Lubricating composition containing a polyester

Abstract

The invention provides a lubricating composition containing an oil of lubricating viscosity and a polyester. The invention further relates to a method of lubricating a driveline device (such as a gear) with the lubricating composition.

Description

4830-01TITLELubricating Composition Containing a Polyester FIELD OF INVENTION

[0001] The invention provides a lubricating composition containing an oil of lubricating viscosity and a polyester. The invention further relates to a method of lubricating a driveline device (such as a gear) with the lubricating composition.BACKGROUND OF THE INVENTION

[0002] Lubricant anti-wear agents like sulfurized olefins, metal dithiophosphate, and other alkyl phosphate amines usually contain sulfur and / or phosphorous. For gear oil applications, sulfur and phosphorus, oxidizes and chemically attacks and embrittles rubber and resin parts of drivelines. In addition, lowering sulfur and phosphorus helps to reduce metal corrosion especially in hybrid electric vehicle (HEV) and electric axle (eAxle) applications, where lubricant oil directly contacts copper and copper alloys.SUMMARY OF THE INVENTION

[0003] The objectives of the present invention include making it possible to significantly reduce the amount of sulfur and phosphorous in gear oil applications, where sulfur and phosphorus chemically attacks and embrittles rubber and resin parts of drivelines. In addition, lowering sulfur and phosphorus helps to reduce metal corrosion especially in hybrid elective vehicles (HEV) / and electric axle (eAxle) applications where lubricant oil directly contacts copper and copper alloys.

[0004] The technology provides a gear lubricant composition containing an oil of lubricating viscosity, a polyester which comprises a self-condensation product of a Cs-22 fatty carboxylic acid containing at least one hydroxyl group, and a phosphorus containing anti-wear agent. In an embodiment, the self-condensation product can further react with an amine. The composition can also include an azole compound.

[0005] Also provided is a method of lubricating an automotive gear with the gear lubricant composition as disclosed.DETAILED DESCRIPTION OF THE INVENTION

[0006] The present invention provides a lubricating composition, a method for lubricating a mechanical device and a use as disclosed above.The Polyester

[0007] As used herein the term “fatty carboxylic acid” used in relation to the polyester means an acid with a carbon chain of 8 to 22, or 10 to 22 carbon atoms.

[0008] As used herein the term “polyester” is intended to include a polymer in which the monomer units are linked together by a group -C(O)O-

[0009] The C8-22 (or Cl 0-20) fatty carboxylic acid containing at least one hydroxyl group from which the polyester of the present invention may be prepared include a compound represented by the formula:wherein R1may be a hydrogen or a hydrocarbyl group containing from 1 to 20 carbon atoms and R2may be a hydrocarbyl ene group containing from 1 to 20 carbon atoms, with the proviso that the total number of carbon atoms present from R1and R2may be 6 or more, or 8 or more. In some embodiments R1contains from 1 to 12, 2 to 10, 4 to 8 or even 6 carbon atoms R2may contain from 2 to 16, 6 to 14, 8 to 12, or even 10 carbon atoms.

[0010] In some embodiments the fatty carboxylic acid used in the preparation of the polyester may be 12-hydroxy stearic acid, ricinoleic acid, 12-hydroxy dodecanoic acid, 5-hydroxy dodecanoic acid, 5-hydroxy decanoic acid, 4-hydroxy decanoic acid, 10-hydroxy undecanoic acid, or combinations thereof.

[0011] In one embodiment the fatty carboxylic acid used in the preparation of the polyester may be 12-hydroxy stearic acid. In one embodiment the fatty carboxylic acid used in the preparation of the polyester may be ricinoleic acid.

[0012] In these embodiments the polyester may (or may not) be capped with a Cl -22, or a C8-20, fatty acid. Examples of suitable acids include oleic acid,palmitic acid, stearic acid, erucic acid, lauric acid, 2-ethylhexanoic acid, 9,11- linoleic acid, 9,12-linoleic acid, 9,12,15-linolenic acid, abietic acid, or combinations thereof.

[0013] The number average molecular weight (Mn) of the polyesters of the invention may be from 500 to 3000, or from 700 to 2500.

[0014] The polyester useful in the present invention may be obtained / obtainable by a self-condensation reaction involving heating one or more hydroxycarboxylic acids or a mixture of the hydroxycarboxylic acid and a carboxylic acid, optionally in the presence of an esterification catalyst. The hydroxycarboxylic acids may, in certain embodiments, have the formula HO-X-COOH wherein X may be a divalent saturated or unsaturated aliphatic radical containing at least 8 carbon atoms and in which there are at least 4 carbon atoms between the hydroxy and carboxylic acid groups, or from a mixture of such a hydroxycarboxylic acid and a carboxylic acid which is free from hydroxy groups. This reaction may be carried out at a temperature in the region of greater than 100°C, such as, for example, 160 °C to 200 °C, until the desired molecular weight has been obtained. The course of the esterification may be followed by measuring the acid value of the product, with the desired polyester, in some embodiments, having an acid value in the range of 10 to 100 mg KOH / g or in the range of 20 to 50 mg KOH / g. The indicated acid value range of 10 to 100 mg KOH / g is equivalent to a number average molecular weight range of 5600 to 560. The water formed in the esterification reaction may be removed from the reaction medium, and this may be conveniently done by passing a stream of nitrogen over the reaction mixture or by carrying out the reaction in the presence of a solvent, such as toluene or xylene, and distilling off the water as it is formed.

[0015] The resulting self-condensation product provides a polyester. The polyester may then be isolated in conventional manner; however, when the reaction is carried out in the presence of an organic solvent whose presence would not be harmful in the subsequent application, the resulting solution of the polyester may be used.

[0016] In the said hydroxycarboxylic acids the radical represented by X may contain from 12 to 20 carbon atoms, optionally where there are between 8 and 14carbon atoms between the carboxylic acid and hydroxy groups. In some embodiments the hydroxycarboxylic acid may contain a second hydroxy group. Typically, the hydroxycarboxylic acid may contain one hydroxy group and one carboxylic acid group.

[0017] Specific examples of such hydroxy carboxylic acids include ricinoleic acid, a mixture of 9- and 10-hydroxystearic acids (obtained by sulphation of oleic acid followed by hydrolysis), and 12-hydroxy stearic acid, and especially the commercially available hydrogenated castor oil fatty acid which contains in addition to 12-hydroxy stearic acid minor amounts of stearic acid and palmitic acid.

[0018] The carboxylic acids which may be used in conjunction with the hydroxy carboxylic acids to obtain these polyesters are preferably carboxylic acids of saturated or unsaturated aliphatic compounds, particularly alkyl and alkenyl carboxylic acids containing a chain of from 8 to 20 carbon atoms. As examples of such acids there may be mentioned lauric acid, palmitic acid, stearic acid and oleic acid.

[0019] In one embodiment the polyester may be derived from commercial 12- hydroxy -stearic acid and may have a number average molecular weight of about 1600. Polyesters such as this are described in greater detail in U.K. Patent Specification Nos. 1373660 and 1342746.

[0020] In an embodiment, the polyester self-condensation product can be reacted with an amine. In another embodiment, an amine can be reacted with the fatty carboxylic acid containing at least one hydroxyl group in the monomer form, followed by the self-condensation reaction as set forth above. Examples of such amines include methylamine, diethylamine and octadecylamine, as well as dodecyldimethylamine, 3-dimethylaminopropylamine and 3- octadecylaminopropylamine. In one embodiment, the polyester can be reacted with dodecyldimethylamine. In embodiments, the polyester can be reacted with 3-dimethylaminopropylamine. In embodiments, the polyester can be reacted with 3- dodecyldimethylamine.

[0021] The polyester can contain a plurality of polyester chains attached to the amine and consequently may contain a mixture of amide and salt linkages depending on the severity of the reactor conditions.

[0022] In certain embodiments the polyester self-condensation product may be present at 0.05 wt.% to 10 wt.%, 0.1 wt.% to 10 wt.%, or 1 wt.% to 8 wt.%, or 2 wt.% to 6.5 wt.% of the lubricating composition. In embodiments, the polyester may be present at 0.05 wt.% to 2 wt.%, or 0.1 wt.% to 1.75 wt.%, or 0.25 wt.% to 1.5 wt.%, or 0.5 wt.% to 1.25 wt.%.Oils of Lubricating Viscosity

[0023] 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 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 Application 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.

[0024] 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 summarized in US Patent US 7,285,516 (see column 11, 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.

[0025] 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 invention and the other performance additives.

[0026] The lubricating composition may be in the form of a concentrate and / or a fully formulated lubricant. If the lubricating composition of the invention (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.Phosphorus containing anti-wear agent

[0027] The lubricant additive composition contains at least one phosphorus antiwear compound. The phosphorus antiwear compound may be an acid, salt or ester. In one embodiment the phosphorus antiwear compounds are in the form of a mixture of two or three, or two to four (typically two or three) phosphorus antiwear compounds. In some embodiments the phosphorus antiwear compounds are in the form of a mixture of phosphites and (thio)phosphate amines compounds.

[0028] In some embodiments the phosphorus antiwear compound is a phosphite. Suitable phosphites include those having at least one hydrocarbyl group with 3 or 4 or more, or 8 or more, or 12 or more, carbon atoms. The phosphite may be a mono-hydrocarbyl substituted phosphite, a di-hydrocarbyl substituted phosphite, or a tri-hydrocarbyl substituted phosphite.

[0029] In one embodiment the phosphite is sulfur-free i.e., the phosphite is not a thiophosphite.

[0030] The phosphite may be represented by the formulae:XIXIIwherein at least one R may be a hydrocarbyl group containing at least 3 carbon atoms and the other R groups may be hydrogen. In one embodiment, two of the R groups are hydrocarbyl groups, and the third is hydrogen. In one embodiment every R group is a hydrocarbyl group, i.e., the phosphite is a tri -hydrocarbyl substituted phosphite. The hydrocarbyl groups may be alkyl, cycloalkyl, aryl, acyclic or mixtures thereof.

[0031] The R hydrocarbyl groups may be linear or branched, typically linear, and saturated or unsaturated, typically saturated.

[0032] In one embodiment, the phosphorus antiwear compound can be a C3-8 hydrocarbyl phosphite, or mixtures thereof, i.e., wherein each R may independently be hydrogen or a hydrocarbyl group having 3 to 8, or 4 to 6 carbon atoms, typically 4 carbon atoms. Typically the C3-8 hydrocarbyl phosphite comprises a dialkyl phosphite where each R is 1 to 14 carbon atoms, or 2 to 12 carbon atoms, or 3 to 8 or 4 to 6 carbon atoms. The dialkyl phosphite can be, for example, dibutyl phosphite or di oleyl phosphite. The C3-8 hydrocarbyl phosphite, or C3-8 dialkyl phosphite, may deliver at least 10 ppm, or at least 20 ppm of the total amount of phosphorus delivered by the phosphorus anti wear compounds. The C3-8 hydrocarbyl phosphite, or C3-8 dialkyl phosphite, may deliver lOppm to 75 ppm, or 20 ppm to 70 ppm, or even 30 ppm to 60 ppm of the total amount of phosphorus delivered by the phosphorus antiwear compounds. The C3-8 hydrocarbyl phosphite, or dialkyl phosphite, may deliver at least 45 wt.%, or 50 wt.% to 100 wt.%, or 50 wt.% to 90 wt.% or 60 wt.% to 80 wt.% of the total amount of phosphorus from the phosphorus antiwear compound.

[0033] In one embodiment, the phosphorus antiwear compound can be a C 12-24 hydrocarbyl phosphite, or mixtures thereof, i.e., wherein each R may independently be hydrogen or a hydrocarbyl group having 12 to 24, or 14 to 20 carbon atoms, typically 16 to 18 carbon atoms. Typically the C12-24 hydrocarbyl phosphite comprises a Cl 6- 18 dialkyl phosphite. Examples of alkyl groups for R3, R4 and R5 include octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonadecyl, eicosyl or mixtures thereof. The C 12-24 hydrocarbyl phosphite, or C 12-24 dialkly phosphite, may be present in the lubricant additive composition at about 0.05 wt.% to about 1.0 wt.% of the lubricant additive composition, or from about 0.1 wt.% to about 0.5 wt.% of the lubricant additive composition.

[0034] In some embodiments, the phosphorous containing compound can include both a C3-8 and a C12-14 hydrocarbyl phosphite.

[0035] The phosphorus antiwear compound can include a phosphite at 0.1 to 2 wt.% of the additive composition, or even from 0.2 to 1.8 wt.%, or 0.2 to 1.4 or 1.6 wt.% of the lubricant additive composition, or even from 0.2 to 1 or 1.2 wt.% of the lubricant additive composition. The phosphorus antiwear compound can include a phosphite at 0.1 to 0.5 wt.% of the additive composition, or even from 0.2 to 0.4 wt.%, or 0.2 to 0.3 wt.% of the lubricant additive composition.

[0036] The phosphorus antiwear compound can be a phosphite ester composition that is the reaction product, e.g., condensation product, of a monomeric phosphorous acid or an ester thereof with at least two alkylene diols. In an embodiment, the foregoing phosphite ester does not contain zinc.

[0037] By “monomeric” phosphorous acid or ester is meant a phosphorous acid or ester, typically containing one phosphorus atom, which may be reacted with a diol to form an oligomeric, polymeric, or other condensed species. The monomeric phosphorous acid or ester thereof may be phosphorous acid itself (H3PO3), although a monomeric partial ester such as a dialkylphosphite may be used for ease of handling or other reasons. The alkyl group or groups may be relatively low molecular weight groups of 1 to 6 or 1 to 4 carbon atoms, such as methyl, ethyl, propyl, or butyl, such that the alcohol generated upon reaction with the alkylene diols may be easily removed. An exemplary phosphorous acid ester isdimethyl phosphite; others include diethyl phosphite, dipropyl phosphite, dioleyl phosphite and dibutyl phosphite. Sulfur-containing analogues may also be employed (e.g., thiophosphites). Other esters include trialkyl phosphites. Mixtures of di-and trialkyl phosphites may also be useful. In these materials, the alkyl groups may be the same or different each independently typically having 1 to 6 or 1 to 4 carbon atoms as described above.

[0038] The monomeric phosphorus acid or ester will be reacted or condensed with at least two alkylene diols to form a phosphorus antiwear compound, which may include a polymeric (or oligomeric) phosphorus ester and optionally monomeric species. The first alkylene diol (i) will be a 1,4- or 1,5- or 1,6- alkylene diol. That is to say, there will be two hydroxy groups in a 1,4 or 1,5 or 1,6 relationship to each other, separated by a chain of 4, 5, or 6 carbon atoms, respectively. The first hydroxy group may be literally on the 1 carbon atom, that is, on the a carbon of the diol, or it may be on a higher numbered carbon atom. For example, the diol may also be a 2,5- or 2,6-, or 2,7-diol or a 3,6- or 3,7- or 3,8-diol, as will be evident to the skilled person. The alkylene diol may be branched (e.g., alkyl -substituted) or unbranched and in one embodiment is unbranched. Unbranched, that is, linear diols (a, co -diols) include 1,4-butanediol, 1,5-pentane diol, and 1,6-hexanediol. Branched or substituted diols include 1,4-pentanediol, 2-methyl- 1,5 -pentanediol, 3-methyl-l,5-pentanediol, 3,3-dimethyl-l,5-pentanediol, 1,5-hexanediol, 2,5- hexanediol, and 2,5-dimethyl-2,5-hexanediol. A diol having one or more secondary hydroxy groups (such as 2,5-hexanediol) may be referred to as a branched or substituted diol, even though the carbon chain itself may be linear. The location of the hydroxy groups in the 1,4-, 1,5-, or 1,6- positions (that is, either positions relative to each other or literal positions) may be helpful to promote oligomerization with the phosphorous species rather than formation of cyclic structures (which would be sterically disfavored). In certain embodiments the first alkylene diol may be 1,6-hexanediol.

