FIELD OF INVENTION [0001] The disclosed technology provides lubricating compositions comprising an oil of lubricating viscosity, an alkaline earth metal sulfonate detergent having a metal ratio of at least 10, in an amount to contribute 3 to 14 g KOH/kg of TBN to the lubricating composition, an ashless, sulfur free, hydrocarbyl phenolic compound in an amount of 0.4 to about 6.0 weight percent (wt%) of the composition, and an ashless dispersant; wherein the lubricating composition has total ash of 0.3 to 1.8 wt%, total detergent soap of 0.1 to 1.2 wt% and wherein the lubricating composition contains less than 0.1 wt% of a sulfur-containing phenolic detergent.

[0002] The disclosed technology further relates to a method of lubricating an internal combustion engine with the lubricating composition.

[0003] The disclosed technology further relates to the use of the of the lubricating composition in an internal combustion engine to improve control of at least one of the following: (i) fuel economy, (ii) corrosion, (iii) cleanliness, (iv) bore wear and (v) seals protection.

BACKGROUND OF THE DISCLOSED TECHNOLOGY [0004] Lubricating compositions for heavy duty diesel engines have historically relied on sulfonate and particularly high soap containing sulfonate detergents for cleanliness. For purposes of this disclosure, "high soap" refers to a detergent having a metal ratio of less than 5. High soap sulfonates contribute heavily to ash and little to lubricant total base number (TBN) and thus, there is a desire to formulate away from the use of high soap sulfonate detergents, while maintaining lubricant properties, such as cleanliness and seals performance. One potential alternative is to replace high soap sulfonates with phenate detergents, which contributed TBN and lower ash; however, regulatory pressure is reducing the desirability of formulating with phenate detergents.

[0005] Accordingly, there remains need for lubricant formulations for heavy duty diesel engines that demonstrate excellent capacity to neutralize acid, good cleanliness and anti- wear properties and acceptable corrosion and seals performance, while limiting phenate detergents and undesirable emissions.

SUMMARY OF THE DISCLOSED TECHNOLOGY

[0006] The obj ectives of the disclosed technology include providing a lubricating composition which results in acceptable or improved control of at least one of the following (i) control of fuel economy, (ii) control of corrosion, (iii) cleanliness, (iv) control of bore wear, and (v) seals protection in an internal combustion engine, which may be a heavy duty diesel internal combustion engine.

[0007] In one embodiment the disclosed technology provides a lubricating composition comprising: an oil of lubricating viscosity, an alkaline earth metal sulfonate detergent having a metal ratio of at least 10, in an amount to contribute 3 to 14 g KOH/kg of TBN to the lubricating composition, an ashless, sulfur-free, hydrocarbyl phenolic compound in an amount 0.4 wt% to about 6.0 wt% of the composition and wherein the lubricating composition has total ash of 0.3 to 1.8 wt%, total detergent soap of 0.1 to 1.2 wt% and wherein the lubricating composition contains less than 0.1 wt% of a sulfur-containing phenolic detergent.

[0008] In one embodiment, the lubricating composition may comprise less than 0.3 wt% or 0.2 wt% or 0.1 wt% or 0.05 wt% or 0.01 wt% of an alkaline earth metal sulfonate detergent having a metal ratio of less than 10 and in another embodiment, may be free or substantially free of an alkaline earth metal sulfonate detergent having a metal ratio of less than 10.

[0009] In another embodiment of the invention, the ashless, sulfur free, hydrocarbyl phenolic compound may comprise an oxyalkylated hydrocarbyl phenolic compound.

[0010] In another embodiment, the oxyalkylated hydrocarbyl phenolic compound may comprise a hydrocarbyl group containing 25 to 200 carbon atoms or 25 to 175 or 25 to 140, or 30 to 100 carbon atoms.

[0011] In another embodiment, the oxyalkylated hydrocarbyl phenolic compound may comprise an oxyalkylated polyisobutylene phenolic compound.

[0012] In another embodiment, the oxyalkylated group of the oxyalkylated hydrocarbyl phenolic compound may have the formula— (R ¹ 0) _n — , wherein each R ¹ is independently selected from the group consisting of an ethylene group, a propylene group, and a butylene group; and n may independently be from 1 to 50, or 1 to 20, or 1 to 10, or 2 to 5. [0013] In accordance with another embodiment, the oxyalkylated hydrocarbyl phenolic compound may be present in an amount of 0.4 wt% to about 5.0 wt% (or 0.4 to 4.0 wt%, or 0.5 to 2.5 wt% or 0.7 to 2.0 wt%) of the lubricating composition.

[0014] According to still another embodiment of the invention, the ashless, sulfur free, hydrocarbyl phenolic compound may comprise an oxyalkylated hydrocarbyl phenolic compound and an alkylated phenolic antioxidant (selected from alkyl phenols, hindered phenols, coupled phenolic compounds and mixtures).

[0015] According to a further embodiment, the alkylated phenolic antioxidant may be derived from a 2,6 dialkyl phenol, wherein each alkyl group is independently selected from alkyl groups containing 3 to 8 carbon atoms.

[0016] According to another embodiment, the alkylated phenolic antioxidant may be present in an amount of at least 0.1 wt%, or 0.2 wt% or 0.5 wt% and up to about 3.0 wt% or 2.5 wt% or 2.0 wt% or 1.5 wt%.

[0017] According to a further embodiment, the ashless dispersant may comprise the reaction product of a high-vinylidene polyisobutylene acylating agent and an amine, wherein the polyisobutylene contains greater than about 50 mole%, 60 mole%, or 70 mole% or greater and usually about 80 mole% or greater or 90 mole% or greater of alpha-vinylidene and/or beta- double bond isomer.

[0018] According to another embodiment, the metal of the alkaline earth metal sulfonate detergent may be selected from calcium, magnesium, and titanium.

[0019] According to still a further embodiment, the lubricating composition may further comprise a boron containing compound.

[0020] In another embodiment, the lubricating composition may be substantially free of phenates.

[0021] In one embodiment, the lubricating composition may have a total TBN of 3 to 15 gKOH/Kg.

[0022] In another embodiment, the lubricating composition may have a phosphorus level between about 0.04 and about 0.12 wt%.

[0023] In one embodiment, the disclosed technology provides a method of lubricating an internal combustion engine comprising supplying to the internal combustion engine a lubricating composition of a lubricating disclosed herein. [0024] In one embodiment, the engine may be a compression-ignition internal combustion engine, which may be a heavy duty diesel internal combustion engine.

[0025] In one embodiment, the vehicle powered by the compression-ignition internal combustion engine may have a maximum laden mass over 3,500 kg.

[0026] The lubricating composition may have a SAE viscosity grade of XW-Y, wherein X may be 0, 5, 10, or 15; and Y may be 16, 20, 30 or 40.

[0027] The internal combustion engine may have a steel surface on a cylinder bore, a cylinder block, and/or a piston ring.

[0028] The disclosed technology may also provide for a method of providing high TBN lubricant composition while maintaining good cleanliness and/or corrosion control in a compression-ignition internal combustion engine comprising supplying to the engine a lubricating composition disclosed herein.

[0029] In one embodiment the disclosed technology provides for the use of the lubricating composition described herein to provide at least one of (i) control of fuel economy, (ii) control of corrosion, (iii) cleanliness (typically control of deposits, typically control/reduction of soot), (iv) control of bore wear and (v) control of seals wear in an internal combustion engine. Typically, the internal combustion engine is a heavy duty diesel internal combustion engine.

DETAILED DESCRIPTION OF THE DISCLOSED TECHNOLOGY Definitions

[0030] As used herein, reference to the amounts of additives present in the lubricating composition disclosed are quoted on an oil free basis, i.e., amount of actives, unless otherwise indicated.

[0031] As used herein, the transitional term "comprising," which is synonymous with "including," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional, un-recited elements or method steps. However, in each recitation of "comprising" herein, it is intended that the term also encompass, as alternative embodiments, the phrases "consisting essentially of and "consisting of," where "consisting of excludes any element or step not specified and "consisting essentially of permits the inclusion of additional un-recited elements or steps that do not materially affect the basic and novel, and essential characteristics of the composition or method under consideration. [0032] As used herein, the term "TBN" means total base number as measured using ASTM D2986-1 1.

