Polymeric Surfactant Compounds

Abstract

The present disclosure relates to a lubricant composition having an oil of lubricating viscosity, a polymeric surfactant compound, and a polymeric surfactant compound, the polymer being an acylated polymer having a number average molecular weight of about 500 to about 50,000 and containing a branched olefin having 8 to 30 carbon atoms. The acylated polymer can be further reacted with an amine or alcohol to form an amide, imide, ester, or combination thereof. The disclosure further relates to a lubricant composition that exhibits good dispersancy and viscosity performance.

Description

[Technical field]

[0001] The present disclosure relates to a lubricant composition comprising an oil of lubricating viscosity, a polymeric surfactant compound, the polymer being an acylated polymer having a number average molecular weight of about 500 to about 50,000, the polymer comprising a branched olefin having 8 to 30 carbon atoms. The acylated polymer may be further reacted with an amine or alcohol to form an amide, imide, ester, or combinations thereof. The present disclosure further relates to a lubricant composition that exhibits good dispersancy and viscosity performance. [Background technology]

[0002] Lubricating oil compositions used to lubricate mechanical equipment contain a base oil of lubricating viscosity, or a mixture of such oils, and additives used to improve the performance characteristics of the oil. For example, additives are used to improve detergency and dispersancy, reduce wear, provide thermal and oxidative stability, reduce oil consumption, inhibit corrosion, and reduce friction losses, among other attributes. It is also desirable for lubricating oil compositions to maintain a relatively stable viscosity over a wide range of temperatures. Viscosity improvers are often used to reduce the extent to which the viscosity decreases as the temperature increases, or to reduce the extent to which the viscosity increases as the temperature decreases, or both. Thus, the viscosity improver improves the viscosity change of the oil containing the viscosity improver with temperature change. The flow characteristics of the oil are improved. However, each such additive is a separate component of the formulated lubricating oil and adds cost. It would be beneficial to have a single multifunctional additive that controls multiple performance characteristics of the lubricating oil without adversely affecting other properties of the lubricating oil, such as polymeric surfactant compounds.

[0003] New lubricating compositions are formulated to meet higher vehicle fuel economy standards, longer drain intervals, and greater driving severity. This need may necessitate the use of higher levels of additives and / or lower lubricant base stock viscosities. However, the use of higher levels of additives may significantly increase the viscosity of the lubricant composition, making it difficult to achieve lower motor oil viscosity grades, such as 0W-8, 0W-16, 0W-20, and 0W-30. Low viscosity grades of motor oils are particularly important in meeting fuel economy guidelines.

[0004] Thus, there is a need for effective deposit control and cleanliness additives that have the viscometric properties for use in low viscosity lubricating compositions. Summary of the Invention [Means for solving the problem]

[0005] The present disclosure relates to lubricant compositions comprising an oil of lubricating viscosity and 0.1% to 20% by weight of a polymeric surfactant compound comprising an acylated polymer having a number average molecular weight of from about 500 to about 50,000 Daltons (Da), the polymer comprising a branched olefin having from 8 to 30 carbon atoms.

[0006] In certain embodiments, the polymer of the acylated polymer can be represented by the formula: -[T] n -[Z] m - During the ceremony, [T] is a branched olefin having 8 to 30 carbon atoms; [Z] is a vinyl monomer capable of polymerizing with a branched olefin; m is 0 to 100, and when m=0, n is at least 1, or at least 2.

[0007] The configuration of [Z] and [T] is linear, branched, or cyclic; the sequential configuration of [Z] and [T] is block, alternating, or random; and the molecular weight of the olefin copolymer ranges from 500 g / mol to 50,000 g / mol.

[0008] In some embodiments, the branched olefin [T] may comprise at least one oligomer of a lower olefin having from 5 to 10 carbon atoms, and in some embodiments, a lower olefin with an additive mixture;

[0009] The additive mixture comprises a polymeric surfactant compound that is an acylated polymer, the polymer having a number average molecular weight of about 500 Da to about 50,000 Da, and includes a branched olefin having 8 to 30 carbon atoms;

[0010] One or more additives selected from the group consisting of antifoam agents, antiwear agents, antioxidants, demulsifiers, detergents, dispersants, extreme pressure agents, friction modifiers, metal deactivators, pour point depressants, rust and corrosion inhibitors, viscosity modifiers, and combinations thereof.

[0011] Another aspect of the disclosure is a process for formulating a lubricant comprising combining an oil of lubricating viscosity with an additive mixture.

[0012] The additive mixture is an acylated polymer comprising a polymer having a number average molecular weight of about 500 Da to about 50,000 Da, and comprising a polymeric surfactant compound comprising a branched olefin having 8 to 30 carbon atoms, the acylated polymer being further reacted with an amine or alcohol to form an amide, imide, ester, or combination thereof.

[0013] One or more additives selected from the group consisting of antifoam agents, antiwear agents, antioxidants, demulsifiers, detergents, dispersants, extreme pressure agents, friction modifiers, metal deactivators, pour point depressants, rust and corrosion inhibitors, viscosity modifiers, and combinations thereof.

[0014] A further aspect of this technology relates to a method of lubricating a mechanical device, for example, by supplying the device with a lubricating composition described herein that contains a graft copolymer viscosity modifier. The mechanical device may be, for example, an internal combustion engine, a driveline device of an automobile, such as a transmission or an axle, or an off-highway vehicle. This technique may also be used in industrial applications, such as industrial hydraulics. The present invention provides, for example, the following items. (Item 1) 1. A lubricating oil composition comprising: a. an oil of lubricating viscosity; b. A lubricating oil composition comprising: 0.1 to 20 weight percent of a polymeric surfactant compound comprising an acylated polymer, said polymer comprising branched olefins containing from 8 to 30 carbon atoms, and combinations thereof, said polymer having a number average molecular weight (Mn) of from 500 to 50,000 Da. (Item 2) 2. The lubricating composition of claim 1, wherein the acylated polymer is further reacted with an amine or alcohol to form imides, amides, esters, and combinations thereof. (Item 3) The polymer is represented by the formula: -[T] n -[Z] m - During the ceremony, [T] is a branched olefin having 8 to 30 carbon atoms; [Z] is a vinyl monomer capable of polymerizing with the branched olefin; 2. The lubricating composition according to item 1, wherein m is 0 to 100, and when m=0, n is at least 1, or at least 2. (Item 4) 2. The lubricating composition of any one of the preceding claims, wherein the branched olefin comprises an oligomer or polymer of at least one lower olefin monomer unit containing from 5 to 10 carbon atoms. (Item 5) The lower olefin monomer is represented by one of the following formulas: [ka] During the ceremony, Ra, Rb, and Rc are H or C 1 ~C 5 may be alkyl, The lubricating composition of any one of the preceding claims, wherein n and m can independently be integers from 0 to 6, with the proviso that n+m is from 1 to 6. (Item 6) The branched olefin is an oligomer of a lower olefin having 5 to 10 carbon atoms, represented by the following formula: [ka] During the ceremony, Ra, Rb, and Rc are each independently H or C. 1 ~C 5 alkyl, provided that at least one of Ra or Rb is C 1 ~C 5 provided that it is alkyl; n and m are each independently an integer from 0 to 6, provided that n+m is 1 to 6; 2. The lubricating composition of any one of the preceding claims, wherein y is an integer from 2 to 6, or from 2 to 4, or from 2 to 3, or is 3. (Item 7) 2. The lubricating composition of any one of the preceding claims, wherein the lower olefin monomer is a branched polyene having 5 to 10 carbon atoms. (Item 8) 2. The lubricating composition of any one of the preceding claims, wherein the lower olefin monomer is isoprene. (Item 9) 2. The lubricating composition of any one of the preceding claims, wherein the branched olefin is a trimer of isoprene having the formula:

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[0015] The present disclosure relates to lubricating compositions having additive packages and methods for lubricating mechanical equipment. The lubricating compositions disclosed herein may include an oil of lubricating viscosity and 0.1% to 20% by weight of a polymeric surfactant compound, the polymer being an acylated polymer comprising a polymer having a number average molecular weight of about 500 to about 50,000 and comprising a branched olefin having 8 to 30 carbon atoms. The acylated polymer may be further reacted with an amine or alcohol to form an amide, imide, ester, or combinations thereof. The present disclosure further relates to lubricant blends that exhibit good dispersancy and viscosity performance.

[0016] Oil of lubricating viscosity One component of the disclosed technology is an oil of lubricating viscosity. As used herein, oil of lubricating viscosity may include natural and synthetic oils, oils derived from hydrocracking, hydroprocessing and hydrofinishing, unrefined oils, refined oils, rerefined oils or mixtures thereof. A more detailed description of unrefined oils, refined oils and rerefined oils is provided in paragraphs

[0054] to

[0056] of WO 2008 / 147704 (a similar disclosure is provided in U.S. Patent Application No. 2010 / 197536, see

[0072] to

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

[0058] to

[0059] of WO 2008 / 147704, respectively (a similar disclosure is provided in U.S. Patent Application No. 2010 / 197536, see

[0075] to

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

[0017] Suitable oils may be produced from biological, i.e., natural, sources or by biotechnological methods, including both natural oils such as vegetable oils and triglyceride oils that may be further refined or purified by standard processes, and oils that may be derived from the direct biological conversion of natural chemicals to oils or the biological formation of building block precursor molecules that may be further converted to oils by known processes.

[0018] Oils of lubricating viscosity may also be defined as specified in “Appendix E-API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils”, April 2008 Edition, section 1.3 Sub-heading 1.3. “Base Stock Categories”. The API guidelines are also summarized in U.S. Pat. No. 7,285,516 (see column 11, line 64 to column 12, line 10), which is incorporated herein by reference.

[0019] In one embodiment, the oil of lubricating viscosity may be an API Group I-IV mineral oil, ester or synthetic oil, or mixtures thereof. In one embodiment, the oil of lubricating viscosity may be an API Group II, Group III, Group IV mineral oil, ester or synthetic oil, or mixtures thereof.

[0020] The amount of oil of lubricating viscosity present is typically the remainder after subtracting from 100% by weight the combined amount of the dispersant additive package according to this disclosure and additional additives, if any.

[0021] The lubricating composition may be in the form of a concentrate and / or in the form of a fully formulated lubricant. When the lubricating composition of the present disclosure (containing the dispersant additive package disclosed herein and, optionally, other additives) is in the form of a concentrate that may be combined with additional oils to form, in whole or in part, a finished lubricant, the ratio of these additives to oil of lubricating viscosity and / or the ratio of these additives to diluent oil is in the range of 1:99 to 99:1 by weight, or in the range of 80:20 to 10:90 by weight. Typically, the lubricating composition contains at least 50% by weight, or at least 60% by weight, or at least 70% by weight, or at least 80% by weight of oil of lubricating viscosity.

[0022] In the present disclosure, the lubricating composition comprises 2.4 ml 2 / s~6.4m 2The oil may comprise a base oil or oil of lubricating viscosity having a kinematic viscosity measured at 100° C. of 4.0 m / s. In some embodiments, the kinematic viscosity is 4.0 m / s. 2 / s~5.0m 2 / s, or 5.2m 2 / s~5.8m 2 / s, or 6.0m 2 / s~6.5m 2 In another embodiment, the kinematic viscosity is 6.2 m 2 / s, or 5.6m 2 / s, or 4.6m 2 / s.

[0023] The lubricating compositions claimed herein may be in the form of concentrates and / or fully formulated lubricants. When the lubricating composition is in the form of a concentrate (which may be combined with additional oil to form, in whole or in part, a finished lubricant), the ratio of the components disclosed herein to oil of lubricating viscosity and / or to diluent oil includes ranges from 1:99 to 99:1 by weight, or from 80:20 to 10:90 by weight.

[0024] Polymeric Surfactant Compounds Another component of the present disclosure relates to polymeric surfactant compounds that are acylated polymers comprising a polymer having a number average molecular weight of about 500 Da to about 50,000 Da, or 2000 Da to about 50,000 Da, or about 2000 Da to about 40,000 Da, or 2000 Da to about 30,000 Da, or about 2000 Da to about 20,000 Da, or about 5,000 Da to about 20,000 Da, the polymer comprising a branched olefin having 8 to 30 carbon atoms. It is also contemplated that the polymeric surfactant compounds are the reaction products of the acylated polymer with an amine or alcohol to form an amide, imide, ester, or combination thereof.

[0025] The acylated polymer may be represented by the formula: -[T] n -[Z] m - During the ceremony, [T] is a branched olefin having 8 to 30 carbon atoms; [Z] is a vinyl monomer capable of polymerizing with a branched olefin; m is 0 to 100, and when m=0, n is at least 1, or at least 2.

[0026] The configuration of [Z] and [T] is linear, branched, or cyclic, the sequential configuration of [Z] and [T] is block, alternating, or random, and the molecular weight of the polymer is in the range of 500 g / mol to 50,000 g / mol, or about 2000 g / mol to about 40,000 g / mol, or about 2000 g / mol to about 30,000 g / mol, or 2000 g / mol to about 20,000 g / mol about 5,000 g / mol to about 20,000 g / mol.

[0027] The branched olefin may comprise, consist essentially of, or consist of at least one oligomer, which itself may comprise, consist essentially of, or consist of a lower olefin of 5 to 10 carbon atoms. Lower olefin, as used herein, refers to an alkyl chain having at least one double bond and at least one tertiary carbon atom. Without limiting branched olefins, examples of such lower olefins may be represented by the following exemplary olefin formula: [ka] In the formula, Ra, Rb, and Rc are H or lower C 1 ~C 5 n and m may be independently integers from 0 to 6, provided that n+m is from 1 to 6, and the lower olefin has from 5 to 10 carbon atoms. Oligomers of such lower olefins may be, for example, oligomers of the formula: [ka] In the formula, Ra, Rb, Rc, m, and n are as defined above, and y is an integer of 2 to 6, or 2 to 4, or 2 to 3, or 3.

[0028] The lower olefin may also be a polyene. That is, the branched olefin may comprise, consist essentially of, or consist of at least one oligomer, which itself may comprise, consist essentially of, or consist of a lower olefin of a 5 to 10 carbon atom polyene compound. As used herein, a "polyene" is a polyunsaturated alkylene compound having at least two double bonds (also known as dienes), and possibly three or four double bonds.

[0029] A polyene compound can be described as an alkyl chain having at least two double bonds in the chain and at least one tertiary carbon atom. Although a polyene compound can contain more than two double bonds, an exemplary polyene compound can be a branched conjugated diene represented by the formula: [ka] In the formula, R 1 , R 2 , R 3 , and R 4 is independently H or lower C 1 -C5 alkyl group, with the proviso that R 1 , R 2 , R 3 , and R 4 at least one of the groups is an alkyl group, and together with the conjugated diene, has a total of 5 to 10 carbon atoms.

[0030] At least one branched olefin can be oligomerized from a 5-10 carbon atom branched lower olefin or branched lower polyene, or the branched olefin can be prepared in some other manner. For example, the branched olefin can be formed by 1,2-monomer addition or 1,4-monomer addition. In one embodiment, oligomers of 5-10 carbon atom lower polyenes can be formed by 1,4-addition of monomers followed by partial hydrogenation of the resulting material to form the branched olefin. Branched olefins can also be produced via biological activity, such as through a cell culture system capable of producing the desired branched olefin, or through fermentation of a composition having the appearance of an oligomer containing monomers equivalent to the 5-10 carbon atom lower olefin or lower polyene compound. For example, WO2011 / 160081 describes a biological pathway for producing isoprene, and the oligomers (also called terpenes, i.e., (C 5 H 8 ) n The present invention provides a use of the isoprene so produced to produce isoprene having the formula: where n is 2, 3, 4, 5 or more. The hydrocarbyl group may also be derived from an alkylating agent produced from a biological pathway, including, for example, a biological pathway for the production of natural phytol from extracts of silkworm excrement, Morns alba leaves, bamboo leaves, pine needles, and ginkgo leaves, as taught in CN102807471 A, Dec. 5, 2012. Other biological pathways are known to produce oligomers (e.g., terpenes) themselves.

[0031] The branched olefins containing lower olefins of 5 to 10 carbon atoms may be, for example, oligomers of the formula: [ka] In the formula, R1, R2, R3, and R4, and y are the same as defined above.

[0032] The 5 to 10 carbon atom lower olefin of the branched olefin can include isoprene of formula IV. [ka]

[0033] In addition to isoprene, suitable lower olefins include 2-methyl-1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 2-methyl-1-pentene, 3-methyl-1-pentene, 2-methyl-1-hexene, 3-methyl-1-hexene, 5-methyl-1-hexene, 4-methyl-1-hexene, 2-methyl-1-heptene, 2,3-dimethyl-1,3-butadiene, 2,4-dimethyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, and mixtures thereof.

[0034] In some embodiments, the branched olefin contains equivalent units to isoprene.

[0035] An isoprene oligomer containing 15-30 carbon atoms will contain 3-6 isoprene monomer units. An isoprene oligomer containing 10-15 carbon atoms will contain 2-3 isoprene monomer units.

[0036] The branched olefin [T] can have one or more of the formulae (1) to (8). [ka] In the formula, R 1 has the formula (9) [ka] R 2 has the formula (10) [ka] R 3 has the formula (11) [ka] R 4 has the formula (12) [ka]

[0037] In certain embodiments, the branched olefin is a trimer of isoprene, which may be envisioned in the following form: [ka] (2E,5E,7E,10E)-3,6,10-trimethyldodeca-2,5,7,10-tetraene [ka] (3E,7E,10E)-2,7,10-trimethyldodeca-1,3,7,10-tetraene [ka] (E)-2,9-Dimethyl-5-(prop-1-en-2-yl)deca-1,3,8-triene [ka] (3E,6E,10E)-2,6,10-trimethyldodeca-1,3,6,10-tretraene [ka] (E)-7,11-Dimethyl-3-methylenedodeca-1,6,10-triene

[0038] Tetramers of isoprene can also be employed in branched olefins and can be envisioned in the following form: [ka] (6E,10E)-7,11,15-trimethyl-3-methylenehexadeca-1,6,10,14-tetraene [ka] (3E,10E,14E)-3,7,11,15-Tetramethylhexadeca-1,3,6,10,14-pentaene [ka] (6E,10E,14E)-7,11,14-trimethyl-3-methylenehexadeca-1,6,10,14-tetraene [ka] (6E,9E,13E)-2,10,13-trimethyl-6-(prop-1-en-2-yl)pentadeca-1,3,9,13-tetraene

[0039] In one embodiment, the branched olefinic groups of the polymer may comprise, consist essentially of, or consist of lower olefins that comprise at least 50 mol % lower olefins equivalent to isoprene, at least 75 mol % lower olefins equivalent to isoprene, or at least 90 mol % lower olefins equivalent to isoprene. In one embodiment, the branched olefins consist of isoprene units.