[0039] The first alkylene dihydroxy compound (diol) may, if desired, have additional hydroxy groups, that is, more than two per molecule, or there may be exactly two. In one embodiment, there are exactly two hydroxy groups per molecule. If there are more than two hydroxy groups, care should be taken toassure that there is no excessive cyclization such as might interfere with the polymerization reaction, if there are fewer than 4 atoms separating any of the hydroxy groups. Also, care should be taken to avoid excessive branching or crosslinking in the product, which could lead to undesirable gel formation. Such problems may be avoided by careful control of reaction conditions such as control of the ratio of reagents and the order of their addition, performing the reaction under suitably dilute conditions, and reacting under low acid conditions. These conditions can be determined by the person skilled in the art with only routine experimentation.

[0040] The phosphorous acid or ester is also reacted with a second alkylene diol (ii). The second alkylene diol is an alkyl-substituted 1,3 -propylene diol with one or more of the alkyl substituents thereof being on one or more of the carbon atoms of the propylene unit, the total number of carbon atoms in the alkyl-substituted 1,3-propylene diol being 5 to 12 or 6 to 12 or 7 to 11 or 8 to 18 or, in certain embodiments, 9. That is, the alkyl-substituted 1,3-propylene diol may be represented by the general formulawhere the various R groups may be the same or different and may be hydrogen or an alkyl group, provided that at least 1 R is an alkyl group and that the total number of carbon atoms in the R groups is 2 to 9 or 3 to 9, so that the total carbon atoms in the diol will be 5 to 12 or 6 to 12, respectively, and likewise for the other ranges of total carbons. By analogy with the above-described, 1,4-, 1,5-, or 1,6-diols, reference here to 1,3 -diols means that the two hydroxy groups are in a 1,3 relationship to each other, that is, separated by a chain of 3 carbon atoms. A 1,3- diol may thus also be named as a 2,4- or 3,5-diol. If the 1 ,3 -diol has one or more secondary hydroxy groups, such a molecule will be considered to be a substituted diol. In one embodiment the number of alkyl substituents is 2 and the total number of carbon atoms in the molecule is 9. Suitable substituents may include, for instance, methyl, ethyl, propyl, and butyl (in their various possible isomers).

[0041] Examples of the second alkylene diol may include 2,2-dimethyl-l,3- propanediol, 2-ethyl-2-butylpropane- 1,3 -diol, 2-ethylhexane- 1,3 -diol, 2,2- dibutylpropane- 1,3 -diol, 2,2-diisobutylpropane- 1,3 -diol, 2-methyl-2-propyl- propane- 1,3 -diol, 2-propyl-propane- 1,3 -diol, 2-butylpropane- 1,3 -diol, 2-pentyl- propane- 1,3 -diol, 2-methyl-2-propylpropane-l,3-diol, 2, 2-di ethylpropane- 1,3- diol, 2,2,4-trimethylpentane-l,3-diol, 2-methylpentane-2,4-diol, 2,4,-dimethyl- 2,4-pentanediol, and 2,4-hexanediol. It should be noted that some of the foregoing nomenclature emphasizes the propane-1, 3-diol structure of the molecules, for clarity. For instance, 2-pentylpropane-l, 3-diol might also be named 2- hydroxymethylheptan-l-ol, but the latter nomenclature does not so clearly illustrate the 1,3-nature of the diol.

[0042] The relative molar amounts of the first alkylene diol (i) and the second alkylene diol (ii) may be in a ratio of 30:70 to 65:35, or alternatively 35:65 to 60:40 or 40:60 to 50:50 or 40:60 to 45:55. If the ratio is less than about 30:70, the resulting product may not fully exhibit the benefits of the disclosed technology, and if it is greater than about 65:35, its compatibility with other components in a lubricant formulation may be reduced.

[0043] The relative molar amounts of the monomeric phosphorous acid or ester thereof (a) and the total molar amounts of the alkylene diols (b) may be in a ratio of 0.9: 1.1 to 1.1 :0.9, or 0.95: 1.05 to 1.05:0.95, or 0.98: 1.02 to 1.02:0.98, or about 1 : 1. Reaction in approximately equimolar ratios will tend to encourage formation of oligomers or polymer formation. An exact 1 : 1 ratio could theoretically lead to extremely long chain formation and consequently very high molecular weight. In practice, however, this is not typically attained since competing reactions and incompleteness of reaction will provide materials of a lesser degree of polymerization, and a certain fraction of the material will be in the form of cyclic monomer.

[0044] The reaction product will typically comprise a mixture of individual species, including some oligomeric or polymeric species as well as cyclic monomeric species. The cyclic monomeric species may comprise 1 phosphorus atom and one alkylene group, derived principally from the 1, 3-diol (ii), as the 1,3- diol is capable of either participation in oligomerization or cyclic ester formation.The oligomeric or polymeric species may typically comprise 2 or 3 to 20 phosphorus atoms, or alternatively 5 to 10 phosphorus atoms, linked together by alkylene groups derived from the diols (i) and (ii), and may exhibit a relative preference for incorporation of the 1,4-, 1,5-, or 1,6-diols, which are less readily able to cyclize with the phosphorus to form a cyclic monomeric species.

[0045] The product may be a mixture of species that may be represented by the structures shown:(oligomeric species) plus(cyclic monomer species) where x and j’ represent the relative amounts of the two diols incorporated into the oligomer. The structure shown is not intended to indicate that the polymer is necessarily a block polymer, since the structures represented by the x and y brackets may be more or less randomly distributed, as influenced by or depending on the availability of the various diol reactants. Each X is independently a terminating group, which may be, for instance, an alkyl group (such as methyl), or hydrogen or a diol-derived moiety which might terminate in an OH group. In the above scheme, for illustrative purposes only, the diene (i) is selected to be 1,6-hexanediol and diene (ii) is selected to be 2-butyl-2-ethyl-l,3-propanediol. Corresponding structures and mixtures would be formed using different diols (i) and (ii).

[0046] The relative amounts of oligomeric species and cyclic monomer species in the reaction mixture will depend, to some extent, on the specific diols selected and the reaction conditions. For reaction products prepared from 1,6-hexane diol and2 -butyl -2-ethyl- 1,3 -propanediol, as in the structures above, the amount of oligomeric product may be approximately as shown in the table below:and the amount of the cyclic monomer may be 100% minus the percentage of the oligomer. It is also possible that, regardless of the specific diols employed, mixtures having the above weight percentages of oligomer and cyclic monomer may be usefully prepared. In certain embodiments, 55 to 60 weight percent of the product is in oligomeric form and 45 to 40 percent is in cyclic monomer form. In some embodiments the relative amount of the cyclic monomeric species to the amount of the oligomeric species is 1 :3 to 1 : 1 or alternatively 1 :3 to 1 :0.8 by weight.

[0047] The condensation reaction between the phosphorus acid or ester and the diol may be accomplished by mixing the reagents and heating until the reaction is substantially complete. Typically, the first and second alkylene diols may be mixed with the phosphorous compound at the same time or nearly the same time, that is, typically before the reaction with one of the alkylene diols is complete. A small amount of a basic material such as sodium methoxide may also be present. If a methyl ester of the phosphorous acid is used as a reagent, substantial completion of the reaction may correspond with the cessation of evolution and distillation of methanol from the reaction mixture. Suitable temperatures include those in the range of 100 to 140°C, such as 110 to 130°C or 115 to 120°C. If reaction temperatures in excess of about 140°C are employed, there is a risk that the desired product may not be formed in useful yields or with useful purity, since competing reactions may occur. Reaction times may typically be up to 12 hours, depending on temperature, applied pressure (if any), agitation, and other variables. In some instances, reaction times of 2 to 8 hours or 4 to 6 hours may be appropriate.

[0048] Other monomers may be included within the reaction mixture if desired. In particular, the inclusion of a polycarboxylic acid, such as a dicarboxylic acid, is sometimes seen as beneficial. For example, inclusion of a relatively minor amount of tartaric acid or citric acid may provide products with useful properties. The amount of polyacid or diacid may an amount suitable to incorporate at least 1, or approximately 1, monomeric unit of poly- or dicarboxylic acid per productoligomer molecule. The amount of polyacid or diacid actually charged to the reaction mixture may be higher than this amount. Without intending to be bound by any theory, it is believed that when a minor amount of tartaric acid is present, it may be incorporated as an end unit of the polymer, possibly being condensed through an ester linkage with an OH group of an alkylene diol. Such materials may exhibit good performance in terms of antiwear protection and corrosion inhibition, as well as seals performance. Suitable polyacids (or their esters or anhydrides) include maleic acid, fumaric acid, tartaric acid, citric acid, phthalic acid, terephthalic acid, malonic acid (e.g., ester), succinic acid, malic acid, adipic acid, oxalic acid, sebacic acid, dodecanedioic acid, glutaric acid, and glutamic acid. Another type of monomer which may be included is a monocarboxylic acid which contains a reactive hydroxy group, or a reactive equivalent of such a material, such as an anhydride, ester, or lactone. Examples include glyoxylic acid, caprolactone, valerolactone, and hydroxystearic acid.

[0049] The lubricant additive composition can include a substantially sulfur-free alkyl phosphate salt, as further described. In this salt composition, at least 30 mole percent of the phosphorus atoms are in an alkyl pyrophosphate structure, as opposed to an orthophosphate (or monomeric phosphate) structure. The percentage of phosphorus atoms in the pyrophosphate structure may be 30 to 100 mole %, or 40 to 90 % or 50 to 80% or 55 to 70 % or 55 to 65%. The remaining amount of the phosphorus atoms may be in an orthophosphate structure or may consist, in part, in unreacted phosphorus acid or other phosphorus species. In one embodiment, up to 60 or up to 50 mole percent of the phosphorus atoms are in mono- or di-alkyl- orthophosphate salt structure.

[0050] The substantially sulfur-free alkyl phosphate salt, as present in the pyrophosphate form (sometimes referred to as the POP structure). In certain embodiments at least 80 mole percent, or at least 85, 90, 95, or 99 percent, of the alkyl groups of the alkyl phosphate salt will be primary alkyl groups. In some embodiments the alkyl groups will have 4 to 22, or 4 to 20, or 4 to 18, or even 4 to 12 carbon atoms, or 5 to 10, or 6 to 8 carbon atoms. Such groups include 2- butyl, 2-pentyl, 3-pentyl, 3-methyl-2-butyl, 2-hexyl, 3-hexyl, cyclohexyl, 4- methyl-2-pentyl, and other such primary groups and isomers thereof having 6, 7,8, 9, 10, 11, or 12 carbon atoms. In some embodiments the alkyl group will have a methyl branch at the a-position of the group, an example being the 4-methyl-2- pentyl (also referred to as 4-methylpent-2-yl) group.

[0051] Such alkyl (including cycloalkyl) groups will typically be provided by the reaction of the corresponding alcohol or alcohols with phosphorus pentoxide (taken herein to be P2O5 although it is recognized the more probable structure may be represented by P4O10). Thus the alkyl phosphate salt may be prepared by the reaction of phosphorus pentoxide with a primary alcohol having 4 to 12 carbon atoms, and reacting the product thereof with the salting material, as described in further detail below.

[0052] While the pyrophosphate ester may be isolated, if desired, from the orthoesters, it is also possible, and may be commercially preferable, to use the reaction mixture without separation of the components.

[0053] The phosphorus antiwear compound may also be an amine alkylthiophosphate, wherein the alkylthiophosphate is represented by the formula (R’O)2PSSH, wherein each R’ is independently a hydrocarbyl group containing from about 3 to about 30, preferably from about 3 up to about 18, or from about 3 up to about 12, or from up to about 8 carbon atoms. Example R’ groups can include isopropyl, isobutyl, n-butyl, sec-butyl, the various amyl, n-hexyl, methylisobutyl carbinyl, heptyl, 2-ethylhexyl, isooctyl, nonyl, behenyl, decyl, dodecyl, and tridecyl groups. Illustrative lower alkylphenyl R’ groups include butylphenyl, amylphenyl, heptylphenyl, etc. Examples of mixtures of R’ groups include: 1 -butyl and 1 -octyl; 1 -pentyl and 2-ethyl-l -hexyl; isobutyl and n-hexyl; isobutyl and isoamyl; 2-propyl and 2-methyl-4-pentyl; isopropyl and sec-butyl; and isopropyl and isooctyl.

[0054] In one embodiment, the alkylthiophosphate of the amine alkylthiophosphate may be reacted with an epoxide or a polyhydric alcohol, such as glycerol. This reaction product may be used alone, or further reacted with a phosphorus acid, anhydride, or lower ester. The epoxide is generally an aliphatic epoxide or a styrene oxide. Examples of useful epoxides include ethylene oxide, propylene oxide, butene oxide, octene oxide, dodecene oxide, styrene oxide, etc. Ethylene oxide and propylene oxide are preferred. The polyhydric alcohols aredescribed above. The glycols may be aliphatic glycols having from 2 to about 12, or from about 2 to about 6, or from 2 or 3 carbon atoms. Glycols include ethylene glycol, propylene glycol, and the like. The alkylthiophosphate, glycols, epoxides, inorganic phosphorus reagents and methods of reacting the same are described in U.S. Pat. Nos. 3,197,405 and 3,544,465 which are incorporated herein by reference for their disclosure to these.

[0055] In one embodiment the phosphorus antiwear compound can include a phosphorus-containing acid, salt or ester, or mixtures thereof. In one embodiment the phosphorus antiwear compound can be in the form of a mixture.

[0056] The phosphorus antiwear compound can include those derived from phosphoric acid, phosphorous acid, thiophosphoric acid, thiophosphorous acid, or mixtures thereof.

[0057] In one embodiment the phosphorus antiwear compound can include (i) a non-ionic phosphorus compound; (ii) an amine salt of a phosphorus compound; or (hi) an ammonium salt of a phosphorus compound.

[0058] In one embodiment the phosphorus antiwear compound can include an ammonium or amine salt of a phosphorus-containing acid or ester.

[0059] The amine salt of a phosphorus acid or ester includes phosphoric acid esters and amine salts thereof; dialkyldithiophosphoric acid esters and amine salts thereof; amine salts of phosphites; and amine salts of phosphorus containing carboxylic esters, ethers, and amides; and mixtures thereof.

[0060] The alkyl groups of the phosphorus antiwear compound can be from 2 to 12 carbons, or from 3 to 10 or 4 to 8 carbon atoms in length.

[0061] The amine salt of a phosphorus acid or ester may be used alone or in combination.

[0062] In one embodiment the amine salt of a phosphorus acid or ester includes a partial amine salt, or a partial amine-metal salt compound or mixtures thereof. In one embodiment the amine salt of a phosphorus acid or ester further contains a sulphur atom in the molecule.

[0063] The pyrophosphate, thiophosphate ester, phosphate ester or mixture of phosphate esters will be reacted with a salting material. The salting material can be a metal to form a metal salt, or an amine to form an amine salt.

[0064] The metal of the metal salt includes aluminium, calcium, magnesium, strontium, chromium, iron, cobalt, nickel, zinc, tin, lead, manganese, silver, or mixtures thereof. In one embodiment the metal is zinc.

[0065] The amine of the amine salt may be represented by R23N, where each R2 is independently hydrogen or a hydrocarbyl group or an ester-containing group, or an ether-containing group, provided that at least one R2 group is a hydrocarbyl group or an ester-containing group or an ether-containing group (that is, not NH3). Suitable hydrocarbyl amines include primary amines having 1 to 18 carbon atoms, or 3 to 12, or 4 to 10 carbon atoms, such as methylamine, ethylamine, propylamine, isopropylamine, butylamine and isomers thereof, pentylamine and isomers thereof, hexylamine and isomers thereof, heptylamine and isomers thereof, octylamine and isomers thereof such as isooctylamine and 2-ethylhexylamine, as well as higher amines. Other primary amines include dodecylamine, fatty amines as n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n- hexadecylamine, n-octadecylamine and oleyamine. Other useful fatty amines include commercially available fatty amines such as “Armeen®” amines (products available from Akzo Chemicals, Chicago, Ill.), such as Armeen® C, Armeen® O, Armeen® OL, Armeen® T, Armeen® HT, Armeen® S and Armeen® SD, wherein the letter designation relates to the fatty group, such as coco, oleyl, tallow, or stearyl groups.