[0033] As used herein, the term "hydrocarbyl", "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. Examples of hydrocarbyl groups include: hydrocarbon substituents, including aliphatic, alicyclic, and aromatic substituents; substituted hydrocarbon substituents, that is, substituents containing non- hydrocarbon groups which, in the context of this disclosed technology, do not alter the predominantly hydrocarbon nature of the substituent; and hetero substituents, that is, substituents which similarly have a predominantly hydrocarbon character but contain other than carbon in a ring or chain. A more detailed definition of the term "hydrocarbyl substituent" or "hydrocarbyl group" is described in paragraphs [01 18] to [01 19] of PCT Publication WO2008/147704, or a similar definition in paragraphs [0137] to [0141] of US Publication 2010-0197536.

[0034] As used herein, the term "detergent soap" means the neutral metal salt of the detergent substrate, where the term "substrate" means the anionic component of the soap.

[0035] As used herein, the term "free of may mean that none of the substance is intentionally added or that the amount present is not detectable by common methods or is not detectable at greater than contaminant amounts. "Substantially free of means that the material is present in an amount less than that amount which will have a commercially useful benefit for the property contributed by the additive in question.

Oils of Lubricating Viscosity

[0036] The lubricating composition comprises an oil of lubricating viscosity. Such oils 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 PCT Publication WO2008/147704, paragraphs [0054] to [0056] (a similar disclosure is provided in US Publication 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 WO2008/147704 (a similar disclosure is provided in US Publication 2010/197536, see [0075] to [0076]). 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.

[0037] 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 7,285,516 (see column 1 1, line 64 to column 12, line 10). In one embodiment, the oil of lubricating viscosity may be an API Group II, Group III, Group IV oil, or mixtures thereof.

[0038] 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 compound of the disclosed technology and the other performance additives.

[0039] The lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant. If the lubricating composition of the disclosed technology (comprising the additives disclosed herein) 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 of these additives 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.

Detergents

[0040] The lubricating compositions may comprise one or more detergents, including at least one alkaline earth metal sulfonate detergent having a metal ratio of at least 10.

[0041] The alkaline earth metal sulfonate detergent having a metal ratio of at least 10 will be present in the lubricating composition in an amount to contribute between about 3 to 14 g KOH/kg of TBN, or about 5 to 12 g KOH/kg of TBN to the lubricating composition. For purposes of clarity, this refers to the sum of the TBN contributed by all of the alkaline earth metal sulfonate detergents having a metal ratio of at least 10 that are in the lubricating composition.

[0042] The lubricating composition will also have a total amount of detergent soap, that is, the sum of all soap from all detergents, of 0.1 to 1.2 wt% or 0.1 to 1.1 wt% or 0.1 to 0.9 wt% (or 0.3 to 0.9 wt% or 0.5 to 0.9 wt%) with respect to the lubricating composition. [0043] Suitable alkaline earth metal sulfonate detergents may include magnesium or calcium sulfonate detergents and mixtures thereof. In one embodiment, the alkaline earth metal sulfonate detergent having a metal ratio of at least 10 may be a calcium sulfonate detergent and in another embodiment, may be a magnesium sulfonate detergent and in still another embodiment may comprise a mixture of a magnesium and calcium sulfonate detergent, each having a metal ratio of at least 10.

[0044] The term "metal ratio" means the ratio of the total equivalents of the metal to the equivalents of the acidic organic compound. A neutral metal salt has a metal ratio of one. A salt having 4.5 times as much metal as present in a normal salt will have metal excess of 3.5 equivalents, or a ratio of 4.5. The term "metal ratio is also explained in standard textbook entitled "Chemistry and Technology of Lubricants", Third Edition, Edited by R. M. Mortier and S. T. Orszulik, Copyright 2010, page 219, sub-heading 7.25. In the present invention, the alkaline earth metal sulfonate detergent will have a metal ratio of 10 and higher or 12 or 14 or 16 or 20 and higher. The metal ratio may be 10 to about 30.

[0045] The alkaline earth metal sulfonate detergent may be overbased. Overbased detergents are known in the art. Overbased materials, otherwise referred to as overbased or superbased salts, are generally single phase, homogeneous Newtonian systems characterized by a metal content in excess of that which would be present for neutralization according to the stoichiometry of the metal and the particular acidic organic compound reacted with the metal. The overbased materials are prepared by reacting an acidic material (typically an inorganic acid or lower carboxylic acid, typically carbon dioxide) with a mixture comprising an acidic organic compound, a reaction medium comprising at least one inert, organic solvent (mineral oil, naphtha, toluene, xylene, etc.) for said acidic organic material, a stoichiometric excess of a metal base, and a promoter such as a calcium chloride, acetic acid, phenol or alcohol. The acidic organic material will normally have a sufficient number of carbon atoms to provide a degree of solubility in oil. The alkaline earth metal sulfonate detergent having a metal ratio of 10 or higher may typically have a total base number of 250 to 600, or 300 to 500.

[0046] In one embodiment the alkaline earth metal sulfonate detergent may be a predominantly linear alkylbenzene sulfonate detergent having a metal ratio of at least 10. Linear alkyl benzenes may have the benzene ring attached anywhere on the linear chain, usually at the 2, 3, or 4 position, or mixtures thereof. The predominantly linear alkylbenzene sulfonate detergent may be particularly useful for assisting in improving fuel economy. In one embodiment, the sulfonate detergent may be a branched alkylbenzene sulfonate detergent. Branched alkylbenzene sulfonate may be prepared from isomerized alpha olefins, oligomers of low molecular weight olefins, or combinations thereof. Typically oligomers include tetramers, pentamers, and hexamers of propylene and butylene. In one embodiment the sulfonate detergent may be a metal salt of one or more oil-soluble alkyl toluene sulfonate compounds.

[0047] While chiefly limited by the range of TBN that is to be contributed to the lubricating composition by the alkaline earth metal sulfonate detergent having a metal ratio of at least 10, according to the present invention, in some embodiments, the alkaline earth metal sulfonate detergent having a metal ratio of at least 10 may be present at 0.2 wt% to 2.5 wt%, or 0.3 wt% to 2.2 wt%, or 0.6 wt% to 1.8 wt%. In one useful embodiment, the alkaline earth metal sulfonate detergent having a metal ratio of at least 10 may comprise a magnesium sulfonate detergent and a calcium sulfonate detergent.

[0048] By contrast, in some embodiments, the lubricating compositions of the present invention will comprise less than 0.3 wt% or less than 0.2 wt% or less than 0.1 wt% of an alkaline earth metal sulfonate detergent having a metal ratio of less than 10 (or 5) and another embodiment, may be free of or substantially free of an alkaline earth metal sulfonate detergent having a metal ratio of less than 10 (or less than 5).

Other Detergents

[0049] The lubricating composition of the present invention may comprise one or more additional detergents, other than the alkaline earth metal sulfonates discussed above, provided the total soap from all detergents does not exceed the limit of 1.2 wt% or 1.1 wt% or 0.9 wt% of the lubricating composition.

[0050] In some embodiments, phenol-based detergents may be present and may be chosen from a non-sulfur containing phenate, a sulfur- coupled phenate, a salixarate, a salicylate, a saligenin, and mixtures thereof.

Phenate Detergents

[0051] Non-sulfur containing phenates and sulfur containing phenates are known in the art. The non-sulfur containing phenate, or sulfur containing phenate may be neutral or overbased. Typically, an overbased non-sulfur containing phenate, or a sulfur containing phenate will have a total base number of 180 to 450 TBN and a metal ratio of 2 to 15, or 3 to 10. A neutral non-sulfur containing phenate, or sulfur containing phenate may have a TBN of 50 to less than 180 and a metal ratio of 1 to less than 2, or 0.05 to less than 2.

[0052] Phenate detergents are typically derived from p-hydrocarbyl phenols. Alkylphenols of this type may be coupled with sulfur and overbased, coupled with aldehyde and overbased, or carboxylated to form salicylate detergents. For purposes of clarity, a carboxylated phenate detergent is referred to herein as a salicylate detergent and not a phenate detergent and thus is not included in phenate detergents for purposes of embodiments containing restrictions on the amount of phenate detergent present. Suitable alkylphenols include those alkylated with oligomers of propylene, i.e. tetrapropenylphenol (i.e. p-dodecylphenol or PDDP) and pentapropenylphenol. Suitable alkylphenols also include those alkylated with oligomers of butane, especially tetramers and pentamers of n-butenes. Other suitable alkylphenols include those alkylated with alpha- olefins, isomerized alpha-olefins, and polyolefins like polyisobutylene.

[0053] In one embodiment, the lubricating composition may comprise a neutral non-sulfur containing phenate, or sulfur containing phenate having a TBN of 50 to less than 180 or 50 to 150 or 50 to 100 and a metal ratio of 1 to less than 2, or 0.05 to less than 2. The non-sulfur containing phenate, or sulfur containing phenate may be in the form of a calcium or magnesium non-sulfur containing phenate, or sulfur containing phenate (typically calcium non-sulfur containing phenate, or sulfur containing phenate).