[0040] In some embodiments, the branched olefins can be hydrogenated. Hydrogenation can be carried out, for example, by any hydrogenation agent known to those skilled in the art. For example, partially hydrogenated oligomers of lower olefin polyene compounds can be prepared by hydrogenating at least a portion of the double bonds in the branched olefins in the presence of a hydrogenation agent such as hydrogen in the presence of a catalyst, or by treating with hydrazine in the presence of a catalyst.

[0041] In some embodiments, the polymer is a homopolymer, a copolymer, or a combination thereof. In certain embodiments, the polymer is a homopolymer of a lower olefin comprising units derived from at least one lower olefin having 5 to 10 carbon atoms, such as a terpene. In other embodiments, the polymer is a copolymer of a branched olefin comprising units derived from at least one lower olefin having 5 to 10 carbon atoms, such as a terpene, and at least one copolymerizable vinyl monomer. In further embodiments, the polymer is derived from styrene and at least one branched olefin comprising units derived from at least one lower olefin having 5 to 10 carbon atoms, such as a terpene. In still further embodiments, the polymer is a random, block, or alternating copolymer. In still further embodiments, the polymer is a diblock, triblock, or other multiblock copolymer.

[0042] In certain embodiments, the polymer is prepared by catalyzed polymerization of β-farnesene in the presence of any catalyst suitable for polymerizing olefins. In other embodiments, the polymer is a homopolymer of β-farnesene and includes one or more units having the formula (1), (2), (3), (4), stereoisomers thereof, or combinations thereof. [ka] In the formula, R 1 has the formula (9) [ka] R 2 has the formula (10) [ka]

[0043] In certain embodiments, the polymer is prepared by polymerizing α-farnesene in the presence of any catalyst suitable for polymerizing olefins. In other embodiments, the polymer is a homopolymer of α-farnesene and includes one or more units having the formula (5), (6), (7), (8), stereoisomers thereof, or combinations thereof. [ka] R 3 has the formula (11) [ka] R 4 has the formula (12) [ka]

[0044] In some embodiments, the polymer is prepared by polymerizing a mixture of α-farnesene and β-farnesene in the presence of any catalyst suitable for polymerizing olefins. In other embodiments, the polymer comprises one or more units having formula (1), (2), (3), (4), (5), (6), (7), or (8), stereoisomers thereof, or combinations thereof disclosed herein. In further embodiments, the one or more units having formula (1), (2), (3), (4), (5), (6), (7), or (8) in the olefin copolymer can be in any order.

[0045] In some embodiments, the polymer comprises two or more units having two different formulas selected from formula (1), (2), (3), (4), (5), (6), (7), or (8), stereoisomers thereof, and combinations thereof. In other embodiments, such polymers have the following formula: x B ywhere each of x and y is at least 1, where each of A and B independently has formula (1), (2), (3), (4), (5), (6), (7), or (8), and A and B are different. In further embodiments, each of x and y is independently greater than 1, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, or more. In some embodiments, A and B are linked in a substantially linear fashion, as opposed to a substantially branched or substantially star-shaped fashion. In other embodiments, A and B are randomly distributed along the polymer chain. In other embodiments, A and B are in two "segments" to provide a polymer with a segmented structure, such as AA--A-BB---B. In other embodiments, As and Bs are alternatively distributed alternatingly along the polymer chain to provide polymers with alternating structures, eg, AB, ABA, ABAB, ABABA, etc.

[0046] In some embodiments, the polymer comprises three or more units having three different formulas selected from formula (1), (2), (3), (4), (5), (6), (7), or (8), stereoisomers thereof, and combinations thereof. In other embodiments, such polymers have the following formula: x B y C zwhere each of x, y, and z is at least 1, and where each of A, B, and C independently has formula (1), (2), (3), (4), (5), (6), (7), or (8), and A, B, and C are different. In further embodiments, each of x, y, and z is independently greater than 1, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, or more. In some embodiments, A, B, and C are linked in a substantially linear fashion, as opposed to a substantially branched or substantially star-shaped fashion. In other embodiments, A, B, and C are randomly distributed along the polymer chain. In other embodiments, A, B, and C are in three "segments" to provide a polymer with a segmented structure, e.g., AA--A-BB--B-CC--C. In other embodiments, A, B, and C are alternatively distributed alternately along the polymer chain to provide polymers with alternating structures, eg, ABCAB, ABCABC, etc.

[0047] In certain embodiments, the polymer is a copolymer. In other embodiments, the polymer is prepared by polymerizing at least one branched olefin, including lower olefins / lower polyenes having 5-10 carbon atoms, such as terpenes, with at least one vinyl monomer having formula (13) in the presence of any catalyst suitable for polymerizing olefins and vinyl monomers. In further embodiments, the polymer disclosed herein comprises (a) one or more units having at least one of formulas (1), (2), (3), and (4) disclosed herein, and (b) one or more units having formula (13), [ka] In the formula, R 5 , R 6 , R 7 , and R 8 Each of R is independently H or a hydrocarbyl group containing 1 to 24 carbon atoms. 5 , R6 , R 7 , and R 8 Each of R is an alkyl group containing 1 to 24 carbon atoms or an aromatic group defined by Hückel theory of 4n+2 π electrons per ring system having 6 to 12 carbon atoms. 5 , R 6 , R 7 R 8 At least one of the groups is a phenyl group.

[0048] In some embodiments, the polymers disclosed herein comprise (a) one or more units having at least one of formulas (5), (6), (7), and (8) disclosed herein, and (b) one or more units having formula (13) disclosed herein. In other embodiments, the polymers disclosed herein comprise (a) one or more units having at least one of formulas (1), (2), (3), (4), (5), (6), (7), or (8) disclosed herein, and (b) one or more units having formula (13) disclosed herein.

[0049] In some embodiments, the polymers disclosed herein are random copolymers. In other embodiments, the polymers disclosed herein are random copolymers, in which the vinyl monomer units and the branched olefin units are randomly distributed. In further embodiments, the polymers disclosed herein are random copolymers, in which the vinyl monomer units and the branched olefin units are randomly distributed, and in which two or more of formulas (1), (2), (3), (4), (5), (6), (7), and (8) in the branched olefin units are randomly, alternately, or in blocks.

[0050] In some embodiments, the polymers disclosed herein are alternating copolymers. In other embodiments, the polymers disclosed herein are alternating copolymers, with vinyl monomer units and branched olefin units being distributed alternately. In further embodiments, the polymers disclosed herein are alternating copolymers, with vinyl monomer units and branched olefin units being distributed alternately, with two or more of formulas (1), (2), (3), (4), (5), (6), (7), and (8) in the branched olefin units being distributed randomly, alternately, or in blocks.

[0051] In certain embodiments, the polymer is a block copolymer having one or more first blocks comprising one or more units having formula (1), (2), (3), (4), or a combination thereof, and one or more second blocks comprising one or more units having formula (13). In further embodiments, the polymer is a block copolymer having one or more first blocks comprising one or more units having formula (5), (6), (7), (8), or a combination thereof, and one or more second blocks comprising one or more units having formula (13). In still further embodiments, there is one first block and two second blocks, and the first block is between two second blocks. In still further embodiments, each of the second blocks comprises units derived from styrene. In some embodiments, the branched olefin block copolymer is a diblock, a triblock, or a combination thereof.

[0052] In some embodiments, the olefin copolymer has the following formula: P x Q ywhere each of x and y is at least 1, where P has formula (13) and Q has formula (1), (2), (3), (4), (5), (6), (7), or (8). In further embodiments, each of x and y is independently greater than 1, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, or more. In some embodiments, P and Q are linked in a substantially linear fashion, as opposed to a substantially branched or substantially star-shaped fashion. In other embodiments, P and Q are randomly distributed along the polymer chain. In other embodiments, P and Q are in two or more blocks or segments to provide a copolymer having a block structure, such as PP--P-QQ---Q or PP--P-QQ---QP---PP. In other embodiments, P and Q are alternately distributed along the polymer chain to provide a copolymer having an alternating structure, e.g., PQ, PQP, PQPQ, PQPQP, etc. In some embodiments, each Q is represented by the formula A, as disclosed herein. x B y Or A x B y C z has.

[0053] In certain embodiments, the amount of formula (1) in the polymers disclosed herein is at most about 85% by weight, at most about 80% by weight, at most about 70% by weight, at most about 60% by weight, or at most about 50% by weight, based on the total weight of the polymer. In other embodiments, the amount of formula (3) in the polymers disclosed herein is at least about 10% by weight, at least about 15% by weight, at least about 20% by weight, at least about 25% by weight, at least about 30% by weight, at least about 40% by weight, at least about 50% by weight, at least about 60% by weight, at least about 70% by weight, at least about 80% by weight, at least about 90% by weight, at least about 95% by weight, or at least about 99% by weight, based on the total weight of the polymer. In further embodiments, the amount of formula (2) in the polymers disclosed herein is from about 1% to about 99%, from about 5% to about 99%, from about 10% to about 99%, or from about 15% to about 99% by weight based on the total weight of the polymer. In still further embodiments, the amount of formula (4) in the polymers disclosed herein is at most about 0.1%, at most about 0.5%, at most about 1%, at most about 2%, or at most about 3% by weight based on the total weight of the polymer. In some embodiments, the polymers disclosed herein are substantially free of formula (1), (2), (3), or (4).

[0054] In certain embodiments, the amount of formula (5), (6), (7), or (8) in the polymers disclosed herein is at most about 1 wt%, at most about 5 wt%, at most about 10 wt%, at most about 20 wt%, at most about 30 wt%, at most about 40 wt%, at most about 50 wt%, at most about 60 wt%, at most about 70 wt%, at most about 80 wt%, or at most about 90 wt%, based on the total weight of the polymer. In other embodiments, the amount of formula (5), (6), (7), or (8) in the polymers disclosed herein is at least about 1 wt%, at least about 2 wt%, at least about 3 wt%, at least about 5 wt%, at least about 10 wt%, at least about 20 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, or at least about 60 wt%, based on the total weight of the polymer. In further embodiments, the amount of formula (5), (6), (7), or (8) in the polymers disclosed herein is from about 1% to about 99%, from about 5% to about 99%, from about 10% to about 99%, or from about 15% to about 99% by weight, based on the total weight of the polymer. In some embodiments, the polymers disclosed herein are substantially free of formula (5), (6), (7), or (8).

[0055] In certain embodiments, the number average molecular weight (M n ) is greater than about 500 Mn, greater than 2,000 Mn, greater than 5,000 Mn, greater than 10,000 Mn, greater than 25,000 Mn, or up to 50,000 Mn. In other embodiments, the number average molecular weight (Mn) is less than 50,000 Mn, less than 25,000 Mn, less than 10,000 Mn, less than 5,000 Mn, less than 2,000 Mn, or as low as 500 Mn.

[0056] In some embodiments, the polymer is a copolymer. In further embodiments, the polymer disclosed herein comprises one or more units derived from a branched olefin having an equivalent amount of at least one monomer with a lower olefin having 5 to 10 carbon atoms in an amount of at least about 5 mole percent, at least about 10 mole percent, at least about 15 mole percent, at least about 20 mole percent, at least about 30 mole percent, at least about 40 mole percent, at least about 50 mole percent, at least about 60 mole percent, at least about 70 mole percent, at least about 80 mole percent, or at least about 90 mole percent of the entire polymer. In still further embodiments, the polymer disclosed herein comprises one or more units derived from a vinyl monomer in an amount of at least about 5 mole percent, at least about 10 mole percent, at least about 15 mole percent, at least about 20 mole percent, at least about 30 mole percent, at least about 40 mole percent, at least about 50 mole percent, at least about 60 mole percent, at least about 70 mole percent, at least about 80 mole percent, or at least about 90 mole percent of the entire polymer.

[0057] Vinyl groups, i.e., -CH=CH, which are copolymerizable with branched olefins as vinyl monomers to make the polymers disclosed herein. 2 Any compound containing ethylene, i.e., CH. 2 =CH 2 In certain embodiments, the vinyl monomer has the formula (14): [ka] In the formula, R 5 , R 6 , R 7 , and R 8 Each of R is independently H or an organyl group. In further embodiments, the organyl group is hydrocarbyl. In certain embodiments, R in formula (13) or (14) 5, R 6 , R 7 , and R 8 Each of R is independently H, alkyl, cycloalkyl, aryl, alkenyl, cycloalkenyl, or alkynyl. In certain embodiments, R of formula (13) or (14) is 5 is aryl, and R 6 , R 7 , and R 8 Each of is H. In a further embodiment, R of formula (13) or (14) 5 is phenyl, and R 6 , R 7 , and R 8 Each of is H.

[0058] In certain embodiments, R of formula (13) or (14) 5 , R 6 , R 7 , and R 8 At least one of R in formula (13) or (14) is H. 5 , R 6 , R 7 , and R 8 Each of is H. In a further embodiment, R of formula (13) or (14) 5 is hydrocarbyl, R 6 , R 7 , and R 8 Each of is H. In still further embodiments, hydrocarbyl is alkyl, cycloalkyl, or aryl. In still further embodiments, R of formula (13) or (14) 5 , R 6 , R 7 , and R 8 None of the following are or contain alkenyl, cycloalkenyl, or alkynyl.

[0059] In some embodiments, the vinyl monomer is a substituted or unsubstituted olefin, such as ethylene or styrene. In other embodiments, the vinyl monomer is ethylene, an α-olefin, or a combination thereof. Some non-limiting examples of suitable α-olefins include styrene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, 1-decene, 1,5-hexadiene, and combinations thereof.

[0060] In some embodiments, the vinyl monomer is an aryl, such as styrene, α-methylstyrene, or divinylbenzene. Additional examples include functionalized vinyl aryls, such as those disclosed by U.S. Patent No. 7,041,761, the entirety of which is incorporated herein by reference.

[0061] In some embodiments, the polymers disclosed herein are derived from at least one farnesene and at least one vinyl monomer, as described by formula (14). Depending on the choice of catalyst, any olefin can be used in the embodiments described herein. Some non-limiting examples of suitable olefins include C olefins containing vinyl unsaturation: 2~20 Aliphatic and C 8~20 Aromatic compounds, as well as cyclobutene, cyclopentene, dicyclopentadiene, and norbornene (C at 5 and 6 positions) 1~20 Other non-limiting examples of suitable olefins include mixtures of such olefins, and C olefins of such olefins. 4~40 and mixtures with diolefin compounds.

[0062] Some non-limiting examples of suitable vinyl monomers include styrene, ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4,6-dimethyl-1-heptene, 4-vinylcyclohexene, vinylcyclohexane, norbornadiene, ethylidenenorbornene, cyclopentene, cyclohexene, dicyclopentadiene, cyclooctene, C 4~40 Dienes (1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, other C 4~40 In certain embodiments, the olefin monomer is propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, or a combination thereof.

[0063] Any catalyst capable of polymerizing or copolymerizing farnesene can be used to make the polymers disclosed herein. Some non-limiting examples of suitable catalysts include organolithium reagents, Ziegler-Natta catalysts, Kaminsky catalysts and other metallocene catalysts. In some embodiments, the catalyst is a Ziegler-Natta catalyst, a Kaminsky catalyst, a metallocene catalyst or a combination thereof.

[0064] In some embodiments, the catalyst further comprises a co-catalyst. In further embodiments, the co-catalyst is a metal hydride, alkyl, or aryl, or a combination thereof. In still further embodiments, the metal is aluminum, lithium, zinc, tin, cadmium, beryllium, or magnesium.

[0065] In some embodiments, the catalyst is an organolithium reagent. Any organolithium reagent that can act as a catalyst for polymerizing olefins can be used herein. Some non-limiting examples of suitable organolithium reagents include n-butyllithium, sec-butyllithium, or tert-butyllithium. Some non-limiting examples of suitable Lewis bases include TMEDA, PMDTA, or sparteine. Some organolithium reagents are disclosed in Zvi Rappoport et al., "The Chemistry of Organolithium Compounds," Part 1 (2004) and Vol. 2 (2006), both of which are incorporated herein by reference.

[0066] In some embodiments, the catalyst is a mixture of an organolithium reagent and a Lewis base. Any Lewis base that can disaggregate the organolithium reagents and make them more soluble and more reactive can be used herein. Agglomerated organolithium reagents generally have one lithium coordinated to multiple carbon atoms and one carbon coordinated to multiple lithium atoms. Some non-limiting examples of suitable Lewis bases include 1,2-bis(dimethylamino)ethane (also known as tetramethylethylenediamine or TMEDA), N,N,N',N',N''-pentamethyldiethylenetriamine (PMDTA), sparteine, and combinations thereof.

[0067] In some embodiments, the catalyst is a Ziegler-Natta catalyst. In general, Ziegler-Natta catalysts can be heterogeneous or homogeneous. In some embodiments, the Ziegler-Natta catalyst used to polymerize the polyfarnesenes disclosed herein is a heterogeneous Ziegler-Natta catalyst. Some useful Ziegler-Natta catalysts are disclosed in J. Boor, "Ziegler-Natta Catalysts and Polymerizations," Saunders College Publishing, pp. 1-687 (1979), and Malcolm P. Stevens, "Polymer Chemistry, an Introduction," Third Edition, Oxford University Press, pp. 236-245 (1999), both of which are incorporated herein by reference.