[0066] Secondary amines that may be used include dimethylamine, diethylamine, dipropylamine, dibutylamine, diamylamine, dihexylamine, diheptylamine, methylethylamine, ethylbutylamine, bis-2-ethylhexylamine, N-methyl-1 -aminocyclohexane, Armeen® 2C, and ethylamylamine. The secondary amines may be cyclic amines such as piperidine, piperazine and morpholine.

[0067] Suitable tertiary amines include tri-n-butylamine, tri -n-octylamine, tridecylamine, tri -lauryl amine, tri-hexadecylamine, and dimethyloleylamine (Armeen® DMOD). Triisodecylamine or tridecylamine and isomers thereof may be used.

[0068] Examples of mixtures of amines include (i) an amine with 11 to 14 carbon atoms on tertiary alkyl primary groups, (ii) an amine with 14 to 18 carbon atoms on tertiary alkyl primary groups, or (iii) an amine with 18 to 22 carbon atoms on tertiary alkyl primary groups. Other examples of tertiary alkyl primary amines include tert-butyl amine, tert-hexylamine, tert-octylamine (such as 1,1- dimethylhexylamine), tert-decylamine (such as 1,1 -dimethyloctylamine), tertdodecylamine, tert -tetradecyl amine, tert-hexadecylamine, tertoctadecylamine, tert-tetracosanylamine, and tert-octacosanylamine. In one embodiment a useful mixture of amines includes “Primene® 81R” or “Primene® JMT.” Primene® 81R and Primene® JMT (both produced and sold by Rohm & Haas) may be mixtures of Cl l to C14 tertiary alkyl primary amines and C18 to C22 tertiary alkyl primary amines, respectively.

[0069] In one embodiment the amine salt of a phosphorus acid or ester as described above can include an amine with about Cn to about C14 tertiary alkyl primary groups or mixtures thereof. In one embodiment the amine salt of a phosphorus compound includes an amine with about C14 to about C18 tertiary alkyl primary amines or mixtures thereof. In one embodiment the amine salt of a phosphorus compound includes an amine with about C18 to about C22 tertiary alkyl primary amines or mixtures thereof.

[0070] In one embodiment the amine salt of a phosphorus acid or ester as described above can be the reaction product of a C14 to C18 alkylated phosphoric acid with Primene® 81R (produced and sold by Rohm & Haas) which is a mixture of Cl l to C14 tertiary alkyl primary amines. In other embodiments the amine may be an ester-containing amine such as an N-hydrocarbyl -substituted y- or 6- amino(thio)ester, which is therefore a secondary amine. One or both of the O atoms of the ester group may be replaced by sulfur, although typically there may be no sulfur atoms.

[0071] There may also be one or more additional substituents or groups at the a, 0, y, or 6 positions of the aminoester. In one embodiment there are no such substituents. In another embodiment there is a substituent at the 0 position. That is, a substituent at the 0 position of the chain may comprise an ester, thioester,carbonyl, or hydrocarbyl group. The analogous structures for a 6-amino ester will be understood to be encompassed.

[0072] In one embodiment the material may be a methyl succinic acid diester, with amine substitution on the methyl group. In certain embodiments the material will be or will comprise a 2-((hydrocarbyl)-aminomethyl succinic acid dihydrocarbyl ester (which may also be referred to as a dihydrocarbyl 2- ((hydrocarbyl)aminom ethyl succinate).

[0073] The N-hydrocarbyl-substituted y-aminoester or y-aminothioester materials disclosed herein may be prepared by a Michael addition of a primary amine, typically having a branched hydrocarbyl group as described above, with an ethylenically unsaturated ester or thio ester of the type described above. The ethylenic unsaturation, in this instance, would be between the 0 and y carbon atoms of the ester.

[0074] The N-hydrocarbyl-substituted 5-aminoester or 6-aminothioester materials disclosed herein may be prepared by reductive amination of the esters of 5-oxy substituted carboxylic acids or 5-oxy substituted thiocarboxylic acids. They may also be prepared by amination of the esters of 5-halogen substituted carboxylic acids or 5-halogen substituted thiocarboxylic acids, or by reductive amination of the esters of 2-amino substituted hexanedioc acids, or by alkylation of the esters of 2-aminohexanedioic acids.

[0075] Further detailed description of the N-substituted y-amino ester and details of its synthesis may be found in WO2014 / 074335, Lubrizol, May 15, 2014. Further detailed description of the N-substituted 6-amino ester and details of its synthesis may be found in PCT application PCT / US2015 / 027958, Lubrizol, filed April 28, 2015 and US 61 / 989306, filed May 6, 2015.

[0076] The amine, of whatever type, will be reacted to neutralize the acidic group(s) on the phosphorus ester component, which will comprise the pyrophosphate ester as described above as well as any orthophosphate esters that may be present.

[0077] When the amine salt is an amine salt of the phosphate ester described above, the amount of the amine salts used in lubricants may be 0.1 to 2.0 weight percent or 0.15 to 1.5 weight percent or 0.15 to 2.5 weight percent.

[0078] When the amine salt is an amine salt of a thiophosphate ester described above, the amount of the amine salts used in the lubricant may be 0.05 to 0.5 weight percent, or 0.1 to 0.3 weight percent, or 0.15 to 2 weight percent.

[0079] The amount of the phosphorous ester product described above used in lubricants may be an amount sufficient to provide 0.01 to 0.3 or to 0.1 weight percent phosphorus to the composition or, in other embodiments, 0.02 to 0.07 weight percent or 0.025 to 0.05 weight percent. The actual amount of the product which corresponds to these amounts of phosphorus will, of course, depend upon its phosphorus content. Suitable amounts of the ester product in the lubricant additive composition may be 0.01 to 1.0 weight percent, or 0.02 to 0.5 weight percent, or 0.03 to 0.30 weight percent, or even 0.05 to 0.25 weight percent.

[0080] While each of the phosphorus antiwear compounds described above may be present in the lubricant additive composition on its own, the lubricant additive composition may also include a mixture of two or more. In some embodiments, the phosphorous containing compound can include a C3-8 hydrocarbyl phosphite and a phosphite ester product. In some embodiments, the phosphorous containing compound can include each of a C3-8 hydrocarbyl phosphite, a C12 to C24 hydrocarbyl phosphite, and a phosphite ester product.

[0081] When the lubricant composition comprises an amine thiophosphate ester salt, the phosphorous antiwear agent may be suitable to provide phosphorous to the lubricant formulation in an amount of 100 to 500 ppm, 150 to 400 part per million, or 200 to 300 ppm.

[0082] In either event, the phosphorus antiwear compound should be present in an amount to deliver 100 to 4000 ppm of phosphorus to the lubricant additive composition. In some embodiments, the at least one phosphorus antiwear compound can be present in an amount to deliver 125 to 3500 ppm of phosphorus, or from 150 to 3000 ppm phosphorus to the lubricant additive composition.

[0083] When the lubricant composition is substantially free of sulfur (less than 1000 ppm, less than 500 ppm, less than 250 part per million, or less than 100 part per million, or less than 50 ppm, or less than 25 ppm, or even less than 15 ppm, or completely free) the phosphorous antiwear agent may be a phosphate salt suitable to provide phosphorous to the lubricant formulation in an amount of 100 to 5000 ppm, or 150 to 4000 ppm, or 200 to 3000 ppm, or 250 to 2000 ppm, or 100 to 1000 ppm, or 1000 to 5000 ppm, 1250 to 4000 ppm, 1500 to 3000 ppm or 1600 to 2700 ppm.Low Molecular Weight -azole

[0084] The composition can also include low molecular weight triazoles and low molecular weight tetrazoles. By low molecular weight, it is meant a compound having a molecular weight between about 50 and 350 Daltons or 50 and 400 Daltons, or between about 55 and 250 Daltons, or between about 60 and 150 or 200 Daltons. Such compounds include, for example, those of formulas I or II:where R1 and R2 can be, individually, H or a Cl to C9 alkyl group

[0085] Examples of azole compounds of formula I can include, for example, 1,2,4- triazole, 3-methyl-l,2,4-triazole and the like. Examples of formula II can include, for example, IH-tetrazole, 5-methyltetrazole, and the like.

[0086] The azole compound can also include N-substituted azole compounds. N- substituted azole compounds may provide corrosion protection on their own, or decompose to a low molecular weight triazole or low molecular weight tetrazole compound under an operating condition of the automotive device; or decomposeto a low molecular weight triazole or low molecular weight tetrazole in the presence of a compound that reacts (“reactive compound”) with the N-substituted azole compound resulting in the release or formation of a low molecular weight triazole or low molecular weight tetrazole compound.

[0087] Formulas I and II may be reacted with an alkyl (meth)acrylate to obtain a compound having an alkyl (meth)acrylate substituent on a ring nitrogen. The formulas may also be reacted to obtain a formula with an amine substituent on a ring nitrogen, for example, by reacting with formaldehyde and the desired amine.

[0088] An example N-substituted azole compound with an amine substituent can include 1,2,4 triazoles of formula III:where R3 and R4 can be, independently C1-C22, or C2-C20, or C3-C18, or C3-C16 or C12, either linear or branched hydrocarbon groups, phenyl group, or two ends of a hydrocarbon chain forming a cyclic structure, or where at least one of R3 and R4 can be H.

[0089] In some embodiments, the N-substituted azole compound can be an N- branched substituted 1,2,4 triazole, such as those of formula III where R3 and R4 can be, independently C1-C22, or C2-C20, or C3-C18, or C3-C16 or C12 branched hydrocarbon groups, or two ends of a hydrocarbon chain forming a cyclic structure. Example structures of formula III can include:

[0090] In some embodiments, the N-substituted azole compound can be an bilinear substituted 1,2,4 triazole, such as those of formula III where R3 and R4 can be, independently linear C1-C22, or C2-C20, or C3-C18, or C3-C16 or C12 hydrocarbon groups (including carbonyl groups or acrylamide groups). Example structures of formula III can include:

[0091] In other embodiments, the N-substituted azole compounds can include, for example, N-single substituted 1,2,4 triazoles, such as those of formula III where R3 and R4 can be, independently C1-C22, or C2-C20, or C3-C18, or C3-C16 orCl 2, either linear or branched hydrocarbon groups, or two ends of a hydrocarbon chain forming a cyclic structure, and where at least one of R3 and R4 is H. Example structures of formula III can include:

[0092] The azole compound can also include N-substituted 1,2,4 triazoles, where the N-substituent is at the 4 position, as in formula IV:IVwhere R3 and R4 are as defined above. Compounds of formula IV may, in some embodiments, be naturally occurring impurities or minor isomers formed during the manufacture of compounds of formula III.

[0093] Other N-substituted azole compounds can include 1,2,3 triazoles of formula V:where R5, can be, independently C1-C22, or C2-C20, or C3-C18, or C3-C16 or C12, either linear or branched hydrocarbon groups, phenyl group, or two ends of a hydrocarbon chain forming a cyclic structure, R6 and R7 can be C1-C4, or Cl- C3, or C1-C2, or where at least one of R5, R6 and R7 can be H, or where both R6and R7 are H, or at least one of R5, R6 and R7 can include carbonyl or acrylamide groups, such as in methyl propionate or ethylhexyl propionate and the like, which may be formed by contacting the azole compound with an acrylate, acrylic acid, acrylamide or combination thereof.

[0094] Further N-substituted azole compounds include tetrazoles of formula VI:where R8 and R9 can be, independently C1-C22, or C2-C20, or C3-C18, or C3- C 16 or Cl 2, either linear or branched hydrocarbon groups, a phenyl group, or two ends of a hydrocarbon chain forming a cyclic structure, or where at least one of R8 and R9 can be H.

[0095] The azole compounds are formulated into a lubricant composition at a level sufficient to provide suitable copper corrosion protection. Often these compounds are provided for vapor phase corrosion protection. In general, levels of about 30 ppm to 5 wt.% of the azole compound are suitable in most applications. In some embodiments, the azole compound can be incorporated at a level of about 50 ppm to 4wt%, or about 250ppm to 3wt%, based on the total weight of the lubricant composition, or even from 500ppm to 2wt% or 1000 ppm to 1 wt.%. In some embodiments, the azole compound can be incorporated at a level of from about 100 ppm to 5000 ppm, or 250 ppm to 2500 ppm, or 500 to 2000 ppm.Other Performance Additives

[0096] A lubricating composition may be prepared by adding the product of the process described herein to an oil of lubricating viscosity, optionally in the presence of other performance additives (as described herein below).

[0097] The lubricant additive composition may also include antioxidants, e.g., aromatic amine antioxidants, hindered phenolic antioxidants including ester-containing hindered phenolic antioxidants, and sulfurized olefin antioxidants. These antioxidants may be present in amounts of 0.01 to 5, or 0.15 to 3or 0.2 to 1.5, 0.2 to 1 or 0.25 to 0.7 percent by weight.

[0098] In one embodiment the lubricant additive composition of the invention includes an aryl amine antioxidant. The aryl amine antioxidant may be a phenyl- a-naphthyl amine (PANA) or a hydrocarbyl substituted diphenylamine, or mixtures thereof. The hydrocarbyl substituted diphenylamine may include mono- or di- C4 to C16-, or C6 to C12-, or C9- alkyl diphenylamine. For example the hydrocarbyl substituted diphenylamine may be octyl diphenylamine, or di-octyl diphenylamine, dinonyl diphenylamine, typically dinonyl diphenylamine.

[0099] When present the aryl amine antioxidant may be present at 0.2 wt.% to 1.2 wt.%, or 0.3 wt.% to 1.0 wt.%, or 0.4 wt.% to 0.9 wt.% or 0.5 wt.% to 0.8 wt.%, of the lubricant additive composition.

[0100] The hindered phenol antioxidant often contains a secondary butyl and / or a tertiary butyl group as a sterically hindering group. The phenol group is often further substituted with a hydrocarbyl group 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, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment the hindered phenol antioxidant may be an ester and may include, e.g., Irganox™ L- 135 from Ciba, or butyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate.

[0101] If present, the hindered phenol antioxidant may be present at 0.1 wt.% to 1 wt.%, or 0.2 wt.% to 0.9 wt.% or 0.1 wt.% to 0.4 wt.%, or 0.4 wt.% to 1.0 wt.%, of the lubricant additive composition.

[0102] Antioxidants also include sulfurized olefins such as mono-, or disulfides or mixtures thereof. These materials generally have sulfide linkages having 1 to 10 sulfur atoms, for instance, 1 to 4, or 1 or 2. Materials which can be sulfurized to employ as sulfurized antioxidants in the lubricant additive composition can include oils, fatty acids and esters, olefins and polyolefins made thereof, terpenes,or Diels-Alder adducts. Details of methods of preparing some such sulfurized materials can be found in U.S. Pat. Nos. 3,471,404 and 4,191,659.

[0103] Polyethers can be prepared by condensing an alcohol, a hydrocarbyl carboxylic acid, or alkylphenol with an alkylene oxide, mixture of alkylene oxides or with several alkylene oxides in sequential fashion in a 1 :2-50 mole ratio of hydric compound to alkylene oxide to form a polyether. U.S. Pat. No. 5,094,667 provides reaction conditions for preparing polyethers, the disclosure of which is incorporated herein by reference. Examples of the alkylene oxides include ethylene oxide, propylene oxide or butylene oxide. The number of alkylene oxide units in the polyether intermediate can be 10-35 or 18-27.

[0104] In one embodiment, the poly ether is prepared from a primary alcohol. Suitable primary alcohols for use herein may contain from 6 to 30 carbon atoms, in another embodiment 8 to 24, or 10 to 20 carbon atoms. Mixtures of alcohols are contemplated. In one embodiment, the alcohol mixture used is at least 50 wt. %, or at least 60 wt. %, or at least 80 wt. %, or at least 90 wt. % of alcohols with at least 10 aliphatic carbon atoms, or at least 12 aliphatic carbon atoms. In one embodiment, the alcohol mixture used contains no more than 5.0 wt. % of C6 and lower linear alcohol, or no more than 2 wt. % or no more than 1 wt. %.

[0105] The primary alcohol may be linear or may be branched at the a-, or P-, or higher position with the proviso that there is no more than 3 branch points or no more than 2 branch points or no more than 1 branch points. In one embodiment, a mixture of linear and branched alcohols is employed.