[0054] In one embodiment, the lubricating composition may comprise 0.1 to 0.9 wt%, or 0.2 to 0.9 wt% or 0.5 to 0.9 wt% or 0.6 to 0.8 wt% of a sulfur free phenate detergent, which may be a formaldehyde (methylene) coupled magnesium or calcium phenate detergent, typically a magnesium phenate detergent, which may be neutral or overbased and is typically neutral.

[0055] In one embodiment, the lubricating composition may comprise less than 0.1 wt%, or less than 0.05 wt%, or even less than 0.01 wt% of a sulfur containing phenate detergent. In one embodiment, the lubricating composition is free or substantially free of a sulfur containing phenate detergent.

[0056] In still another embodiment, the lubricating composition may comprise less than 0.1 wt%, or less than 0.05 wt%, or even less than 0.01 wt% of any phenate detergent. In one embodiment the lubricating composition may be free of an overbased phenate, and in a different embodiment the lubricating composition may be free of a non-overbased phenate. In another embodiment, the lubricating composition may be free of a metal containing phenate detergent. In another embodiment, the lubricating composition may be free of an ashless containing phenate detergent.

Salicylate Detergents

[0057] The lubricating composition may comprise a metal containing salicylate detergent that may be neutral or overbased. Salicylate detergents are known in the art. The salicylate detergent may have a TBN of 50 to 400, or 150 to 350, and a metal ratio of 0.5 to 10, or 0.6 to 2.

[0058] Suitable metal containing salicylate detergents may include derivates of alkylated salicylic acid, or alkylsalicylic acid. Alkylsalicylic acid may be prepared by alkylation of salicylic acid or by carbonylation of alkylphenol. When alkylsalicylic acid is prepared from alkylphenol, the alkylphenol is selected in a similar manner as the phenates described above. In one embodiment, alkylsalicylate of the invention include those alkylated with oligomers of propylene, i.e. tetrapropenylphenol (i.e. p- dodecylphenol or PDDP) and pentapropenylphenol. Suitable alkylphenols also include those alkylated with oligomers of butane, especially tetramers and pentamers of n-butenes. Other suitable alkylphenols include those alkylated with alpha-olefms, isomerized alpha-olefins, and polyolefins like polyisobutylene.

[0059] In one embodiment, the lubricating composition comprises a calcium salicylate detergent, a magnesium salicylate detergent or mixtures thereof, typically a calcium salicylate detergent.

[0060] When present, the metal containing salicylate detergent may be present at 0.01 to 0.8 wt%, or 0.1 to 0.5 wt%, or 0.1 to 0.4 wt% or 0.2 to 0.5 wt% of the lubricating composition.

Salixarate/Saligenin/Hybrid Phenol Detergents

[0061] The lubricating composition may comprise a metal containing salixarate detergent that may be neutral or overbased. Salixarate derivatives and methods of their preparation are described in greater detail in U.S. Patent 6,200,936 and PCT Publications WO01/56968 and WO03/18728. It is believed that the salixarate derivatives have a predominantly linear, rather than macrocyclic, structure, although both structures are intended to be encompassed by the term "salixarate." Additionally Linear" does not exclude branching or other structures in the substituent R groups.

[0062] The salixarate may have a TBN of 50 to 300, or 100 to 260 and a metal ratio of 1 to 10, or 2 to 6.5. [0063] When present, the metal containing salixarate detergent may be present 0.01 to 0.8 wt%, or 0.1 to 0.5 wt%, or 0.1 to 0.4 wt% or 0.2 to 0.5 wt% of the lubricating composition.

[0064] In one embodiment, the lubricating composition may comprise a metal containing saligenin detergent. The saligenin may be a calcium or magnesium (typically magnesium) detergent. Saligenin derivatives and methods of their preparation are described in greater detail inter alia U.S. Patent 6,310,009.

[0065] When present, the metal containing saligenin detergent may be present at 0.01 to 0.8 wt%, or 0.1 to 0.5 wt%, or 0.1 to 0.4 wt% or 0.2 to 0.5 wt% of the lubricating composition.

[0066] In one embodiment the lubricating composition may comprise a metal containing carboxylate detergent. The carboxylate may be a calcium or magnesium (typically magnesium) detergent.

[0067] When present, the metal containing carboxylate detergent may be present at 0.01 to 0.8 wt%, or 0.1 to 0.5 wt%, or 0.1 to 0.4 wt% or 0.2 to 0.5 wt% of the lubricating composition.

[0068] Where present, the metal-containing phenol detergents 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.

[0069] The metal cation of the metal containing detergents may be from an alkaline earth metal such as calcium, barium or magnesium, or an alkali metal such as sodium, or potassium.

Ashless Sulfur Free Hydrocarbyl Compound

[0070] The lubricating compositions of the present invention further comprises an ashless, sulfur free, hydrocarbyl phenolic compound in an amount from 0.4 to about 6.0 wt%, or 1.0 to 6.0 wt% or 1.0 to 5.0 wt% or 1.5 to 5.0 wt% or 1.5 to 4.0 wt% or 1.5 to 3.0 wt% of the lubricating composition.

[0071] In one embodiment, the ashless sulfur free hydrocarbyl compound comprises an oxyalkylated hydrocarbyl phenolic compound. Oxyalkylated Hydrocarbyl Phenol

[0072] The oxyalkylated hydrocarbyl phenolic compound may be represented by the formula:

wherein

each R ² may be independently hydrogen or a hydrocarbyl group of 1 to 6 carbon atoms; R ³ may be hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or an acyl group represented by -C(=0)R ⁵ ;

R ⁵ may be a hydrocarbyl group of 1 to 24 carbon atoms;

each R ⁴ may be independently a hydrocarbyl group of 20 to 200 or 25 to 175 or 25 to 140, or 30 to 100, or 40 to 96 carbon atoms;

n = 1 to 20, or 1 to 10; and

m = 1 to 3.

[0073] The oxyalkylated hydrocarbyl phenol may be represented by the formula:

wherein

one R ² may be methyl, and the second R ² may be hydrogen;

R ³ may be hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or an acyl group represented by -C(=0)R ⁵ ;

R ⁵ may be a hydrocarbyl group of 1 to 24 carbon atoms;

R ⁴ is a hydrocarbyl group of 20 to 200 carbon atoms (typically R ⁴ contains 20 to 200 or 25 to 175 or 25 to 140, or 30 to 100, or 40 to 96 carbon atoms);

n = 1 to 20, or 1 to 10; and [0074] The oxyalkylated hydrocarbyl phenol may be represented by the formula:

wherein

one R ² may be methyl, and the second R ² may be hydrogen;

R ³ may be hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or an acyl group represented by -C(=0)R ⁵ ;

R ⁵ may be a hydrocarbyl group of 1 to 24 carbon atoms;

R ⁴ is a polyalk(en)yl group containing 20 to 200 or 25 to 175 or 25 to 140, or 30 to 100, or 40 to 96 carbon atoms;

n = 1 to 8, or 2 to 8; and

m = 1.

[0075] The oxyalkylated hydrocarbyl phenol may be represented by the formula:

wherein

one R ² may be methyl, and the second R ² may be hydrogen;

R ³ may be hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or an acyl group represented by -C(=0)R ⁵ ;

R ⁵ may be a hydrocarbyl group of 1 to 24 carbon atoms;

R ⁴ is a polyisobutenyl group containing 20 to 200 or 25 to 175 or 25 to 140, or 30 to 100, or 40 to 96 carbon atoms;

n = 1 to 8, or 2 to 8 (or 3 to 5); and [0076] In embodiments of any of the formulas of the oxyalkylated hydrocarbyl phenol set forth above, where there is a single R ⁴ group (that is, m=l), the R ⁴ group of each of the formulae above may be located in the para-position relative to the oxyalkylated group, and the resultant formula may be represented by structure:

wherein variables R ² to R ⁵ , and n are defined previously.

[0077] In one embodiment, the oxyalkylated hydrocarbyl phenol of the disclosed technology may be represented by the formula:

wherein R ⁴ may be a polyolefinic group such as a polypropenyl or a polyisobutenyl group (typically a polyisobutenyl group), and variables R ² , R ³ , R ⁵ ,and n are defined previously. The polyisobutenyl group may have a number average molecular weight of 250 to 2500, or 350 to 2300, or 500 to 2000. In one embodiment the polyisobutenyl group has a number average molecular weight of 800 to 1100 or 850 to 1050. The polypropenyl group may have a number average molecular weight of 740 to 1200, or 800-850. In one embodiment the polypropenyl group has a number average molecular weight of 825.