[0068] In certain embodiments, the Ziegler-Natta catalyst can be impregnated into a support material. Some suitable support materials are disclosed in Malcolm P. Stevens, "Polymer Chemistry, an Introduction," Third Edition, Oxford University Press, p. 251 (1999), which is incorporated herein by reference.

[0069] In certain embodiments, the catalyst used herein is or includes a Kaminsky catalyst, also known as a homogeneous Ziegler-Natta catalyst. Kaminsky catalysts can be used to produce olefin copolymers. Some Kaminsky or homogeneous Ziegler-Natta catalysts are disclosed in Malcolm P. Stevens, "Polymer Chemistry, an Introduction," Third Edition, Oxford University Press, pp. 245-251 (1999), and John Scheirs and Walter Kaminsky, "Metallocene-Based Polyolefins: Preparation, Properties, and Technology," Volume 1, Wiley (2000), both of which are incorporated herein by reference.

[0070] In certain embodiments, the catalyst for making the olefin copolymers disclosed herein is or includes a metallocene catalyst. Some metallocene catalysts are disclosed in Tae Oan Ahn et al., "Modification of a Ziegler-Natta catalyst with a metallocene catalyst and its olefin polymerization behavior," Polymer Engineering and Science, 39(7), p.1257 (1999), and John Scheirs and Walter Kaminsky, "Metallocene-Based Polyolefins: Preparation, Properties, and Technology," Volume 1, Wiley (2000), both of which are incorporated herein by reference.

[0071] Examples of polymers useful in the compositions disclosed herein are taught in U.S. Pat. Nos. 7,655,739, 7,759,444, 7,868,114, 7,868,115, 8,217,128, 8,334,353, 8,048,976, 8,592,543, 8,592,543, 8,889,808, 9,862,906, and 10,294,439.

[0072] In some embodiments, the polymers disclosed herein can be partially or fully hydrogenated by any hydrogenation agent known to those skilled in the art. For example, saturated or partially saturated polymers can be prepared by (a) polymerizing a branched polyolefin disclosed herein in the presence of a catalyst disclosed herein to form a polymer, and (b) hydrogenating at least a portion or all of the double bonds in the polymer in the presence of a hydrogenation agent. In some embodiments, the branched olefin is copolymerized with a vinyl monomer disclosed herein to form a polymer, which is then partially or fully hydrogenated.

[0073] In certain embodiments, the hydrogenation reagent is hydrogen in the presence of a hydrogenation catalyst. In some embodiments, the hydrogenation catalyst is Pd, Pd / C, Pt, PtO 2 , Ru(PPh 3 ) 2 Cl 2, Raney Nickel or a combination thereof. In one embodiment, the catalyst is a Pd catalyst. In another embodiment, the catalyst is 5% Pd / C. In a further embodiment, the catalyst is 10% Pd / C in a high pressure reactor, and the hydrogenation reaction is allowed to proceed to completion. Generally, after completion, the reaction mixture can be washed, concentrated and dried to obtain the corresponding hydrogenated product. Alternatively, any reducing agent capable of reducing C=C bonds to CC bonds can be used. For example, olefin copolymers can be hydrogenated by treatment with hydrazine in the presence of a catalyst such as 5-ethyl-3-methyllumiflavinium perchlorate under oxygen atmosphere to obtain the corresponding hydrogenated product. The reduction reaction with hydrazine is disclosed in Imada et al., J. Am. Chem. Soc., 127, 14544-14545 (2005), which is incorporated herein by reference.

[0074] In some embodiments, carboxylic acid functional groups or reactive equivalents are grafted onto the polymer to form acylated polymers. Ethylenically unsaturated carboxylic acid materials are typically grafted onto the polymer backbone. These materials that are attached to the polymer typically contain at least one ethylenic bond (before reaction) and at least one (such as two) carboxylic acid (or anhydride thereof) group or polar group that can be converted to said carboxyl group by oxidation or hydrolysis. Maleic anhydride or its derivatives are suitable. Maleic anhydride or its derivatives are grafted onto the polymer to obtain two carboxylic acid functional groups. Examples of additional unsaturated carboxylic acid materials include itaconic anhydride or the corresponding dicarboxylic acids such as maleic acid, fumaric acid, and their esters, and cinnamic acid and its esters.

[0075] The ethylenically unsaturated carboxylic acid material can be grafted onto the polymer in a variety of ways. It can be grafted onto the polymer in solution or in the melt, with or without the use of a radical initiator. Free radical induced grafting of the ethylenically unsaturated carboxylic acid material can also be carried out in a solvent such as hexane or mineral oil. It can be carried out at elevated temperatures ranging from 100°C to 250°C, for example 120°C to 190°C, or 150°C to 180°C, for example above 160°C.

[0076] Free radical initiators that may be used include peroxides, hydroperoxides, and azo compounds, typically those having boiling points greater than about 100° C. and thermally decomposing within the grafting temperature range to provide free radicals. Representatives of these free radical initiators include azobisisobutyronitrile and 2,5-dimethyl-hex-3-yn-2,5-bis-tertiary butyl peroxide. The initiators may be used in amounts of 0.005% to 1% by weight, based on the weight of the reaction mixture solution. Grafting may be carried out in an inert atmosphere, such as under a nitrogen blanket. The resulting acylated polymer intermediate is characterized by having carboxylic acid acylation functionality within its structure.

[0077] In some embodiments, the acylated polymers react with alcohols or amines to form amides, imides, esters, or combinations thereof. The reaction may consist of condensation to form imides, amides, half amides, or amide esters, or amine salts. Primary amino groups typically condense to form amides, or in the case of maleic anhydride, imides. Note that in certain embodiments, the amine has a single primary amino group.

[0078] Suitable amines may include aromatic amines, such as amines in which the carbon atom of the aromatic ring structure is directly bonded to the amino nitrogen.Amines may also be aliphatic.In certain embodiments, aliphatic amines can be used alone or in combination with each other or in combination with aromatic amines.The amount of aromatic amines may be small in some embodiments compared to the amount of non-aromatic amines, or in some examples, the composition is substantially free or free of aromatic amines.

[0079] Examples of aromatic amines that can be used in the present compositions to synthesize suitable polyether aromatic amines include N-arylphenylenediamines represented by the formula: [ka] In the formula, R 7 R is a branched or linear hydrocarbyl radical having from about 4 to about 24 carbon atoms selected from H, -NHaryl, -NHalkaryl, or alkyl, alkenyl, alkoxyl, aralkyl, or alkaryl; 9 is -NH 2 .-(NH(CH 2 ) n ) m NH 2 , -NHalkyl, -NHaralkyl, -CH-aryl-NH, where n and m each have a value of about 1 to about 10; R 8 is hydrogen, alkyl, alkenyl, alkoxyl, aralkyl, or alkaryl having from about 4 to about 24 carbon atoms.

[0080] Suitable N-arylphenylenediamines include N-phenylphenylenediamines (NPPDA), such as N-phenyl-1,4-phenylenediamine, N-phenyl-1,3-phenylenediamine, and N-phenyl-1,2-phenylenediamine, as well as N-naphthyl-1,4-phenylenediamine. Other derivatives of NPPDA, such as N-propyl-N'-phenylphenylenediamine, may also be included.

[0081] In certain embodiments, the amine reacted with the acylated polymer is an amine having at least three or four aromatic groups and can be represented by the formula: [ka] In the formula, each independent variable, R1 can be hydrogen or a C1-C5 alkyl group (typically hydrogen), R2 can be hydrogen or a C1-C5 alkyl group (typically hydrogen), U can be an aliphatic, alicyclic, or aromatic group, with the proviso that when U is aliphatic, the aliphatic group can be a straight chain or branched alkylene group containing 1-5 or 1-2 carbon atoms, and w can be 1-10, or 1-4, or 1-2 (typically 1).

[0082] Other examples of aromatic amines include aniline, N-alkylanilines such as N-methylaniline, and N-butylaniline, di-(para-methylphenyl)amine, naphthylamine, 4-aminodiphenylamine, N,N-dimethylphenylenediamine, 4-(4-nitrophenylazo)aniline (Disperse Orange 3), sulfamethazine, 4-phenoxyaniline, 3-nitroaniline, 4-aminoacetanilide, 4-amino-2-hydroxy-benzoic acid phenyl ester (phenyl aminosalicylate), 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. Suitable amines are referenced in US Pat. No. 7,790,661, incorporated herein by reference.

[0083] In one embodiment, the compound having an oxygen atom capable of condensing with the acylated polymer can be represented by the formula: [ka] wherein X is an alkylene group containing from about 1 to about 4 carbon atoms, and R2, R3, and R4 are hydrocarbyl groups. [ka] wherein X is an alkylene group containing from about 1 to about 4 carbon atoms, and R3 and R4 are hydrocarbyl groups.

[0084] Examples of nitrogen or oxygen containing compounds that can be condensed with an acylating agent and further have a tertiary amino group can include, but are not limited to, dimethylaminopropylamine, N,N-dimethyl-aminopropylamine, N,N-diethyl-aminopropylamine, N,N-dimethyl-aminoethylamine ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, the isomeric butylenediamines, pentanediamine, hexanediamine, heptanediamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenetetramine, and bis(hexamethylene)triamine, diaminobenzene, diaminopyridine, or mixtures thereof. Nitrogen or oxygen containing compounds that can be condensed with the acylating agent and further have a tertiary amino group can further include amino alkyl substituted heterocyclic compounds such as 1-(3-aminopropyl)imidazole and 4-(3-amino-propyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-di-amino-N-methyldipropylamine, 3',3-aminobis(N,N-dimethylpropylamine). Another type of nitrogen or oxygen containing compound that can be condensed with the acylating agent and further have a tertiary amino group includes alkanolamines, including but not limited to triethanolamine, trimethanolamine, N,N-dimethylaminopropanol, N,N-di-ethylaminopropanol, N,N-diethylaminobutanol, N,N,N-tris(hydroxyethyl)amine, N,N,N-tris(hydroxymethyl)amine.

[0085] In certain embodiments, the non-aromatic amines can be used alone or in combination with each other or in combination with aromatic amines. The amount of aromatic amine may in some embodiments be small compared to the amount of non-aromatic amine, or in some examples, the composition is substantially free or free of aromatic amines.

[0086] In one embodiment, the polymer is reacted with a polyether aromatic compound. Typically, the polyether aromatic compound will have at least two functional groups, each of which can react with a monocarboxylic acid or its ester, or a dicarboxylic acid, its anhydride or ester, or a mixture thereof. Suitable polyether aromatic compounds include, but are not limited to, the following: polyether aromatic compounds derived from aromatic amine compounds. In one embodiment, the polyether aromatic compound is derived from an aromatic compound containing at least one amine group, and the polyether can react with a monocarboxylic acid or its ester, or a dicarboxylic acid, its anhydride or ester.

[0087] Examples of suitable polyether aromatic amines include compounds having the following structure: [ka] where A represents an aromatic amine moiety to which an ether group is linked through at least one amine group on the aromatic moiety; R 1 and R 6 are independently hydrogen, alkyl, alkaryl, aralkyl, or aryl, or mixtures thereof, 2 , R 3 , R 4 , and R 5 is independently hydrogen, or an alkyl containing from about 1 to about 6 carbon atoms, or a mixture thereof; and a and x are independently integers from about 1 to about 50.

[0088] The acylated polymer can be reacted with a polyetheramine or polyetherpolyamine. A typical polyetheramine compound will contain at least one ether unit and be chain terminated with at least one amine moiety. Polyetherpolyamines are derived from C amines such as ethylene oxide, propylene oxide, and butylene oxide. 2 ~C 6 Examples of polyether polyamines are sold under the Jeffamine® brand and are commercially available from Hunstman Corporation.

[0089] Another aspect of the disclosure includes a process for formulating a lubricant comprising combining an oil of lubricating viscosity with an additive mixture; (a) the additive mixture is an acylated polymer comprising a polymer having a number average molecular weight of about 300 Da to about 50,000 Da, or about 2000 Da to about 50,000 Da, or preferably about 2000 Da to about 25,000 Da, and comprises a polymeric surfactant compound comprising a branched olefin having 8 to 30 carbon atoms; (b) one or more additives selected from the group consisting of antifoam agents, antiwear agents, antioxidants, demulsifiers, detergents, dispersants, extreme pressure agents, friction modifiers, metal deactivators, pour point depressants, rust and corrosion inhibitors, viscosity modifiers, and combinations thereof.

[0090] Another aspect of the disclosure is a process for formulating a lubricant comprising combining an oil of lubricating viscosity with an additive mixture; (a) the additive mixture is an acylated polymer comprising a polymer having a number average molecular weight of about 500 Da to about 50,000 Da, the acylated polymer comprising a branched olefin having 8 to 30 carbon atoms, the acylated polymer comprising a polymeric surfactant compound that is further reacted with an amine or an alcohol to form an amide, an imide, an ester, or a combination thereof; (b) one or more additives selected from the group consisting of antifoam agents, antiwear agents, antioxidants, demulsifiers, detergents, dispersants, extreme pressure agents, friction modifiers, metal deactivators, pour point depressants, rust and corrosion inhibitors, viscosity modifiers, and combinations thereof.

[0091] Another aspect of the disclosure is a process for formulating a lubricant comprising combining an oil of lubricating viscosity with an additive mixture, wherein the lubricating composition has a High Temperature High Shear (HTHS) of less than 3.5 cP, or less than 3 cP, or less than 2.5 cP, as measured by ASTM D4683.

[0092] A further aspect of this technology relates to a method of lubricating a mechanical device, for example, by supplying the device with a lubricating composition described herein that contains a graft copolymer viscosity modifier. The mechanical device may be, for example, an internal combustion engine, a driveline device of an automobile, such as a transmission or an axle, or an off-highway vehicle. This technique may also be used in industrial applications, such as industrial hydraulics.

[0093] Another aspect of the present disclosure is an internal combustion engine lubricated with an engine oil, the improvement comprising an engine oil according to any of the preceding paragraphs.

[0094] The lubricating compositions described above can be utilized in internal combustion engines. The engine components may have steel or aluminum surfaces (typically steel surfaces) and may be coated with, for example, a diamond-like carbon (DLC) coating.

[0095] The aluminum surface may be comprised of an aluminum alloy, which may be a eutectic or hypereutectic aluminum alloy (such as those derived from aluminum silicate, aluminum oxide, or other ceramic materials). The aluminum surface may be present on a cylinder bore, cylinder block, or piston ring having an aluminum alloy or aluminum composite.

[0096] The internal combustion engine may be fitted with an emission control system or a turbocharger. Examples of emission control systems include diesel particulate filters (DPFs), or systems that use selective catalytic reduction (SCR).

[0097] The lubricant composition for internal combustion engines may be suitable for any engine lubricant, regardless of sulfur, phosphorus, or sulfated ash (ASTM D-874) content. The sulfur content of the engine oil lubricant may be 1 wt.% or less, or 0.8 wt.% or less, or 0.5 wt.% or less, or 0.3 wt.% or less. In one embodiment, the sulfur content may range from 0.001 wt.% to 0.5 wt.%, or 0.01 wt.% to 0.3 wt.%. The phosphorus content may be 0.2 wt.% or less, or 0.12 wt.% or less, or 0.1 wt.% or less, or 0.085 wt.% or less, or 0.08 wt.% or less, or even 0.06 wt.% or less, 0.055 wt.% or less, or 0.05 wt.% or less. In one embodiment, the phosphorus content may be 100 ppm to 1000 ppm, or 200 ppm to 600 ppm. The total sulfated ash content may be 2% by weight or less, or 1.5% by weight or less, or 1.1% by weight or less, or 1% by weight or less, or 0.8% by weight or less, or 0.5% by weight or less, or 0.4% by weight or less. In one embodiment, the sulfated ash content may be 0.05% to 0.9% by weight, or 0.1% to 0.2% by weight or 0.45% by weight.

[0098] In one embodiment, the lubricating composition may be an engine oil, and the lubricating composition may be characterized as having at least one of: (i) a sulfur content of less than or equal to 0.5 wt. %, (ii) a phosphorus content of less than or equal to 0.1 wt. %, (iii) a sulfated ash content of less than or equal to 1.5 wt. %, or a combination thereof.

[0099] Another aspect of the present disclosure is a process for formulating an engine oil, the process comprising combining an oil of lubricating viscosity with an additive mixture;

[0100] The additive mixture is an acylated polymer comprising a polymer having a number average molecular weight of about 300 Da to about 50,000 Da, or about 2000 Da to about 50,000 Da, or preferably about 2000 Da to about 25,000 Da, and includes a polymeric surfactant compound containing a branched olefin having 8 to 30 carbon atoms.

[0101] One or more additives selected from the group consisting of antifoam agents, antiwear agents, antioxidants, demulsifiers, detergents, dispersants, extreme pressure agents, friction modifiers, metal deactivators, pour point depressants, rust and corrosion inhibitors, viscosity modifiers, and combinations thereof, and additive mixtures without variations in combinations of additives, or relative proportions thereof within the additive mixture that meet or exceed the performance requirements of one or more of the following engine oil certification programs: ILSAC GF-5, ILSAC GF-6, API SN, dexos, CJ-4, ACEA-A1, ACEA-A2, ACE A-A3, ACEA-B1, ACEA-B2, ACEA-B3, ACEA-B4, ACEA-E1, ACEA-E2, ACEA-E3, ACEA-E4, and PC-11.