[0106] Examples of useful primary linear alcohols include, decanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, or mixtures thereof. In one embodiment the linear alcohol contains 10 to 30, or 10 to 25, or 12 to 22 carbon atoms (typically 10 to 22 carbon atoms).

[0107] Other exemplary primary alcohols include commercially available mixtures of alcohols. These include oxoalcohols which may comprise, for example, various mixtures of alcohols having from 8-24 carbon atoms. Of the various commercial alcohols useful herein, one 12 to 18 aliphatic carbon atoms.The alcohols in the mixture may include one or more of, for example, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, and octadecyl alcohol. Several suitable sources of these alcohol mixtures are the technical grade alcohols sold under the name NEODOL® alcohols (Shell Oil Company, Houston, Tex.) and under the name ALFOL® alcohols (Sasol, Westlake, La.), and fatty alcohols derived from animal and vegetable fats and sold commercially by, for example, Henkel, Sasol, and Emery

[0108] In some embodiments, the alcohol includes one or more a Guerbet alcohols. Guerbet alcohols may be described as alcohols made via the Guerbet reaction, which was named after Marcel Guerbet. In a Guerbet reaction, a primary aliphatic alcohol is converted to its P-alkylated dimer alcohol (i.e., a branched, primary, saturated alcohol). In some embodiments, the alcohol includes at least one compound with the structure: HO — CH2 — (R1 )„ — CR2R3R4 where R1 is a alkylene group containing from 1 to 20 carbon atoms, n is either 0 or 1, and each of R2, R3 and R4 are independently hydrogen or alkyl groups containing from 1 to 20 carbon atoms. In some embodiments, n is zero, and R2 and R3 are alkyl groups, and R4 is hydrogen. In such embodiments, R2 and R3 may contain from 4 to 14, or even from 6 to 12 carbon atoms. In still further embodiments, R2 and R3 contain 6 and 8, or 10 and 12 carbon atoms. Suitable examples of the alcohol useful in the invention include 2-ethylhexanol, 2 -butyl octanol, 2-hexyldecanol, 2- octyldodecanol, 2-decyltetradecanol, 2-dodecylhexadecanol, or any combination thereof. These types of alcohols are commercially available from Sasol and marketed as ISOFOL® alcohols. In some embodiments, the alcohol includes 2- hexyldecanol, 2-decyltetradecanol, or any combination thereof. In some embodiments, the alcohol includes 2-hexyldecanol. In some embodiments, the alcohol includes 2-decyltetradecanol.

[0109] In another embodiment, the alcohol can be an alcohol with an isoalkly group. An isoalkyl group is a group of atoms resulting from the removal of a hydrogen atom from a methyl group situated at the end of the straight chain segment of an isoalkane. Particularly useful alcohols with an isoalkyl group are those where the methyl group is attached to the penultimate carbon atom of themain chain. Exemplary alcohols of this type are isodecanol, isododecanol, isotridecanol, isotetradecanol, isopentadecanol, isohexadecanol, isoheptadecanol, isooctadecanol, isononadecanol, isoeicosanol.

[0110] In an embodiment, the polyether can be of the formulaFormula I wherein R1 is hydrocarbyl group having 6 to 30 carbon atoms, R2 is hydrogen or an alkyl group having 1 to 5 carbon atoms, and R3 is hydrogen, an C1-C4 alkyl group, -C(O)R4, wherein R4 is a C1-C4 alkyl group and x is an integer from 10- 40 (15-35 or 20-30 or 22-26).[OHl] In an embodiment the polyether can be that of formula I wherein the hydrocarbyl group R1 is a linear aliphatic group from 6 to 30 carbon atoms, in another embodiment 8 to 24, or 10 to 20 carbon atoms, in yet another embodiment from 10 to 18 carbon atoms.

[0112] In an embodiment the polyether can be that of formula I wherein the hydrocarbyl group R1 is a branched aliphatic group from 6 to 30 carbon atoms, in another embodiment 8 to 24, or 10 to 20 carbon atoms, in yet another embodiment from 10 to 18 carbon atoms.

[0113] In an embodiment the polyether can be that of formula I wherein the hydrocarbyl group R1 can be a linear aliphatic group from 6 to 30 carbon atoms, in another embodiment 8 to 24, or 10 to 20 carbon atoms, in yet another embodiment from 10 to 18 carbon atoms and R3can be hydrogen.

[0114] In an embodiment the polyether can be that of formula I wherein the hydrocarbyl group Rican be a branched aliphatic group from 6 to 30 carbon atoms, in another embodiment 8 to 24, or 10 to 20 carbon atoms, in yet another embodiment from 10 to 18 carbon atoms and R3can be hydrogen.

[0115] In different embodiments the polyethers can be that of formulae I can be present in an amount ranging from 0.1 weight % to 5 weight %, or 0.2 to 3.0 weight%, or 0.25 to 2 weight % or 0.25 to 1.0 weight percent of the lubricating composition.

[0116] In one embodiment, the polyethercan be prepared from an alkylphenol. The alkyl group of the alkylphenols can be 1 to 30 carbon atoms, in another embodiment 10 to 20 carbon atoms.

[0117] In some embodiments, the polyether may comprise an oxyalkylated hydrocarbyl phenol represented by Formula II:FORMULA II wherein each R2can be independently hydrogen or a hydrocarbyl group of 1 to 6 carbon atoms; R3can be hydrogen, a C1-C4 alkyl group, -C(=0)R4, wherein R4can be a C1-C4 alkyl group, and each R5can be independently a hydrocarbyl group of 1 to 220, or 20 to 220, wherein at least one R5 contains 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. In some embodiments each, R4 of Formula Ilcan be a hydrocarbyl group of 1 to 24 carbon atoms; 10 to 24 (such as from 12 to 24, from 14 to 24, from 16 to 24, from 18 to 24, from 20 to 24, from 22 to 24, from 10 to 22, from 12 to 22, from 14 to 22, from 16 to 22, from 18 to 22, from 20 to 22, from 10 to 20, from 12 to 20, from 14 to 20, from 16 to 20, from 18 to 20, from 10 to 18, from 12 to 18, from 14 to 18, from 16 to 18, from 10 to 16, from 12 to 16, from 14 to 16, from 10 to 14, from 12 to 14, or from 10 to 12) carbon atoms.

[0118] The oxyalkylated hydrocarbyl phenol of Formula II can be selected such that the R2group can be methyl, R3can be hydrogen, an alkyl group of 1 to 4 carbon atoms, or an acyl group represented by -C(=O)R4; R4can be an alkyl group of 1 to 4 carbon atoms; each R5 can be a hydrocarbyl group of 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.

[0119] The oxyalkylated hydrocarbyl phenol of Formula II can be selected such that the R2 group can be methyl, and the second R2can be hydrogen; R3 can behydrogen, an alkyl group of 1 to 4 carbon atoms, or an acyl group represented by -C(=0)R4, R4 can be an alkyl group of 1 to 4 carbon atoms; R5 can be a hydrocarbyl group of 1 to 220 or 20 to 220 carbon atoms, wherein at least one R5 comprises a polyalk(en)yl group containing 25 to 200, or 35 to 180 or 40 to 180 to 60 to 180 or 40 to 96 carbon atoms; n = 2 to 8; and m = 1.

[0120] The oxyalkylated hydrocarbyl phenol of Formula II can be selected such that the R2 group can be methyl, and the second R2can be hydrogen; R3 can be hydrogen, an alkyl group of 1 to 4 carbon atoms, or an acyl group represented by -C(=O)R4, R4 can be an alkyl group of 1 to 4 carbon atoms; R5 can be a hydrocarbyl group of 1 to 220 or 20 to 220 carbon atoms comprises a polyisobutenyl group containing 25 to 200, or 35 to 180 or 40 to 180 to 60 to 180 or 40 to 96 carbon atoms; n = 2 to 8 (or 3 to 5); and m = 1.

[0121] The oxyalkylated hydrocarbyl phenol of Formula II can be selected such that the R2 group can be methyl, R3 can be hydrogen, an alkyl group of 1 to 4 carbon atoms, or an acyl group represented by -C(=O)R4, R4 can be an alkyl group of 1 to 4 carbon atoms; R5 can be an aliphatic hydrocarbyl group having from 10 to 24 (such as from 12 to 24, from 14 to 24, from 16 to 24, from 18 to 24, from 20 to 24, from 22 to 24, from 10 to 22, from 12 to 22, from 14 to 22, from 16 to 22, from 18 to 22, from 20 to 22, from 10 to 20, from 12 to 20, from 14 to 20, from 16 to 20, from 18 to 20, from 10 to 18, from 12 to 18, from 14 to 18, from 16 to 18, from 10 to 16, from 12 to 16, from 14 to 16, from 10 to 14, from 12 to 14, or from 10 to 12) carbon atoms, n = 2 to 8 (or 3 to 5); and m = 1

[0122] The R5 group of each of the formulae II above may be located in the para position relative to the oxyalkylated group, and the resultant formula can be represented by the structure:wherein variables R2 to R5, and n, are defined previously.

[0123] In one embodiment, the oxyalkylated hydrocarbyl phenol of the present invention can be represented by Formula 11(a), wherein R5 can be a polyolefinic group such as a polypropenyl or a polyisobutenyl group (typically a polyisobutenyl group), and variables R2, R3, R4, and n are defined previously. The polyisobutenyl group has a number average molecular weight of 350 to 2500, or 550 to 2300, or 750 to 1150 or 350 to 550. In one embodiment, the polyisobutenyl group has a number average molecular weight of 950-1000 or 500 to 600 or 300 to 400. 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.

[0124] In one embodiment, the oxyalkylated hydrocarbyl phenol of the present invention can be represented by Formula 11(b)Formula 11(b) wherein R5 can be a polyolefinic group such as a polypropenyl or a polyisobutenyl group (typically a polyisobutenyl group), and variables R2, R3, R4, and n, are defined previously. The polyisobutenyl group may have a number average molecular weight of350 to 2500, or 550 to 2300, or 750 to 1150. In one embodiment, the polyisobutenyl group has a number average molecular weight of 950-1000.

[0125] The oxyalkylated group of the oxyalkylated hydrocarbyl phenol has the formula — (R1O)„ — , wherein R1 can 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.

[0126] The oxyalkylated group of the oxyalkylated hydrocarbyl phenol may be either a homopolymer or copolymer or oligomers thereof. If the oxyalkylated group can be in the form of a copolymer, or oligomer thereof, the oxyalkylated group may have either random or block architecture.

[0127] In one embodiment, the oxyalkylated group (or Rl) can be a propylene, or butylene group i.e., the oxyalkylated group does not require an ethylene group. If an ethylene group can be present the oxyalkylate group may be a copolymer, or oligomer thereof with either propylene or butylene oxide i.e., blocks of (i) — CH2CH2O— with (ii) — CH2CH2CH2CH2O— or — CH2CH(CH3)CH2O— or — CH2CH(CH3)O— .

[0128] In one embodiment, the oxyalkylated group can be based upon propylene oxide.

[0129] The oxyalkylated hydrocarbyl phenol can 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.

[0130] The base catalyst may include, but can be not limited to, sodium chloroacetate, sodium hydride or potassium hydroxide

[0131] The aliphatic hydrocarbyl group (also represented by R4) can 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 R4 groups, with the second group being methyl. If a second R4 group can be present and can be methyl, then the oxyalkylated hydrocarbyl phenol can be a cresol.

[0132] In different embodiments the polyethers of formulae II can be present in an amount ranging from 0.1 weight % to 5 weight %, or 0.2 to 3.0 weight %, or 0.25 to 2 weight % or 0.25 to 1.0 weight percent of the lubricating composition.

[0133] In one embodiment, the polyether can be prepared from a hydrocarbyl carboxylic acid with from 8 to 24 carbon atoms, in another embodiment from 12 to 24 carbon atoms in yet another embodiment from 14-18 carbon atoms.

[0134] In some embodiments, the polyether may comprise an oxyalkylated hydrocarbyl phenol represented by Formula III:Formula III wherein the hydrocarbyl group R1 can be a linear or branched aliphatic group having from 7 to 23 carbon atoms, in another embodiment 11 to 23 or 13 tol7 carbon atoms R2 can be hydrogen or an alkyl group having 1 to 5 carbon atoms, and R3 can be hydrogen, an C1-C4 alkyl group, or -C(0)R4, R4 can be a C1-C4 alkyl group and n can be an integer from 10-40 (15-35 or 20-30 or 22-26) m can be an integer from 1 to 3.

[0135] Examples of the oxyalkylated hydrocarbyl carboxylic acids include but are not limited to tall oil fatty acid initiated polypropyleneoxide (22-24) ester-ol, butanol initiated polypropyleneoxide (23-25) ether-tallow fatty acid ester, tallow fatty acid initiated polypropyleneoxide (22-24) ester-ol. These alkoxylates can be made from the reaction of a fatty acid such as tall oil fatty acids (TOFA) that is, the mixture of fatty acids predominately oleic and linoleic and contains residual rosin acids or tallow acid that is, the mixture of fatty acids predominately stearic, palmitic and oleic with an alcohol terminated polyether such as polypropylene glycol in the presence of an acidic catalyst, usually methane sulphonic acid. These alkoxylates can also be made from the reaction of glycerol dioleate and propylene oxide in the presence of catalyst

[0136] In different embodiments the polyethers of formulae III can be present in an amount ranging from 0.1 weight % to 5 weight %, or 0.2 to 3.0 weight %, or 0.25 to 2 weight % or 0.25 to 1.0 weight percent of the lubricating composition.

[0137] The lubricant additive composition can also contain a poly(meth)acrylate polymer viscosity modifier. As used herein ranges below for the viscosity modifier are measured by GPC using polystyrene standards with a weight average molecular weight ranging from 350 to 100,000.

[0138] The lubricant additive composition in one embodiment includes a linear poly(meth)acrylate polymer with a weight average molecular weight of 5,000 to 25,000, or 8000 to 20,000.

[0139] The linear poly(meth)acrylate polymer may be present in the lubricant additive composition at about 0.1 wt.% to about 5 wt.%, or 0.1 wt.% to 4 wt.%, or 0.2 wt.% to 3 wt.%, or 0.5 wt.% to 3 wt.%, or 1.0 wt.% to 4 wt.%, 0.6 wt% to 4 wt%, or 0.75 wt% to 3 wt%, or 0.2 wt% to 0.75 wt%of the lubricant additive composition.

[0140] The poly(meth)acrylate polymer may be derived from a monomer composition comprising:(a) 50 wt.% to 95 wt.%, or 60 wt.% to 80 wt.% of an alkyl (meth)acrylate, wherein the alkyl group of the (meth)acrylate has 10 to 15 carbon atoms; (b) 1 wt.% to 40 wt.%, or 4 wt.% to 35 wt.% of an alkyl (meth)acrylate, wherein the alkyl group of the (meth)acrylate has 1 to 9 carbon atoms; (c) 1 wt.% to 10 wt.%, or 1 wt.% to 8 wt.% of a monomer having dispersant functionality, (d) 0 wt.% to 4 wt.%, or 0 wt.% to 2 wt.%, or 0 wt.% of a vinyl aromatic monomer (typically styrene); and (e) 0 wt.% to 9 wt.%, or 0 wt.% to 6 wt.% of an alkyl (meth)acrylate, wherein the alkyl group of the (meth)acrylate has 16 to 18 carbon atoms. In one embodiment the linear polymer may contain 0 wt.% to 20 wt.% of 16 to 18 alkyl (meth)acrylate.

