphatic carbon atoms. The organic compounds to be sulfurized may, in some cases, include metal cations (e.g., from Group I or II, e.g., sodium, potassium, barium, calcium); halogen groups (e.g., chloro, bromo, or iodo); and / or oxygen-containing groups, such as ester groups.

[0059] Example sulfurized organic compounds include dibenzyl mono- and disulfides, sulfurized isobutylene, sulfurized methyl esters of oleic acid, sulfurized alkylphenols, sulfurizedCase No. 4850-01-16- dipentene, sulfurized terpenes, and sulfurized Diels-Alder adducts, and phosphosulfurized hydrocarbons such as the reaction product of phosphorus sulfide with turpentine or methyl oleate, and the like.

[0060] The sulfurized organic compound or mixture of compounds particularly useful herein contain(s) little or no active sulfur. Active sulfur compounds include a chain of at least two connected sulfur atoms. The chain of sulfur atoms allows the molecule to break easily between sulfur atoms and the reactive sulfur species formed can cause corrosion of some metals, such as copper. Inactive sulfur compounds contain fewer than two connected sulfur atoms, i.e., each sulfur atom is connected to an atom other than sulfur. Some compounds may include both active sulfur and inactive sulfur, with some of the sulfur content being in a chain of two or more sulfur atoms while the remainder of the sulfur occurs as single sulfur atoms

[0061] The sulfurized organic compound or mixture of sulfurized organic compounds, where two or more such compounds are used, may have an active sulfur content, as determined at 150°C by ASTM D1662, of no more than 8 wt. %, or no more than 6 wt. %, or no more than 5 wt %, or no more than 4 wt. %, %, or no more than 3.5 wt. %, or no more than 3 wt. %, or no more than 2.5 wt %, or as little as 0 wt. % of active sulfur. In some embodiments, the active sulfur is at least 0.1 wt. %, or at least 0.5 wt. %, or at least 1.0 wt. %, or at least 1.5 wt. %, or at least 1.8 wt. %, of the sulfurized organic compound or mixture of sulfurized organic compounds. Where two or more sulfurized organic compound are employed, the active sulfur content is the average (weighted mean) active sulfur content.

[0062] The sulfurized organic compound or mixture of sulfurized organic compounds, where two or more such compounds are used, may have a total sulfur content, as determined in accordance with ASTM D1552-16 (2021), “Standard Test Method for Sulfur in Petroleum Products by High Temperature Combustion and Infrared (IR) Detection or Thermal Conductivity Detection (TCD),” hereinafter D1552, of at least 1 wt. %, or at least 1.5 wt. %, or at least 2 wt %, or no more than 18 wt. %, or no more than 15 wt. %, or no more than 14.0 wt. %, or no more than 12.0 wt. %, or no more than 5 wt, %. Where two or more sulfurized organic compounds are employed, the total sulfur content is the average (weighted mean) sulfur content.

[0063] In one embodiment, the percentage, by weight, of the total sulfur (as determined by ASTM D1552) in the sulfurized organic compound that is active sulfur (as determined by ASTMCase No. 4850-01-17- D1662) may be no more than 25 wt. %, or no more than 22 wt. %, or no more than 20 wt. %, or no more than 18 wt, %, or no more than 15 wt.%, or no more than 14 wt, %, or no more than 12wt.%, or no more than 5 wt.% and may be as little as 0 wt. %, or in some embodiments, at least 1 wt. %, or at least 1.5 wt. %, at least 2 wt.% or at least 6 wt. %, or at least 10 wt. %, or at least 15 wt. %. Put another way, a ratio by weight of active sulfur to sulfur which is not active sulfur in the sulfurized organic compound may be no more than 25:75, or no more than 22:82, or no more than 20:80.

[0064] The sulfurized organic compound(s) may be present in a sufficient amount to provide the lubricating composition with at least 0.01 wt.%, or at least 0.03 wt.%, or at least 0.05 wt.%, or up to 0.5 wt.%, or up to 0.3 wt% or up to 0.2 wt.% sulfur. Other sources of sulfur in the lubricating composition may provide additional amounts of sulfur. In one embodiment, the lubricating composition includes no more than 0.4 wt.% total sulfur, or no more than 0.3 wt. % total sulfur.

[0065] The sulfurized organic compound(s) may be present in a sufficient amount to provide the lubricating composition with up to 0.1 wt% or up to 0.015 wt% or active sulfur or at least 0.003 wt% or at least 0.004 wt% of active sulfur. In general, the sulfurized organic compound(s) are the only sources of active sulfur in the lubricating composition.

[0066] The sulfurized organic compound may be selected from oligomeric polysulfides, alkyl polysulfides, sulfurized esters, sulfurized alpha olefins, sulfurized fats, and sulfurized soybean oil.

[0067] Oligomeric poly sulfides can be of the general form shown in the formula:R1- Sx - [(C(R')vH2-v)n - Sx]p — R2where R1and R2are each independently a C2-C20 alkyl, e.g., a C3, or C4 or higher alkyl, or a C16 or lower alkyl,each R' is independently a C1-C20 alkyl, or a C6 or lower alkyl;each n is independently at least 1, or at least 2, or up to 8, e.g., 3-5, such as 3 or 4;p is independently at least 1, or at least 2, or up to 8;each v is from 0-2, e.g., v is 0, andCase No. 4850-01-18- each x is independently at least 1, or at least 2, or up to 3, or higher, with the proviso that the limits noted above on active sulfur of the sulfurized organic compound(s) are met.

[0068] In general (e.g., for at least 80% of the S -, groups, or at least 90% of the S -, groups, or in some cases all of the Sxgroups) the values of x are no more than 1. The lubricating composition may thus be substantially free of compounds the above formula where x is 4 or higher. “Substantially free” in this context, means that x is 4 or higher in no more than 5%, or no more than 2%, or no more than 1%, or no more than 0.5% of the Sxgroups. The total sulfur content (ASTM D1552) of such oligomeric polysulfides and mixtures thereof may range from 5-45 wt. %, or at least 10 wt. %. The active sulfur content (ASTM D1662) of such oligomeric poly sulfides and mixtures thereof may range from 0.5-10 wt. %, or up to 9 wt. %

[0069] Alkyl poly sulfides can be of the general form shown in the formula:R1— Sx— R2where R1and R2are each independently a C2-C20 alkyl, e.g., a C3 or higher alkyl, or a C16 or lower alkyl; andeach x is independently at least 1, and in some cases may be at least 2, or up to 3, or higher, with the proviso that the limits noted above on active sulfur of the sulfurized organic compound(s) are met. This generally means the value of x is no more than 1.5, or no more than 1.2, on average, and that the lubricating composition is substantially free of compounds of the above formula where x is 4 or higher.