[0078] In one embodiment, the oxyalkylated hydrocarbyl phenol of the disclosed technology may be represented by the formula:

wherein R ⁴ may be a polyolefinic group such as a polypropenyl or a polyisobutenyl group (typically a polyisobutenyl group), and variables R ² , R ³ , R ⁵ , and n, are defined previously. The polyisobutenyl group may have a number average molecular weight of 250 to 2500, or 350 to 2300, or 500 to 2000. In one embodiment the polyisobutenyl group has a number average molecular weight of 800 to 1100 or 850 to 1050.

[0079] The oxyalkylated group of the oxyalkylated hydrocarbyl phenol has formula— (R ¹ 0) _n — , wherein R ¹ may be an ethylene, propylene, butylene group, or mixtures thereof; and n may independently be from 1 to 50, or 1 to 20, or 1 to 10, or 2 to 5.

[0080] The oxyalkylated group of the oxyalkylated hydrocarbyl phenol may be either a homopolymer or copolymer or oligomers thereof. If the oxyalkylated group is in the form of a copolymer, or oligomer thereof, the oxyalkylated group may have either random or block architecture.

[0081] In one embodiment the oxyalkylated group (or R ¹ may be a propylene, or butylene group i.e., the oxyalkylated group does not require an ethylene group. If an ethylene group is present the oxyalkylate group may be a copolymer, or oligomer thereof with either propylene or butylene oxide i.e., blocks of (i) -CH ₂ CH ₂ 0- with (ii) -CH ₂ CH ₂ CH ₂ CH ₂ 0- or -CH ₂ CH(CH ₂ CH ₃ )0- or -CH ₂ CH(CH ₃ )0-.

[0082] In one embodiment the oxyalkylated group may be based upon propylene oxide.

[0083] The oxyalkylated hydrocarbyl phenol may be prepared by reacting a hydrocarbyl substituted phenol with an alkylene oxide (typically ethylene oxide, propylene oxide or butylene oxide), optionally in the presence of a base catalyst. Typically the reaction occurs in the presence of a base catalyst.

[0084] The base catalyst may include sodium chloroacetate, sodium hydride or potassium hydroxide.

[0085] The aliphatic hydrocarbyl group (also represented by R ⁴ ) may be linear or branched, typically with at least one branching point. The aliphatic hydrocarbyl group typically has one, although it may in some embodiments be desirable to have to R ⁴ groups, with the second group being methyl. If a second R ⁴ group is present and is methyl, then the oxyalkylated hydrocarbyl phenol is a cresol. [0086] In different embodiments, the oxyalkylated hydrocarbyl phenol of the disclosed technology may be present in an amount ranging from 0.4 wt% to 5 wt%, or 0.5 to 3 wt%, or 0.8 to 2.0 wt% of the lubricating composition. Typically, the oxyalkylated hydrocarbyl phenol may be present in an amount from 0.5 to 2.0 wt% of the lubricating composition. Ashless Phenolic Antioxidants

[0087] The ashless, sulfur free hydrocarbyl phenolic compound may further comprise, in addition to the oxyalkylated hydrocarbyl phenolic compound discussed above, an ashless, hydrocarbyl phenolic antioxidant.

[0088] Useful hydrocarbyl phenolic antioxidant may include a simple alkyl phenol, a hindered phenol, or coupled phenolic compounds.

[0089] The hindered phenol antioxidant often contains 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. Examples of suitable hindered phenol antioxidants include 2,6-di-tert- butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl- 2,6-di-tert-butylphenol, 4-propyl-2,6-di- tert-butylphenol or 4-butyl-2,6-di-tert- butylphenol, 4-dodecyl-2,6-di-tert-butylphenol, or butyl 3- (3,5-ditert-butyl-4-hydroxyphenyl)propanoate. Other useful 2,6-dialkyl phenols may include those wherein each alkyl group is independently selected from alkyl groups having 2 to 16 or 2 to 12 or 2 to 8 or 3 to 5 carbon groups. In one embodiment, the hindered phenol antioxidant may be an ester and may include, e.g., Irganox™ L-135 from Ciba.

[0090] Coupled phenols often 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-t-butyl-4-heptylphenol); 4,4'-bis(2,6-di-t-butyl phenol), 2,2'-methylenebis(4- methyl-6-t-butylphenol), and 2,2'-methylene bis(4-ethyl-6-t-butylphenol).

[0091] Phenols of the invention also 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, 1,4-dihydroxy -2 -naphthoic acid, 3,5-dihydroxynaphthoic acid, 3,7 -dihydroxy naphthoic acid, and mixtures thereof.

[0092] In one embodiment, the ashless, hydrocarbyl phenolic antioxidant comprises a hindered phenol. [0093] In another embodiment, the hindered phenol is derived from 2,6-dialkyl phenol, and in another embodiment, the ashless, hydrocarbyl phenolic antioxidant is 2,6 ditertbutyl phenol.

[0094] In one embodiment, the lubricating composition of the invention comprises an ashless, alkylated phenolic antioxidant in a range of 0.1 wt% to 3.0 wt%, or 0.1 wt% to 1.5 wt%, or 0.2 wt% to 1.2 wt%, or 0.5 wt% to 1.2 wt% of the lubricating composition.

Other Ashless Phenolic Detergents

[0095] The ashless, sulfur free hydrocarbyl phenolic compound may further comprise, in addition to the oxyalkylated hydrocarbyl phenolic compound discussed above, an ashless, hydrocarbyl phenolic detergent. Ashless phenolic detergents are extensively taught in PCT Publication WO10/101801 and U. S. Patent 5,827,805.

[0096] Suitable ashless phenolic detergents are those that contain a quaternary pnictogen cation, in the absence of ash contributing metal cation. The anion portion of the detergent will be an organic anion having at least one aliphatic hydrocarbyl group of sufficient length to impart oil solubility to the detergent. (As used herein, the term "aliphatic" is intended to encompass "alicyclic." That is, the aliphatic hydrocarbyl groups may be linear, branched, or cyclic or may contain carboxylic moieties, but are to be distinguished from "aromatic" groups, which are not to be considered "aliphatic"). Suitable aliphatic hydrocarbyl groups, if they are in the form of a substituent on an aromatic ring (as in alkylphenates or alkylbenzenesulfonates) may contain 4 to 400 carbon atoms, or 6 to 80 or 6 to 30 or 8 to 25 or 8 to 15 carbon atoms. The sulfur-free anionic portion of the detergent may thus be any of the anions derived from the acidic, phenolic organic materials that are used to prepare conventional detergents. As mentioned above, these include phenols, providing phenate detergents with phenate anions, hydrocarbyl-substituted salicylic acids, providing salicylate detergents with salicylate anions, as well as salixarate, and saligenin detergents, and mixtures thereof.

[0097] If present, the lubricating composition may comprise an ashless, sulfur free phenolic detergent in a range of 0.1 wt% to 0.9 wt%, or 0.1 wt% to 0.7 wt%, or 0.2 wt% to 0.6 wt%, or 0.2 wt% to 0.5 wt% of the lubricating composition.

Ashless Dispersant

[0098] The lubricating composition further comprises an ashless dispersant, which may comprise mixture of ashless dispersants. [0099] The dispersant may comprise one or more of (i) the reaction products of a conventional polyolefin acylating agent and an aromatic amine, aliphatic amine, or mixtures thereof, and (ii) the reaction product of a high-vinylidene polyisobutylene acylating agent and an amine, preferably a polyamine. The dispersant may be a succinimide dispersant, a Mannich dispersant, a succinamide dispersant, a polyolefin succinic acid ester, amide, or ester-amide, or mixtures thereof. The dispersant may be present as a single dispersant. The dispersant may be present as a mixture of two or more (typically two or three) different dispersants, wherein at least one may be a succinimide dispersant.

[00100] Acylating agents are compounds that can provide an acyl group in an acylation reaction. Typical examples of acylating agents are, for example, succinic acid, maleic acid, itaconic acid, fumaric acid, cinnamic acid, reactive equivalents and derivatives thereof.

[00101] The acylating agent may be a polyolefin acylating agent prepared from a conventional polyolefin. Conventional polyolefins are derived from polymerized C2-C6 mono olefins. The polymers may be homopolymers, copolymer or interpolymers. The preferred polyolefin is polyisobutylene (PIB) formed by polymerizing the C4-raffinate of a cat cracker or ethylene plant butane/butene stream using aluminum chloride or other acid catalyst systems.