[0141] In one embodiment the linear polymer includes a poly(meth)acrylate (typically a polymethacrylate) with units derived from a mixture of alkyl (meth)acrylate ester monomers containing, (a) 8 to 24, or 10 to 18, or 12 to 15 carbon atoms in the alcohol-derived portion of the ester group and (b) 6 to 11, or 8 to 11, or 8 carbon atoms in the alcohol-derived portion of the ester group, and which have 2-(Cl-4 alkyl)-substituents, and optionally, at least one monomer selected from the group consisting of (meth)acrylic acid esters containing 1 to 7 carbon atoms in the alcohol-derived portion of the ester group and which are different from (meth)acrylic acid esters (a) and (b), vinyl aromatic compounds (or vinyl aromatic monomers); and nitrogen-containing vinyl monomer; provided that no more than 60% by weight, or no more than 50% by weight, or no more than 35% by weight of the esters contain not more than 10 carbon atoms in the alcoholderived portion of the ester group. The linear polymer of this type is described in more detail in US 6,124,249, or EP 0 937 769 Al paragraphs

[0019] and

[0031] to

[0067] , (The “alcohol-derived portion” refers to the “-OR” portion of an ester, when written as R'C(=O)-OR, whether or not it is actually prepared by reactionwith an alcohol.) Optionally, the linear polymer may further contain a third monomer. The third monomer may be styrene, or mixtures thereof. The third monomer may be present in an amount 0% to 25% of the polymer composition, or from 1% to 15% of the composition, 2% to 10% of the composition, or even from 1% to 3% of the composition.

[0142] Typically, the mole ratio of esters (a) to esters (b) in the copolymer ranges from 95:5 to 35:65, or 90: 10 to 60:40, or 80:20 to 50:50.

[0143] The esters are usually aliphatic esters, typically alkyl esters. In one embodiment the ester of (a) may be a C12-15 alkyl (meth)acrylate and the ester of (b) may be 2-ethylhexyl (meth)acrylate.

[0144] In one embodiment, the ester groups in ester (a) contain branched alkyl groups. The ester groups may contain 2 to 65%, or 5 to 60% of the ester groups having branched alkyl groups. The branched alkyl groups may be ^-branched and may contain 8 to 60, or 8 to 30, or 8 to 16 carbon atoms. For examples branched alkyl groups may be derived from 2-ethylhexanol, 2 -butyl octanol, 2-hexyldecanol, 2-octyldodecanol, 2-decyltetradecanol, or mixtures thereof, or commercially available alcohols such as Isofol® branched Guerbet alcohols available from Sasol.

[0145] The Cl -4 alkyl substituents may be methyl, ethyl, and any isomers of propyl and butyl.

[0146] The weight average molecular weight of the linear poly(meth)acrylate may be 45,000 or less, or 35,000 or less, or 25,000 or less, or 8000 to 25,000, or, 10,000 to 35,000, or 12,000 to 20,000.

[0147] The linear polymer may be called a viscosity modifier, or a dispersant viscosity modifier as it may exhibit dispersant functionality. Reference to a “dispersant viscosity modifier” herein is exclusive of dispersants, which are a separate class of compounds. The linear polymer may be used as a sole viscosity modifier (or dispersant viscosity modifier) present at 0.5 wt.% to 4 wt.% of a linear (meth)acrylic polymer viscosity modifier having dispersant functionality, wherein the linear polymer has a weight average molecular weight of 5,000 to 25,000, or10,000 to 20,000, and wherein oil the of lubricating viscosity has a kinematic viscosity at 100°C of 4 to 6 cSt (mm2 / s) and a viscosity index of 120 to 150.

[0148] The lubricant additive composition in one embodiment may contain only two linear polymer viscosity modifiers having dispersant functionality, wherein the linear polymer has a weight average molecular weight of 5,000 to 25,000, or 10,000 to 20,000.

[0149] In one embodiment the lubricant additive composition may comprise 0.1 wt% to 4 wt.% (or 0.2 wt.% to 3 wt.%) of a linear (meth)acrylic polymer viscosity modifier having dispersant functionality, wherein the linear polymer has a weight average molecular weight of greater than 25,000 to 400,000 (or to 350,000) or 30,000 to 150,000. The linear (meth)acrylic polymer a weight average molecular weight of greater than 25,000 to 400,000 (or to 350,000) may be considered chemically similar to the linear (meth)acrylic polymer a weight average molecular weight of 5,000 to 25,000 except the weight average molecular weight is different.

[0150] The lubricant additive composition may comprise a linear polymer viscosity modifier having dispersant functionality comprises: 0.1 wt.% to 5 wt.% (or 1 wt.% to 4 wt.%) of a linear (meth)acrylic polymer viscosity modifier having dispersant functionality, wherein the linear polymer has a weight average molecular weight of 10,000 to 20,000; and 0.1 wt.% to 4 wt.% (or 1 wt.% to 3 wt.%) of a linear (meth)acrylic polymer viscosity modifier having dispersant functionality, wherein the linear polymer has a weight average molecular weight of greater than 20,000 to 250,000 (or 30,000 to 150,000).

[0151] As described hereinafter the molecular weight of the viscosity modifier has been determined using known methods, such as GPC analysis using polystyrene standards. Methods for determining molecular weights of polymers are well known. The methods are described for instance: (i) P.J. Flory, “Principles of star polymer Chemistry”, Cornell University Press 91953), Chapter VII, pp 266-315; or (ii) “Macromolecules, an Introduction to star polymer Science”, F. A. Bovey and F. H. Winslow, Editors, Academic Press (1979), pp 296-312.

[0152] The polymer or copolymer substrate employed in the derivatized graft copolymer will contain grafted carboxylic acid functionality or a reactiveequivalent of carboxylic acid functionality (e.g., anhydride or ester). The reactive carboxylic acid functionality will typically be present as a pendant group attached by, for instance, a grafting process. The olefin polymer may be derived from isobutylene or isoprene. In certain embodiments, the polymer may be prepared from ethylene and propylene or it may be prepared from ethylene and a higher olefin within the range of (C3 -C10) alpha-monoolefins, in either case grafted with a suitable carboxylic acid-containing species (i.e., monomer).

[0153] More complex polymer substrates, often designated as interpolymers, may be prepared using a third component. The third component generally used to prepare an interpolymer substrate may be a polyene monomer selected from conjugated or non-conjugated dienes and trienes. The non-conjugated diene component may be one having from about 5 to about 14 carbon atoms. The diene monomer may be characterized by the presence of a vinyl group in its structure and can include cyclic and bicyclo compounds. Representative dienes include 1,4- hexadiene, 1,4-cyclohexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5- methylene-2-norbornene, 1,5-heptadiene, and 1,6-octadiene. A mixture of more than one diene can be used in the preparation of the interpolymer.

[0154] The triene component may also be present, which will have at least two non-conjugated double bonds and up to about 30 carbon atoms. Typical trienes include l-isopropylidene-3a,4,7,7a-tetrahydroindene, 1- isopropylidenedi cyclopentadiene, and 2-(2-methylene-4-methyl-3-pentenyl)- [2.2.1] bicyclo-5-heptene.

[0155] Suitable backbone polymers of the olefin polymer variety include ethylene propylene copolymers, ethylene-propylene-alpha olefin terpolymers, ethylene-alpha olefin copolymers, ethylene propylene copolymers further containing a non-conjugated diene, and isobutylene / conjugated diene copolymers, each of which can be subsequently supplied with grafted carboxylic functionality.

[0156] The polymerization reaction to form the olefin polymer substrate may be carried out in the presence of a catalyst in a solvent medium. The polymerization solvent may be any suitable inert organic solvent that is liquid under reaction conditions for solution polymerization of monoolefins, which can be conducted in the presence of a Ziegler-Natta type catalyst or a metallocene catalyst. In a typical preparation of a polymer substrate, hexane is first introducedinto a reactor and the temperature in the reactor is raised moderately to about 30°C. Dry propylene is fed to the reactor until the pressure reaches about 130-150 kPa above ambient (40-45 inches of mercury). The pressure is then increased to about 200 kPa (60 inches of mercury) by feeding dry ethylene and 5-ethylidene-2- norbornene to the reactor. The monomer feeds are stopped and a mixture of aluminum sesquichloride and vanadium oxytri chloride is added to initiate the polymerization reaction. Completion of the polymerization reaction is evidenced by a drop in the pressure in the reactor.

[0157] Ethylene-propylene or higher alpha monoolefin copolymers may consist of 15 to 80 mole % ethylene and 20 to 85 mole % propylene or higher monoolefin, in some embodiments, the mole ratios being 30 to 80 mole % ethylene and 20 to 70 mole % of at least one C3 to C10 alpha monoolefin, for example, 50 to 80 mole % ethylene and 20 to 50 mole % propylene. Terpolymer variations of the foregoing polymers may contain up to 15 mole % of a non-conjugated diene or triene.

[0158] In these embodiments, the polymer substrate, such as the ethylene copolymer or terpolymer, can be an oil-soluble, substantially linear, rubbery material. Also, in certain embodiments the polymer can be in forms other than substantially linear, that is, it can be a branched polymer or a star polymer. The polymer can also be a random copolymer or a block copolymer, including diblocks and higher blocks, including tapered blocks and a variety of other structures. These types of polymer structures are known in the art and their preparation is within the abilities of the person skilled in the art.

[0159] The terms polymer and copolymer are used generically to encompass ethylene and / or higher alpha monoolefin polymers, copolymers, terpolymers or interpolymers. These materials may contain minor amounts of other olefinic monomers so long as their basic characteristics are not materially changed.

[0160] The polymer of the disclosed technology may have a number average molecular weight (by gel permeation chromatography, polystyrene standard), which can typically be 2,000 to 75,000, 4,000 to 65,000, 5,000 to 65,000, or 9,000 to 55,000, or 11,000 to 52,000, or 40,000 to 50,000.

[0161] An ethylenically unsaturated carboxylic acid material is typically grafted onto the polymer backbone. These materials which are attached to thepolymer typically contain at least one ethylenic bond (prior to reaction) and at least one, such as two, carboxylic acid (or its anhydride) groups or a polar group which is convertible into said carboxyl groups by oxidation or hydrolysis. Maleic anhydride or a derivative thereof is suitable. It grafts onto the olefin polymer, (e.g., ethylene copolymer or terpolymer) to give two carboxylic acid functionalities. Examples of additional unsaturated carboxylic materials include chlormaleic anhydride, itaconic anhydride, or the corresponding dicarboxylic acids, such as maleic acid, fumaric acid and their esters, as well as cinnamic acid and esters thereof.

[0162] The ethylenically unsaturated carboxylic acid material may be grafted onto the polymer (such as the ethylene / propylene copolymer) in a number of ways. It may be grafted onto the polymer in solution or in molten form with or without using a radical initiator. The free-radical induced grafting of ethylenically unsaturated carboxylic acid materials may also be conducted in solvents, such as hexane or mineral oil. It may be carried out at an elevated temperature in the range of 100°C to 250°C , e.g., 120°C to 190°C, or 150°C to 180°C, e.g., above 160°C. If it is conducted in a solvent such as a mineral lubricating oil solution, the solution may contain, e g., 1 to 50 wt. %, or 5 to 30 wt. %, based on the initial total oil solution, of the ethylene / propylene copolymer.

[0163] The free-radical initiators which may be used include peroxides, hydroperoxides, and azo compounds, typically those which have a boiling point greater than about 100°C and which decompose thermally within the grafting temperature range to provide free radicals. Representative of these free-radical initiators include azobisisobutyronitrile and 2,5-dimethyl-hex-3-yne-2,5-bis- terti ary -butyl peroxide. The initiator may be used in an amount of 0.005% to 1% by weight based on the weight of the reaction mixture solution. The grafting may be carried out in an inert atmosphere, such as under nitrogen blanketing. The resulting polymer intermediate is characterized by having carboxylic acid acylating functions within its structure.

[0164] In a melt process for forming a graft polymer, with the optional use of a radical initiator, the unsaturated carboxylic acid may be grafted onto molten rubber using rubber masticating or shearing equipment. The temperature of the molten material in this process may be 150°C to 400°C. Optionally, as a part ofthis process or separate from this process, mechanical shear and elevated temperatures can be used to reduce the molecular weight of the polymer to a value that will eventually provide the desired level of shear stability for the lubricant application. In one embodiment, such mastication can be done in a twin screw extruder properly configured to provide high shear zones, capable of breaking down the polymer to the desired molecular weight. Shear degradation can be done before or after grafting with the maleic anhydride. It can be done in the absence or presence of oxygen. The shearing and grafting steps can be done in the same extruder or in separate extruders, in any order.

[0165] In an alternative embodiment, the unsaturated carboxylic acid material, such as maleic anhydride, can be first condensed with a monoamine or polyamine, typically having a single primary amino group (described below) and the condensation product itself then grafted onto the polymer backbone in analogous fashion to that described above.

[0166] In another alternative embodiment, the condensation product can be formed by the reaction of the monoamine or polyamine with the unsaturated carboxylic acid material in an extruder.

[0167] The carboxylic acid functionality can also be provided by a graft process with glyoxylic acid or its homologues or a reactive equivalent thereof of the general formula R3C(O)(R4)nC(O)OR5. In this formula R3and R5are hydrogen or hydrocarbyl groups and R4is a divalent hydrocarbylene group, n is 0 or 1. Also include are the corresponding acetals, hemiacetals, ketals, and hemiketals. Preparation of grafts of such glyoxylic materials onto hydrocarbonbased polymers is described in detail in U.S. Patent 6,117,941.

[0168] The amount of the reactive carboxylic acid on the polymer chain, and in particular the amount of grafted carboxylic acid on the chain is typically 0.5 to 6 weight percent, or 1 to 5 weight percent, or 2 to 3 weight percent, based on the weight of the polymer backbone. These numbers represent the amount of carboxylic-containing monomer with particular reference to maleic anhydride as the graft monomer. The amounts may be adjusted to account for acid monomers having higher or lower molecular weights or greater or lesser amounts of acid functionality per molecule, as will be apparent to the person skilled in the art. The grafting may be of an extent to provide an acid functionalized polymer having atotal acid number (TAN per ASTM D664) of 10 to 50, or 20 to 40, or 25 to 35, or about 31.

[0169] The acid-containing polymer is reacted with a monoamine or a polyamine typically having a single primary amino group. If the olefin polymer is an ethyl ene / propylene copolymer, then said polyamine is not a poly(ethyleneamine). The reaction may consist of condensation to form an imide, amide, or half-amide or amide-ester (assuming a portion of alcohol is also reacted) or an amine salt. A primary amino group will typically condense to form an amide or, in the case of maleic anhydride monomer, an imide. It is noted that in certain embodiments the amine will have a single primary amino group, that is, it will not have two or more primary amino groups (except perhaps a very small an inconsequential amount of additional primary amino groups within the entire amine component, e.g., less than 5% or 2% or 1% or 0.5%, or 0.01 to 0.1%, especially 1% or less, such as 0.01 to 1%, of amine groups being primary). This feature will minimize the amount of crosslinking that might otherwise occur. Poly(ethyleneamine)s may generally, and in an oversimplified manner, be depicted as H2N-(C2H4-NH-)n-C2H4-NH2, where n may be, for instance, 2 through 6. These typically have on average about 2 primary amino groups, so their use is typically undesirable for functionalization of ethyl ene / propylene copolymers, so that any undesirable crosslinking may be minimized or avoided. In those embodiments in which the polyamine is not a poly(ethyleneamine), the amine component employed to make the condesnation product will be free of or substantially free of poly(ethyleneamine), such as less than 5 percent by weight of the amine component is poly(ethyleneamine), or less than 1 percent, or 0.01 to 0.1 percent by weight.