[0070] The total sulfur content (ASTM D1552) of such alkyl polysulfides and mixtures thereof may range from 5-20 wt. %, or at least 10 wt. %. The active sulfur content (ASTM D1662) of such alkyl poly sulfides and mixtures thereof may range from 0.5-45 wt. %, or up to 10 wt. %, or up to 9 wt. %, or up to 5 wt. %. The molecular weight may range from 200 to 2000 Dalton.

[0071] Example sulfurized esters include sulfurized fatty acid esters of an aliphatic alcohol, such as glycerol, e.g., monoglycerides, diglycerides, and triglycerides, such as sulfurized triglycerides of the general form shown in the formula:CH2— O—C(=O)— R3CH2— O— C(=O)—R4CH2"”O““C(:::O)”“R’Case No. 4850-01-19- where R3, R4, and R5are each independently a C8 or higher alkyl or alkenyl group, or a CIO or higher alkyl or alkenyl group, or up to a C30 or up to a C24 alkyl or alkenyl group; andwherein at least one of R3, R4, and R5is linked to a sulfur atom of a sulfur- containing moiety, intermediate ends of the alkyl group.

[0072] Example sulfur-containing moieties can be of the general form:— Sx—, which forms a link between two of R3, R4, and R3; or— Sx— Rb, where R6is a C4 or higher, or a C6, or higher, or a C8 or higher, or a CIO or higher, or up to a C50, linear or branched alkyl or alkenyl group, such as — CH2CH=CHCH2(CH2CH2)qCH3, where q is at least 5, or at least 10, or up to 15; or a mixture thereof;where each x is independently at least 1, and in some cases may be at least 2, or up to 3, or higher, but substantially free of compounds of the above formula where x is 4 or higher, with the proviso that the limits noted above on active sulfur of the sulfurized organic compound(s) are met.

[0073] One example sulfurized fatty acid ester is a sulfurized triglyceride of the general form shown in the formula:—Sx— R6CH2— O— C(=O)— R7CH— R8CH2— O— C(=O)— R9CH— R10SxCH2— O— C(=O)— R11CH— R12where R” is as described above, e.g., CH2CH:::Cf: ICH2(CH2CH2)i3-i5CH3;each of R7, R8, R9, R10, R11, and R12is independently a C2 to C8 alkyl or alkenyl group, e.g., R7is (CH2)6, R8is (CH2)6CH3, R9is (CH2)7, R10is (CH2)6CH3, R11is (CH2)6, and R12is (CH2)6CH3;and each x is independently as described above.Case No. 4850-01-20-

[0074] The total sulfur content (ASTM D1552) of the sulfurized triglyceride according to the above formulas may be at least 5 wt. %, or at least 7 wt. %, or up to 15 wt. %, or up to 12 wt. %.

[0075] The active sulfur (ASTM D1662) of the sulfurized esters or mixture thereof may be less than 5 wt. %, e.g., from 3 - 4 wt. %.

[0076] Other sulfurized esters include sulfurized cycloaliphatic dialkylesters and dialkenyl esters of the general form shown in the formula:where each of R13and R14is independently a C2 or higher alkyl group, such as a C3 or higher, or C4 or higher, or up to CIO, or up to C6 alkyl or alkenyl group, e.g., a linear C4 alkyl group; andx is as described above, e.g., x is 1 or 2.

[0077] The sulfur content of the sulfurized cycloaliphatic diester(s) may be at least 5 wt. % or at least 10 wt, % or up to 15 wt. %, such as 10-14 wt. % and the active sulfur may be 1 to 5 wt. %. For example, the active sulfur content of a mixture of sulfurized cycloaliphatic dibutylesters of the form shown in the above formula may be at least 1 wt. % or at least 1.5 wt. % or up to 5 wt. %, such as up to 3 wt. %.

[0078] Example sulfurized organic compounds include sulfurized olefins (sulfurized alkenes), which can be obtained by reacting a sulfurizing agent with an alkene, such as isobutylene, in the presence of a catalyst. Sulfurizing agents include elemental sulfur, hydrogen sulfide, sulfur halide, sodium sulfide, and a mixture of hydrogen sulfide and sulfur or sulfur dioxide. The amount of sulfurizing agent employed may be calculated based on the total olefinic unsaturation of the mixture. For example, 0.5 to 1.2 moles of sulfur are employed per mole of olefinic bonds. The olefinic compound may contain from 2 to 50 carbon atoms.

[0079] Example sulfurized olefins can be obtained from isobutylene, sulfur and hydrogen sulfide, by catalytic processes using solid catalysts such as those described in U. S. Pat. Nos 6,472,354B2 and 4,876,389A, by reacting a mercaptan and sulfur in the presence of a basicCase No. 4850-01-21- catalyst. They can also be produced by a two-step process, as described in U. S. Pat. No.4,937,385A, which includes synthesizing a mercaptan from an alkene and H2S in the presence of a solid catalyst and then bringing the mercaptan with sulfur and another heterogeneous catalyst together to form the sulfurized olefin.

[0080] A sulfurized olefin as illustrated in herein can be prepared as described in U. S. Pat. No 4,957,651. The method employs a cosulfurized mixture of two or more reactants selected from (1 ) at least one fatty acid ester of a polyhydric alcohol, (2) at least one fatty acid, (3) at least one olefin, and (4) at least one fatty acid ester of a monohydric alcohol. Reactant (3), the olefin component, includes at least one olefin. The olefin may be an aliphatic olefin, containing 4 to 40 carbon atoms, such as from 8 to 36 or 12 to 18 carbon atoms. Terminal olefins, or alpha-olefins, are particularly suitable, especially those having from 12 to 20 carbon atoms.