[0102] Another aspect of the present disclosure is a process for formulating an engine oil, the process comprising combining an oil of lubricating viscosity with an additive mixture; (a) the additive mixture is an acylated polymer comprising a polymer having a number average molecular weight of about 500 Da to about 50,000 Da and comprising a branched olefin having 8 to 30 carbon atoms, the acylated polymer comprising a polymeric surfactant compound that is further reacted with an amine or an alcohol to form an amide, imide, ester, or combination thereof; (b) One or more additives selected from the group consisting of antifoam agents, antiwear agents, antioxidants, demulsifiers, detergents, dispersants, extreme pressure agents, friction modifiers, metal deactivators, pour point depressants, rust and corrosion inhibitors, viscosity modifiers, and combinations thereof, and additive mixtures without variations in combinations of additives, or relative proportions thereof within the additive mixture that meet or exceed the performance requirements of one or more of the following engine oil certification programs: ILSAC GF-5, ILSAC GF-6, API SN, dexos, CJ-4, ACEA-A1, ACEA-A2, ACE A-A3, ACEA-B1, ACEA-B2, ACEA-B3, ACEA-B4, ACEA-E1, ACEA-E2, ACEA-E3, ACEA-E4, and PC-11.

[0103] In one method embodiment, the method may include lubricating a manual transmission by supplying the lubricant composition as described above to the manual transmission. The manual transmission may have a synchromesh, or in another embodiment, the manual transmission does not have a synchromesh. The synchromesh may be composed of aluminum, steel, bronze, molybdenum, brass (sintered or unsintered), carbon in the form of fibers, graphite material (optionally in combination with a cellulosic material), or cellulosic material, or phenolic resin.

[0104] In another method embodiment, the method may include lubricating a gear, gearbox, or axle gear by supplying to the gear, gearbox, or axle a lubricant composition as described above.

[0105] In another embodiment, the method may include lubricating an automatic transmission by supplying the lubricant composition as described above to the automatic transmission, including a continuously variable transmission (CVT), an infinitely variable transmission (IVT), or a toroidal transmission, or a continuous slip torque converting clutch (CSTCC), a stepped automatic transmission, or a dual clutch transmission (DCT).

[0106] In yet another method embodiment, the method may include lubricating an agricultural tractor transmission by providing a lubricant composition as described above. A lubricated agricultural tractor transmission typically has wet brakes, a transmission, a hydrolic, a final drive, and a power take-off system. These components are typically lubricated by a single lubricant provided from a common sump. The transmission may be a manual transmission or an automatic transmission.

[0107] Another aspect of the present disclosure is a process for formulating a gear oil, the process comprising combining an oil of lubricating viscosity with an additive mixture; (a) the additive mixture is an acylated polymer comprising a polymer having a number average molecular weight of about 300 Da to about 50,000 Da, or about 2000 Da to about 50,000 Da, or preferably about 2000 Da to about 25,000 Da, and comprises a polymeric surfactant compound comprising a branched olefin having 8 to 30 carbon atoms; (b) One or more additives selected from the group consisting of antifoam agents, antiwear agents, antioxidants, demulsifiers, detergents, dispersants, extreme pressure agents, friction modifiers, metal deactivators, pour point depressants, rust and corrosion inhibitors, viscosity modifiers, and combinations thereof, and additive mixtures without variations in combinations of additives, or relative proportions thereof within the additive mixture that meet or exceed the performance requirements of one or more of the following API gear oil categories: API GL-4, GL-5, MIL-L-2105D, MIL-PRF-2105E, MT-1, and SAE Standard J2360.

[0108] Another aspect of the present disclosure is a process for formulating a gear oil, the process comprising combining an oil of lubricating viscosity with an additive mixture; (a) the additive mixture is an acylated polymer comprising a polymer having a number average molecular weight of about 500 Da to about 50,000 Da and comprising a branched olefin having 8 to 30 carbon atoms, the acylated polymer comprising a polymeric surfactant compound that is further reacted with an amine or an alcohol to form an amide, imide, ester, or combination thereof; (b) One or more additives selected from the group consisting of antifoam agents, antiwear agents, antioxidants, demulsifiers, detergents, dispersants, extreme pressure agents, friction modifiers, metal deactivators, pour point depressants, rust and corrosion inhibitors, viscosity modifiers, and combinations thereof, and additive mixtures without variations in combinations of additives or relative proportions thereof within the additive mixture that meet or exceed the performance requirements of one or more of the following gear oil categories: API GL-4, GL-5, MIL-L-2105D, MIL-PRF-2105E, MT-1, and SAE Standard J2360.

[0109] Another aspect of the present disclosure is a process for formulating an automatic transmission fluid, the process comprising combining an oil of lubricating viscosity with an additive mixture; (a) the additive mixture is an acylated polymer comprising a polymer having a number average molecular weight of about 300 Da to about 50,000 Da, or about 2000 Da to about 50,000 Da, or preferably about 2000 Da to about 25,000 Da, and comprises a polymeric surfactant compound comprising a branched olefin having 8 to 30 carbon atoms; (b) One or more additives selected from the group consisting of antifoam agents, antiwear agents, antioxidants, demulsifiers, detergents, dispersants, extreme pressure agents, friction modifiers, metal deactivators, pour point depressants, rust and corrosion inhibitors, viscosity modifiers, and combinations thereof, and additive mixtures without variations in additive combinations or relative proportions thereof within additive mixtures that meet or exceed the performance requirements of one or more of the following performance categories: DEXRON ULV, MERCON ULV, Mopar ATF+4, DEXRON III / MERCON, DEXRON VI / MERCON V, MERCON V-Most Ford, Mercury, Lincoln, Mazda B-Series, 2001-08 Mazda Tribute, MERCON LV, MERCON SP, Toyota ATF Type T-IV(T4), and Toyota ATF WS.

[0110] Another aspect of the present disclosure is a process for formulating an automatic transmission fluid, the process comprising combining an oil of lubricating viscosity with an additive mixture; (a) the additive mixture is an acylated polymer comprising a polymer having a number average molecular weight of about 500 Da to about 50,000 Da and comprising a branched olefin having 8 to 30 carbon atoms, the acylated polymer comprising a polymeric surfactant compound that is further reacted with an amine or an alcohol to form an amide, imide, ester, or combination thereof; (b) One or more additives selected from the group consisting of antifoam agents, antiwear agents, antioxidants, demulsifiers, detergents, dispersants, extreme pressure agents, friction modifiers, metal deactivators, pour point depressants, rust and corrosion inhibitors, viscosity modifiers, and combinations thereof, and additive mixtures with no variations in additive combinations or relative proportions thereof within additive mixtures that meet or exceed the performance requirements of one or more of the following performance categories: DEXRON ULV, MERCON ULV, Mopar ATF+4, DEXRON III / MERCON, DEXRON VI / MERCON V, MERCON V-Most Ford, Mercury, Lincoln, Mazda B-Series, 2001-08 Mazda Tribute, MERCON LV, MERCON SP, Toyota ATF Type T-IV (T4), and Toyota ATF WS.

[0111] Additives: Dispersants The compositions disclosed herein may further comprise an ashless dispersant. The dispersant may be a succinimide dispersant, a Mannich dispersant, a polyolefin succinic acid ester, amide, or ester-amide, or a mixture thereof. In one embodiment, the dispersant may be a borated succinimide dispersant. In one embodiment, the dispersant may be present as a single dispersant. In one embodiment, the dispersant may be present as a mixture of two or three different dispersants, at least one of which may be a succinimide dispersant.

[0112] The succinimide dispersant may be derived from an aliphatic polyamine or mixtures thereof. The aliphatic polyamine may be an aliphatic polyamine such as ethylene polyamine, propylene polyamine, butylene polyamine, or mixtures thereof. In one embodiment, the aliphatic polyamine may be an ethylene polyamine. In one embodiment, the aliphatic polyamine may be selected from the group consisting of ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, polyamine distillation bottoms, and mixtures thereof.

[0113] The succinimide dispersant may be derived from an aromatic amine, an aromatic polyamine, or a mixture thereof. The aromatic amine may be 4-aminodiphenylamine (ADPA) (also known as N-phenylphenylenediamine), a derivative of ADPA (described in U.S. Patent Publications 2011 / 0306528 and 2010 / 0298185), nitroaniline, aminocarbazole, amino-indazolinone, aminopyrimidine, 4-(4-nitrophenylazo)aniline, or a combination thereof. In one embodiment, the dispersant is a derivative of an aromatic amine, the aromatic amine having at least three discontinuous aromatic rings.

[0114] The succinimide dispersant may be a derivative of a polyetheramine or polyetherpolyamine. A typical polyetheramine compound will contain at least one ether unit and be chain terminated with at least one amine moiety. Polyetherpolyamines are derived from C amines such as ethylene oxide, propylene oxide, and butylene oxide. 2 ~C 6 Examples of polyether polyamines are sold under the Jeffamine® brand and are commercially available from Hunstman Corporation.

[0115] The dispersant may be an N-substituted long chain alkenyl succinimide. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimides. Typically, the polyisobutylene from which the polyisobutylene succinic anhydride is derived has a number average molecular weight of 350 to 5000, or 550 to 3000, or 750 to 2500. Succinimide dispersants and their preparation are described, for example, in U.S. Pat. Nos. 3,172,892, 3,219,666, 3,316,177, 3,340,281, 3,351,552, 3,381,022, 3,433,744, 3,444,170, 3,467, 3,471, 3,472, 3,473, 3,476, 3,477, 3,478, 3,479, 3,480, 3,481, 3,482, 3,483, 3,484, 3,485, 3,486, 3,487, 3,489, 3,489, 3,490, 3,500, 3,510, 3,520, 3,521, 3,522, 3,523, 3,526, 3,527, 3,528, 3,529, 3,530, 3,540, 3,541, 3,542, 3,545, 3,546, 3,547, 3,548, 3,549, 3,550, 3,551, 3,552, ,668, 3,501,405, 3,542,680, 3,576,743, 3,632,511, 4,234,435, Re26,433, and 6,165,235, 7,238,650, as well as EP Patent No. 0355895B1.

[0116] Dispersants may also be post-treated in conventional manner by reaction with any of a variety of agents, among them boron compounds, urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds.

[0117] Dispersants are various forms of boric acid (metaboric acid, HBO 2 >, Orthoboric acid, H 3 BO 3 , and tetraboric acid, H 2 B 4 O 7The borated dispersants may be borated using one or more of a variety of agents selected from the group consisting of boron oxide, boron trioxide, and alkyl borates, including boric acid, ...

[0118] Suitable polyisobutylenes for use in succinimide dispersants may include those formed from polyisobutylene or highly reactive polyisobutylenes having a terminal vinylidene content of at least about 50 mole %, such as about 60 mole %, and particularly about 70 mole % to about 90 mole % or greater. Suitable polyisobutenes include BF 3 In one embodiment, the borated dispersant is derived from a polyolefin having a number average molecular weight of 350 to 3000 Daltons and a vinylidene content of at least 50 mole percent, or at least 70 mole percent, or at least 90 mole percent.

[0119] Dispersants may be prepared / obtained / obtainable by what is referred to as the "direct alkylation process" from the reaction of succinic anhydride by an "ene" or "thermal" reaction. The "ene" reaction mechanism and general reaction conditions are outlined in "Maleic Anhydride", pages 147-149 (edited by B.C. Trivedi and B.C. Culbertson, published by Plenum Press in 1982). Dispersants prepared by processes involving the "ene" reaction may be polyisobutylene succinimides with less than 50 mole %, or 0-30 mole %, or 0-20 mole %, or 0 mole % of carbon rings present in the dispersant molecules. The "ene" reaction may have a reaction temperature of less than 180°C to 300°C, or 200°C to 250°C, or 200°C to 220°C.

[0120] Dispersants may also be obtained / obtainable from a chlorine-assisted process, which often involves Diels-Alder chemistry and leads to the formation of carbon ring bonds. This process is known to those skilled in the art. The chlorine-assisted process may produce dispersants that are polyisobutylene succinimides with carbon rings present in 50 mole % or more, or 60-100 mole % of the dispersant molecules. Both thermal and chlorine-assisted processes are described in more detail in U.S. Pat. No. 7,615,521, columns 4-5, and in Preparative Examples A and B.

[0121] Dispersants can be used alone or as part of a mixture of non-borated or borated dispersants. When a mixture of dispersants is used, there can be 2 to 5, or 2 to 3, or 2 dispersants.

[0122] The polyolefin dispersant may comprise a polyalphaolefin (PAO) containing dispersant selected from the group consisting of polyalphaolefin succinimides, polyalphaolefin succinamides, polyalphaolefin acid esters, polyalphaolefin oxazolines, polyalphaolefin imidazolines, polyalphaolefin succinamide imidazolines, and combinations thereof.

[0123] Polyalphaolefins (PAOs) useful as feedstocks in forming PAO-containing dispersants are derived from the oligomerization or polymerization of ethylene, propylene, and α-olefins. Suitable α-olefins include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, and 1-octadecene. Commercial production of PAOs typically uses feedstocks containing mixtures of two or more of the aforementioned monomers, as well as other hydrocarbons. PAOs can be in the form of dimers, trimers, tetramers, polymers, and the like.

[0124] PAOs can be reacted with maleic anhydride (MA) to form polyalphaolefin succinic anhydrides (PAO-SA), and the anhydrides can then be reacted with one or more of polyamines, aminoalcohols, and alcohols / polyols to form polyalphaolefin succinimides, polyalphaolefin succinamides, polyalphaolefin succinate esters, polyalphaolefin oxazolines, polyalphaolefin imidazolines, polyalphaolefin-succinamide-imidazolines, and mixtures thereof.

[0125] Another class of ashless dispersants are Mannich bases, which are materials formed by the condensation of high molecular weight alkyl-substituted phenols, alkylene polyamines, and aldehydes such as formaldehyde, and are described in more detail in U.S. Pat. No. 3,634,515.

[0126] Useful nitrogen-containing dispersants include the product of a Mannich reaction between (a) an aldehyde, (b) a polyamine, and (c) an optionally substituted phenol. The phenol may be substituted such that the Mannich product has a molecular weight of less than 7500. Optionally, the molecular weight may be less than 2000, less than 1500, less than 1300, or, for example, less than 1200, less than 1100, less than 1000. In some embodiments, the Mannich product has a molecular weight of less than 900, less than 850, or less than 800, less than 500, or less than 400. The substituted phenol may be substituted with up to four groups on the aromatic ring. For example, it may be a tri- or di-substituted phenol. In some embodiments, the phenol may be a mono-substituted phenol. The substitutions may be in the ortho, and / or meta, and / or para positions. To form the Mannich product, the molar ratio of aldehyde to amine is 4:1 to 1:1, or 2:1 to 1:1. The molar ratio of aldehyde to phenol may be at least 0.75:1, preferably 0.75-1-4:1, preferably 1:1-4:1, more preferably 1:1-2:1. To form the preferred Mannich product, the molar ratio of phenol to amine is preferably at least 1.5:1, more preferably at least 1.6:1, more preferably at least 1.7:1, for example at least 1.8:1, preferably at least 1.9:1. The molar ratio of phenol to amine may be up to 5:1, for example it may be up to 4:1 or up to 3.5:1. Suitably it is up to 3.25:1, up to 3:1, up to 2.5:1, up to 2.3:1 or up to 2.1:1.

[0127] In certain embodiments, the fuel composition may comprise a quaternary ammonium salt. The quaternary ammonium salt may comprise (a) a compound comprising (i) at least one tertiary amino group, and (ii) a hydrocarbyl substituent having a number average molecular weight of from 100 to 5000, or from 250 to 4000, or from 100 to 4000, or from 100 to 2500, or from 3000, and (b) a quaternizing agent suitable for converting the tertiary amino group of (a)(i) to a quaternary nitrogen. These quaternary ammonium salts are disclosed in U.S. Patent Nos. 7,951,211, issued May 31, 2011, and 8,083814, issued December 27, 2011, as well as U.S. Publication Nos. 2013 / 0118062, published May 16, 2013, 2012 / 0010112, published January 12, 2012, 2013 / 0133243, published May 30, 2013, and 200 US2008 / 0113890 published on May 15, 2008, US2011 / 0219674 published on September 15, 2011, US2012 / 0149617 published on May 14, 2012, US2013 / 0225463 published on August 29, 2013, US2011 / 0258917 published on October 27, 2011, US2011 / 031 published on December 29, 2011 No. 5107, US2013 / 0074794 published on March 28, 2013, US2012 / 0255512 published on October 11, 2012, US2013 / 0333649 published on December 19, 2013, US2013 / 0118062 published on May 16, 2013, and International Publication No. WO 2011 / 141731 published on November 17, 2011, and International Publication No. WO 2011 / 141731 published on August 11, 2011. These compounds are described more thoroughly in WO 2011 / 095819 published on 2011-04, WO 2013 / 017886 published on 7 February 2013, WO 2013 / 070503 published on 16 May 2013, WO 2011 / 110860 published on 15 September 2011, WO 2013 / 017889 published on 7 February 2013, and WO 2013 / 017884 published on 7 February 2013.

[0128] In certain embodiments, the quaternizing agent used to prepare the additional quaternized ammonium salt may be a dialkyl sulfate, an alkyl halide, a hydrocarbyl-substituted carbonate, a hydrocarbyl epoxide, a carboxylate, an alkyl ester, or a mixture thereof. In some cases, the quaternizing agent may be a hydrocarbyl epoxide. In some cases, the quaternizing agent may be a hydrocarbyl epoxide in combination with an acid. In some cases, the quaternizing agent may be a salicylate, an oxalate, or a terephthalate. In some embodiments, the hydrocarbyl epoxide may be an alcohol-functionalized epoxide or a C 4 ~C 14 It is an epoxide.

[0129] In some embodiments, the quaternizing agent is multifunctional, resulting in an additional quaternary ammonium salt being the bound quaternary ammonium salt.

[0130] Engine oils: If present, the additional other dispersant may be present in the composition from 0.01% to 12% or from 0.1% to 8% or from 0.5% to 6% by weight of the composition.

[0131] Driveline: If present, the additional other dispersing agent may be present in the composition at 0.1% to 10% or 0.1% to 8% or 1% to 6% or 0% to 5% by weight of the composition.