[0170] Suitable primary amines may include aromatic amines, such as amines wherein a carbon atom of the aromatic ring structure is attached directly to the amino nitrogen. The amines may be monoamines or polyamines. The aromatic ring will typically be a mononuclear aromatic ring (i.e., one derived from benzene) but can include fused aromatic rings, such as those derived from naphthalene. Examples of aromatic amines include aniline, N-alkylanilines such as N-methyl aniline, and N-butylaniline, di-(para-methylphenyl)amine, naphthylamine, 4-aminodiphenylamine, N,N-dimethylphenylenediamine, 4-(4-nitrophenyl- azo)aniline (disperse orange 3), sulfamethazine, 4-phen oxy aniline, 3 -nitroaniline, 4-aminoacetanilide, 4-amino-2-hydroxy-benzoic acid phenyl ester (phenyl amino salicylate), N-(4-amino-5-methoxy-2-methyl-phenyl)-benzamide (fast violet B), N-(4-amino-2,5-dimethoxy-phenyl)-benzamide (fast blue RR), N-(4-amino-2,5- diethoxy-phenyl)-benzamide (fast blue BB), N-(4-amino-phenyl)-benzamide and 4-phenylazoaniline. Other examples include para-ethoxyaniline, para-dodecyl- aniline, cyclohexyl-substituted naphthylamine, and thienyl-substituted aniline. Examples of other suitable aromatic amines include amino-substituted aromatic compounds and amines in which an amine nitrogen is a part of an aromatic ring, such as 3 -aminoquinoline, 5-aminoquinoline, and 8-aminoquinoline. Also included are aromatic amines such as 2-aminobenzimidazole, which contains one secondary amino group attached directly to the aromatic ring and a primary amino group attached to the imidazole ring. Other amines include N-(4-anilinophenyl)-3- aminobutanamide (i.e., <|)-NH-<|)-NH-COCH2CH(CH3)NH2). Additional aromatic amines include aminocarbazoles, aminoindoles, aminopyrroles, amino- indazolinones, aminoperimidines, mercaptotriazoles, aminophenothiazines, aminopyridiens, aminopyrazines, aminopyrimidines, pyridines, pyrazines, pyrimidines, aminothiadiazoles, aminothiothiadiazoles, and aminobenzotriaozles. Other suitable amines include 3-amino-N-(4-anilinophenyl)-N-isopropyl butanamide, and N-(4-anilinophenyl)-3-{(3-aminopropyl)-(cocoalkyl)amino} butanamide. Other aromatic amines which can be used include various aromatic amine dye intermediates containing multiple aromatic rings linked by, for example, amide structures. Examples include materials of the general structure (|)- CONH-(|)-NH2 where the phenyl groups may be substituted. Suitable aromatic amines include those in which the amine nitrogen is a substituent on an aromatic carboxylic compound, that is, the nitrogen is not sp2hybridized within an aromatic ring.

[0171] Aliphatic or cycloaliphatic amines include monoamines having, e.g., 1 to 8 carbon atoms, such as methylamine, ethylamine, and propylamine, as well as various higher amines. Aliphatic diamines or polyamines can also be used, and typically will have only a single primary amino group. Examples include dimethylaminopropylamine, di ethylaminopropylamine, dibutylaminopropylamine,dimethylaminoethylamine, di ethylaminoethylamine, dibutylaminoethylamine, 1- (2-aminoethyl)piperidine, 1 -(2-aminoethyl)pyrrolidone, aminoethylmorpholine, and aminopropylmorpholine.

[0172] In certain embodiments aromatic amines can be used alone or in combination with each other or in combination with aliphatic or cycloaliphatic amines. The amount of such an aliphatic or cycloaliphatic amine may, in some embodiments, be a minor amount compared with the amount of the aromatic amine.

[0173] In one embodiment that amine component comprises a monoamine. In one embodiment the amine component contains a single aromatic ring, and in one embodiment the amine component comprises 3 -nitroaniline. If the amine component comprises an aromatic amine, in certain embodiments the grafted olefin polymer may be further condensed with an aliphatic amine. In one embodiment the amine component may comprise an amine containing one or more ether linkages, i.e., an ether amine or a polyetheramine. Polyetheramines and their methods of preparation are described in greater detail in U.S. Pat. No. 6,458,172, columns 4 and 5.

[0174] In certain embodiments the grafted olefin polymer may have a nitrogen content of 0.4 to 1.6 percent by weight, or 0.2 to 3, or 0.3 to 2, or 0.4 to 1.6, or 0.5 to 1.4, or 0.85 to 2 percent by weight. The amount of the condensation reaction product of the olefin polymer may be 0.14 to 1.5, or 0.25 to 1.5, or 0.25 to 1, or 0.4 to 1 percent by weight.

[0175] In one embodiment, the lubricant additive can also include a boron containing compound.

[0176] The lubricant additive composition can contain a boron-containing compound in an amount sufficient to provide from about 75ppm to about 500 ppm of boron to the lubricant additive composition, or from about 85 to about 450 ppm or about 95 to about 350 ppm boron, or from about 100 to about 400ppm boron to the lubricant additive composition.

[0177] The boron can be delivered by many types of boron-containing compounds.

[0178] The boron-containing compound can be a dispersant post-treated with a source of boron, as described above.

[0179] The boron-containing compound can include boron containing friction modifiers, such as, for example, borated fatty epoxides, borated glycerol esters, and borated alkoxylated fatty amines.

[0180] The boron containing compound can also include borated detergents. The borated detergents can include, for example, overbased borated materials, which are described in U.S. Patents 5,403,501 and 4,792,410.

[0181] The boron containing compound can also include a borate ester. The borate ester may be a compound represented by one or more of the formulae:wherein each R can be, independently a hydrocarbyl group, as that term is defined herein, and any two adjacent R groups may together form a cyclic group. Mixtures of two or more of the foregoing may be used. The total number of carbon atoms in the R groups in each formula should be sufficient to render the compound soluble in the base oil. Generally, the total number of carbon atoms in the R groups is at least about 3, and in one embodiment at least about 5, and in one embodimentat least about 8. There is no limit to the total number of carbon atoms in the R groups that is required, but a practical upper limit is about 400 or about 500 carbon atoms.

[0182] In embodiments, each R can independently be a hydrocarbyl group containing 1 to 14, or from 2 to 13 or even 3 to 10 or 12 carbon atoms, provided the sum total number of carbon atoms in all R is 3 or more, preferably 4 or more and even more preferably 6 or more. In some embodiments, each R, independently, can be a C3 to C22, or C3 to C18, or C3 to C12 alkyl. Examples of useful R groups include isopropyl, n-butyl, isobutyl, amyl, 4-methyl-2-pentyl, 2-ethyl-l -hexyl, isooctyl, decyl, dodecyl, 2-propylheptyl, tetradecyl, 2-pentenyl, dodecenyl, phenyl, naphthyl, alkylphenyl, and the like.

[0183] Suitable examples of the borate ester include, for example, tripropyl borate, tributyl borate, tripentyl borate, trihexyl borate, triheptyl borate, trioctyl borate, trinonyl borate and tridecyl borate. Other borate ester examples can include, for example, the compound of formula I, wherein each R is, independently, a C3 to C22, or C3 to Cl 8, or C3 to C12 alkyl, such as, for example, tri-2-ethylhexyl borate, tris(2-propylheptyl) borate and mixtures thereof. In an embodiment the borate ester can be a C8 borate ester, or a CIO borate ester. In one embodiment the borate ester can be tris(2-propylheptyl) borate. In some embodiments the borate ester can be tri-2-ethylhexyl borate.

[0184] In one embodiment, the borated ester can be represented by the formula B(OC5H11)3 or B(OC4H9)3. In one embodiment, the borated ester can be tri-n- butyl borate.

[0185] In one embodiment, the borated ester can be a phenolic compound represented by the formulaVIIwherein in formula VII: Rl, R2, R3 and R4 are independently hydrocarbyl groups of 1 to about 12 carbon atoms; and R5 and R6 are independently alkylene groups of 1 to about 6 carbon atoms, and in one embodiment about 2 to about 4 carbon atoms, and in one embodiment about 2 or about 3 carbon atoms. In one embodiment, Rl and R2 independently contain 1 to about 6 carbon atoms, and in one embodiment each is a t-butyl group. In one embodiment, R3 and R4 are independently hydrocarbyl groups of about 2 to about 12 carbon atoms, and in one embodiment about 8 to about 10 carbon atoms. In one embodiment, R5 and R6 are independently — CH2CH2 - or — CH2CH2CH2 -.

[0186] In one embodiment, the borated ester can be a compound represented by the formula:wherein in formula IX, each R is independently hydrogen or a hydrocarbyl group. Each of the hydrocarbyl groups may contain from 1 to about 12 carbon atoms, and in one embodiment 1 to about 4 carbon atoms. An example is 2,2'-oxy-bis-(4,4,6- timethyl-l,3,2-dioxaborinane).

[0187] The borate ester may be employed in the lubricant additive composition at about 0.2 or 0.3 to about 2.0 wt.% based on the weight of the lubricant additivecomposition, or in some cases about 0.35 to 2.0 wt.%, and in one embodiment from about 0.25 to about 1.0 wt.%, and in one embodiment about 0.25 to about 0.75 wt.%.

[0188] In one embodiment, the lubricant additive composition can include an ester of a polyol and an aliphatic carboxylic acid containing 12 to 24 carbon atoms.

[0189] Polyols include diols, triols, and alcohols with higher numbers of alcoholic OH groups. Polyhydric alcohols include ethylene glycols, including di-, tri- and tetraethylene glycols; propylene glycols, including di-, tri- and tetrapropylene glycols; glycerol; butane diol; hexane diol; sorbitol; arabitol; mannitol; sucrose; fructose; glucose; cyclohexane diol; erythritol; and pentaerythritols, including di- and tripentaerythritol; preferably, diethylene glycol, triethylene glycol, glycerol, sorbitol, pentaerythritol and dipentaerythritol.

[0190] The aliphatic carboxylic acids which form the esters are those acids containing 12 to 24 carbon atoms. Such acid can be characterized by the following general formula R1 — (CO)OH, wherein R1 can be a hydrocarbyl group, which can be a straight chain hydrocarbyl group, a branched chain or cyclic-containing hydrocarbyl group, or mixtures thereof. Straight chain hydrocarbyl group containing 12 to 24 carbon atoms are preferred, for instance, 14 to 20 or 16 to 18 carbon atoms. Such acids can be used in combination with acids with more or fewer carbon atoms as well.

[0191] Generally the acid R1 — (CO)OH can be a monocarboxylic acid since polycarboxylic acids tend to form polymeric products if the reaction conditions and amounts of reactants are not carefully regulated. Mixtures of monocarboxylic acids and minor amounts of dicarboxylic acids or anhydrides, however, can be used in preparing the esters. Examples of carboxylic acids include dodecanoic acid, stearic acid, lauric acid, behenic acid, and oleic acid.

[0192] The foregoing esters are in particular the monoesters of such polyols and such carboxylic acids. A preferred ester is glycerol monooleate. It is to be understood that glycerol monooleate, as is the case with other such materials, in its commercially available grade, is a mixture which includes such materials as glycerol, oleic acid, other long chain acids, glycerol dioleate, and glyceroltrioleate. The commercial material is believed to include about 60 ± 5 percent by weight of the chemical species "glycerol monooleate," along with 35 ± 5 percent glycerol dioleate, and less than about 5 percent trioleate and oleic acid. The amounts of the monoesters, described below, are calculated based on the actual, corrected, amount of polyol monoester present in any such mixture.

[0193] The amount of the foregoing ester in the lubricant additive composition is typically on the order of from about 0.01 to about 1.0 wt.%, but can also be from about 0.05 to about 0.5 or 0.8 or about 0.1 to about 0.6 wt.% of the lubricant additive composition.

[0194] In addition to the foregoing ester, the lubricant additive composition can also contain an ester of an alcohol, and an aliphatic carboxylic acid containing about 4 to about 8 carbon atoms.

[0195] The alcohol includes both monohydric alcohol and polyhydric alcohol (i.e., polyol). The carbon atoms of the alcohol may be linear, branched, or mixtures thereof.

[0196] Suitable polyols are the same as mentioned above.

[0197] When branched, the alcohol may be a Guerbet alcohol, or mixtures thereof. The Guerbet alcohols may have alkyl groups including the following: 1) alkyl groups containing C15-16 polymethylene groups, such as 2-C1-15 alkylhexadecyl groups (e.g. 2-octylhexadecyl) and 2-alkyl-octadecyl groups (e.g. 2- ethyloctadecyl, 2-tetradecyl-octadecyl and 2-hexadecyloctadecyl); 2) alkyl groups containing C13-14 polymethylene groups, such as 1-C1-15 alkyl -tetradecyl groups (e.g. 2-hexyltetradecyl, 2-decyltetradecyl and 2-undecyltridecyl) and 2-C1-15 alkyl-hexadecyl groups (e.g. 2-ethyl-hexadecyl and 2-dodecylhexadecyl); 3) alkyl groups containing CIO-12 polymethylene groups, such as 2-C1-15 alkyl-dodecyl groups (e.g. 2-octyldodecyl) and 2-C1-15 alkyl-dodecyl groups (2-hexyldodecyl and 2-octyldodecyl), 2-C1-15 alkyl-tetradecyl groups (e.g. 2-hexyltetradecyl and 2-decyltetradecyl); 4) alkyl groups containing C6-9 polymethylene groups, such as 2-C1-15 alkyl-decyl groups (e.g. 2-octyldecyl) and 2,4-di-Cl-15 alkyl-decyl groups (e.g. 2-ethyl-4-butyl -decyl group); 5) alkyl groups containing Cl -5 polymethylene groups, such as 2-(3-methylhexyl)-7-methyl-decyl and 2-(l,4,4-trimethylbutyl)-5,7,7-trimethyl-octyl groups; and 6) and mixtures of two or more branched alkyl groups, such as alkyl residues of oxoalcohols corresponding to propylene oligomers (from hexamer to undecamer), ethylene / propylene (molar ratio 16: 1-1 : 11) oligomers, iso-butene oligomers (from pentamer to octamer), C5- 17 a-olefin oligomers (from dimer to hexamer).

[0198] Examples of a suitable branched monohydric alcohol include 2- ethylhexanol, 2-butyloctanol, 2-hexyldecanol, 2-octyldodecanol, 2-decyltetra- decanol, iso-tridecanol, iso-octanol, oleyl alcohol, Guerbet alcohols, or mixtures thereof. Examples of a monohydric linear alcohol include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, or mixtures thereof. In one embodiment the monohydric alcohol contains 6 to 30, or 8 to 20, or 8 to 15 carbon atoms (typically 8 to 15 carbon atoms).

[0199] The aliphatic carboxylic acids which form the esters are those acids containing 4 to 8 carbon atoms. While aliphatic, the aliphatic carboxylic acids can contain ethylenic unsaturation along the C4 to C8 alkyl group backbone. In addition, such acids can be mono-carboxylic or di-carboxylic acids or anhydrides, or mixtures thereof. Examples of carboxylic acids include, for example, succinic acid, maleic acid, fumaric acid, glutaconic acid, glutaric acid, adipic acid, citraconic acid, mesaconic acid, pimelic acid, suberic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid and the like.

[0200] A particularly preferred ester can be an adipate ester, such as, for example, a C8-13 or C8-12 adipate ester, such as diisoctyl adipate or di-tridecyl adipate. Other esters can include, for example, pentaerythritol esters, neo-pentyl esters and tri-methylol esters.

[0201] The amount of the foregoing ester in the lubricant additive composition is typically on the order of from about 0.1 to about 3.0 wt.%, but can also be from about 0.2 to about 2.5 or about 0.3 to about 2.0 wt.% of the lubricant additive composition.

[0202] The carboxylic esters are prepared by the very well-known reaction of at least one carboxylic acid (or reactive equivalent thereof, such as ester, halide, or anhydride) with at least one of the above-described hydroxy compounds.

[0203] Another component of the lubricant additive composition can be a metal deactivator. Examples of such materials include 2,5-dimercapto-l,3,4-thiadiazole and / or derivatives thereof. Such materials are described in European Patent Publication 0761805, incorporated herein by reference.

[0204] The metal deactivators that are useful herein reduce the corrosion of metals, such as copper. Metal deactivators are also referred to as metal passivators. These metal deactivators are typically nitrogen and / or sulfur containing heterocyclic compounds, such as dimercaptothiadiazoles, triazoles, aminomercaptothiadiazoles, imidazoles, thiazoles, tetrazoles, hydroxyquinolines, oxazolines, imidazolines, thiophenes, indoles, indazoles, quinolines, benzoxazines, dithiols, oxazoles, oxatriazoles, pyridines, piperazines, triazines, and derivatives of any one or more thereof. The metal deactivator preferably comprises at least one triazole, which may be substituted or unsubstituted. Examples of suitable compounds are benzotri azole, alkyl -substituted benzotriazole (e.g., tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), aryl -substituted benzotriazole (e.g., phenol benzotriazoles, etc.), and alkylaryl- or arylalkyl-substituted benzotriazole and substituted benzotriazoles where the substituent may be hydroxy, alkoxy, halo (especially chloro), nitro, carboxy and carb oxy alkoxy. Preferably, the triazole is a benzotriazole or an alkylbenzotriazole in which the alkyl group contains 1 to about 20 carbon atoms, preferably 1 to about 8 carbon atoms. Benzotriazole and tolyltriazole are useful.