[0081] A sulfurized organic compound as illustrated herein can be the reaction product of a sulfurizing agent and at least one Diels-Alder adduct, in a molar ratio of at least 0.75: 1. The molar ratio of sulfur source to Diels- Aider adduct may be from 0.75: 1 to 1:1.2 The Diels-Alder adducts can be prepared from dienophiles having at least one carboxylic ester group represented by — C(O)O Ro, where Ro is the residue of a saturated aliphatic alcohol of up to 40 carbon atoms, the aliphatic alcohol from which — Ro. is derived being a mono or polyhydric alcohol, which may be selected from alkylene glycols, alkanols, alkoxy-substituted alkanols, ethanol, ethoxy ethanol, propanol, butanol, beta-diethylamino-ethanol, dodecyl alcohol, diethylene glycol, tripropylene glycol, tetrabutylene glycol, hexanol, octanol, isooctyl alcohol and mixtures thereof. Generally, not more than two C(O)O - Rogroups will be present, and in one embodiment, only one --- C(O)O — Ro group. Such materials can also be described as cyclohexene compounds bearing ester substituents. An example sulfurized organic compound of this type is sulfurized 4-carbobutoxy cyclohexene. This and other sulfurized organic compounds can be further treated with other materials such as an aryl phosphate, e.g., triphenyl phosphite.

[0082] The sulfurization reaction may be effected at an elevated temperature, e.g., 50-350° C or 100-200° C, with efficient agitation and often in an inert atmosphere such as nitrogen, optionally in the presence of an inert solvent.

[0083] Sulfurized organic compounds used in the present invention may have an active sulfur content of no more than 8 wt%, or no more than 6 wt%, or no more than 5 wt%, or no more thanCase No. 4850-01-22“4.0 wt%, or no more than 3 wt%, or no more than 2 wt% of the sulfurized organic compound. In one embodiment, the sulfurized organic compound has a total sulfur content of at least 1 wt% or at least 1.5 wt%, or at least 2 wt%, or no more than 18 wt%, or no more than 15 wt%, or no more than 14 wt%, or no more than 12 wt%, or no more than 5 wt% of the sulfurized organic compound

[0084] In one embodiment, the sulfurized organic compound is present in the lubricating composition in an amount to deliver at least 0.01 wt%, or at least 0.03 wt%, or up to 0.5 wt%, or up to 0.3 wt%, or up to 0.2 wt% sulfur to the lubricating composition. In another embodiment, the sulfurized organic compound is present in an amount to deliver up to 0.1 wt% of active sulfur, or up to 0.01 wt%, or up to 0.008 wt%, or up to 0.005 wt% of active sulfur to the lubricating composition. In still another embodiment, the lubricating composition contains at least 0.1 wt%, or at least 0.15 wt% or at least 0.2 wt% or up to 1 wt%, or up to 0.8 wt% or up to 0.6 wt%, or up to 0.5 wt% or 0.2 wt% of the sulfurized organic compound.

[0085] The lubricating composition of the present invention may also contain an additional dispersant. Suitable dispersants may include carboxylic, amine, Mannich, post-treated, and polymeric dispersant. Dispersants are often known as ashless-type dispersants because, prior to mixing in a lubricating oil composition, they do not contain ash-forming metals and they do not normally contribute any ash forming metals when added to a lubricant and polymeric dispersants.

[0086] Another class of ashless dispersant is Mannich bases. Mannich dispersants are the reaction products of alkyl phenols with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines). The alkyl group typically contains at least 30 carbon atoms.

[0087] Any of the described dispersants may also be post-treated by conventional methods by a reaction with any of a variety of agents. Among these are boron, urea, thiourea, dimercaptothiadiaz oles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, phosphorus compounds and / or metal compounds.

[0088] The optional dispersant can also be a polymeric dispersant. Polymeric dispersants are interpolymers of oil solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substituents, e.g., aminoalkylacrylates or acrylamides and poly-(oxyethylene )-substituted acrylates.Case No. 4850-01-23-

[0089] In one embodiment, the dispersant may comprise an oxyalkylated hydrocarbyl phenol. For example, the oxyalkylated hydrocarbyl phenol may be represented by the structure.wherein each R2is independently hydrogen or a hydrocarbyl group of 1 to 6 carbon atoms; R3is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or an acyl group represented by -C(=O)R5, R5is a hydrocarbyl group of 1 to 24 carbon atoms each R4is independently a hydrocarbyl group of 1 to 220, or 20 to 220, wherein at least one R4contains 25 to 200, or 35 to 180 or 40 to 180 to 60 to 180 or 40 to 96 carbon atoms; n = 1 to 10; and m = 1 to 3.

[0090] In other embodiments, The R4group of the formula above may be located in the para position relative to the oxyalkylated group, and the resultant formula is represented by the structure:wherein variables R2to R5, and n, are defined previously.

[0091] Dispersant viscosity modifiers include functionalized polyolefins, for example, ethylene¬ propylene copolymers that have been functionalized with an acylating agent such as maleic anhydride and an amine: polymethacrylates functionalized with an amine, or esterified styrenemaleic anhydride copolymers reacted with an amine. More detailed description of dispersant viscosity modifiers are disclosed in International Publication W02006 / 015130 or U S Patents 4,863,623; 6,107,257; 6,107,258, and 6,117,825 In one embodiment, the dispersant viscosity modifier may include those described in U. S. Patent 4,863,623 (see column 2, line 15 to columnCase No. 4850-01“24“3, line 52) or in International Publication W02006 / 015130 (see page 2, paragraph

[0008] and preparative examples are described at paragraphs

[0065] to

[0073] ),

[0092] In one embodiment, the invention provides a lubricating composition further comprising a molybdenum compound. The molybdenum compound may be selected from the group consisting of molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, amine salts of molybdenum compounds, and mixtures thereof. The molybdenum compound may provide the lubricating composition with 0 to 1000 ppm, or 5 to 1000 ppm, or 10 to 750 ppm, or 5 ppm to 300 ppm, or 20 ppm to 250 ppm of molybdenum.