[0132] Metal-containing cleaners The compositions disclosed herein may further comprise a metal-containing detergent.Metal-containing detergents are well known in the art.They are generally composed of metal salts of acidic organic substrates, especially metal salts of alkali metals and alkaline earth metals.Metal-containing detergents may be neutral, i.e., stoichiometric salts of metal and substrate, also called neutral soap or soap, or overbased.

[0133] Metal overbased detergents, metal-containing overbased detergents, or superbased salts, also referred to as overbased metal detergents, are characterized by a metal content in excess of that required for neutralization in accordance with the stoichiometry of the metal and the particular acidic organic compound (i.e., the substrate with which the metal reacts). Overbased detergents may include one or more of non-sulfur-containing phenates, sulfonates, salicylates, and mixtures thereof.

[0134] The amount of excess metal is generally expressed as a substrate to metal ratio. The term "metal ratio" is used in the prior art and herein to define the ratio of the total chemical equivalents of metal in the overbased salt to the chemical equivalents of metal in the salt that would be expected to result from the reaction between hydrocarbyl-substituted organic acids. The hydrocarbyl-substituted phenol or mixtures thereof are overbased, and the basic metal compound follows the known chemical reactivity and stoichiometry of the two reactants. Thus, in normal or neutral salts (i.e., soaps), the metal ratio is 1, and in overbased salts, the metal ratio is greater than 1, especially greater than 1.3. Overbased metal detergents may have a metal ratio of 5 to 30, or a metal ratio of 7 to 22, or a metal ratio of at least 11.

[0135] Metal-containing detergents may also include "hybrid" detergents formed with mixed surfactant systems containing phenate and / or sulfonate components, such as phenate-salicylate, sulfonate-phenate, sulfonate-salicylate, sulfonate-phenate-salicylate, as described, for example, in U.S. Pat. Nos. 6,429,178, 6,429,179, 6,153,565, and 6,281,179. For example, when a hybrid sulfonate / phenate detergent is used, the hybrid detergent is considered to be equivalent in amount to separate phenate and sulfonate detergents that incorporate similar amounts of phenate and sulfonate soaps, respectively. Overbased phenates and salicylates typically have a total base number of 180 to 450 TBN. Overbased sulfonates typically have a total base number of 250 to 600, or 300 to 500. Overbased detergents are known in the art.

[0136] Alkylphenols are often used as building blocks and / or components of overbased detergents. Alkylphenols may be used to prepare phenate, salicylate, salixarate or saligenin detergents or mixtures thereof. Suitable alkylphenols may include para-substituted hydrocarbylphenols. The hydrocarbyl group may be a straight or branched chain aliphatic group of 1 to 60 carbon atoms, 8 to 40 carbon atoms, 10 to 24 carbon atoms, 12 to 20 carbon atoms or 16 to 24 carbon atoms. In one embodiment, the alkylphenol overbased detergent is prepared from an alkylphenol or mixture thereof that is free or substantially free (i.e., contains less than 0.1 weight percent) of p-dodecylphenol. In one embodiment, the lubricating composition contains less than 0.3 weight percent alkylphenol, less than 0.1 weight percent alkylphenol, or less than 0.05 weight percent alkylphenol.

[0137] The overbased metal-containing detergent may be an alkali metal salt or an alkaline earth metal salt. In an embodiment, the overbased detergent may be a sodium, calcium, magnesium salt of phenates, sulfur-containing phenates, sulfonates, salixarates, and salicylates, or a mixture thereof. In an embodiment, the overbased detergent is a calcium detergent, a magnesium detergent, or a mixture thereof. In an embodiment, the overbased calcium detergent may be present in an amount that provides the lubricating composition with at least 500 ppm by weight of calcium and no more than 3000 ppm by weight of calcium, or at least 1000 ppm by weight of calcium, or at least 2000 ppm by weight of calcium, or no more than 2500 ppm by weight of calcium. In an embodiment, the overbased detergent may be present in an amount that provides the lubricating composition with no more than 500 ppm by weight of magnesium, or no more than 330 ppm by weight, or no more than 125 ppm by weight, or no more than 45 ppm by weight of magnesium. In one embodiment, the lubricating composition is essentially free of magnesium (i.e., contains less than 10 ppm magnesium) resulting from overbased detergents. In one embodiment, the overbased detergent may be present in an amount that provides the lubricating composition with at least 200 ppm by weight magnesium, or at least 450 ppm by weight magnesium, or at least 700 ppm by weight magnesium. In one embodiment, both calcium-containing detergents and magnesium-containing detergents may be present in the lubricating composition. The calcium detergents and magnesium detergents may be present such that the weight ratio of calcium to magnesium is 10:1 to 1:10, or 8:3 to 4:5, or 1:1 to 1:3. In one embodiment, the overbased detergent is free or substantially free of sodium.

[0138] In one embodiment, the sulfonate detergent may be primarily a linear alkylbenzene sulfonate detergent having a metal ratio of at least 8, as described in U.S. Patent Publication No. 2005 / 065045 (and granted as U.S. Patent No. 7,407,919), paragraphs

[0026] to

[0037] . The linear alkylbenzene sulfonate detergent may be particularly useful in helping to improve fuel economy. The linear alkyl group may be attached to the benzene ring anywhere along the linear chain of the alkyl group, but is often attached to the 2, 3 or 4 position of the linear chain, and in some cases is attached primarily to the 2 position, resulting in a linear alkylbenzene sulfonate detergent.

[0139] Salicylate detergents and overbased salicylate detergents can be prepared in at least two different ways. Carbonylation (also called carboxylation) of p-alkylphenols is described in many references, including U.S. Pat. No. 8,399,388. Carbonylation can be followed by overbasing to form overbased salicylate detergents. Suitable p-alkylphenols include those having linear and / or branched hydrocarbyl groups of 1 to 60 carbon atoms. Salicylate detergents can also be prepared by alkylation of salicylic acid followed by overbasing, as described in U.S. Pat. No. 7,009,072. Salicylate detergents prepared in this manner can be prepared from linear and / or branched alkylating agents (usually 1-olefins) containing 6 to 50 carbon atoms, 10 to 30 carbon atoms, or 14 to 24 carbon atoms. In one embodiment, the overbased detergent is a salicylate detergent. In one embodiment, the salicylate detergent is free of unreacted p-alkylphenol (i.e., contains less than 0.1 wt. %), hi one embodiment, the salicylate detergent is prepared by alkylation of salicylic acid.

[0140] The metal-containing overbased detergent may be present at 0.2% to 15%, or 0.3% to 10%, or 0.3% to 8%, or 0.4% to 3% by weight of the composition. For example, in heavy duty diesel engines, the detergent may be present at 2% to 3% by weight of the lubricating composition. For passenger car engines, the detergent may be present at 0.2% to 1% by weight of the lubricating composition.

[0141] Engine oils: When present, the metal-containing overbased detergent may be present in the composition from 0.01% to 9%, or from 0.5% to 8%, or from 1% to 5% by weight of the composition.

[0142] Driveline: In automotive gear oils, for example, the detergent may be present in the lubricating composition in an amount of 0.05% to 1% by weight, or 0.1% to 0.9% by weight. In manual transmission fluids, for example, the detergent may be present in the lubricating composition in an amount of at least 0.1% by weight, 0.14% to 4% by weight, or 0.2% to 3.5% by weight, or 0.5% to 3% by weight, or 1% to 2% by weight, or 0.5% to 4% by weight, or 0.6% to 3.5% by weight, or 1% to 3% by weight, or at least 1% by weight, for example 1.5% to 2.8% by weight.

[0143] The metal-containing detergent provides sulfated ash to the lubricating composition. The sulfated ash may be determined by ASTM D874. In one embodiment, the lubricating composition includes a metal-containing surfactant in an amount that provides at least 0.4 weight percent sulfated ash based on the total composition. In another embodiment, the metal-containing detergent is present in an amount that provides at least 0.6 weight percent sulfated ash, or at least 0.75 weight percent sulfated ash, or even at least 0.9 weight percent sulfated ash to the lubricating composition. In one embodiment, the metal-containing overbased detergent is present in an amount that provides 0.1 weight percent to 0.8 weight percent sulfated ash to the lubricating composition.

[0144] In addition to ash and TBN, the overbased detergent contributes a soapy detergent, also referred to as a neutral detergent salt, to the lubricating composition. The soap, which is a metal salt of a substrate, may act as a surfactant in the lubricating composition. In one embodiment, the lubricating composition includes 0.05 wt. % to 1.5 wt. % of a soapy detergent, or 0.1 wt. % to 0.9 wt. % of a soapy detergent. In one embodiment, the lubricating composition contains 0.5 wt. % or less of a soapy detergent. The overbased detergent may have a weight ratio of ash:soap of 5:1 to 1:2.3, or 3.5:1 to 1:2, or 2.9:1 to 1:1:7.

[0145] Polymer Viscosity Modifiers: The compositions disclosed herein may further contain a polymeric viscosity modifier, a dispersant viscosity modifier, or a combination thereof. Dispersant viscosity modifiers may generally be understood to be functionalized (i.e., derivatized) forms of polymers similar to that of the polymeric viscosity modifiers.

[0146] The polymeric viscosity modifier may be an olefin (co)polymer, a poly(meth)acrylate (PMA), or a mixture thereof. In one embodiment, the polymeric viscosity modifier is an olefin (co)polymer.

[0147] The olefin polymer may be derived from isobutylene or isoprene. In one embodiment, the olefin polymer is prepared from ethylene and higher olefins in the range of C3 to C10 alpha-monoolefins, for example, the olefin polymer may be prepared from ethylene and propylene.

[0148] In one embodiment, the olefin polymer may be a polymer of 15 to 80 mole percent ethylene, e.g., 30 mole percent to 70 mole percent ethylene, 20 to 85 mole percent C3 to C10 monoolefin, e.g., propylene, e.g., 30 to 70 mole percent propylene or more mono-olefins. Terpolymer variants of olefin copolymers may be used, which may contain up to 15 mole percent non-conjugated dienes or non-conjugated trienes. The non-conjugated dienes or non-conjugated trienes may have from 5 to about 14 carbon atoms. The non-conjugated diene or triene monomers may be characterized by the presence of a vinyl group in the structure and may include cyclic and bicyclic compounds. Representative dienes include 1,4-hexadiene, 1,4-cyclohexadiene, dicyclopentadiene, 5-ethyldiene-2-norbornene, 5-methylene-2-norbornene, 1,5-heptadiene, and 1,6-octadiene.

[0149] In one embodiment, the olefin copolymer may be a copolymer of ethylene, propylene, and butylene. The polymer may be prepared by polymerizing a mixture of monomers including ethylene, propylene, and butylene. These polymers may be referred to as copolymers or terpolymers. The terpolymer may contain about 5 mol% to about 20 mol% or about 5 mol% to about 10 mol% of structural units derived from ethylene, about 60 mol% to about 90 mol% or about 60 mol% to about 75 mol% of structural units derived from propylene, and about 5 mol% to about 30 mol% or about 15 mol% to about 30 mol% of structural units derived from butylene. Butylene may include any isomer or mixture thereof, such as n-butylene, isobutylene, or mixtures thereof. Butylene may include butene-1. Commercially available butylene may include butene-1, as well as butene-2, and butadiene. The butylene may comprise a mixture of butene-1 and isobutylene, the weight ratio of butene-1 to isobutylene being less than or equal to about 1:0.1. The butylene may comprise butene-1 and be free or essentially free of isobutylene.

[0150] In one embodiment, the olefin copolymer may be a copolymer of ethylene and butylene. The polymer may be prepared by polymerizing a mixture of monomers including ethylene and butylene, the monomer composition being free or substantially free of propylene monomer (i.e., containing less than 1% by weight of intentionally added monomer). The copolymer may contain 30-50 mole percent structural units derived from butylene and about 50 mole percent to 70 mole percent structural units derived from ethylene. The butylene may include a mixture of butene-1 and isobutylene, the weight ratio of butene-1 to isobutylene being about 1:0.1 or less. The butylene may include butene-1 and free or essentially free of isobutylene.

[0151] Useful olefin polymers, particularly ethylene-α-olefin copolymers, have number average molecular weights in the range of 4500 to 500,000, for example, 5000 to 100,000, or 7500 to 60,000, or 8000 to 45,000.

[0152] The formation of functionalized ethylene-α-olefin copolymers is well known in the art, for example, those described in US Patent No. 7,790,661, column 2, line 48 to column 10, line 38. Further detailed descriptions of similar functionalized ethylene-α-olefin copolymers can be found in WO 2006 / 015130 or US Patent Nos. 4,863,623, 6,107,257, 6,107,258, 6,117,825, and US 7,790,661. In one embodiment, the functionalized ethylene-α-olefin copolymers can include those described in US Patent No. 4,863,623 (see column 2, line 15 to column 3, line 52) or WO 2006 / 015130 (page 2, paragraph

[0008] and preparation examples are described in paragraphs

[0065] to

[0073] ).

[0153] In one embodiment, the lubricating composition may include an additional dispersant viscosity modifier (DVM) other than the graft copolymer viscosity modifier of the present disclosure. The DVM may include an olefin polymer modified by the addition of a polar moiety.

[0154] Olefin polymers are functionalized by modifying the polymer with the addition of polar moieties. In a useful embodiment, the functionalized copolymer is the reaction product of an olefin polymer grafted with an acylating agent. In an embodiment, the acylating agent may be an ethylenically unsaturated acylating agent. Useful acylating agents are typically α,β-unsaturated compounds having at least one ethylenic bond (before reaction) and at least one, e.g., two carboxylic acid (or anhydride thereof) groups, or polar groups that can be converted to said carboxyl groups by oxidation or hydrolysis. The acylating agent is grafted onto the olefin polymer to obtain two carboxylic acid functional groups. Examples of useful acylating agents include maleic anhydride, chloromaleic anhydride, itaconic anhydride, or their reactive equivalents, e.g., the corresponding dicarboxylic acids such as maleic acid, fumaric acid, cinnamic acid, (meth)acrylic acid, esters of these compounds, and acid chlorides of these compounds.

[0155] In one embodiment, the functionalized ethylene-α-olefin copolymer comprises an olefin copolymer grafted with acyl groups that are further functionalized with hydrocarbyl amines, hydrocarbyl alcohol groups, amino or hydroxy terminated polyether compounds, and mixtures thereof.

[0156] Amine functionality can be added to an olefin polymer (typically an ethylene-α-olefin copolymer, such as an ethylene-propylene copolymer) by reacting the olefin polymer with an acylating agent (typically maleic anhydride) and a hydrocarbyl amine having a primary or secondary amino group. In one embodiment, the hydrocarbyl amine can be selected from aromatic amines, aliphatic amines, and mixtures thereof.

[0157] In one embodiment, the hydrocarbyl amine component may comprise at least one aromatic amine containing at least one amino group capable of condensing with the acyl group to provide a pendant group, and at least one additional group comprising at least one nitrogen, oxygen, or sulfur atom, the aromatic amine being selected from the group consisting of (i) nitro-substituted anilines, (ii) amines comprising two aromatic moieties linked by a C(O)NR-, -C(O)O-, -O-, N=N-, or -SO2- group, where R is hydrogen or hydrocarbyl, one of the aromatic moieties bearing the condensable amino group, (iii) aminoquinolines, (iv) aminobenzimidazoles, (v) N,N-dialkylphenylenediamines, (vi) aminodiphenylamines (also N,N-phenyldiamines), and (vii) ring-substituted benzylamines.

[0158] In one embodiment, the hydrocarbyl amine component may include at least one aliphatic amine containing at least one amino group that can be condensed with the acyl group to provide a pendant group and at least one additional group that includes at least one nitrogen, oxygen, or sulfur atom. Suitable aliphatic amines include polyethylene polyamines (such as tetraethylene pentamine (TEPA), triethylene tetraamine (TETA), pentaethylene hexamine (PEHA), and polyamine bottoms), N,N-dimethylaminopropylamine (DMAPA), N-(aminopropyl)morpholine, N,N-diisostearyl aminopropylamine, ethanolamine, and combinations thereof.

[0159] In another embodiment, the polar moiety added to the functionalized ethylene-α-olefin copolymer can be derived from a hydrocarbyl alcohol group that contains at least one hydroxy group that can be condensed with the acyl group to provide a pendant group, and at least one additional group that contains at least one nitrogen, oxygen, or sulfur atom. The alcohol functional group can be added to the olefin polymer by reacting the olefin copolymer with an acylating agent (typically maleic anhydride) and a hydrocarbyl alcohol. The hydrocarbyl alcohol can be a polyol compound. Suitable hydrocarbyl polyols include ethylene glycol and propylene glycol, trimethylolpropane (TMP), pentaerythritol, and mixtures thereof.

[0160] In another embodiment, the polar moieties added to the functionalized ethylene-α-olefin copolymer may be amine-terminated polyether compounds, hydroxy-terminated polyether compounds, and mixtures thereof. The hydroxy-terminated or amine-terminated polyethers may be selected from the group including polyethylene glycol, or polypropylene glycol, or a mixture of one or more amine-terminated polyether compounds containing units derived from ethylene oxide, propylene oxide, butylene oxide, or any combination thereof, or any combination thereof. Suitable polyether compounds include the Synalox® series of polyalkylene glycol compounds, the UCON™ OSP series of polyether compounds available from Dow Chemical, and the Jeffamine® series of polyetheramines available from Huntsman.

[0161] In one embodiment, the lubricating composition may include a poly(meth)acrylate polymer viscosity modifier. As used herein, the term "(meth)acrylate" and its cognates mean either methacrylate or acrylate, as will be readily understood.

[0162] In one embodiment, the poly(meth)acrylate polymer is prepared from a monomer mixture that includes (meth)acrylate monomers having alkyl groups of various lengths. The (meth)acrylate monomers may include linear or branched alkyl groups. The alkyl groups may include 1 to 24 carbon atoms, for example, 1 to 20 carbon atoms.