[0205] In one embodiment, the metal deactivator is the reaction product of a dispersant with a dimercaptothiadiazole. The dispersants may be generally characterized as the reaction products of carboxylic acids with amines and / or alcohols. These reaction products are commonly used in the lubricant arts as dispersants and are sometimes referred to generically as dispersants despite the fact that they may have other uses in addition to or instead of that as dispersants. The carboxylic dispersants include succinimide dispersants, ester type dispersantsand the like. Succinimide dispersants are generally the reaction of a polyamine with an alkenyl succinic anhydride or acid. Ester type dispersants are the reaction product of an alkenyl succinic anhydride or acid with a polyol compound. The reaction product may then be further treated with an amine such as a polyamine. Examples of useful dispersants are disclosed in U.S. Pat. Nos. 3,219,666 and 4,234,435, incorporated herein by reference. Useful dispersants also include the ashless dispersants discussed below. Generally the reaction occurs between the dispersant and the dimercaptothiadiazole by mixing the two and heating to a temperature above about 100 °C. U.S. Pat. Nos. 4,140,643 and 4,136,043 describe compounds made by the reaction of such dispersants with a dimercaptothiadiazole. These patents are incorporated herein by reference for their disclosure of dispersants, dimercaptothiadiazole, the method for reacting the two and the products obtained from such reaction.

[0206] In one embodiment, the metal deactivator is the reaction product of a phenol with an aldehyde and a dimercaptothiadiazole. The phenol is preferably an alkyl phenol wherein the alkyl group contains at least about 6, preferably from 6 to about 24, more preferably about 6, or about 7, to about 12 carbon atoms. The aldehyde is preferably an aldehyde containing from 1 to about 7 carbon atoms or an aldehyde synthon, such as formaldehyde. Preferably, the aldehyde is formaldehyde or paraformaldehyde. The aldehyde, phenol and dimercaptothiadiazole are typically reacted by mixing them at a temperature up to about 150 °C, preferably about 50 °C to about 130 °C, in molar ratios of about 0.5 to about 2 moles of phenol and about 0.5 to about 2 moles of aldehyde per mole of dimercaptothiadiazole. Preferably, the three reagents are reacted in equal molar amounts.

[0207] In one embodiment, the metal deactivator is a bis(hydrocarbyldithio)thiadiazole. Preferably each hydrocarbyl group is independently an alkyl, aryl or aralkyl group, having from 6 to about 24 carbon atoms. Each hydrocarbyl can be independently t-octyl, nonyl, decyl, dodecyl or ethylhexyl. The metal deactivator can be bis-2,5-tert-octyl-dithio-l,3,4- thiadiazole or a mixture thereof with 2-tert-octylthio-5-mercapto-l,3,4- thiadiazole. These materials are available commercially under the trade name ofAmoco 150, which is available from Amoco Chemical Company. These dithiothiadi azole compounds are disclosed as Component (d) in PCT Publication WO 88 / 03551, incorporated by reference for its disclosure of dithiothiadiazole compounds. In the preferred embodiments the metal deactivator is a dimercaptothiadiazole derivative. The following D-l and D-2 are specific examples.

[0208] Example D-l

[0209] 2,5-dimercapto-l,3,4-thiadiazole oxidatively coupled with t-nonyl mercaptan; 100% chemical, 36% S, 64% N.

[0210] Example D-2

[0211] Heptylphenol coupled with 2,5-dimercapto-l,3,4-thiadiazole using formaldehyde (the thiadiazole is generated in situ); 20% oil, 17.75% S, 5.5% N.

[0212] When used, the amount of metal deactivator in the lubricant additive composition can be generally in the range of about 0.01 to about 0.5 wt.% by weight of the lubricant additive composition. In some embodiments, the amount of the metal deactivator can be in the range of about 0.02 to about 0.42 wt.% or about 0.03 to about 0.33 wt,% or about 0.04 to about 0.24 wt.% by weight of the lubricant additive composition.

[0213] Another component of the present invention can be a borated epoxide containing 12-24 carbon atoms. This material can alternatively described as a borate ester of a vicinal diol containing 12 to 24 carbon atoms. Such a material may be represented by the structureswherein each of Rl, R2, R3, and R4 are independently hydrogen or an aliphatic radical, or any two thereof together with the carbon atom or atoms to which theyare attached form a cyclic radical. Preferably at least one of the R groups can be an alkyl group containing at least 8 or at least 10 carbon atoms. In one embodiment one of the R groups can be such an alkyl group and the remaining R groups are hydrogen. Borated epoxides are described in detail in U.S. Pat. No. 4,584,115. Borated epoxides are generally prepared by reacting an epoxide with a boron source such as boric acid or boron trioxide. Borated epoxides are not themselves epoxides, but are the ring-opened boron-containing reaction products of epoxides. Suitable epoxides include commercial mixtures of C14-16 or C14-18 or C16-18 epoxides, which can be purchased from Elf-Atochem or Union Carbide and which can be prepared from the corresponding olefins by known methods. Purified epoxy compounds such as 1,2-epoxyhexadecane can be purchased from Aldrich Chemicals. The borated compounds are prepared by blending the boron compound and the epoxide and heating them at a suitable temperature, typically 80° to 250°C, until the desired reaction has occurred. An inert liquid, such as toluene, xylene, or dimethylformamide can be used as a reaction medium. Water is formed and is typically distilled off during the reaction. Alkaline reagents can be used to catalyze the reaction. A preferred borated epoxide can be the borated epoxide of a predominantly 16 carbon olefin. The amount of the borate epoxide can be 0.01 or 0.05 to 0.5 or 1.0 parts by weight of the composition, or alternatively 0.1 to 0.9 percent.

[0214] The lubricant additive composition may also include a calcium-containing detergent. While the calcium-containing detergent is preferably not present, it can be included in an amount to deliver up to 300 ppm of calcium to the composition, or from 30 ppm to 300 ppm, or 30 ppm to 275 ppm of calcium, or from 60 ppm to 250 ppm, or even from 60 ppm to 225 ppm of calcium.

[0215] In some embodiments, the calcium-containing detergent may be present at 900 ppm or less, or from 1 to 900 ppm, or even from 5 to 800 ppm or 10 to 700 ppm, or even from 15 to 600 or 500 ppm.

[0216] The calcium-containing detergent may be an overbased detergent, a nonoverbased detergent, or mixtures thereof. Typically the detergent is overbased.

[0217] The preparation of the calcium-containing detergent is known in the art. Patents describing the preparation of overbased calcium-containing detergentsinclude U.S. patents 2,501,731; 2,616,905; 2,616,911; 2,616,925; 2,777,874; 3,256,186; 3,384,585; 3,365,396; 3,320,162; 3,318,809; 3,488,284; and 3,629,109.

[0218] The calcium-containing detergent may be a non-overbased detergent (may also be referred to as a neutral detergent). The TBN of a non-overbased may be 20 to less than 200, or 30 to 100, or 35 to 50 mg KOH / g. The TBN of a non- overbased calcium-containing detergent may also be 20 to 175, or 30 to 100 mg KOH / g. When a non-overbased calcium-containing detergent is prepared from a strong acid such as a hydrocarbyl -substituted sulphonic acid, the TBN may be lower (for example 0 to 50 mg KOH / g, or 10 to 20 mg KOH / g).

[0219] As used herein the TBN values quoted and associated range of TBN is on “an as is basis,” i.e., containing conventional amounts of diluent oil. Conventional amounts of diluent oil typically range from 30 wt.% to 60 wt.% (often 40 wt.% to 55 wt.%) of the detergent component.

[0220] The calcium-containing detergent may be an overbased detergent, having, for example, a TBN of greater than 200 mg KOH / g (typically 250 to 600, or 300 to 500 mg KOH / g).

[0221] The overbased calcium-containing detergent may be formed by the reaction of a basic calcium compound and an acidic detergent substrate. The acidic detergent substrate may include an alkyl aromatic sulphonic acid (such as, alkyl naphthalene sulphonic acid, alkyl toluene sulphonic acid or alkyl benzene sulphonic acid), an alkyl salicylic acid, or mixtures thereof.

[0222] The basic calcium compound is used to supply basicity to the detergent. The basic calcium compound is a compound of a hydroxide or oxide of the calcium.

[0223] The oxides and / or hydroxides may be used alone or in combination. The oxides or hydroxides may be hydrated or dehydrated, although hydrated is typical. In one embodiment the basic calcium compound may be calcium hydroxide, which may be used alone or mixtures thereof with other metal basic compounds. Calcium hydroxide is often referred to as lime. In one embodiment the calcium basiccompound may be calcium oxide which may be used alone or mixtures thereof with other metal basic compounds.

[0224] In one embodiment the calcium-containing detergent may be a sulphonate, or mixtures thereof. The sulphonate may be prepared from a mono- or di- hydrocarbyl-substituted benzene (or naphthalene, indenyl, indanyl, or bicyclopentadienyl) sulphonic acid, wherein the hydrocarbyl group may contain 6 to 40, or 8 to 35 or 9 to 30 carbon atoms.

[0225] The hydrocarbyl group may be derived from polypropylene or a linear or branched alkyl group containing at least 10 carbon atoms. Examples of a suitable alkyl group include branched and / or linear decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonodecyl, eicosyl, un-eicosyl, do-eicosyl, tri-eicosyl, tetra-eicosyl, penta-eicosyl, hexaeicosyl or mixtures thereof.

[0226] In one embodiment the hydrocarbyl -substituted sulphonic acid may include polypropene benzenesulphonic acid and / or C16-C24 alkyl benzenesulphonic acid, or mixtures thereof.

[0227] In one embodiment a calcium sulphonate detergent may be a predominantly linear alkylbenzene sulphonate detergent having a metal ratio of at least 8 as is described in paragraphs

[0026] to

[0037] of US Patent Application 2005065045 (and granted as US 7,407,919). In some embodiments 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.

[0228] When neutral or slightly basic, a calcium sulphonate detergent may have TBN of less than 100, or less than 75, typically 20 to 50 mg KOH / g, or 0 to 20 mg KOH / g.

[0229] When overbased, a calcium sulphonate detergent may have a TBN greater than 200, or 300 to 550, or 350 to 450 mg KOH / g.

[0230] Phenate detergents are typically derived from p-hydrocarbyl phenols or, generally, alkylpheols. Alkylphenols of this type may be coupled with sulfur and overbased, coupled with aldehyde and overbased, or carboxylated to formsalicylate detergents. Suitable alkylsalicylates include those alkylated with oligomers of propylene, oligomers of butene, especially tetramers and pentamers of n-butenes, as well as those alkylated with alpha-olefins, isomerized alphaolefins, and polyolefins like polyisobutylene. In one embodiment, the lubricant additive composition comprises less than 0.2 wt.%, or less than 0.1 wt.%, or even less than 0.05 wt.% of a salicylate detergent derived from PDDP. In one embodiment, the lubricant additive composition comprises a salicylate detergent that is not derived from PDDP. In one embodiment, the lubricant additive composition comprises a salicylate detergent prepared from PDDP, such detergent contains less than 1.0 weight percent unreacted PDDP, or less than 0.5 weight percent unreacted PDDP, or is substantially free of PDDP.

[0231] The detergent may be borated or non-borated.

[0232] Chemical structures for sulphonates, and salicylate detergents are known to a person skilled in the art. The standard textbook entitled “Chemistry and Technology of Lubricants”, Third Edition, Edited by R. M. Mortier and S. T. Orszulik, Copyright 2010, pages 220 to 223 under the sub-heading 7.2.6 provide general disclosures of said detergents and their structures.

[0233] In one embodiment the calcium-containing detergent may be an overbased calcium sulphonate, an overbased calcium salicylate, or mixtures thereof. Typically the detergent may be an overbased calcium sulphonate.

[0234] In one embodiment the calcium-containing detergent may be in a mixture with a zinc-, barium-, sodium-, or magnesium- containing detergent. The zinc-, barium-, sodium-, or magnesium- containing detergent is also well known in the art and described in the same references describing a calcium-containing detergent. The TBN and metal ratios may however, differ slightly. The zinc-, barium-, sodium-, or magnesium- containing detergent may be a phenate, a sulphur-containing phenate, sulphonate, salixarate or salicylate. Typically a zinc- , barium-, sodium-, or magnesium- containing detergent may be a magnesium phenate, a magnesium sulphur-containing phenate, or a magnesium sulphonate.

[0235] A more detailed description of the expressions “metal ratio”, TBN and “soap content” are known to a person skilled in the art and explained in standardtextbooks, such as, for example, “Chemistry and Technology of Lubricants”, Third Edition, Edited by R. M. Mortier and S. T. Orszulik, Copyright 2010, pages 219 to 220 under the sub-heading 7.2.5. Detergent Classification.

[0236] The lubricant additive composition preferably exhibits an electrical conductivity of up to 1x10-9 S / cm as measured by ASTM D2624, or from 9.5x10- 10 S / cm, or from 9x10-10 S / cm, or from 8.5x10-10 S / cm, or from 8x10-10 S / cm, or from 7.0x10-10 S / cm as measured by ASTM D2624, or from 6.5x10-10 S / cm, or 6.0x10-10 S / cm or 5.5x10-10 S / cm or 5.0x10-10 S / cm conductivity at 100°C and 500 V. It is highly preferably that the lubricant additive composition has no conductivity, but practically speaking conductivities on the order of 4.0x10-10 or 4.5x10-10 at 100°C may be achievable.

[0237] In an embodiment, the lubricant additive composition is substantially free of friction modifiers. In some embodiments, the lubricant additive composition is completely free of friction modifiers.

[0238] The lubricant additive composition may be in the form of a concentrate and / or a fully formulated lubricant when added to a base oil. That is, the lubricant additive composition can be added to a base oil to prepare a lubricating composition.

[0239] In an embodiment, the lubricant composition can have a total sulfur level from all additives (i.e., not including base oil) of about 0 to about 5 wt.%, or 0.5 or 0.6 to about 3 wt.%, or from about 0.5 or 0.6 to about 2 wt.% or from about 1 or 1.5 to about 5 wt.% or from about 2 to about 5 wt.%. In another embodiment, the lubricant composition can have a total sulfur level from all additives (i.e., not including base oil) of about 0.2 to about 0.75 wt%, or from about 0.25 to about 0.5 wt.%.

[0240] In an embodiment, the lubricant composition can be substantially free, or free of sulfur, meaning the amount from all additives (i.e., not including base oil) can be less than 1000 ppm, less than 500 ppm, less than 250 part per million, or less than 100 part per million of sulfur, or be completely free of sulfur.

[0241] The lubricant composition can have a total phosphorous level of about 300 ppm to about 4000 ppm, or even about 400 ppm to about 3000 ppm, or 500 ppm toabout 2500 ppm._In an embodiment, the total phosphorous level of the lubricant composition can be greater than 1000 ppm, or greater than 1500 ppm, or greater than 2000 ppm, or 2500 ppm or even greater than 4000 ppm. The total phosphorous level can also be 100 to 4000 ppm. In some embodiments, the total phosphorus level can be 125 to 3500 ppm, or from 150 to 3000 ppm. The total phosphorous level can also be 100 to 1000 ppm. In some embodiments, the total phosphorus level can be 150 to 500 ppm, or from 300 to 500 ppm.

[0242] A lubricating composition containing the lubricant additive composition may have a kinematic viscosity at 40°C by ASTM D445 of from 7 or 8 to about 35 cSt, or 10 cSt to 30 cSt, or for example, from 14 cSt to 25 cSt, or even 15 cSt to 22 cSt, or from 9 cSt to 25 or 22 cSt, or, for example, from 10 cSt to 25 or 22 cSt, or even from 14 cSt to 25 or 22 cSt, or from 18 cSt to 22 cSt.