[0093] In one embodiment, the invention provides a lubricating composition further comprising a friction modifier. Examples of friction modifiers include long chain fatty acid derivatives of amines, fatty esters, or epoxides; fatty imidazolines such as condensation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; or fatty alkyl tartramides. The term fatty, as used herein, can mean having a C8-22 linear alkyl group

[0094] Friction modifiers may also encompass materials such as sulfurized fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil or monoester of a polyol and an aliphatic carboxylic acid.

[0095] In one embodiment the friction modifier may be selected from the group consisting of long chain fatty acid derivatives of amines, long chain fatty esters, or long chain fatty' epoxides; fatty imidazolines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; and fatty alkyl tartramides. The friction modifier may be present at 0 wt % to 6 wt %, or 0.05 wt % to 4 wt %, or 0.1 wt % to 2 wt % of the lubricating composition.

[0096] In one embodiment, the friction modifier may be a long chain fatty acid ester. In another embodiment the long chain fatty acid ester may be a mono-ester or a diester or a mixture thereof, and in another embodiment, the long chain fatty acid ester may be a triglyceride.

[0097] The lubricating composition may further include metal deactivators, including derivatives of benzotriazoles (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles, or 2-alkyldithiobenzothiazoles; foam inhibitors, including copolymers of ethyl acrylate and 2-ethylhexylacrylate and copolymers of ethyl acrylate and 2-ethylhexylacrylate and vinyl acetate; demulsifiers including trialkylCase No. 4850-01-25- phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxidepropylene oxide) polymers, and pour point depressants, including esters of maleic anhydride¬ styrene, polymethacrylates, polyacrylates or polyacrylamides.

[0098] Pour point depressants that may be useful in the compositions of the invention further include polyalphaolefins, esters of maleic anhydride-styrene, poly(meth)acrylates, polyacrylates or polyacrylamides.

[0099] The lubricant composition for an internal combustion engine may be suitable for any engine lubricant irrespective of the sulfur, phosphorus or sulfated ash (ASTM D-874) content. The sulfur content of the engine oil lubricant may be 1.1 wt % or less, or 0.9 wt % or less, or 0.5 wt % or less, or 0.3 wt % or less. In one embodiment, the sulfur content may be in the range of 0.001 wt % to 0.5 wt %, or 0.01 wt % to 0.3 wt % or 05 to 1.0 wt %. The phosphorus content may be 0.2 vrt % or less, or 0.12 wt % or less, or 0.1 wt % or less, or 0.085 wt % or less, or 0.08 wt % or less, or even 0.06 wt % or less, 0.055 wt % or less, or 0.05 wt % or less. In one embodiment the phosphorus content may be 100 ppm to 1000 ppm, or 200 ppm to 900 ppm, or 300 to 875, or 400 to 850, or 600 to 800. The total sulfated ash content may be 2 wt % or less, or 1.5 wt % or less, or 1.1 wt % or less, or 1 wt % or less, or 0.8 wt % or less, or 075 wt % or less, or 0.7 wt % or less, 0.65 wt % or less. In one embodiment, the sulfated ash content may be 0.05 wt % to 0.9 wt %, or 0, 1 wt % to 0.75 wt % or to 0.3 wt % to 0,7 wt%, or 0.5 to 0.65 wt%.

[0100] In one embodiment, the lubricating composition may be an engine oil, wherein the lubricating composition may be characterized as having at least one of (i) a sulfur content of 0.5 wt % or less, (ii) a phosphorus content of 0.1 wt % or less, (iii) a sulfated ash content of 1.0 wt % or less, or combinations thereof.

[0101] Generally, the lubricant is added to the lubricating system of the internal combustion engine, which then delivers the lubricating composition to the critical parts of the engine, during its operation, that require lubrication. The engine components may have a surface of steel or aluminum (typically a surface of steel) and may also be coated for example with a diamondlike carbon (DLC) coating. Lubricant compositions of the present invention may can improve the wear in the engine.

[0102] An aluminum surface may be comprised of an aluminum alloy that may be a eutectic or hyper-eutectic aluminum alloy (such as those derived from aluminum silicates, aluminumCase No. 4850-01-26-oxides, or other ceramic materials). The aluminum surface may be present on a cylinder bore, cylinder block, or piston ring having an aluminum alloy, or aluminum composite.

[0103] The internal combustion engine may be fitted with an emission control system or a turbocharger. Examples of the emission control system include diesel particulate filters (DPF), or systems employing selective catalytic reduction (SCR).

[0104] The instant lubricating compositions may also be used to reduce or eliminate Low Speed Preignition (“LSPI”) in an engine. In one embodiment, lubricating compositions disclosed herein may be used in a method of reducing LSPI in a direct injection engine by supplying the lubricating composition to said engine. LSPI events may be catastrophic in nature. Hence drastic reduction or even elimination of LSPI events during normal or sustained operation of a direct fuel injection engine is desirable.

[0105] When operating a direct injection engine at speeds less than or equal to 3,000 rpm and under a load with a break mean effective pressure (BMEP) of greater than or equal to 10 bars, an LSPI even may occur. A LSPI event may consist of one or more LSPI combustion cycles, and generally consists of multiple LSPI combustion cycles which occur in a consecutive fashion or alternating fashion with normal combustion cycles in between. Without being bound to a particular theory', LSPI may result from a combustion of oil droplet(s), or a droplet(s) of oil-fuel mixture, or combinations thereof, which may accumulate, for example, in the top land crevices volume of a piston, or the piston ring-land and ring-groove crevices. The lubricant oil may be transferred from below the oil control ring to the piston top land area due to unusual piston ring movements. At low speed, high load conditions, in-cylinder pressures dynamics (compression and firing pressures) may be considerably different from incylinder pressures at lower loads, particularly due to strongly retarded combustion phasing and high boost and peak compression pressures which can influence ring motion dynamics.

[0106] At the foregoing loads, LSPI, which may be accompanied by subsequent detonation and / or severe engine knock, can cause severe damage to the engine very quickly (often within 1 to 5 engine cycles). Engine knock may occur with LSPI given that, after the normal spark from the igniter is provided, multiple flames may be present. The present invention aims to provide a method for inhibiting or reducing LSPI events, the method involving supplying to the engine a lubricant composition as disclosed herein.Case No. 4850-01

[0107] Generally, the lubricant is added to the lubricating system of the internal combustion engine, which then delivers the lubricating composition to the critical parts of the engine, during its operation, that require lubrication. The engine components may have a surface of steel or aluminum (typically a surface of steel) and may also be coated for example with a diamondlike carbon (DLC) coating.