[0163] The poly(meth)acrylate polymers described herein may be prepared by mixing monomers derived from saturated alcohols, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-methylpentyl (meth)acrylate, 2-propylheptyl (meth)acrylate, 2-butyloctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, 2-tert-butylheptyl (meth)acrylate, 3-isopropylheptyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth)acrylate, 2-methyldodecyl (meth)acrylate, tridecyl (meth)acrylate, methyl ... (meth)acrylate, 5-methyltridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, 2-methylhexadecyl (meth)acrylate, heptadecyl (meth)acrylate, 5-isopropylheptadecyl (meth)acrylate, 4-tert-butyloctadecyl (meth)acrylate, 5-ethyloctadecyl (meth)acrylate, 3-isopropyloctadecyl-(meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, meth)acrylates such as oleyl (meth)acrylate derived from unsaturated alcohols, and cycloalkyl (meth)acrylates such as 3-vinyl-2-butylcyclohexyl (meth)acrylate or bornyl (meth)acrylate.

[0164] Other examples of monomers include alkyl (meth)acrylates with long-chain alcohol derived groups, which can be obtained, for example, by reacting (meth)acrylic acid with a long-chain fatty alcohol (by direct esterification) or by reacting methyl (meth)acrylate with a long-chain fatty alcohol (by transesterification), which generally results in a mixture of esters such as (meth)acrylates and alcohol groups of various chain lengths. These fatty alcohols include Oxo Alcohol® 7911, Oxo Alcohol® 7900, and Oxo Alcohol® 1100 from Monsanto; Alfol® 79 from ICI; Nafol® 1620, Alfol® 610, and Alfol® 810 from Condea (now Sasol); Epal® 610 and Epal® 810 from Ethyl Corporation; Linevol® ​​79, Linevol® ​​911, and Dobanol® 25L from Shell AG; Lial® 125 from Condea Augusta, Milan; Dehydad® and Lorol® from Henkel KGaA (now Cognis); and Linopol® 7-11 and Acropol® 91 from Ugine Kuhlmann.

[0165] In one embodiment, the poly(meth)acrylate polymer comprises a dispersant monomer. The dispersant monomer includes a monomer that can be copolymerized with the (meth)acrylate monomer to contain one or more heteroatoms in addition to the carbonyl group of the (meth)acrylate. The dispersant monomer may contain a nitrogen-containing group, an oxygen-containing group, or a mixture thereof.

[0166] Oxygen-containing compounds include hydroxyalkyl (meth)acrylates, such as 3-hydroxypropyl (meth)acrylate, 3,4-dihydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,5-dimethyl-1,6-hexanediol (meth)acrylate, 1,10-decanediol (meth)acrylate, carbonyl-containing (meth)acrylates, such as 2-carboxyethyl (meth)acrylate, carboxymethyl (meth)acrylate, oxazolidinylethyl, N-(methacryloyloxy)formamide, acetonyl (meth)acrylate, acrylate, N-methacryloylmorpholine, N-methacryloyl-2-pyrrolidinone, N-(2-methacryloyl-oxyethyl)-2-pyrrolidinone, N-(3-methacryloyloxypropyl)-2-pyrrolidinone, N-(2-methacryloyloxypentadecyl)-2-pyrrolidinone, N-(3-methacryloyloxy-heptadecyl)-2-pyrrolidinone; glycol di(meth)acrylates, such as 1,4-butanediol (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-ethoxyethoxymethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, or mixtures thereof.

[0167] The nitrogen-containing compound may be a (meth)acrylamide or a nitrogen-containing (meth)acrylate monomer. Examples of suitable nitrogen-containing compounds include N,N-dimethylacrylamide, N-vinylcarbonamide such as N-vinylformamide, vinylpyridine, N-vinylacetamide, N-vinylpropionamide, N-vinylhydroxyacetamide, N-vinylimidazole, N-vinylpyrrolidinone, N-vinylcaprolactam, dimethylaminoethyl acrylate (DMAEA), dimethylaminoethyl methacrylate (DMAEMA), dimethylaminobutylacrylamide, dimethylaminopropyl methacrylate (DMAPMA), dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, dimethylaminoethyl acrylamide or mixtures thereof.

[0168] The dispersant monomer may be present in an amount up to 5 mole percent of the monomer composition of the (meth)acrylate polymer. In one embodiment, the poly(meth)acrylate is present in an amount from 0 to 5 mole percent, 0.5 to 4 mole percent, or 0.8 to 3 mole percent of the polymer composition. In one embodiment, the poly(meth)acrylate is free or substantially free of dispersant monomer.

[0169] In one embodiment, the poly(meth)acrylate comprises a block copolymer or a tapered block copolymer. A block copolymer is formed from a monomer mixture containing one or more (meth)acrylate monomers, for example, a first (meth)acrylate monomer forms a discrete block of polymer that is bonded to a second discrete block of polymer formed from a second (meth)acrylate monomer. A block copolymer has substantially discrete blocks formed from the monomers in the monomer mixture, whereas a tapered block copolymer can have one end composed of a relatively pure first monomer and the other end composed of a relatively pure second monomer. The middle of the tapered block copolymer is more of a gradient composition of the two monomers.

[0170] In one embodiment, the poly(meth)acrylate polymer (P) comprises at least one polymer block (B) that is insoluble or substantially insoluble in oil of lubricating viscosity. 1 ), and a second polymer block (B 2 ) is a block copolymer or a tapered block copolymer.

[0171] In one embodiment, the poly(meth)acrylate polymer may have a structure selected from linear, branched, hyperbranched, crosslinked, star (also referred to as "radial"), or a combination thereof. Star or radial refers to a multi-arm polymer. Such polymers include (meth)acrylate-containing polymers that contain three or more arms or branches, and in some embodiments, the arms or branches contain at least about 20, or at least 50, or 100, or 200, or 350, or 500, or 1000 carbon atoms. The arms are generally attached to a polyvalent organic moiety that functions as a "core" or "coupling agent". Multi-arm polymers may be referred to as radial or star polymers, or even "comb" polymers, or otherwise as polymers having multiple arms or branches, as described herein.

[0172] The random, block or other linear poly(meth)acrylates have a weight average molecular weight (M) of 1000 to 400,000 daltons, 1000 to 150,000 daltons, or 15,000 to 100,000 daltons. w In one embodiment, the poly(meth)acrylate may be a linear block copolymer having a Mw of 5,000 to 40,000 Daltons or 10,000 to 30,000 Daltons.

[0173] The radial, crosslinked or star copolymers can be derived from linear random or diblock copolymers having the molecular weights described above. The star polymers can have a weight average molecular weight of 10,000 to 1,500,000 daltons, or 40,000 to 1,000,000 daltons, or 300,000 to 850,000 daltons.

[0174] The polymeric viscosity modifier and / or dispersant viscosity modifier may be used in the functional fluid or lubricant composition at a concentration of up to 20% or 60% or 70% by weight. Concentrations of 0.1% to 12% or 0.1% to 4% by weight, or 0.2% to 3% by weight, or 1% to 12% by weight, or 3% to 10% by weight may be used.

[0175] The lubricating compositions may contain from 0.05% to 2% by weight, or from 0.08% to 1.8% by weight, or from 0.1% to 1.2% by weight of one or more polymeric viscosity modifiers and / or dispersant viscosity modifiers as described herein.

[0176] Engine oils: If present, the one or more polymeric viscosity modifiers and / or dispersant viscosity modifiers may be present in the composition at from 0.001% to 10% by weight, or from 0% to 5% by weight, or from 0% to 4% by weight, or from 0.05% to 2% by weight, or from 0.2% to 1.2% by weight of the lubricant composition.

[0177] Driveline: When present, the one or more polymeric viscosity modifiers and / or dispersant viscosity modifiers may be present in the composition at from 0.1% to 70% or from 1% to 60% or from 0.1% to 40% or from 0.1% to 15% or from 15% to 70% by weight of the composition.

[0178] Anti-wear Agent The composition prepared according to the present disclosure may optionally include at least one antiwear agent. Examples of suitable antiwear agents suitable for use herein include titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, metal dihydrocarbyl dithiophosphates (such as zinc dialkyldithiophosphates), phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides. In one embodiment, the antiwear agent may include tartrates or tartrimides, as described in U.S. Publication Nos. 2006 / 0079413, 2006 / 0183647, and 2010 / 0081592. The tartrates or tartrimides may contain alkyl ester groups, with the total number of carbon atoms in the alkyl groups being at least 8. In one embodiment, the antiwear agent may include citrate, as disclosed in US Publication No. 2005 / 0198894.

[0179] In one embodiment, the composition may further include a phosphorus-containing antiwear agent. Exemplary phosphorus-containing antiwear agents include zinc dialkyldithiophosphates, phosphites, phosphates, phosphonates, and ammonium phosphate salts, and mixtures thereof.

[0180] The compositions disclosed herein may include one or more oil-soluble titanium compounds that may function as antiwear agents, friction modifiers, antioxidants, deposit control additives, or more than one of these functions. Exemplary oil-soluble titanium compounds are disclosed in U.S. Pat. No. 7,727,943 and U.S. Publication No. 2006 / 0014651. Exemplary oil-soluble titanium compounds include titanium(IV) alkoxides, such as titanium(IV) isopropoxide and titanium(IV) 2-ethylhexoxide. Such alkoxides can be formed from monohydric alcohols, vicinal 1,2-diols, polyols, or mixtures thereof. The monohydric alkoxides can have 2 to 16, or 3 to 10 carbon atoms. In one embodiment, the titanium compound includes an alkoxide of a vicinal 1,2-diol or polyol. The 1,2-vicinal diol includes a fatty acid monoester of glycerol, and the fatty acid can be, for example, oleic acid. Other exemplary oil-soluble titanium compounds include titanium carboxylates, such as titanium neodecanoate.

[0181] If present in the composition, the amount of oil soluble titanium compound is included as part of the antiwear agent.

[0182] In another embodiment, the composition may have an anti-wear additive comprising an amine phosphate salt. The C2-C18 (or C2-C8 or C16-C18) di- or tri-hydrocarbyl phosphite, or mixtures thereof, may be represented by the formula: [ka] In the formula, at least one of R6, R7, and R8 can be a hydrocarbyl group containing at least 4 carbon atoms, and the others can be hydrogen or hydrocarbyl groups. In one embodiment, R6, R7, and R8 are all hydrocarbyl groups. The hydrocarbyl groups can be alkyl groups, cycloalkyl groups, aryl groups, acyclic groups, or mixtures thereof. In the formula with all three groups R6, R7, and R8, the compound can be a tri-hydrocarbyl substituted phosphite, i.e., R6, R7, and R8 are all hydrocarbyl groups, and in some embodiments, can be alkyl groups. Typically, di- or tri-hydrocarbyl phosphites include dibutyl phosphite or oleyl phosphite.

[0183] The phosphorus-containing antiwear agent may include a zinc dialkyldithiophosphate, a non-ionic phosphorus compound which may be a hydrocarbyl phosphite, (i) a non-ionic phosphorus compound which may be a hydrocarbyl phosphite, or (ii) an amine salt of a phosphorus compound, or mixtures thereof.

[0184] In one embodiment, the compositions disclosed herein do not contain zinc dialkyldithiophosphate. In one embodiment, the lubricant compositions disclosed herein contain zinc dialkyldithiophosphate. The phosphorus-containing compound can be a non-ionic phosphorus compound. In one embodiment, the phosphorus-containing compound includes two or more (possibly up to four) non-ionic phosphorus compounds. Typically, the non-ionic phosphorus compounds can have an oxidation of +3 or +5. Different embodiments include phosphite esters, phosphate esters, or mixtures thereof. In one embodiment, the phosphorus-containing compound includes a non-ionic phosphorus compound (C 4~6 hydrocarbyl phosphites), and amine salts of phosphoric acids or esters.

[0185] In one embodiment, the phosphorus-containing compound is 4~6 C includes non-ionic phosphorus compounds that are hydrocarbyl phosphites, or mixtures thereof. 4~6 Hydrocarbyl phosphites include those represented by the formula: [ka] wherein each R''' may independently be hydrogen or a hydrocarbyl group having 4 to 6 carbon atoms, typically 4 carbon atoms, provided that at least one of the R''' groups is hydrocarbyl. Typically, C 4~6 Hydrocarbyl phosphites include dibutyl phosphite.

[0186] C 4~6 The hydrocarbyl phosphite may deliver at least 175 ppm, or at least 200 ppm, of the total amount of phosphorus delivered by the phosphorus-containing compound.

[0187] C 4~6 The hydrocarbyl phosphite may deliver at least 45% by weight, or 50% to 100% by weight, or 50% to 90% by weight, or 60% to 80% by weight of the total amount of phosphorus from the phosphorus-containing compound.

[0188] The phosphorus-containing compound can include a second phosphite whose formula is similar to that disclosed above, except that R"' can contain 2 to 40, 8 to 24, or 11 to 20 carbon atoms, provided that the second phosphite is C 4~6 Provided that it is not a hydrocarbyl phosphite. Examples of suitable hydrocarbyl groups include propyl, dodecyl, butadecyl, hexadecyl, octadecyl, propenyl, dodecenyl, butadecenyl, hexadeencyl, or octadecenyl groups.

[0189] As used herein, the term "alk(en)yl" is intended to include moieties that have alkyl and / or alkenyl groups.

[0190] In one embodiment, the phosphorus-containing compound is 4~6 A hydrocarbyl phosphite (typically dibutyl phosphite) and C12~18 It comprises a mixture of alk(en)yl hydrogen phosphite and, optionally, phosphoric acid. In different embodiments, phosphoric acid is either present or absent.

[0191] In one embodiment, the phosphorus-containing compound is 4~6 Hydrocarbyl phosphite (typically dibutyl phosphite) and C 16~18 The alkyl(alkenyl) hydrogen phosphite may be a mixture of alkyl hydrogen phosphite and alkenyl hydrogen phosphite, or a mixture of alkenyl hydrogen phosphite and alkyl hydrogen phosphite. In one embodiment, the alkyl(alkenyl) hydrogen phosphite may be a mixture of alkenyl hydrogen phosphite, alkyl hydrogen phosphite, and optionally phosphoric acid. Phosphoric acid may or may not be present.

[0192] In one embodiment, the phosphorus-containing compound is 4~6 Hydrocarbyl phosphite (typically dibutyl phosphite) and C 11~14 The alkyl(alkenyl) hydrogen phosphite may be a mixture of alkyl hydrogen phosphite and alkenyl hydrogen phosphite, or a mixture of alkenyl hydrogen phosphite and alkyl hydrogen phosphite. In one embodiment, the alkyl(alkenyl) hydrogen phosphite may be a mixture of alkenyl hydrogen phosphite and alkyl hydrogen phosphite and optionally phosphoric acid.

[0193] In one embodiment, the phosphorus-containing compound is 4~6 It comprises a mixture of a hydrocarbyl phosphite (typically dibutyl phosphite) and phosphoric acid. In one embodiment, the lubricant composition comprises a package comprising a phosphorus-containing compound and a non-ionic phosphorus compound that is a hydrocarbyl phosphite.

[0194] In one embodiment, the composition comprises, as described above, 8~20 Hydrocarbyl phosphite, or C 12~18Hydrocarbyl phosphite, or C 16~18 Further included are hydrocarbyl phosphites.

[0195] In the above embodiment, the amine salt of phosphoric acid may be derived from an amine salt of a phosphate. The amine salt of phosphoric acid may be represented by the formula: [ka] In the formula, R 3 and R 4 may independently be hydrogen or a hydrocarbon, typically containing from 4 to 40, or from 6 to 30, or from 6 to 18, or from 8 to 18 carbon atoms, provided that at least one is a hydrocarbon group; R 5 , R 6 , R 7 , and R 8 may independently be hydrogen or a hydrocarbyl group, provided that at least one is a hydrocarbyl group.

[0196] R 3 and / or R 4 The hydrocarbon group may be straight chain, branched, or cyclic.

[0197] R 3 and / or R 4 Examples of hydrocarbon groups for include straight-chain or branched alkyl groups, including methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl.

[0198] R 3 and / or R 4Examples of cyclic hydrocarbon groups for include cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl, diethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl, diethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl, methylethylcycloheptyl, and diethylcycloheptyl.

[0199] In one embodiment, the phosphate may be the amine salt of a mixture of mono-alkyl and di-alkyl phosphate esters. The mono-alkyl and di-alkyl groups may be linear or branched.

[0200] The amine salt of phosphoric acid may be derived from an amine such as a primary amine, a secondary amine, a tertiary amine, or a mixture thereof. The amine may be aliphatic or cyclic, aromatic or non-aromatic, typically aliphatic. In one embodiment, the amine comprises an aliphatic amine, such as a tertiary aliphatic primary amine.

[0201] Examples of suitable primary amines include ethylamine, propylamine, butylamine, 2-ethylhexylamine, bis-(2-ethylhexyl)amine, octylamine, and dodecylamine, as well as fatty amines such as n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, and oleamine. Other useful fatty amines include commercially available fatty amines such as "Armeen" amines (products available from Akzo Chemicals, Chicago, Illinois), such as Armeen C, Armeen O, Armeen OL, Armeen T, Armeen HT, Armeen S, and Armeen SD, where the letter designation refers to the aliphatic, such as coco, oleyl, tallow, or stearyl group.

[0202] Examples of suitable secondary amines include dimethylamine, diethylamine, dipropylamine, dibutylamine, diamylamine, dihexylamine, diheptylamine, methylethylamine, ethylbutylamine, N-methyl-1-amino-cyclohexane, Armeen® 2C, and ethylamylamine. The secondary amines may be cyclic amines such as piperidine, piperazine, and morpholine.

[0203] Examples of tertiary amines include tri-n-butylamine, tri-n-octylamine, tri-decylamine, tri-laurylamine, tri-hexadecylamine, and dimethyloleylamine (Armeen® DMOD).