[0243] A lubricating composition containing the lubricant additive composition may have a kinematic viscosity at 100 °C by ASTM D445 of between 2 and 25 cSt A lubricating composition containing the lubricant additive composition may have a kinematic viscosity at 100 °C by ASTM D445 of between 2 and 15 cSt. A lubricating composition containing the lubricant additive composition may have a kinematic viscosity at 100 °C by ASTM D445 of between 2 and 12 cSt. A lubricating composition containing the lubricant additive composition may have a kinematic viscosity at 100 °C by ASTM D445 of between 2 and 9 cSt. A lubricating composition containing the lubricant additive composition may have a kinematic viscosity at 100 °C by ASTM D445 of between 2 and 7 cSt. A lubricating composition containing the lubricant additive composition may have a kinematic viscosity at 100 °C by ASTM D445 of between 2 and 6 cSt. A lubricating composition containing the lubricant additive composition may have a kinematic viscosity at 100 °C by ASTM D445 of between 2 and 4 cSt.

[0244] The lubricant additive composition will be suitable for lubricating a driveline of an electric vehicle, and in particular, a gearbox of an electric motor in the electric vehicle when in the form of a lubricating composition. In particular, the lubricant additive composition will be suitable for lubricating a transmission in a vehicle with an electric motor, which may be a full electric vehicle or a hybrid-electric vehicle having both an electric motor and an engine powered by hydrocarbon or other fuels.

[0245] In particular, the disclosed technology provides a method of lubricating a driveline power transmitting device, comprising supplying thereto a lubricating composition as described herein, that is, containing base oil, succinimide dispersant, azole corrosion inhibitor, phosphorus antiwear compound, and antioxidant, and operating the driveline power transmitting device for a sufficient period to allow the lubricating composition to achieve the improved results as described herein.

[0246] In particular, the disclosed technology provides a method of lubricating a driveline power transmitting device, comprising supplying thereto a lubricating composition as described herein, that is, containing base oil, succinimide dispersant, azole corrosion inhibitor, phosphorus antiwear compound, an antioxidant, and viscosity modifier, and operating the driveline power transmitting device for a sufficient period to allow the lubricating composition to achieve the improved results as described herein.

[0247] The driveline power transmitting device may comprise at least two gears as in a gearbox of a vehicle (e.g., a manual transmission) or in an axle or differential, or in other driveline power transmitting devices. The driveline power transmitting device may also include bearings. The rolling elements of the bearings may be cylindrical or ball in design. Lubricated gears may include amboid, or spiral bevel, or more commonly hypoid gears, such as those for example in a drive axle. The axles may have a gear ratio of 2: 1 to 8: 1, and the ring gear maybe be approximately 13 to 64 cm in diameter. The axle may incorporate an open differential or some type of traction enabling device. The axle may be part of a drivetrain with one or more drive axles, such as a tandem or tridem design, in which the axles may be coupled together with a power divider. Application of these axles includes light, medium and heavy duty vehicles (e.g. vocational or line haul service), and could be used on or off highway. The axle may be from a traditional petroleum powered vehicle, may be from an electrically driven vehicle, or a hybrid thereof. The electrically driven axle can combine an electric motor, power electronics and transmission in a unit directly powering the vehicle's axle.

[0248] One aspect is therefore a method of lubricating an electric vehicle comprising supplying to a driveline of the electric vehicle a lubricating composition containing the lubricant additive composition as described herein, and operating the driveline

[0249] Another aspect is a method of lubricating a transmission, and particularly a transmission in a vehicle with an electric motor, comprising supplying to the transmission a lubricating composition containing the lubricant additive composition as described herein, and operating the transmission.

[0250] The lubricant should be able to meet the aspects expected of it in normal operation of the driveline power transmitting device.

[0251] The transmissions in which the lubricant additive composition may be suitable include automatic transmissions and dual clutch transmissions. The transmission may or may not include a shifting clutch, and, where the transmission includes a shifting clutch, the clutch may be a dry clutch or a wet clutch. In one embodiment, the lubricant may be used on a transmission that does not contain a shifting clutch. In another embodiment, the lubricant additive composition may be employed in a transmission having a wet clutch. In a further embodiment, the lubricant additive composition may be employed on a transmission having a dry clutch.

[0252] The driveline device may be a manual transmission that may or may not contain a synchronizer system, or an axle. In one embodiment the driveline device contains a synchronizer, or axle.

[0253] In one embodiment the driveline device contains a synchronizer. The synchronizer system may have an operating surface comprising brass, carbon, molybdenum, phenolic resin, or a sintered metal (typically bronze), or mixtures thereof.

[0254] The following examples provide illustrations of the invention. These examples are non-exhaustive and are not intended to limit the scope of the invention.EXAMPLESTable I11) All treat rates are oil-free.2) Additive package includes at least one antioxidant, at least one detergent, at least one dispersant, and at least one antifoam agent.

[0255] 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.

[0256] 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 toherein should be interpreted as being a commercial grade material which may contain the isomers, by-products, 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 invention may be used together with ranges or amounts for any of the other elements.

[0257] 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. Examples of hydrocarbyl groups include: hydrocarbon substituents, including aliphatic, alicyclic, and aromatic substituents; substituted hydrocarbon substituents, that is, substituents containing nonhydrocarbon groups which, in the context of this invention, 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

[0118] to

[0119] of International Publication W02008147704, or a similar definition in paragraphs

[0137] to

[0141] of published application US 2010-0197536.Clause 1 A gear lubricant composition comprising an oil of lubricating viscosity, a polyester which comprises a self-condensation product of a Cs-22 fatty carboxylic acid containing at least one hydroxyl group, and a phosphorus containing anti-wear agent.Clause 2 The gear lubricant composition of Clause 1, comprising from 0.05 to 2 wt.% of the polyester.Clause 3 The gear lubricant composition of Clause 1, comprising the polyester at from 0.05 wt.% to 1.75 wt.%.Clause 4 The gear lubricant composition of Clause 1, comprising the polyester at from 0.05 wt.% to 1.5 wt.%.Clause 5 The gear lubricant composition of Clause 1, comprising the polyester at from 0.05 wt.% to 1.25 wt.%.Clause 6 The gear lubricant composition of Clause 1, comprising the polyester at from 0.1 wt.% to 2 wt.%.Clause 7 The gear lubricant composition of Clause 1, comprising the polyester at from 0.1 wt.% to 1.75 wt.%.Clause 8 The gear lubricant composition of Clause 1, comprising the polyester at from 0.1 wt.% to 1.5 wt.%.Clause 9 The gear lubricant composition of Clause 1, comprising the polyester at from 0.1 wt.% to 1.25 wt.%.Clause 10 The gear lubricant composition of Clause 1, comprising the polyester at from 0.25 wt.% to 2 wt.%.Clause 11 The gear lubricant composition of Clause 1, comprising the polyester at from 0.25 wt.% to 1.75 wt.%.Clause 12 The gear lubricant composition of Clause 1, comprising the polyester at from 0.25 wt.% to 1.5 wt.%.Clause 13 The gear lubricant composition of Clause 1, comprising the polyester at from 0.25 wt.% to 1.25 wt.%.Clause 14 The gear lubricant composition of Clause 1, comprising the polyester at from 0.5 wt.% to 2 wt.%.Clause 15 The gear lubricant composition of Clause 1, comprising the polyester at from 0.5 wt.% to 1.75 wt.%.Clause 16 The gear lubricant composition of Clause 1, comprising the polyester at from 0.5 wt.% to 1.5 wt.%.Clause 17 The gear lubricant composition of Clause 1, comprising the polyester at from 0.5 wt.% to 1.25 wt.%.Clause 18 The gear lubricant composition of Clause 1, comprising the polyester at from 0.05 wt.% to 0.1 wt.%.Clause 19 The gear lubricant composition of Clause 1, comprising the polyester at from 0.05 wt.% to 0.25 wt.%.Clause 20 The gear lubricant composition of Clause 1, comprising the polyester at from 0.05 wt.% to 0.5 wt.%.Clause 21 The gear lubricant composition of Clause 1, comprising the polyester at from 0.1 wt.% to 0.25 wt.%.Clause 22 The gear lubricant composition of Clause 1, comprising the polyester at from 0.1 wt.% to 0.5 wt.%.Clause 23 The gear lubricant composition of Clause 1, comprising the polyester at from 0.25 wt.% to 0.5 wt.%.Clause 24 The gear lubricant composition of Clause 1, comprising the polyester at from 1.75 wt.% to 2 wt.%.Clause 25 The gear lubricant composition of Clause 1, comprising the polyester at from 1.5 wt.% to 2 wt.%.Clause 26 The gear lubricant composition of Clause 1, comprising the polyester at from 1.25 wt.% to 2 wt.%.Clause 27 The gear lubricant composition of Clause 1, comprising the polyester at from 1.25 wt.% to 1.75 wt.%.Clause 28 The gear lubricant composition of Clause 1, comprising the polyester at from 1.25 wt.% to 1.5 wt.%.Clause 29 The gear lubricant composition of any previous clause, wherein the fatty carboxylic acid is represented by the formula:where R1 is a hydrogen or a hydrocarbyl group containing from 1 to 20 carbon atoms and R2 is a hydrocarbylene group containing from 1 to 20 carbon atoms, with the proviso that the total number of carbon atoms present from R1 and R2 is 6 or more.Clause 30 The gear lubricant of Clause 29 where R1contains from 1 to 12 carbon atoms.Clause 31 The gear lubricant of Clause 29 where R2contains from 2 to 16 carbon atoms.Clause 32 The gear lubricant of Clause 29 where R1contains from 2 to 10 carbon atoms.Clause 33 The gear lubricant of Clause 29 where R2contains from 6 to 14 carbon atoms.Clause 34 The gear lubricant of Clause 29 where R1contains from 4 to 8 carbon atoms.Clause 35 The gear lubricant of Clause 29 where R2contains from 8 to 12 carbon atoms.Clause 36 The gear lubricant of Clause 29 where R1contains 6 carbon atoms.Clause 37 The gear lubricant of Clause 29 where R2contains 10 carbon atoms.Clause 38 The gear lubricant composition of any previous clause, wherein the fatty carboxylic acid is hydroxystearic acid.Clause 39 The gear lubricant composition of any previous clause, wherein the fatty carboxylic acid is ricinoleic acid.Clause 40 The gear lubricant composition of any previous clause, wherein the fatty carboxylic acid is 12-hydroxy dodecanoic acid.Clause 41 The gear lubricant composition of any previous clause, wherein the fatty carboxylic acid is 5-hydroxy dodecanoic acid.Clause 42 The gear lubricant composition of any previous clause, wherein the fatty carboxylic acid is 5-hydroxy decanoic acid.Clause 43 The gear lubricant composition of any previous clause, wherein the fatty carboxylic acid is 4-hydroxy decanoic acid.Clause 44 The gear lubricant composition of any previous clause, wherein the fatty carboxylic acid is 10-hydroxy undecanoic acid.Clause 45 The gear lubricant composition of any previous clause, wherein the polyester is capped with a Cl -22 fatty.Clause 46 The gear lubricant composition of any previous clause, wherein the polyester is capped with a C8-20, fatty acid.Clause 47 The gear lubricant composition of any previous clause, wherein the polyester is capped with oleic acid.Clause 48 The gear lubricant composition of any previous clause, wherein the polyester is capped with palmitic acid.Clause 49 The gear lubricant composition of any previous clause, wherein the polyester is capped with stearic acid.Clause 50 The gear lubricant composition of any previous clause, wherein the polyester is capped with erucic acid.Clause 51 The gear lubricant composition of any previous clause, wherein the polyester is capped with lauric acid.Clause 52 The gear lubricant composition of any previous clause, wherein the polyester is capped with 2-ethylhexanoic acid.Clause 53 The gear lubricant composition of any previous clause, wherein the polyester is capped with 9,11 -linoleic acid.Clause 54 The gear lubricant composition of any previous clause, wherein the polyester is capped with 9,12-linoleic acid.Clause 55 The gear lubricant composition of any previous clause, wherein the polyester is capped with 9,12,15-linolenic acid.Clause 56 The gear lubricant composition of any previous clause, wherein the polyester is capped with abietic acid.Clause 57 The gear lubricant composition of any previous clause, wherein the polyester has a number average molecular weight (Mn) from 500 to 3000.Clause 58 The gear lubricant composition of any previous clause, wherein the polyester has a number average molecular weight (Mn) from 700 to 2500.Clause 59 The gear lubricant composition of any previous clause, wherein the selfcondensation product is further reacted with an amine.Clause 60 The gear lubricant composition of any previous clause, wherein an amine is reacted with the fatty carboxylic acid containing at least one hydroxyl group in the monomer form, followed by a self-condensation reaction.Clause 61 The gear lubricant composition of Clause 59 or Clause 60, wherein the amine comprises methylamine.Clause 62 The gear lubricant composition of any of Clause 59 to Clause 61, wherein the amine comprises diethylamine.Clause 63 The gear lubricant composition of any of Clause 59 to Clause 62, wherein the amine comprises octadecylamine.Clause 64 The gear lubricant composition of any of Clause 59 to Clause 63, wherein the amine comprises dodecyldimethylamine.Clause 65 The gear lubricant composition of any of Clause 59 to Clause 64, wherein the amine comprises 3 -dimethylaminopropylamine.Clause 66 The gear lubricant composition of any of Clause 59 to Clause 65, wherein the amine comprises 3 -octadecylaminopropylamine.Clause 67 The gear lubricant composition of any of Clause 59 to Clause 66, wherein the amine comprises 3- dodecyldimethylamineClause 68 The gear lubricant composition of any previous clause, wherein the selfcondensation product of the C8-22 fatty carboxylic acid containing at least one hydroxyl group produces a polyester with 2 to 10 repeat units.Clause 69 The gear lubricant composition of any previous clause, wherein the phosphorous containing anti-wear agent comprises at least one of a phosphite, phosphite ester, or phosphate.Clause 70 The gear lubricant composition of any previous clause, further comprising an azole compound.Clause 71 The gear lubricant of Clause 70 wherein the azole comprises a compound of:Orwhere R1 and R2 can be, individually, H or a Cl to C9 alkyl group and where R3 and R4 can be, independently C1-C22 linear or branched hydrocarbon groups, phenyl group, or two ends of a hydrocarbon chain forming a cyclic structure, or where at least one of R3 and R4 can be H.Clause 72 The gear lubricant composition of any previous clause, comprising no more than 100 ppm sulfur.Clause 73 A method of lubricating an automotive gear comprising supplying to the gear a gear lubricant composition of any previous clause, and operating the gear.

[0258] 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.

Claims

What is claimed is:

1. A gear lubricant composition comprising an oil of lubricating viscosity, a polyester which comprises a self-condensation product of a Cs-22 fatty carboxylic acid containing at least one hydroxyl group, and a phosphorus containing anti-wear agent.

2. The gear lubricant composition of claim 1, comprising from 0.05 to 2 wt.% of the polyester.

3. The gear lubricant composition of any previous claim, wherein the fatty carboxylic acid is represented by the formula:where R1is a hydrogen or a hydrocarbyl group containing from 1 to 20 carbon atoms and R2is a hydrocarbylene group containing from 1 to 20 carbon atoms, with the proviso that the total number of carbon atoms present from R1and R2is 6 or more.

4. The gear lubricant composition of any previous claim, wherein the fatty carboxylic acid is hydroxystearic acid.

5. The gear lubricant composition of any previous claim, wherein the selfcondensation product is further reacted with an amine.

6. The gear lubricant composition of any previous claim, wherein the selfcondensation product of the -22 fatty carboxylic acid containing at least one hydroxyl group produces a polyester with 2 to 10 repeat units.

7. The gear lubricant composition of any previous claim, wherein the phosphorous containing anti-wear agent comprises at least one of a phosphite, phosphite ester, or phosphate.

8. The gear lubricant composition of any previous claim, further comprising an azole compound.

9. The gear lubricant of claim 8 wherein the azole comprises a compound of:Orwhere R1 and R2 can be, individually, H or a Cl to C9 alkyl group and where R3 and R4 can be, independently C1-C22 linear or branched hydrocarbon groups, phenyl group, or two ends of a hydrocarbon chain forming a cyclic structure, or where at least one of R3 and R4 can be H.

10. The gear lubricant composition of any previous claim, comprising no more than 100 ppm sulfur.

11. A method of lubricating an automotive gear comprising supplying to the gear a gear lubricant composition of any previous claim, and operating the gear.

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