[0108] An aluminum surface may be comprised of an aluminum alloy that may be a eutectic or hyper-eutectic aluminum alloy (such as those derived from aluminum silicates, aluminum oxides, or other ceramic materials). The aluminum surface may be present on a cylinder bore, cylinder block, or piston ring having an aluminum alloy, or aluminum composite.

[0109] The internal combustion engine may be fitted with an emission control system or a turbocharger. Examples of the emission control system include diesel particulate filters (DPF), or systems employing selective catalytic reduction (SCR).

[0110] The internal combustion engine of the present invention is distinct from a gas turbine. In an internal combustion engine, individual combustion events translate from a linear reciprocating force into a rotational torque through the rod and crankshaft. In contrast, in a gas turbine (which may also be referred to as a jet engine) a continuous combustion process generates a rotational torque continuously without translation and can also develop thrust at the exhaust outlet. These differences in operation conditions of a gas turbine and internal combustion engine result in different operating environments and stresses.

[0111] In one embodiment of the invention, the engine is operated at speeds between 500 rpm and 3000 rpm, or 800 rpm to 2800 rpm, or even 1000 rpm to 2600 rpm, or less than 3,000 rpm, or less than 2,500 rpm, or less than 2,000 rpm. Additionally, the engine may be operated with a break mean effective pressure of 10 bars to 15 bars, or 10 to 20 bars, or 10 to 30 bars or 12 bars to 24 bars.

[0112] In one embodiment, the instant disclosure relates to a lubricant composition disclosed herein wherein the lubricant composition is capable of reducing low speed preignition events in a spark-ignited direct injection internal combustion engine operated under a load with a brake mean effective pressure (BMEP) of greater than or equal to 10 bars at speeds less than or equal to 3,000 rpm.Case No. 4850-01-28-

[0113] In another embodiment, the instant disclosure relates to a method for reducing low speed preignition by supplying to a spark-ignited direct injection internal combustion engine a lubricant composition as disclosed herein. The method further includes supplying to a spark-ignited direct injection internal combustion engine operated under a load with a break mean effective pressure (BMEP) of greater than or equal to 10 bars and at speeds less than or equal to 3,000 rpm, any one of the lubricant compositions as disclosed herein.

[0114] In some embodiments, the engine may be fueled with a liquid hydrocarbon fuel, a liquid nonhydrocarbon fuel, or mixtures thereof.

[0115] The instant disclosure further relates to use of any one of the lubricant compositions disclosed herein to reduce low speed preignition in a spark-ignited direct injection internal combustion engine.

[0116] The internal combustion engine of the present invention is distinct from a gas turbine. In an internal combustion engine, individual combustion events translate from a linear reciprocating force into a rotational torque through the rod and crankshaft. In contrast, in a gas turbine (which may also be referred to as a jet engine) a continuous combustion process generates a rotational torque continuously without translation and can also develop thrust at the exhaust outlet. These differences in operation conditions of a gas turbine and internal combustion engine result in different operating environments and stresses,

[0117] In some embodiments, the engine may be fueled with a liquid hydrocarbon fuel, a liquid nonhydrocarbon fuel, or mixtures thereof.

[0118] In one embodiment, the lubricating composition of the present invention has a Total Base Number (TBN) measured according to ASTM D2896-21 of less than 11, or less than 10, or less than 9, or less than 8, or at least 4, or at least 5, or at least 6.

[0119] The present invention provides a method for reducing wear in an engine by supplying to the engine in an engine comprising supplying to the engine the lubricating composition described herein. The engine may be a heavy duty diesel engine or a passenger car gasoline engine. The present invention also provides a method for reducing piston deposits comprising supplying to an engine the lubricating composition described herein. In addition, the present invention provides a method of reducing sulfated ash without lowering detergent ash. Further, the present invention provides for the use of the lubricatingCase No. 4850-01-29- composition as described herein for improving oxidative stability of a lubricating composition or reducing piston deposits in an engine. Engines where the lubricating composition may be used include heavy duty diesel engines and gasoline powered passenger car engines,

[0120] In different embodiments, the lubricating composition may have a composition as described in the following table.Table of EmbodimentsAdditive EmbodimentsA B CPrimary ZDDP 0.20 -■ 1.75 0.50 - 1.50 0.70 - 1.10 Secondary ZDDP 0 - 0.25 0.10 - 0.20 0.18 - 0.19 Calcium Detergent 0.10- 1 70 0.25 - 1.30 0.40 - 1.10 Magnesium Detergent 0.10 - 0.70 0.13 - 0.50 0.16 - 0.30 Ashless Dispersant 0.5 to 8.6 0.8 to 7.5 1.6 to 6.5 Ashless Antioxidant 0.1 to 6.0 0.25 to 4.2 0.5 to 3.75 Corrosion Inhibitor 0.01 - 0.25 0.025 - 0.20 0.05 - 0.15 Sulfurized Olefin 0.05 - 1.2 0.10 - 1.0 0.15 - 0.80 Dispersant Viscosity Modifier 0 to 5.0 0 to 2.6 0.1 to 1.8 F ri cti on Modi fi er O to 1.5 0.01 to 1.2 0.01 to 0.75 Viscosity Modifier 0 to 8 0.2 to 4 0.4 to 2.1 / Xny Other Performance Additive 0 to 3 0.05 to 2.5 0.1 to 1.5Oil of Lubricating Viscosity 75 to 98 82 to 95 87 to 93EXAMPLES

[0121] The disclosure will be further illustrated by the following examples, which set forth particularly advantageous embodiments. While the examples are provided to illustrate the invention, they are not intended to limit it.