[0204] In one embodiment, the amine is in the form of a mixture. Examples of suitable mixtures of amines include (i) tertiary alkyl primary amines having 11 to 14 carbon atoms, (ii) tertiary alkyl primary amines having 14 to 18 carbon atoms, or (iii) tertiary alkyl primary amines having 18 to 22 carbon atoms. Other examples of tertiary alkyl primary amines include tert-butylamine, tert-hexylamine, tert-octylamine (such as 1,1-dimethylhexylamine), tert-decylamine (such as 1,1-dimethyloctylamine), tert-dodecylamine, tert-tetradecylamine, tert-hexadecylamine, tert-octadecylamine, tert-tetracosanylamine, and tert-octacosanylamine.

[0205] In one embodiment, suitable mixtures of amines are "Primene® 81R" and "Primene® JMT." Primene® 81R and Primene® JMT (both produced and sold by Rohm & Haas) are mixtures of C11-C14 tertiary alkyl primary amines and C18-C22 tertiary alkyl primary amines, respectively.

[0206] Amine salts of phosphoric acid can be prepared as described in U.S. Patent No. 6,468,946. Column 10, lines 15-63 describe a phosphoric acid ester formed by reaction of a phosphorus compound, followed by reaction with an amine to form the amine salt of the phosphoric acid hydrocarbyl ester. Column 10, lines 64-12, line 23 describe a preparation of phosphorus pentoxide reacted with an alcohol (having 4-13 carbon atoms), followed by reaction with an amine (typically Primene® 81-R) to form the amine salt of the phosphoric acid hydrocarbyl ester.

[0207] When present in a lubricating composition, the composition may comprise at least 0.01 wt. %, or at least 0.1 wt. %, or at least 0.5 wt. % of the anti-wear agent, and in some embodiments up to 3 wt. %, up to 1.5 wt. %, or up to 0.9 wt. % of the anti-wear agent.

[0208] Antioxidants The compositions prepared according to the present disclosure may include at least one antioxidant. Exemplary antioxidants useful herein include phenolic and aminic antioxidants such as diarylamine, alkylated diarylamine, hindered phenol, and mixtures thereof. The diarylamine or alkylated diarylamine may be phenyl-α-naphthylamine (PANA), alkylated diphenylamine, alkylated phenylnaphthylamine, or mixtures thereof. Exemplary alkylated diphenylamines include dinonyl diphenylamine, nonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine, didecyl diphenylamine, decyl diphenylamine, and mixtures thereof. Exemplary alkylated diarylamines include octyl, dioctyl, nonyl, dinonyl, decyl, and didecyl phenylnaphthylamine. Hindered phenol antioxidants often contain secondary butyl and / or tertiary butyl groups as sterically hindering groups. The phenol group may be further substituted with a hydrocarbyl group (e.g., linear or branched alkyl) and / or a bridging group linking to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol, 4-butyl-2,6-di-tert-butylphenol, and 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester, such as those described in U.S. Pat. No. 6,559,105. One such hindered phenol ester is sold as Irganox™ L-135, available from Ciba.

[0209] In one embodiment, the composition includes an amine antioxidant. The amine antioxidant can be a phenyl-α-naphthylamine (PANA) or a hydrocarbyl-substituted diphenylamine, or a mixture thereof. The hydrocarbyl-substituted diphenylamine can be a mono- or di-C 4 ~C 16 - or C 6 ~C 12 - or C 9 For example, the hydrocarbyl-substituted diphenylamine may be octyldiphenylamine, or dioctyldiphenylamine, dinonyldiphenylamine, typically dinonyldiphenylamine.

[0210] The composition may optionally contain at least one other antioxidant, which are known and include sulfurized olefins, hindered phenols, molybdenum dithiocarbamates, and mixtures thereof.

[0211] Hindered phenol antioxidants often contain secondary butyl and / or tertiary butyl groups as steric hindrance groups. The phenol group can often be further substituted with hydrocarbyl groups and / or bridging groups linked 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 can be an ester, such as Irganox™ L-135 from Ciba or butyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate.

[0212] Antioxidants may include diarylamines, alkylated diarylamines, hindered phenols, molybdenum compounds (such as molybdenum dithiocarbamates), hydroxyl thioethers, trimethylpolyquinolines (e.g., 1,2-dihydro-2,2,4-trimethylquinoline), or mixtures thereof.

[0213] The diarylamine or alkylated diarylamine may be phenyl-α-naphthylamine (PANA), alkylated diphenylamine, or alkylated phenylnaphthylamine, or mixtures thereof. The alkylated diphenylamine may include dinonylated diphenylamine, nonyl diphenylamine, octyl diphenylamine, dioctylated diphenylamine, didecyl diphenylamine, decyl diphenylamine, benzyl diphenylamine, and mixtures thereof. In an embodiment, the diphenylamine may include nonyl diphenylamine, dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine, or mixtures thereof. In an embodiment, the alkylated diphenylamine may include nonyl diphenylamine or dinonyl diphenylamine. The alkylated diarylamine may include octyl, dioctyl, nonyl, dinonyl, decyl, or didecyl phenylnaphthylamine. In an embodiment, the diphenylamine is alkylated with benzene and t-butyl substituents.

[0214] Hindered phenol antioxidants often contain secondary butyl and / or tertiary butyl groups as steric hindrance groups. The phenol group may be further substituted with hydrocarbyl groups (usually linear or branched alkyl) and / or bridging groups that link 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, for example, Irganox™ L-135 from BASF GmbH. A more detailed description of suitable ester-containing hindered phenol antioxidant chemistry can be found in U.S. Pat. No. 6,559,105.

[0215] Examples of molybdenum dithiocarbamates which may be used as antioxidants include commercially available materials sold under trade names such as Molyvan 822®, Molyvan® A, Molyvan® 855, and Adeka Sakura-Lube™ S100, S165, S600, and S525 from RTVanderbilt Co., Ltd., or mixtures thereof. An example of an ashless dithiocarbamate which may be used as an antioxidant or antiwear agent is Vanlube® 7723 from RTVanderbilt Co., Ltd.

[0216] The antioxidant may include a substituted hydrocarbyl monosulfide having the formula: [ka] In the formula, R 6 may be a saturated or unsaturated, branched or linear alkyl group having 8 to 20 carbon atoms; R 7 , R 8 , R9 , and R 10 is independently hydrogen or alkyl containing 1 to 3 carbon atoms. In some embodiments, the substituted hydrocarbyl monosulfide comprises n-dodecyl-2-hydroxyethyl sulfide, 1-(tert-dodecylthio)-2-propanol, or a combination thereof. In some embodiments, the substituted hydrocarbyl monosulfide is 1-(tert-dodecylthio)-2-propanol.

[0217] If present, the amount of antioxidant may be from 0.01 to 5 or 3 weight percent of the lubricating composition.

[0218] When present in a lubricating composition, the composition may comprise at least 0.1 wt. %, or at least 0.5 wt. %, or at least 1 wt. % antioxidant, and in some embodiments up to 3 wt. %, or up to 2.75 wt. %, or up to 2.5 wt. % antioxidant.

[0219] If present, the amine antioxidant may be present in a composition, such as a driveline composition, at 0.2% to 1.2%, or 0.3% to 1.0%, or 0.4% to 0.9%, or 0.5% to 0.8% by weight of the composition. If present, the secondary antioxidant may be present at 0.1% to 1%, or 0.2% to 0.9%, or 0.1% to 0.4%, or 0.4% to 1.0% by weight of the composition.

[0220] The lubricant may include an antioxidant or mixtures thereof. The antioxidant may be present in the technical composition at 0% to 4.0%, or 0.02% to 3.0%, or 0.03% to 1.5% by weight of the composition.

[0221] Extreme Pressure Agents: The compositions prepared according to the present disclosure may include extreme pressure agents. Exemplary extreme pressure agents that are soluble in oil include sulfur- and chlorosulfur-containing EP agents, dispersants dimercaptothiadiazole or CS 2Derivatives (typically succinimide dispersants), chlorinated hydrocarbon EP agents and derivatives of phosphorus EP agents. Examples of such EP agents include chlorinated waxes; sulfurized olefins (such as sulfurized isobutylene), hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazoles and their oligomers; organic sulfides and polysulfides, such as dibenzyl disulfide, bis-(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenols, sulfurized dipentenes, sulfurized terpenes, and sulfurized Diels-Alder adducts; phosphorus sulfurized hydrocarbons, such as phosphorus sulfide olein. reaction products with acid turpentine or methyl oleate; phosphorus esters, such as dihydrocarbon phosphites and trihydrocarbon phosphites; such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl phenyl phosphite; dipentyl phenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene substituted phenol phosphites; metal thiocarbamates, such as zinc dioctyldithiocarbamate and barium heptylphenol diacid; 2 O 5 and mixtures thereof, including the amine salts of the reaction products of dialkyldithiophosphoric acids with propylene oxide, followed by further reaction with propylene oxide; and mixtures thereof. Some useful extreme pressure agents are described in U.S. Pat. No. 3,197,405.

[0222] When present, the lubricating composition may comprise at least 0.01 wt.%, or at least 0.1 wt.%, or at least 0.5 wt.%, or at least 3 wt.%, of an extreme pressure agent, and in some embodiments up to 6 wt.%, or up to 3 wt.%, or up to 1 wt.% of an extreme pressure agent.

[0223] Driveline: Polysulfide extreme pressure agents typically provide from about 0.5 to about 5 weight percent or from about 1 to about 3 weight percent sulfur to the lubricating composition.

[0224] Foam suppressor The compositions prepared according to the present disclosure may include a foam suppressor. Foam suppressors that may be useful in the lubricant composition include polysiloxanes, copolymers of ethyl acrylate, 2-ethylhexyl acrylate, and optionally vinyl acetate; demulsifiers including fluorinated polysiloxanes, trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides, and (ethylene oxide-propylene oxide) polymers.

[0225] Antifoaming agents, also known as antifoam agents, are known in the art and include organosilicone and non-silicon antifoaming agents. Examples of organosilicones include dimethyl silicone and polysiloxane. Examples of non-silicon antifoaming agents include copolymers of ethyl acrylate and 2-ethylhexyl acrylate, copolymers of ethyl acrylate, 2-ethylhexyl acrylate and vinyl acetate, polyethers, polyacrylates, and mixtures thereof. Particularly useful polyacrylate antifoaming agents for fuels are copolymers of tert-butyl acrylate and 3,3,5-trimethylhexyl acrylate, and polymers of tert-butyl acrylate, 3,3,5-trimethylhexyl acrylate, and poly(ethylene glycol) acrylate. In some embodiments, the antifoaming agent is a polyacrylate. Another example of a non-silicone antifoaming agent includes polyacrylamides. In some embodiments, the polyacrylate can be a fluorinated polyacrylate.

[0226] Engine Oils: When the lubricating compositions are for lubricating the crankcase of a spark ignition or compression ignition engine, the compositions disclosed herein may include an antifoam component in an amount of 0.05% to 2% by weight, or 0.1% to 1.2% by weight, or 0.2% to 0.75% by weight.

[0227] Driveline: In some embodiments, the compositions disclosed herein are lubricating compositions for driveline devices that may include an antifoam component in an amount of at least 50 ppm, or at least 100 ppm, or from 50 ppm to 1000 ppm, or from about 50 to about 500, or from 50 ppm to 450 ppm or 400 ppm of the total composition on an oil-free basis.

[0228] Corrosion / rust inhibitors / metal deactivators: The composition prepared according to the present disclosure may include a corrosion inhibitor.Corrosion inhibitors / metal deactivators that may be useful in the exemplary composition include fatty amines, octylamine octanoate, condensation products of dodecenyl succinic acid or anhydride, and polyamines, fatty acids such as oleic acid with derivatives of benzotriazole (e.g., tolyltriazole), 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, and 2-alkyldithiobenzothiazole.

[0229] The composition may also include a rust inhibitor. Suitable rust inhibitors include hydrocarbyl amine salts of alkyl phosphoric acids, hydrocarbyl amine salts of dialkyl dithio phosphoric acids, hydrocarbyl amine salts of hydrocarbyl aryl sulfonic acids, fatty carboxylic acids or esters thereof, esters of nitrogen-containing carboxylic acids, ammonium sulfonates, alkylated succinic acid derivatives reacted with imidazolines, alcohols or ethers, or any combination thereof, or mixtures thereof.

[0230] Suitable hydrocarbyl amine salts of alkyl phosphates may be represented by the formula: [ka] In the formula, R 26 and R 27 are independently hydrogen, an alkyl chain, or a hydrocarbyl, typically R 26 and R 27 At least one of R is hydrocarbyl; 26 and R27 contains 4 to 30, or 8 to 25, or 10 to 20, or 13 to 19 carbon atoms; R 28 , R 29 , and R 30 are independently hydrogen, an alkyl branched or linear alkyl chain having 1 to 30, or 4 to 24, or 6 to 20, or 10 to 16 carbon atoms; R 28 , R 29 , and R 30 are independently hydrogen, an alkyl branched or linear alkyl chain, or R 28 , R 29 , and R 30 At least one or two of the following are hydrogen:

[0231] R 28 , R 29 , and R 30 Examples of suitable alkyl groups for include butyl, secbutyl, isobutyl, tert-butyl, pentyl, n-hexyl, sechexyl, n-octyl, 2-ethyl, hexyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonadecyl, eicosyl, or mixtures thereof.

[0232] In one embodiment, the hydrocarbyl amine salt of an alkyl phosphoric acid is 11 ~C 14 C with Primene® 81R, a mixture of tertiary alkyl primary amines (produced and sold by Rohm & Haas). 14 ~C 18 It is a reaction product of alkylated phosphoric acid.

[0233] The hydrocarbyl amine salts of dialkyl dithiophosphoric acids can include rust inhibitors such as hydrocarbyl amine salts of dialkyl dithiophosphoric acids, which can be the reaction products of heptyl or octyl or nonyl dithiophosphoric acids with ethylene diamine, morpholine, or Primene® 81R, or mixtures thereof.

[0234] The hydrocarbyl amine salts of hydrocarbyl aryl sulfonic acids may include the ethylene diamine salt of dinonyl naphthalene sulfonic acid.

[0235] Examples of suitable fatty carboxylic acids or esters thereof include glycerol monooleate and oleic acid.

[0236] The composition may include a metal deactivator, or mixtures thereof. The metal deactivator may be selected from derivatives of benzotriazole, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, 2-alkyldithiobenzothiazole, or dimercaptothiadiazole. Examples of such derivatives include 2,5-dimercapto-1,3,4-thiadiazole, or oligomers thereof, hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole, hydrocarbylthio-substituted 2,5-dimercapto-1,3,4-thiadiazole, or oligomers thereof. Oligomers of hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole are typically formed by forming sulfur-sulfur bonds between 2,5-dimercapto-1,3,4-thiadiazole units to form oligomers of two or more of the thiadiazole units. Examples of suitable thiadiazole compounds include at least one of dimercaptothiadiazole, 2,5-dimercapto-[1,3,4]-thiadiazole, 3,5-dimercapto-[1,2,4]-thiadiazole, 3,4-dimercapto-[1,2,5]-thiadiazole, or 4-5-dimercapto-[1,2,3]-thiadiazole. Typically, readily available materials such as 2,5-dimercapto-1,3,4-thiadiazole or hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole or hydrocarbylthio-substituted 2,5-dimercapto-1,3,4-thiadiazole are commonly utilized. In different embodiments, the number of carbon atoms on the hydrocarbyl substituent includes 1-30, 2-25, 4-20, 6-16, or 8-10. The 2,5-dimercapto-1,3,4-thiadiazole can be 2,5-dioctyldithio-1,3,4-thiadiazole, or 2,5-dinonyldithio-1,3,4-thiadiazole. The metal deactivators can also be described as corrosion inhibitors.

[0237] Engine oils: The rust inhibitors may be present in the lubricating composition in the range of 0-2% by weight, or 0.05%-2% by weight, 0.1%-1.0% by weight, 0.2%-0.5% by weight of the lubricating oil composition. The rust inhibitors may be used alone or in mixtures thereof.

[0238] Pour point depressants: Compositions prepared according to the present disclosure may include pour point depressants. Exemplary pour point depressants that may be useful in the lubricating compositions include polyalphaolefins, esters of maleic anhydride-styrene copolymers, polymethacrylates, polyacrylates, and polyacrylamides.

[0239] Pour point depressants are known in the art and include esters of maleic anhydride-styrene copolymers, polymethacrylates, polyacrylates, polyacrylamides, condensation products of haloparaffin waxes with aromatic compounds, vinyl carboxylate polymers, and terpolymers of dialkyl fumarates, vinyl esters of fatty acids, ethylene-vinyl acetate copolymers, alkylphenol formaldehyde condensation resins, alkyl vinyl ethers, and mixtures thereof.

[0240] The pour point depressant may be present in the lubricating composition in the range of 0.01% to 2%, or 0.05% to 1%, or 0.1% to 0.6% by weight of the lubricating oil composition. The rust inhibitors may be used alone or in mixtures thereof.

[0241] Friction modifiers The compositions prepared according to the present disclosure may include friction modifiers. Friction modifiers that may be useful in the exemplary compositions include fatty acid derivatives such as amines, esters, epoxides, fatty imidazolines, condensation products of carboxylic acids with polyalkylene polyamines, and amine salts of alkyl phosphates. The friction modifier may be an ashless friction modifier. Such friction modifiers are typically those that do not produce any sulfated ash when subjected to the conditions of ASTM D 874. An additive is said to be "non-metal-containing" if it does not contribute any metal content to the lubricant composition. As used herein, the term "fatty alkyl" or "fatty" with respect to friction modifiers means a carbon chain having 8 to 30 carbon atoms, typically a linear carbon chain.