[00102] The polyolefin made in this manner is termed a conventional polyisobutylene (PIB) and is characterized by having unsaturated end groups shown in Table 1 with estimates of their mole percents based on moles of polyisobutylenes. The structures are as shown in EPO 355 895. Conventional PIBs are available commercially under numerous trade names including Parapol® from Exxon and Lubrizol® 3104 from Lubrizol.

Table 1

PIB Terminal Groups (a) Typical Percent in (b) Typical Percent in

Conventional PIB High Vinylidene PIB

I

II

CH ₃

H ₂ J, _ch 63-67%) tri- substituted absent or minor

^C H ³

III

22-28% tetrasubstituted 1-15%

IV

CH ₃ CH ₃

IV and IVa

IV

CH ₂

(I 5-8% 0-4% C C C CH ₃

V

OTHER 0-10%

[00103] The number average molecular weight (Mn) range of the polyolefins is from about 300- 10,000 or even up to 50,000. However, for instance, the preferred range for polyisobutylenes is Mn of about 300-5,000 and the most preferred upper limit Mn is in the range of about Mn 300- 2,500. In general, the polyolefm may be prepared from polymerisable monomers containing about 2 to about 16, or about 2 to about 8, or about 2 to about 6 carbon atoms. Often, the polymerisable monomers comprise one or more of propylene, isobutene, 1-butene, isoprene, 1, 3-butadiene, or mixtures thereof. [00104] The reaction products of a conventional polyolefin acylating agent and an aromatic amine, aliphatic amine, or mixtures thereof, can encompass both mixtures of aromatic containing and aliphatic containing conventional polyolefin acylating agents and a mixture of conventional polyolefin acylating agents wherein single agents contain either one or a mixture of aromatic and aliphatic amines.

[00105] As used herein, the term "aliphatic amine" refers to a molecule containing nitrogen in which none of the nitrogens are aromatic. The aliphatic amine may be an aliphatic polyamine such as ethylene polyamine (i.e., a poly(ethyleneamine)), a propylene polyamine, a butylene polyamine, or a mixture of two or more thereof. The aliphatic polyamine may be ethylene polyamine. The aliphatic polyamine may be selected from ethyl enediamine, di ethyl enetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms, or a mixture of two or more thereof.

[00106] The reaction products of (i) with aliphatic amines may be succinimide dispersants, succinamide dispersants, succinic acids, amides, or ester-amides, or mixtures thereof.

[00107] The reaction products of (i) with aliphatic amines may also be polyolefin succinic acid esters, amides, or ester-amides. For instance, a polyolefin succinic acid ester may be a polyisobutylene succinic acid ester of pentaerythritol, or mixtures thereof. A polyolefin succinic acid ester-amide may be a polyisobutylene succinic acid reacted with an alcohol (such as pentaerythritol) and an amine (such as a polyamine, typically diethylenetriamine, polyamine still bottoms, tetraethylenepentamine (TEPA), and the like).

[00108] Additionally, the reaction products of (i) with aliphatic amines may be N-substituted long chain alkenyl succinimides. An example of an N-substituted long chain alkenyl succinimide is polyisobutylene succinimide, that is, a polyisobutene substituted succinimide dispersant.

[00109] Succinimide dispersants and their preparation are disclosed, for instance in US Patents 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, 3,632,51 1, 4,234,435, RE26,433, 6, 165,235, 7,238,650 and EP Patent Publication 0 355 895 A.

[00110] The reaction products of (i) may contain aromatic amines. As used herein, the term "aromatic amine" refers to a molecule containing at least one aromatic nitrogen. In one embodiment, an aromatic nitrogen is a nitrogen either within an aromatic ring or directly bonded to an aromatic ring. In another embodiment, aromatic nitrogen refers only to nitrogen directly bonded to an aromatic ring.

[00111] Aromatic amines may have one or more aromatic moieties linked by a hydrocarbylene group and/or a heteroatom such as N-phenyl-l,4-phenylenediamine (4-amino diphenylamine). The aromatic amine may be a nitro-substituted aromatic amine. Examples of nitro-substituted aromatic amines may include 2-nitroaniline, 3-nitroaniline, and 4-nitroaniline. 3-nitroaniline may be particularly useful. Other aromatic amines may be present along with the nitroaniline. Condensation products with nitroaniline and optionally also with Disperse Orange 3 (that is, 4-(4- nitrophenylazo)aniline) are disclosed in U.S. Publication 2006/0025316.

[00112] The amine may be an amine having at least 2, or at least 3, or at least 4 aromatic groups, for instance, from about 4 to about 10, or from about 4 to about 8, or from about 4 to about 6 aromatic groups, and at least one primary or secondary amino group or, alternatively, at least one secondary amino group. The amine may comprise both a primary and at least one secondary amino group. The amine may comprise at least about 4 aromatic groups and at least 2 of any combination of secondary or tertiary amino groups.

[00113] An example of an amine having 2 aromatic groups is N-phenyl-p-phenylenediamine. An example of an amine having at least 3 or 4 aromatic groups may be represented by Formula (1):

Formula 1

wherein, independently, each variable is as follows: R ¹ may be hydrogen or a C1-5 alkyl group (typically hydrogen); R ² may be hydrogen or a C1-5 alkyl group (typically hydrogen); U may be an aliphatic, alicyclic or aromatic group (when U is aliphatic, the aliphatic group may be a linear or branched alkylene group containing 1 to about 5, or 1 to about 2 carbon atoms); and w may be from 1 to about 10, or 1 to about 4, or 1 to 2 (typically 1). When U is an aliphatic group, U may be an alkylene group containing 1 to about 5 carbon atoms. Alternatively, the amine may also be represented by Formula (la)

w

Formula (la)

[00114] wherein each variable U, R ¹ , and R ² are the same as described above and w is 0 to about 9, or 0 to about 3, or 0 to about 1 (typically 0).

[00115] Further, aromatic amines suitable to be employed in the reaction products of (i) can be found in U.S. Patent 7,253,231 to Devlin at al., issued August 7, 2007, the content of which are incorporated herein by reference.

[00116] In one embodiment, at least 10 mol% of the reaction products of (i) can contain an aromatic amine. In another embodiment, at least 10 mol% but not more than 60 mol% of the reaction products of (i) can contain an aromatic amine. Preferably, at least 15 mol% but no more than 50 mol% can contain an aromatic amine, and most preferably at least 20 mol% and no more than 40 mol% contain an aromatic amine. In another embodiment, greater than 30 mol% of the reaction products of (i) can contain an aromatic amine, or from 30 mol% to about 80 mol%, or 40 mol% to about 95 mol%. In one example, the dispersant mixture may comprise a mixture of (1) the reaction product of a succinated polyisobutylene with one or more polyethylenepolyamines, wherein the polyisobutylene has an average of between 1.2 and 1.6 succinic acid moieties per polymer, and (2) the reaction product of succinated polyisobutylene with one or more aromatic polyamines, such as, for example, 4-amino diphenylamine, wherein the polyisobutylene has an average of between 1.2 and 1.6 succinic acid moieties per polymer.

[00117] In a further embodiment, at least 3% of the nitrogen from the amines in the reaction products of (i) can be aromatic nitrogen. Alternately, at least 10%, or at least 15%, or at least 20 mol% of the nitrogen from the amines in the reaction products of (i) can be aromatic nitrogen. In another embodiment, at least 3% but not more than 60 mol% of the nitrogen from the amines in the reaction products of (i) can be aromatic nitrogen. Preferably, at least 4% but not more than 55% of the nitrogen from the amines in the reaction products of (i) can be aromatic nitrogen, and most preferably at least 5% and no more than 50 mol% can be aromatic nitrogen.

[00118] The dispersants of (i) may be present in the lubricant composition at a concentration in the range from about 0.01 wt% to about 20 wt%, or from about 0.1 wt% to about 15 wt%, or from about 0.1 wt% to about 10 wt%, or from about 1 wt% to about 6 wt%, or from about 1 to about 3 wt% of the lubricating composition. Preferably, the dispersant of (i) is present at about 2.0, or 2.5, or 3.0 wt.%.

[00119] The high vinylidene polyisobutylene acylating agent of (ii) can be derived from a high vinylidene polyisobutylene having a number average molecular weight (Mn) of no more than about 2500 daltons, or no more than 2000 daltons or 1800 daltons, and in one embodiment no more than 1500 daltons or 1250 daltons. The high vinylidene polyisobutylene acylating agent is reacted with an amine, preferably a polyamine, and preferably an aliphatic polyamine. The aliphatic amine may be an aliphatic polyamine such as ethylene polyamine (i.e., a poly(ethyleneamine)), a propylene polyamine, a butyl ene polyamine, or a mixture of two or more thereof. The aliphatic polyamine may be ethylene polyamine. The aliphatic polyamine may be selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms, or a mixture of two or more thereof.