[0122] A series of lubricating compositions were prepared as set forth in Table 1. Unless otherwise indicated all treat rates are weight % of the total lubricating composition. The lubricating compositions were evaluatedCase No. 4850-01-30- Table 1Component Ex. 1 Ex. 2 Ex.3 Ex. 4 Group III Base Oil 72.8 72.5 72.7 72.8 Non-dispersant Viscosity Modifier 1.16 1.16 1.16 1.16 Aminic Anti-Oxidant 0.5 0.5 0.5 0.5 Magnesium Sulphonate Detergent 0.29 0.29 0.29 0.29 Primary' ZDDP 0 1.003 0 0 C3 / C6 Secondary ZDDP 0.182 0.000 0.000 0.692 C6 Secondary ZDDP 0.607 0 0.828 0 Calcium Detergents 0.795 0.795 0.795 0.795 Sulphurized Olefin Antioxidant 0.2 0.2 0.2 0.2 Dispersants 2.928 2.928 2.928 2.928 Borated Dispersant 1.71 1.71 1.71 1.71 Phenolic Anti-Oxidant 1 1 1 1 OtherAdditives117.827 17.914 17.888 18.073 Total 100 100 100 100 Sulfated Ash (ASTM D874) 0.78 0.79 0.75 0.79 Calcium 0.1084 0.1084 0.1084 0.1084 Magnesium 0.0475 0.0475 0.0475 0.0475 Phosphorous 0.0761 0.0763 0.0765 0.0760 Sulfur 0.1977 0.2010 0.1980 0.1993 Zinc 0.0832 0.0850 0.0833 0.0840 TON (ASTM D2896) 7.0 7.0 7.0 7.0 RNT Wear Test - N42 Valvetronic RNT Test2Wear rate ratio vs baselineBaseline 0.34 0.9 1.29(comparative 1)1Pour point depressant, antifoam, friction modifier, borate ester, diluent oil, diluent oil from additives- Available from ISP Testing Institute, ISP Sazbergen GmbH & Co. KG. wvvw.isp-testingcom; only parts 0, 3, and 4 of the Test were tun for screening purposes

[0123] A series of lubricating compositions were prepared as summarized in Table 2. Unless otherwise indicated all treat rates are weight % of the total lubricating composition.Case No 4850-01- 31 - Table 2Component Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Group III73.1 74.5 73.15 70 59.8 70.8 71.15 71.4 66.65 72.6 78 60 Base OilPAO 6 0 0 0 0 15 0 0 0 0 0 0 15 PAO 4 0 0 0 0 0 0 0 0 10 0 0 0 Non dispersantViscosity 1.136 1.024 1.136 1.384 0.568 1.144 1.12 1.104 0.712 1.2 0.632 0.568 ModifierSynalox100-120B0 0 0 0 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 CorrosioninhibitorAminic0.5 0.5 0.45 0.5 1.5 1.5 1.45 1.5 2.5 0.8 2.5 1.5 AntioxidantMagnesium 0.29 0.29 0.29 0.29 0.145 0.232 0.232 0.232 0.168 0.168 0.168 0.232 DetergentPrimary0 0 0 0 0.745 0.745 0.745 0.745 0.736 0.736 0.736 0.745 ZDDPC3 / C6Secondary 0.182 0.182 0.182 0.182 0.182 0.182 0.182 0.182 0.191 0.191 0.191 0.182 ZDDPC6 Secondary0.607 0.607 0.607 0.607 0 0 0 0 0 0 0 0 ZDDPCalcium0.795 0.795 0.795 0.795 1.104 0.995 0.995 0.995 0.932 0.932 0.932 0.929 DetergentsSulphurisedOlefin 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0 0 0 0.2 AntioxidantDispersants12.78 2.78 2.78 2.78 5.41 5.194 5.194 5.052 3.806 3.806 3.806 5.41 Borated1.71 1.71 1.71 1.71 0.57 0 57 0.57 0.57 1.14 1 14 1.14 0 57DispersantCase No. 4850-0]-32- Component Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Metal 0 0 0 0 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 DeactivatorMolydithio- 0 0 0 1 0.04 0 0 0.04 0.2 0.025 0.025 0.03 carbamatePhenolic1 1 1 1 1 1 1 1 0.3 0.3 0.3 1 AntioxidantOther17.7 16.411 17.7 20.551 13.586 17.288 17.012 16.830 12.515 17.952 11.420 13.484 Components2Total 100 100 100 100 100 100 100 100 100 100 100 100 Sulfated Ash0.785* 0.7850* 0.7847* 0.7846* 0 8042* 0.7978* 0.7978* 0.8097* 0.7965* 0.7440* 0.7440* 0.8042* (ASTM D874)Calcium 0.1032 0.1083* 0.1061 0.1084* 0 1560* 0.1367 0.1372* 0.1372* 0.1265 0.1298* 0.124 0.1365* Magnesium 0.0481 0.0474* 0.0494 0.0475* 0.02407* 0.0378 0.0381* 0.0381* 0.0285 0.0277* 0.0271 0.0381* Phosphorous 0.0751 0.0761* 0.0783 0.0761* 0.0767* 0.0781 0.0767* 0.0767* 0.0768 0.0770* 0.0752 0.0767* Sulfur 0.1992 0.1968* 0.2048 0.1977* 02036* 0.1878 0.2012* 0.2086* 0 195 0.1742* 0.1702 0.2038* Zinc 0.0891 0.0831* 0.0869 0.0832* 00853* 0.0825 0.0853* 0.0853* 0.0842 0.0856* 0.0841 0.0853* TBN (ASTM7.2 7.1 6.98* 9.29* 8.9* 8.9* 8.9* 8.9* 7.3 8.7* 9.4* D29861.*- CalculatedMg / C a ratio 0.435 0.435 0.435 0.438 0.154 0.274 0.274 0.278 0.210 0.210 0 210 0.279 B48 IUCT – In UseCorrosionTest3White sludgephase comp of c c B BcorrosionOil phasecomp of B c B BcorrosionCase No. 4850-0]Component Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Water Content249 190 249SOT ppmWater Content2.88 1.01 23850 cycles %wtWater Content100 cycles 5.76 222 4 57%wtWater Content8.56 3.29 6.83POT %wtM2ValvetronicRNT WearTest1Wear rate 1.35 0.38 0.5 Wear rate ref(official 0.8 0.58 0.7 reference)Ratio CND1.69 0.66 0.71 RefLSPI TestingFresh LSPIAverage1 5 1IterationsMax Iterations 2 8 3Aged LSPI6Average10 5 6 IterationsMax Iterations 15 8 71Mixture of PIB Succinimide dispersants²Pour point depressant, antifoam, friction modifier, borate ester, diluent oil, diluent oil from additives3Available from ISP Testing Institute, ISP Sazbergen GmbH & Co. KG. www.isp-testing.comCase No 4850-01-34-4Available from ISP Testing. Institute. ISP Sazbergen GmbH & Co. KG. www.isp-testing.com•’ Low Speed Pre-ignition events are measured in two engines, a Ford 2.0L Ecoboost engine and a GM 2.0L Ecotec Both of these engines are turbocharged gasoline direct injection (GDI) engines. The Ford Ecoboost engine is operated at 1750 rpm and 17.0 bar BMEP. The engine is operated at these conditions for a total of 175,000 combustion cycles and LSPI events are counted. The two stages are repeated four times and the number of pre-ignition events are reported as an average The GM Ecotec engine is operated at 2000 rpm and 22.0 bar BMEP with an oil sump temperature of 100°C. The test consists of nine phases of 15,000 combustion cycles with each phase separated by an idle period. Thus combustion events are counted over 135.000 combustion cycles LSPI events are determined by monitoring peak cylinder pressure (PP) and mass fraction bum (MFB) of the fuel charge in the cylinder. When both criteria are met. it is determined that an LSPI event has occurred. The threshold for peak cylinder pressure is typically 9.000 to 10,000 kPa. The threshold for MFB is typically such that at least 2% of the fuel charge is burned late. i.e. before 5.5 degrees After Top Dead Center (ATDC). LSPI events can be reported as events per 100,000 combustion cycles, events per cycle, and / or combustion cycles per event6Residual Effectiveness in Aged Lubricant: The effectiveness of the lubricating compositions described herein in reducing or inhibiting pre-ignition events may be evaluated and characterized, as described above. Residual effectiveness in reducing or inhibiting pre-ignition events may also be evaluated for lubricant compositions that have aged greater than 50 operational hours or 75 operational hours or 100 operational hours or 150 operational hours; that is, hours lubricating an operating GDi engine under simulated driving (or other simulated operational) conditions. In one example, lubricants may be aged by operating the engine with the lubricant under conventional speeds and loads that simulate one or more driving cycles over a desired number of operational hours. To evaluate residual effectiveness in reducing or inhibiting L SPI, fresh and aged oil samples of the same formulation maybe subsequently tested, as provided in the LSPI test procedures disclosed above, or otherwise in an operational engine model that replicates the load and speed conditions where LSPI events would be anticipated and detectable The number of detected LSPI events for the fresh versus the aged oil samples may be compared to each other or to other formulations to determine the extent the lubricant retains the capacity to reduce or inhibit LSPI events after aging. It is known that some of the materials described above may interact in the final formulation, so that the components of the final formulation may be different from those that are initially added. The products formed thereby, including the products formed upon employing lubricant composition in its intended use, may not be susceptible of easy description Nevertheless, all such modifications and reaction products are included within the scope of the present invention.Case No. 4850-01.35 -

[0124] It is known that some of the materials described above may interact in the final formulation, so that the components of the final formulation may be different from those that are initially added. The products formed thereby, including the products formed upon employing lubricant composition of the present invention in its intended use, may not be susceptible of easy description. Nevertheless, all such modifications and reaction products are included within the scope of the present invention; the present invention encompasses lubricant composition prepared by admixing the components described above.

[0125] Unless otherwise stated herein, reference to treat rates or amounts of components present in the lubricating compositions disclosed herein are quoted on an oil free basis, i.e., amount of active.

[0126] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character including one or more double bonds. Examples of hydrocarbyl groups include: hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic- substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring); substituted hydrocarbon substituents, that is, substituents containing non- hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy); hetero substituents, that is, substituents which, while having a predominantly hydrocarbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms and encompass substituents as pyridyl, furyl, thienyl and imidazolyl. Heteroatoms include sulfur, oxygen, and nitrogen. In general, no more than two, or no more than one, non- hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; alternatively, there may be no non-hydrocarbon substituents in the hydrocarbyl group.

[0127] The present disclosure is not to be limited in terms of the particular embodiments described in this application, which are intended as illustrations of various aspects. ManyCase No. 4850-01-36- modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art Functionally equivalent methods and components within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds, or compositions, which can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0128] As used in this document, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art. Nothing in this disclosure is to be construed as an admission that the embodiments described in this disclosure are not entitled to antedate such disclosure by virtue of prior invention. As used in this document, the term "comprising" means "including, but not limited to."

[0129] While various compositions, methods, and devices are described in terms of "comprising" various components or steps (interpreted as meaning "including, but not limited to"), the compositions, methods, and devices can also "consist essentially of or "consist of" the various components and steps, and such terminology should be interpreted as defining essentially closed-member groups.

[0130] With respect to the use of substantially any plural and / or singular terms herein, those having skill in the art can translate from the plural to the singular and / or from the singular to the plural as is appropriate to the context and / or application. The various singular / plural permutations may be expressly set forth herein for sake of clarity.

[0131] It will be understood by those within the art that, in general, terms used herein, and especially in the appended claims (e.g., bodies of the appended claims) are generally intended as "open" terms (e.g., the term "including" should be interpreted as "including but not limited to," the term "having" should be interpreted as "having at least," the term "includes" should be interpreted as "includes but is not limited to," etc.). It will be further understood by those within the art that ifCase No. 4850-01-37- a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation, no such intent is present. For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases "at least one" and "one or more" to introduce claim recitations. However, the use of such phrases should not be construed to imply that the introduction of a claim recitation by the indefinite articles "a" or "an" limits any particular claim containing such introduced claim recitation to embodiments containing only one such recitation, even when the same claim includes the introductory phrases "one or more" or "at least one" and indefinite articles such as "a" or "an" (e.g., "a" and / or "an" should be interpreted to mean "at least one" or "one or more"); the same holds true for the use of definite articles used to introduce claim recitations. In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should be interpreted to mean at least the recited number (e.g., the bare recitation of "two recitations," without other modifiers, means at least two recitations, or two or more recitations). Furthermore, in those instances where a convention analogous to "at least one of A, B, and C, etc." is used, in general, such a construction is intended in the sense one having skill in the art would understand the convention (e.g., "a system having at least one of A, B, and C" would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.). In those instances where a convention analogous to "at least one of A, B, or C, etc." is used, in general, such a construction is intended in the sense one having skill in the art would understand the convention (e g., "a system having at least one of A, B, or C" would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.). It will be further understood by those within the art that virtually any disjunctive word and / or phrase presenting two or more alternative terms, whether in the description, claims, or drawings, should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phrase " A or B" will be understood to include the possibilities of " A” or " B" or " A and B "