[00120] As shown in Table 1, a high vinylidene PIB can be characterized as having a major amount, typically more than 50 mol% of an alpha-vinylidene, often referred to as methylvinylidene, and/or beta- double bond isomer (respectively -CH ₂ C(CH ₃ )=CH ₂ and/or - CH=C(CH ₃ ) ₂ ), and minor amounts of other isomers including a tetrasubstituted double bond isomer. Because of their high vinylidene double bond isomer content, high vinylidene PIBs are considered to be more reactive and to undergo a higher conversion to derivatives which are better performers in comparison to derivatives from conventional PIBs. High vinylidene PIBs generally can contain greater than about 50 mole%, 60 mole%, or 70 mole% or greater and usually about 80 mole% or greater or 90 mole% or greater of alpha-vinylidene and/or beta- double bond isomer and about 1 to 10 mole% of tetrasubstituted double bond isomer. In an embodiment of the invention the high vinylidene PIB has an alpha- and/or beta-vinylidene double bond isomer content of 55 mole% or greater, and in other embodiments has an alpha-vinylidene and/or beta- double bond isomer content of 65, of 75, or of 85 mole% or greater. High vinylidene PIBs are prepared by polymerizing isobutylene or an isobutylene containing composition with a milder acidic polymerization catalyst such as BF ₃ . High vinylidene PIBs are available commercially from several producers including BASF and Texas Petroleum Chemicals.

[00121] In such an embodiment where the polyolefin is a high vinylidene polyolefin, the polyolefin can have an average of between about 0.5 and 1.0 acylating agent moieties per polymer. For example, the dispersant mixture may comprise a PIB-succinimide wherein the PIB from which the PIB-succinimide is derived contains at least 50mol% methylvinylidene terminated molecules.

[00122] The dispersants of (ii) may be present in the lubricant composition at a concentration in the range from about 0.01 wt% to about 20 wt%, or from about 0.1 wt% to about 15 wt%, or from about 2.0 wt% to about 10 wt%, or from about 1 wt% to about 8 wt%, or from about 2 to about 8 wt% of the lubricating composition. Preferably the dispersant of (i) is present at about 6.5 or 7.0 or 8.0 wt.%.

[00123] Dispersants derived from the reaction product of a high vinylidene polyisobutylene acylating agent and an amine and their preparation are disclosed in WO Publication 2013/122898.

[00124] The dispersants may also be post-treated by conventional methods by a reaction with any of a variety of agents. Among these are boron compounds (such as boric acid), urea, thiourea, dimercaptothiadiazoles, carbon disulphide, aldehydes, ketones, carboxylic acids such as terephthalic acid, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds. In one embodiment the post- treated dispersant is borated. In one embodiment the post-treated dispersant is reacted with dimercaptothiadiazoles. In one embodiment the post-treated dispersant is reacted with phosphoric or phosphorous acid. In one embodiment the post-treated dispersant is reacted with terephthalic acid and boric acid (as described in US Publication 2009/0054278.

[00125] In one embodiment the dispersant may be borated or non-borated. The dispersant may comprise a blend of borated and non-borated dispersants. Typically a borated dispersant may be a succinimide dispersant. In one embodiment, the ashless dispersant is boron- containing, i.e., has incorporated boron and delivers said boron to the lubricant composition. Typically, the borated dispersant contains from 0.1% to 5%, or from 0.5% to 4%, or from 0.7% to 3% by weight boron. In one embodiment, the borated dispersant may be a borated acylated amine, such as a borated succinimide dispersant. Borated dispersants are described in U.S. Patents 3,000,916, 3,087,936, 3,254,025, 3,282,955, 3,313,727, 3,491,025, 3,533,945, 3,666,662 and 4,925,983. Borated dispersant are prepared by reaction of one or more dispersants with one or more boron compounds. Any of the dispersants described herein may be borated, either during the reaction of the hydrocarbyl substituted acylating agent and the amine or after. [00126] In one embodiment, the boron compound may be an alkali or mixed alkali metal and alkaline earth metal borate. These metal borates are generally hydrated particulate metal borates which are known in the art. Alkali metal borates include mixed alkali and alkaline metal borates. U.S. Patents 3,997,454, 3,819,521, 3,853,772, 3,907,601, 3,997,454 and 4,089,790 disclose suitable alkali and alkali metal and alkaline earth metal borates and their methods of manufacture. In one embodiment the boron compound is boric acid.

[00127] The boron-containing dispersant may be present in an amount to deliver at least 25 ppm boron, at least 50 ppm boron, or at least 100 ppm boron to the lubricant composition. In one embodiment, the lubricant composition is free of a boron-containing dispersant, i.e., delivers no more than 10 ppm boron to the final formulation.

Other Performance Additives

[00128] The lubricating composition of the disclosed technology may further include other additives. In one embodiment the disclosed technology provides a lubricating composition further comprising at least one of dispersant other than an ashless dispersant discussed above, an antiwear agent, a dispersant viscosity modifier, a friction modifier, a viscosity modifier, an antioxidant, a foam inhibitor, a demulsifier, a pour point depressant or mixtures thereof.

[00129] Antioxidants (other than phenolic antioxidants addressed previously) include sulfurized olefins, diarylamines, alkylated diarylamines, molybdenum compounds (such as molybdenum dithiocarbamates), hydroxyl thioethers, or mixtures thereof. In one embodiment, the lubricating composition includes an antioxidant, or mixtures thereof. The antioxidant may be present at 0 wt% to 15 wt%, or 0.1 wt% to 10 wt%, or 0.5 wt% to 5 wt%, or 0.5 wt% to 3 wt%, or 0.3 wt% to 1.5 wt% of the lubricating composition.

[00130] The diarylamine or alkylated diarylamine may be a phenyl-a-naphthylamine (PANA), an alkylated diphenylamine, or an alkylated phenylnapthyl amine, or mixtures thereof. The alkylated diphenylamine may include di-nonylated diphenylamine, 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, dioctyl, nonyl, di-nonyl, decyl or di-decyl phenylnapthylamines. [00131] In one embodiment, the lubricating composition may be a lubricating composition further comprising a molybdenum compound. The molybdenum compound may be an antiwear agent or an antioxidant. The molybdenum compound may be be chosen from 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 5 ppm to 300 ppm, or 20 ppm to 250 ppm of molybdenum.

[00132] Examples of molybdenum dithiocarbamates, which may be used as an antioxidant, include commercial materials sold under the trade names such as Vanlube 822™ and Molyvan™ A from R. T. Vanderbilt Co., Ltd., and Adeka Sakura-Lube™ S-100, S-165, S- 600 and 525, or mixtures thereof.

[00133] In one embodiment, the lubricating composition further includes a viscosity modifier. The viscosity modifier is known in the art and may include hydrogenated styrene- butadiene rubbers, ethylene-propylene copolymers, polymethacrylates, polyacrylates, hydrogenated styrene-isoprene polymers, hydrogenated diene polymers, polyalkyl styrenes, polyolefins, esters of maleic anhydride-olefin copolymers (such as those described in PCT Publication WO2010/014655), esters of maleic anhydride-styrene copolymers, or mixtures thereof.

[00134] The dispersant viscosity modifier may 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 styrene-maleic anhydride copolymers reacted with an amine. More detailed description of dispersant viscosity modifiers are disclosed in PCT Publication WO2006/015130 or U. S. Patents 4,863,623, 6, 107,257, 6, 107,258, 6, 1 17,825 and 7,790,661. In one embodiment, the dispersant viscosity modifier may include those described in U.S. Patent 4,863,623 (see column 2, line 15 to column 3, line 52) or in PCT Publication WO2006/015130 (see page 2, paragraph [0008] and preparative examples are described paragraphs [0065] to [0073]). In one embodiment the dispersant viscosity modifier may include those described in U. S. Patent 7,790,661 column 2, line 48 to column 10, line 38.

[00135] In one embodiment the lubricating composition of the disclosed technology further comprises a dispersant viscosity modifier. The dispersant viscosity modifier may be present at 0 wt% to 5 wt%, or 0 wt% to 4 wt%, or 0.05 wt% to 2 wt%, or 0.2 wt% to 1.2 wt% of the lubricating composition.

[00136] In one embodiment the friction modifier may be be chosen from long chain fatty acid derivatives of amines, long chain fatty esters, or derivatives of long chain fatty epoxides; fatty imidazolines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fatty glycolates; and fatty glycolamides. The friction modifier may be present at 0 wt% to 6 wt%, or 0.01 wt% to 4 wt%, or 0.05 wt% to 2 wt%, or 0.1 wt% to 2 wt% of the lubricating composition.

[00137] As used herein the term "fatty alkyl" or "fatty" in relation to friction modifiers means a carbon chain having 10 to 22 carbon atoms, typically a straight carbon chain.

[00138] Examples of suitable friction modifiers include long chain fatty acid derivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines such as condensation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fatty phosphonates; fatty phosphites; borated phospholipids, borated fatty epoxides; glycerol esters; borated glycerol esters; fatty amines; alkoxylated fatty amines; borated alkoxylated fatty amines; hydroxyl and polyhydroxy fatty amines including tertiary hydroxy fatty amines; hydroxy alkyl amides; metal salts of fatty acids; metal salts of alkyl salicylates; fatty oxazolines; fatty ethoxylated alcohols; condensation products of carboxylic acids and polyalkylene polyamines; or reaction products from fatty carboxylic acids with guanidine, aminoguanidine, urea, or thiourea and salts thereof.

[00139] Friction modifiers may also encompass materials such as sulfurized fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil or soybean oil monoester of a polyol and an aliphatic carboxylic acid.

[00140] 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 and in another embodiment the long chain fatty acid ester may be a triglyceride.

[00141] The lubricating composition optionally further includes at least one antiwear agent. Examples of suitable antiwear agents include titanium compounds, tartaric acid derivatives such as tartrate esters, amides or tartrimides, oil soluble amine salts of phosphorus compounds, sulfurized olefins, metal dihydrocarbyldithiophosphates (such as zinc dialkyldithiophosphates), phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides.

[00142] The antiwear agent may in one embodiment include a tartrate or tartrimide as disclosed in PCT Publication WO2006/04441 1 or Canadian Patent 1, 183, 125. The tartrate or tartrimide may contain alkyl-ester groups, where the sum of carbon atoms on the alkyl groups is at least 8. The antiwear agent may in one embodiment include a citrate as is disclosed in US Publication 2005-0198894.

[00143] The lubricating composition may further include a phosphorus-containing antiwear agent. Typically the phosphorus-containing antiwear agent may be a zinc dialkyldithiophosphate, phosphite, phosphate, phosphonate, and ammonium phosphate salts, or mixtures thereof. Zinc dialkyldithiophosphates are known in the art. The antiwear agent may be present at 0 wt% to 3 wt%, or 0.1 wt% to 1.5 wt%, or 0.5 wt% to 0.9 wt% of the lubricating composition.

[00144] Another class of additives includes oil-soluble titanium compounds as disclosed in US Patent 7,727,943 and US Publication 2006-0014651. The oil-soluble titanium compounds may function as antiwear agents, friction modifiers, antioxidants, deposit control additives, or more than one of these functions. In one embodiment, the oil soluble titanium compound may be a titanium (IV) alkoxide. The titanium alkoxide may be formed from a monohydric alcohol, a polyol or mixtures thereof. The monohydric alkoxides may have 2 to 16, or 3 to 10 carbon atoms. In one embodiment, the titanium alkoxide may be titanium (IV) isopropoxide. In one embodiment, the titanium alkoxide may be titanium (IV) 2-ethylhexoxide. In one embodiment, the titanium compound comprises the alkoxide of a vicinal 1,2-diol or polyol. In one embodiment, the 1,2-vicinal diol comprises a fatty acid mono-ester of glycerol, often the fatty acid may be oleic acid.

[00145] In one embodiment, the oil soluble titanium compound may be a titanium carboxylate. In one embodiment the titanium (IV) carboxylate may be titanium neodecanoate. [00146] Foam inhibitors that may be useful in the compositions of the disclosed technology include polysiloxanes, copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including fluorinated polysiloxanes, trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide- propylene oxide) polymers.

[00147] Pour point depressants that may be useful in the compositions of the disclosed technology include polyalphaolefins, esters of maleic anhydride-styrene copolymers, poly(meth)acrylates, polyacrylates or polyacrylamides.

[00148] Demulsifiers include trialkyl phosphates, and various polymers and copolymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures thereof different from the non-hydroxy terminated acylated polyalkylene oxide of the disclosed technology.

[00149] Metal deactivators include derivatives of benzotriazoles (typically tolyltriazole),

1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles or 2-alkyldithiobenzothiazoles.

The metal deactivators may also be described as corrosion inhibitors.

[00150] Seal swell agents include sulpholene derivatives Exxon Necton-37™ (FN 1380) and Exxon Mineral Seal Oil™ (FN 3200).

[00151] The lubricating composition of the disclosed technology may also include a boron containing compound.

[00152] In one embodiment, the boron containing compound may be selected from borated dispersants discussed above, borated friction modifiers, and mixtures thereof. The boron- contai ning compound may include a borate ester or a borated alcohol.

[00153] The boron containing compound may be present in an amount to deliver at least

25 ppm to 2000 ppm, and in one embodiment 25 ppm to 600 ppm, and in one embodiment 25 ppm to 300 ppm, and in one embodiment 100 ppm to 200 ppm and in one embodiment, at least 25 ppm boron, at least 50 ppm boron, or at least 100 ppm boron to the lubricant composition. In one embodiment, the lubricant composition may be free of a boron- containing compound, i.e. all components deliver no more than 10 ppm boron to the final formulation.

[00154] An engine lubricating composition in different embodiments may have a composition as disclosed in the following table 2: Table 2

Table 1 - exemplary engine lubricating composition.

[00155] An ashless sulphur free hydrocarbyl phenolic compound may comprise the following components disclosed in the following table 3 (wt% with respect to the total amount of ashless, sulfur free, hydrocarbyl phenolic compound on an oil free basis).

Table 3 - Exemplary ashless, sulfur free, hydrocarbyl phenolic compounds

Table 2 - exemplary ashless sulfur free hydrocarbyl phenolic compositions Industrial Application

[00156] In one embodiment, the disclosed technology provides a method of lubricating an internal combustion engine. The engine components may have a surface of steel or aluminum.

[00157] An aluminum surface may be derived from an aluminum alloy that may be a eutectic or a 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.

[00158] In a particularly useful embodiment, the internal combustion engine is the engine in a heavy duty vehicle. A heavy duty vehicle (HDV) containing the internal combustion engine of the present invention may have a laden mass (sometimes referred to as gross vehicle weight rating (GVWR)) of over 2700 kg (or 6000 USA pounds), or over 2900 kg, or over 3000 kg, or over 3300 kg, or over 3500 kg, or over 3700 kg, or over 3900 kg (or 8500 USA pounds). Typically, the upper limit on the laden mass or GVWR is set by national government and may be 10000 kg, or 9000 kg, or 8000 kg, or 7500 kg. The upper ranges of laden mass may be up to 400,000 kg, or up to 200,000 kg, or up to 60,000 kg, or up to 44,000 kg, or up to 40,000 kg. Typically a laden mass above 120,000 is for an off-highway vehicle.

[00159] The vehicle containing the internal combustion engine having a laden mass of over 2700 kg (or 3,500 kg) may be a heavy duty diesel engines equipped with compression ignition engines or positive ignition natural gas (NG) or LPG engines. In contrast, the European Union indicates that for new light duty vehicles (passenger cars and light commercial vehicles) included within the scope of ACEA testing section "C" have a "technically permissible maximum laden mass" not exceeding 2610 kg.

[00160] Typically, the internal combustion engine may be a diesel engine suitable for powering a vehicle having a laden mass over 3,500 kg.

[00161] In one embodiment, the internal combustion engine is a heavy duty diesel compression ignition (or spark assisted compression ignition) internal combustion engine.

[00162] In one embodiment, the internal combustion engine may be a diesel fueled engine. Diesel fueled engines may be fueled with a mixture of conventional diesel fuel and bio- derived diesel fuel (i.e., bio-diesel). In one embodiment, the diesel engine fuel may comprise 5 volume percent to 100 volume percent bio-diesel (i.e., B5 to b l OO); in one embodiment the diesel fuel comprises 5 volume percent to 50 volume percent bio-diesel or 8 volume percent to 30 volume percent bio-diesel. In one embodiment the diesel fuel is substantially free of (i.e., contains less than 1 volume percent) bio-diesel. In one embodiment, the internal combustion engine may be a heavy duty diesel engine.