[0132] In addition, where features or aspects of the disclosure may be described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.Case No. 4850-01-38-

[0133] As will be understood by one skilled in the art, for any and all purposes, such as in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as "up to," "at least," and the like include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member. Thus, for example, a group having 1-3 wt. % refers to groups having 1, 2, or 3 wt.%. Similarly, a group having 1-5 wt. % refers to groups having 1, 2, 3, 4, or 5 wt. %, and so forth, including all points therebetween.

[0134] Moreover, where a recited range for a treat rate is provided, it is contemplated that such range shall include treat rates for individual components and / or a mixture of components. Thus, for example, a range of 1 to 3 wt % contemplates that a given component may be present in a range of 1 to 3 wt % or that a mixture of similar components can be present in a range from 1 to 3 wt %.

[0135] As used herein, the term "about" means that a value of a given quantity is within ±20% of the stated value. In other embodiments, the value is within ±15% of the stated value. In other embodiments, the value is within ±10% of the stated value. In other embodiments, the value is within ±5% of the stated value. In other embodiments, the value is within ±2.5% of the stated value. In other embodiments, the value is within ±1% of the stated value.

[0136] Unless otherwise stated, ‘"wt %” as used herein shall refer to the weight percent based on the total weight of the lubricating composition on an oil-free basis.

Claims

Case No. 4850-01-39- What is claimed is:

1. A lubricating composition for an internal combustion engine, comprising:an oil of lubricating viscosity;zinc dialkyl dithiophosphate in an amount to deliver 600 ppm to 800 ppm phosphorous to the lubricating composition,a calcium detergent;a magnesium detergent;wherein the ratio of magnesium provided by the magnesium detergent to calcium provided by the calcium detergent is from 0.16 to 0.3 or 0.16 to 0.28.

2. The lubricating composition of claim 1, wherein the calcium detergent has a TBN of 100 to 700 or 300 to 600 (ASTM D2896).

3. The lubricating composition of claim 2, wherein the calcium detergent comprises or consists of a calcium salicylate detergent.

4. The lubricating composition of any of claims 1 to 3, wherein the magnesium detergent comprises a magnesium sulfonate having a TBN of 100 to 900 or 120 to 850 (ASTM D2896).

5. The lubricating composition of claim 4, wherein the magnesium detergent comprises or consists of a magnesium sulfonate detergent.

6. The lubricating composition of any of claims 1 to 5, wherein the zinc dialkyl di thiophosphate comprises a mixture of primary zinc dialkyl dithiophosphate and secondary zinc dialkyl dithiophosphate.

7. The lubricating composition of claim 4, wherein the secondary zinc dialkyl dithiophosphate is present in an amount sufficient to deliver 200 ppm to 400 ppm or 200 ppm to 350 ppm, or 200 ppm to 300 ppm phosphorous to the lubricating composition.Case No. 4850-01-40- 8. The lubricating composition of any of claims 1 to 7, wherein the oil of lubricating viscosity has a viscosity of 4 cSt to 8 cSt or 4 cSt to 6 cSt (ASTM D445 at 100°C).

9. The lubricating composition of any of claims 1 to 8, wherein the oil of lubricating viscosity comprises or consists of a Group III oil.

10. The lubricating composition of any of claims 1 to 9, wherein the oil of lubricating viscosity comprises or consists of a Group IV oil.

11. The lubricating composition of any of claims 1 to 10, wherein the oil of lubricating viscosity comprises a mixture of Group III oil and Group IV oil.

12. The lubricating composition of any of claims 1 to 11, further comprises an alkylated alkoxy late.

13. The lubricating composition of any of claims 1 to 12, wherein the alkylated alkoxylate comprises or consists of a polyetheramine prepared via cyanoethylation and hydrogenation of poly ether from a C 12- 15 alcohol having an average of 24 repeating units from propylene oxide.

14. The lubricating composition of any of claims 1 to 7, wherein the alkylated alkoxylate comprises or consists of polypropylene glycol monobutyl ether.

15. The lubricating composition of any of claims 1 to 14, wherein the lubricating composition comprises less than 1 wt% ash measured by ASTM D874.

16. The lubricating composition of any of claims 1 to 15, wherein the calcium detergent is present in an amount to deliver 800 ppm to 1450 ppm calcium to the lubricating composition.Case No. 4850-01-41- 17. The lubricating composition of any of claims 1 to 16, wherein the magnesium detergent is present in an amount sufficient to deliver at least 350 ppm magnesium to the lubricating composition.

18. A method for lubricating an internal combustion engine comprising suppling to the internal combustion engine the lubricating composition of any of claims 1 to 17.

19. The method of claim 18, wherein the internal combustion engine is a spark-ignited direct injection internal combustion engine operated under a load with a break mean effective pressure (BMEP) of greater than or equal to 10 bars and at speeds less than or equal to 3000 rpm.

20. A method for reducing low speed pre-ignition in an engine, comprising suppling to a spark-ignited direct injection internal combustion engine the lubricating composition of any of claims 1 to 17.

21. The method of claim 20, wherein the engine is operated under a load with a break mean effective pressure (BMEP) of greater than or equal to 10 bars and at speeds less than or equal to 3,000 rpm.

22. The method of claim 19 or 20, wherein the engine is fueled with a liquid hydrocarbon fuel, a liquid nonhydrocarbon fuel, or mixtures thereof.

23. The use of the lubricating composition of any of claims 1 to 17 to reduce low speed pre¬ ignition in an engine.

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