[00163] 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 wt% or less, or 0.8 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%. The phosphorus content may be 0.2 wt% 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 0.04 wt% to 0.12 wt%. In one embodiment, the phosphorus content may be 100 ppm to 1000 ppm, or 200 ppm to 600 ppm. The total sulfated ash content may be 0.3 wt% to 1.2 wt%, or 0.5 wt% to 1.2 wt% or 1.1 wt% of the lubricating composition. In one embodiment, the sulfated ash content may be 0.5 wt% to 1.2 wt% of the lubricating composition. The TBN (as measured by ASTM D2896) of the engine oil lubricant may be 3 mg KOH/g to 15 mg KOH/g, or 4 mg KOH/g to 12 mg KOH/g, or 5 mg KOH/g to 10 mg KOH/g, or 7 mg KOH/g to 10 mg KOH/g.

[00164] 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 0.12 wt% or less, and (iii) a sulfated ash content of 0.5 wt% to 1.1 wt% of the lubricating composition.

[00165] In one embodiment, use of a lubricating composition taught herein for lubricating a compression ignition, internal combustion engine is disclosed. Use of the lubricating composition may be to provide one of (i) fuel economy, (ii) corrosion, (iii) cleanliness, (iv) bore wear and (v) seal protection.

[00166] The following examples provide illustrations of the disclosed technology. These examples are non-exhaustive and are not intended to limit the scope of the disclosed technology. EXAMPLES

Representative Preparative Example

Example F (5 equivalents of propylene oxide to 1 equivalent of polyisobutylene phenol):

[00167] Polyisobutylene (950 Mn) phenol (1 wt. eq.) was charged into a reactor, and heated to 175 F. To the reactor was added KOH pellets (0.0075 wt. eq.), and the reactor was heated to 265 F. Full vacuum was applied to remove the water generated. The content was them cooled to 245 F. Propylene oxide (0.235 wt. eq.) was charged to the reaction vessel slowly while maintaining the temperature between 245 F and 255 F. Once the reaction finished. Magnesol and Celite was added to the reaction mixture, which was stirred for addition 4 hr at 250 F. The mixture was filtered through Celite to afford the product.

[00168] Inventive examples A, B, C, D and F through V were prepared in a similar fashion and are summarized in Table 4.

Table 4 - Examples of oxyalkylated hydrocarbyl phenolic compounds

PP-1 : 4-Alkylphenol where alkyl is lOOOMn Pib;

PP-2: 4-Alkylphenol where alkyl is 550Mn Pib;

PP-3 : 4-Alkylphenol where alkyl is 1500Mn Pib;

PP-4: 4-Alkylphenol where alkyl is 2000Mn Pib;

*Conceptive examples

**Mixtures represent feed ratios

Lubricant Examples BL- 1 , BL-2, and EX-1 to EX-5

[00169] A series of 15W-40 engine lubricants of lubricating viscosity are prepared containing the additives described above as well as conventional additives including polymeric viscosity modifier, ashless succinimide dispersant, overbased detergents, antioxidants (combination of phenolic ester, diarylamine, and sulfurized olefin), zinc dialkyldithiophosphate (ZDDP), as well as other performance additives. All of the lubricants were prepared based on a common formulation as follows in Table 5.

Table 5 - Lubricating Oil Compositions ¹

1. All concentrations are on an oil free (i.e. active basis)

2. Ca or Mg alky lsulfo nates .

3. Ca or Mg phenates.

4. 2000 Mn PIB succinimide dispersants

5. Including viscosity modifiers and dispersant viscosity modifiers.

6. Aminic antioxidants & sulfurized olefins

7. Additional additives include friction modifiers, foam inhibitors, corrosion inhibitors etc.

8. Hinder phenol antioxidants

9. Functionalized phenolic antioxidant

10. Example F

11. 290 TBN Ca salicylates Table 6 - Lubricating Oil Characterization

[00170] BL-1 employs both low soap sulfonate detergents and high soap sulfonate detergents. When the high soap sulfonate detergent was replaced with low soap detergents, (BL-2) at equal ash, the % soap went down and the TBN (D2896 & D4739) went up as a result. The inventive examples EX-1 & EX-2 were top treated with oxyalkylated hydrocarbyl phenol (Example F). In EX-3 & EX-4, the phenated detergents were replaced with Ca salicylate as equal ash.

[00171] The lubricants described above are evaluated in Cat IN engine test (D6750). Cat IN engine test evaluate the deposit generating tendency of lubricant in a direct-inj ection, diesel engine. Overall the results obtained for each lubricant are as follows:

Table 7 - Cat IN Performance

[00172] As seen from the data, when the soap level was reduced from BL-1 to BL-2. Cleanliness was compromised as a result which was reflected in the WDN (268 to 456). It is known that soap provides cleanliness benefit. When oxyalkylated hydrocarbyl phenol was added, the cleanliness was significantly improved (EX-1 & EX-2). When the phenated detergent was replaced with salicylates, the cleanliness performance was retained even with a slight decrease in soap level (EX-3 & EX-4).

Lubricant Examples BL-3, and EX-5

[00173] A series of 15W-40 engine lubricants of lubricating viscosity are prepared containing the additives described above as well as conventional additives including polymeric viscosity modifier, ashless succinimide dispersant, overbased detergents, antioxidants (combination of phenolic ester, diarylamine, and sulfurized olefin), zinc dialkyldithiophosphate (ZDDP), as well as other performance additives. All of the lubricants were prepared based on a common formulation as follows in Table 8. Table 8 - Lubricating Oil Compositions ¹

centrations are on an oil free (i.e. active basis)

g alkylsulfonates.

n PIBsuccinimide dispersants

g viscosity modifiers and dispersant viscosity modifiers.

antioxidants & sulfurized olefins

nal additives include friction modifiers, foam inhibitors, corrosion inhibitors etc. phenol antioxidants

e F

Table 9 - Lubricating Oil Characterization

[00174] BL-3 employs high level of high soap sulfonate detergents. When the high soap sulfonate detergent was partially replaced with low soap detergents (EX-5) at equal ash, the % soap went down and the TBN (D2896 & D4739) went up as a result. The inventive examples EX-5 was also treated with oxyalkylated hydrocarbyl phenol (Example F).

[00175] The lubricants described above are evaluated in cleanliness bench tests MHT TEOST & Sludge bench test. MHT TEOST evaluates the oxidation and deposit forming tendency of the engine oils. Sludge bench test evaluates the sludge dispersing capability of an engine oil. The overall the results obtained for each lubricant are as follows:

Table 10 - Bench Test Performance

[00176] Both bench tests showed noticeable improvement when oxyalkylated hydrocarbyl phenol (Example F) was used.

Lubricant Example EX-6

[00177] A series of 15W-40 engine lubricants of lubricating viscosity are prepared containing the additives described above as well as conventional additives including polymeric viscosity modifier, ashless succinimide dispersant, overbased detergents, antioxidants (combination of phenolic ester, diarylamine, and sulfurized olefin), zinc dialkyldithiophosphate (ZDDP), as well as other performance additives. All of the lubricants were prepared based on a common formulation as follows in Table 1 1. Table 1 1 - Lubricating Oil Compositions ¹

1. All concentrations are on an oil free (i.e. active basis)

2. Ca or Mg alkylsulfonates.

3. 2000 Mn PIBsuccinimide dispersants

4. Including viscosity modifiers and dispersant viscosity modifiers.

5. Aminic antioxidants & sulfurized olefins

6. Additional additives include friction modifiers, foam inhibitors, corrosion inhibitors etc.

7. Hinder phenol antioxidants

8. Example F

Table 12 - Lubricating Oil Characterization

[00178] The lubricants described above are evaluated in Cat IN engine test (D6750). Cat IN engine test evaluate the deposit generating tendency of lubricant in a direct-inj ection, diesel engine. Overall the results obtained for each lubricant are as follows:

Table 13 - Bench Test Performance [00179] The disclosed technology is capable of at least one of (i) control of fuel economy, (ii) control of corrosion, (iii) cleanliness (typically control of deposits, typically control/reduction of soot), (iv) control of bore wear and (v) protection of seals, typically in a heavy duty diesel internal compression combustion engine.

[00180] 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 disclosed technology 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 disclosed technology; the disclosed technology encompasses lubricant composition prepared by admixing the components described above.

[00181] Each of the documents referred to above is incorporated herein by reference. Except in the Examples, or where otherwise explicitly indicated, all numerical quantities in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, and the like, are to be understood as modified by the word "about." Unless otherwise indicated, each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, byproducts, derivatives, and other such materials which are normally understood to be present in the commercial grade. However, the amount of each chemical component is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, unless otherwise indicated. It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined. Similarly, the ranges and amounts for each element of the disclosed technology may be used together with ranges or amounts for any of the other elements.

[00182] While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.