[0242] In one embodiment, the ashless friction modifier may be represented by the formula: [ka] In the formula, D and D' are independently -O-, >NH, >NR 23 , both D and D' groups are combined to form an R 21 E is selected from an imide group formed by forming a -N< group; 24 -OR 25 -,>CH 2 , >CHR 26 , >CR 26 R 27 , >C(OH)(CO 2 R 22 ), >C(CO 2 R 22 ) 2 , and CHOR 28 wherein R 24 and R 25 are independent of each other, >CH 2 , >CHR 26 , >CR 26 R 27 , >C(OH)(CO 2 R 22 ), and >CHOR 28 and q is 0 to 10, except that when q=1, E is >CH 2If n=2, then both E are >CH 2 p is 0 or 1, and R 21 are independently hydrogen or a hydrocarbyl group typically containing 1 to 150 carbon atoms, except that R 21 is hydrogen, then p is 0 and q is 1 or greater; R 22 is a hydrocarbyl group typically containing 1 to 150 carbon atoms, R 23 , R 24 , R 25 , R 26 , and R 27 are independently hydrocarbyl groups; R 28 is hydrogen or a hydrocarbyl group that typically contains 1 to 150 carbon atoms, 4 to 32 carbon atoms, 8 to 24 carbon atoms. In certain embodiments, the hydrocarbyl group R 23 , R 24 , and R 25 can be a straight chain or predominantly straight chain alkyl group.

[0243] In certain embodiments, the ashless friction modifier is a fatty ester, amide, or imide of various hydroxy-carboxylic acids, such as tartaric acid, malic acid, lactic acid, glycolic acid, and mandelic acid. Examples of suitable materials include di(2-ethylhexyl) tartaric acid (i.e., di(2-ethylhexyl) tartrate), di(C 8 ~C 10 ) Tartrate, Di (C 12 ~ 15 ) tartrate, dioleyl tartrate, oleyl tartrimide, and oleyl maleimide.

[0244] In certain embodiments, the ashless friction modifier may be selected from long chain fatty acid derivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines, such as condensation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkyl phosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fatty phosphonates; fatty phosphites; borated phospholipids, borated fatty epoxides; glycerol esters; borated glycerol esters; fatty amines; alkoxylated fatty amines; borated alkoxylated fatty amines; polyhydroxy fatty amines, including hydroxyl, and tertiary hydroxy fatty amines; hydroxyalkylamides; metal salts of fatty acids; metal salts of alkyl salicylates; fatty oxazolines; fatty ethoxylated alcohols; condensation products of carboxylic acids and polyalkylene polyamines; or reaction products of fatty carboxylic acids with guanidine, aminoguanidine, urea, or thiourea, and salts thereof.

[0245] Friction modifiers may also include materials such as sulfurized fatty compounds and sunflower or soybean oil monoesters of olefins, polyols and aliphatic carboxylic acids.

[0246] In another embodiment, the friction modifier may be a long chain fatty ester. In another embodiment, the long chain fatty ester may be a monoester, and in another embodiment, the long chain fatty ester may be a triglyceride.

[0247] Molybdenum compounds are also known as friction modifiers. Exemplary molybdenum compounds do not contain dithiocarbamate moieties or ligands.

[0248] Nitrogen-containing molybdenum materials include molybdenum-amine compounds as described in U.S. Patent No. 6,329,327, and organomolybdenum compounds made from the reaction of a molybdenum source, a fatty oil, and a diamine as described in U.S. Patent No. 6,914,037. Other molybdenum compounds are disclosed in U.S. Publication No. 2008 / 0280795. Molybdenum amine compounds are compounds containing hexavalent molybdenum atoms and have the formula NR 29 R 30 R 31 can be obtained by reacting with a primary, secondary, or tertiary amine represented by the formula: 29 , R 30 , and R 31 is independently hydrogen or a hydrocarbyl group of 1 to 32 carbon atoms; R 29 , R 30 , and R 31 at least one of which is a hydrocarbyl group of 4 or more carbon atoms or is represented by the formula: [ka] In the formula, R 32 represents a chain hydrocarbon group having 10 or more carbon atoms, s is 0 or 1, R 33 and / or R 34 represents a hydrogen atom, a hydrocarbon group, an alkanol group, or an alkylamino group having 2 to 4 carbon atoms; when s=0, R 33 and R 34 Neither of the groups are hydrogen atoms or hydrocarbon groups.

[0249] Specific examples of suitable amines include monoalkyl (or alkenyl)amines, such as tetradecylamine, stearylamine, oleylamine, tallow alkylamines, hardened tallow alkylamines, and soybean alkylamines; dialkyl (or alkenyl)amines, such as N-tetradecylmethylamine, N-pentadecylmethylamine, N-hexadecylmethylamine, N-stearylmethylamine, N-oleylmethylamine, N-docosylmethylamine, N-tallow alkylmethylamines, N-hardened tallow alkylmethylamines, N-soybean alkylmethylamines, ditetradecylamine, dipentadecylamine, dihexadecylamine, diisopropyl ... Stearylamine, dioleylamine, didocosylamine, bis(2-hexyldecyl)amine, bis(2-octyldodecyl)amine, bis(2-decyltetradecyl)amine, tallow dialkylamine, hardened tallow dialkylamine, and soybean dialkylamine; and trialkylamines (trialkenylamines), such as tetradecyldimethylamine, hexadecyldimethylamine, octadecyldimethylamine, tallow alkyl dimethylamine, hardened tallow alkyl dimethylamine, soybean alkyl dimethylamine, dioleylmethylamine, tritetradecylamine, tristearylamine, and trioleylamine. Suitable secondary amines have two alkyl (or alkenyl) groups with 14 to 18 carbon atoms.

[0250] Examples of compounds containing hexavalent molybdenum atoms include molybdenum trioxide and its hydrates (MoO 3 . nH 2 O), molybdic acid (H 2 MoO 4 ), alkali metal molybdates (Q 2 MoO 4 ) (wherein Q represents an alkali metal such as sodium or potassium), ammonium molybdate {(NH 4 ) 2 MoO 4 or heptamolybdate (NH 4 ) 6 [Mo 7 O 24].4H 2 O}, MoOCl 4 , MoO 2 Cl 2 , MoO 2 Br 2 , Mo 2 O 3 Cl 6 Molybdenum trioxide or its hydrates, molybdic acid, alkali metal molybdates, and ammonium molybdate are often preferred due to their availability. In one embodiment, the lubricating composition includes a molybdenum amine compound.

[0251] Other organomolybdenum compounds suitable for use in the present compositions may be the reaction products of fatty oils, monoalkylated alkylenediamines, and a molybdenum source. This type of material is generally made in two steps, the first step involving the preparation of an aminoamide / glyceride mixture at high temperature, and the second step involving the incorporation of molybdenum.

[0252] Examples of fatty oils that can be used include cottonseed oil, peanut oil, coconut oil, linseed oil, palm kernel oil, olive oil, corn oil, palm oil, castor oil, rapeseed oil (low or high erucic acid), soybean oil, sunflower oil, menhaden oil, sardine oil, and tallow. These fatty oils are commonly known as glyceryl esters of fatty acids, triacylglycerols, or triglycerides.

[0253] Examples of some monoalkylated alkylenediamines that can be used include methylaminopropylamine, methylaminoethylamine, butylaminopropylamine, butylamino-ethylamine, octylaminopropylamine, octylaminoethylamine, dodecylaminopropylamine, dodecylaminoethylamine, hexadecylaminopropylamine, hexadecylaminoethylamine, octadecyl-aminopropylamine, octadecylaminoethylamine, isopropyloxypropyl-1,3-diaminopropane, and octyloxypropyl-1,3-diaminopropane. Monoalkylated alkylenediamines derived from fatty acids can also be used. Examples include N-cocoalkyl-1,3-propanediamine (Duomeen® C), N-tall oil alkyl-1,3-propanediamine (Duomeen® T), and N-oleyl-1,3-propanediamine (Duomeen® O), all commercially available from Akzo Nobel.

[0254] Sources of molybdenum for incorporation into the fatty oil / diamine complex are generally oxygen-containing molybdenum compounds, including ammonium molybdate, sodium molybdate, molybdenum oxide, and mixtures thereof, similar to those described above. One suitable source of molybdenum is molybdenum trioxide (MoO 3 ).

[0255] Commercially available nitrogen-containing molybdenum compounds include, for example, Sakuralube® 710 available from Adeka, which is a molybdenum amine compound, and Molyvan® 855 available from RT Vanderbilt.

[0256] In one embodiment, the friction modifier can be formed by condensation of a hydroxyalkyl compound with an acylating agent or amine. A more detailed description of the hydroxyalkyl compound is provided in U.S. Patent Application No. 60 / 725,360, filed October 11, 2005, inventors Bartley, Lahiri, Baker, and Tipton, at paragraphs 8, 19-21. The friction modifiers disclosed in U.S. Patent Application No. 60 / 725,360 can be represented by the formula R 1 R 2 NC(O)R 3 wherein R 1 and R 2 are each independently a hydrocarbyl group of at least 6 carbon atoms; R 3 is a hydroxyalkyl group of 1 to 6 carbon atoms, or a group formed by condensation of said hydroxyalkyl group through its hydroxyl group with an acylating agent. Preparation examples are disclosed in Examples 1 and 2 (paragraphs 68 and 69). In one embodiment, the amide of the hydroxyl alkyl compound is glycolic acid, i.e., hydroxyacetic acid, HO-CH 2 It is prepared by reacting --COOH with an amine.

[0257] In one embodiment, the friction modifier has the formula R 4 R 5 NR 6 wherein R 4 and R 5 are each independently an alkyl group of at least 6 carbon atoms; R 6 is hydrogen, a hydrocarbyl group, a hydroxyl-containing alkyl group, or an amine-containing alkyl group. A more detailed description of friction modifiers is provided in U.S. Patent Application Serial No. 05 / 037897, at paragraphs 8 and 19-22.

[0258] In one embodiment, the friction modifier can be derived from the reaction of a carboxylic acid or its reactive equivalent with an amino alcohol, the friction modifier containing at least two hydrocarbyl groups, each containing at least six carbon atoms. Examples of such friction modifiers include the reaction products of isostearic acid or alkyl succinic anhydrides with tris-hydroxymethylaminomethane. A more detailed description of such friction modifiers is disclosed in paragraphs 8 and 9-14 of WO 04 / 007652.

[0259] Friction modifiers include fatty amines, borated glycerol esters, fatty acid amides, non-borated fatty epoxides, borated fatty epoxides, alkoxylated fatty amines, borated alkoxylated fatty amines, metal salts of fatty acids, fatty imidazolines, metal salts of alkyl salicylates (also referred to as detergents), metal salts of sulfonates (also referred to as detergents), condensation products of carboxylic acids or polyalkylene-polyamines, or amides of hydroxyalkyl compounds.

[0260] In one embodiment, the friction modifier comprises a fatty acid ester of glycerol. The end product may be in the form of a metal salt, an amide, an imidazoline, or mixtures thereof. The fatty acid may contain 6 to 24, or 8 to 18 carbon atoms. The fatty acid may be branched or linear, saturated or unsaturated. Suitable acids include 2-ethylhexanoic acid, decanoic acid, oleic acid, stearic acid, isostearic acid, palmitic acid, myristic acid, palmitoleic acid, linoleic acid, lauric acid, and linolenic acid, as well as acids from the natural products tallow, palm oil, olive oil, peanut oil, corn oil, and beef foot oil. In one embodiment, the fatty acid is oleic acid. When in the form of a metal salt, typically the metal comprises zinc or calcium, and the products include overbased and non-overbased products. Examples are overbased calcium salts, and acids of the general formula Zn 4 Oleate 6A basic oleic acid-zinc salt complex which can be represented by the formula: O. When in the amide form, the condensation products include those prepared with ammonia, or primary or secondary amines such as diethylamine and diethanolamine. When in the imidazoline form, the condensation products of the acid with a polyamine such as a diamine or polyethylene polyamine. In one embodiment, the friction modifier is a condensation product of a fatty acid having C8 to C24 atoms with a polyalkylene polyamine, in particular the product of isostearic acid with tetraethylene pentamine.

[0261] In one embodiment, the friction modifier comprises one formed by the condensation of a hydroxyalkyl compound with an acylating agent or amine. A more detailed description of the hydroxyalkyl compound is given in paragraphs 9 and 20-22 of WO2007 / 0044820. The friction modifiers disclosed in WO2007 / 044820 are represented by the formula R 12 R 13 NC(O)R 14 In the formula R 12 and R 13 are each independently a hydrocarbyl group of at least 6 carbon atoms; R 14 is a hydroxyalkyl group of 1 to 6 carbon atoms or a group formed by condensation of said hydroxyalkyl group through its hydroxyl group with an acylating agent. Preparation examples are disclosed in Examples 1 and 2 (paragraphs 72 and 73 of WO 2007 / 044820). In one embodiment, the amide of the hydroxyl alkyl compound is glycolic acid, i.e., hydroxyacetic acid, HO-CH 2 It is prepared by reacting --COOH with an amine.

[0262] In one embodiment, the friction modifier comprises the reaction product of di-coco alkylamine (or di-coco amine) with glycolic acid. The friction modifier comprises the compounds prepared in Preparations 1 and 2 of WO2008 / 014319.

[0263] In one embodiment, the friction modifier comprises an alkoxylated alcohol. A detailed description of suitable alkoxylated alcohols is described in U.S. Patent Application Publication No. 2005 / 0101497, paragraphs 19 and 20. Alkoxylated amines are also described in U.S. Patent No. 5,641,732, column 7, line 15 to column 9, line 25.

[0264] In one embodiment, the friction modifier comprises a hydroxylamine compound as defined in U.S. Patent No. 5,534,170 at column 37, line 19 to column 39, line 38. Optionally, the hydroxylamine comprises a borated product as such products are described in U.S. Patent No. 5,534,170 at column 39, line 39 to column 40, line 8.

[0265] In one embodiment, the friction modifier comprises an alkoxylated amine, such as an ethoxylated amine derived from 1.8% Ethomeen™ T-12 and 0.90% Tomah™ PA-1, as described in U.S. Patent No. 5,703,023, column 28, lines 30-46, Example E. Other suitable alkoxylated amine compounds include commercially available alkoxylated fatty amines known by the trade name "ETHOMEEN" and available from Akzo Nobel. Representative of these ETHOMEEN™ materials are ETHOMEEN™ C / 12 (bis[2-hydroxyethyl]-coco-amine), ETHOMEEN™ C / 20 (polyoxyethylene

[10] cocoamine), ETHOMEEN™ S / 12 (bis[2-hydroxyethyl]soyamine), ETHOMEEN™ T / 12 (bis[2-hydroxyethyl]-tallow-amine), ETHOMEEN™ T / 15 (polyoxyethylene-[5]tallow-amine), ETHOMEEN™ 0 / 12 (bis[2-hydroxyethyl]oleyl-amine), ETHOMEEN™ 18 / 12 (bis[2-hydroxyethyl]octadecylamine), and ETHOMEEN™ 18 / 25 (polyoxyethylene

[15] octadecylamine). Fatty amines and ethoxylated fatty amines are also described in U.S. Pat. No. 4,741,848.

[0266] In one embodiment, the friction modifier comprises a polyol ester as described in US Pat. No. 5,750,476 at column 8, line 40 to column 9, line 28.

[0267] In one embodiment, the friction modifier comprises a low efficacy friction modifier as described in U.S. Patent No. 5,840,662 at column 2, line 28 to column 3, line 26. U.S. Patent No. 5,840,662 further discloses certain materials and methods for preparing the low efficacy friction modifier at column 3, line 48 to column 6, line 25.

[0268] In one embodiment, the friction modifier comprises the reaction product of an isomerized alkenyl-substituted succinic anhydride and a polyamine as described in U.S. Patent No. 5,840,663 at column 2, lines 18-43. Particular embodiments of the friction modifier described in U.S. Patent No. 5,840,663 are further disclosed at column 3, line 23 to column 4, line 35. Preparation examples are further disclosed at column 4, line 45 to column 5, line 37 of U.S. Patent No. 5,840,663.

[0269] In one embodiment, the friction modifier comprises an alkyl phosphonate mono- or di-ester commercially sold by Rhodia under the trade name Duraphos® DMODP.

[0270] The condensation of fatty acids with polyamines typically results in the formation of at least one compound selected from hydrocarbyl amides, hydrocarbyl imidazolines, and mixtures thereof. In one embodiment, the condensation product is a hydrocarbyl imidazoline. In one embodiment, the condensation product is a hydrocarbyl amide. In one embodiment, the condensation product is a mixture of hydrocarbyl imidazolines and hydrocarbyl amides. Typically, the condensation product is a mixture of hydrocarbyl imidazolines and hydrocarbyl amides.

[0271] The fatty acid may be derived from a hydrocarbyl carboxylic acid. The hydrocarbyl group may be alkyl, cycloalkyl, or aryl, although alkyl is typical, and the hydrocarbyl group may be linear or branched. Typically, the fatty acid contains 8 or more, 10 or more, 13 or more, 14 or more carbon atoms (including the carbon of the carboxy group). Typically, the fatty acid contains 8 to 30, 12 to 24, or 16 to 18 carbon atoms. Other suitable carboxylic acids may include polycarboxylic acids or carboxylic acids or anhydrides having 2 to 4 carbonyl groups, typically 2. Polycarboxylic acids may include succinic acid and anhydrides, and Diels-Alder reaction products of unsaturated monocarboxylic acids with unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, and itaconic acid. Fatty carboxylic acids include fatty monocarboxylic acids containing 8 to 30, 10 to 26, or 12 to 24 carbon atoms.

[0272] Examples of suitable fatty acids may include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, eicosic acid, and tall oil acid. In one embodiment, the fatty acid is stearic acid, which may be used alone or in combination with other fatty acids.

[0273] In one embodiment, one or both friction modifiers may be a nitrogen-containing compound, and typically both friction modifiers are nitrogen-containing.

[0274] In one embodiment, one of the friction modifiers is a condensation product of a fatty acid having C8 to C24 atoms and a polyalkylene polyamine, in particular the product of isostearic acid with tetraethylene pentamine.

[0275] As used herein, the term "fatty alkyl" or "fatty" in reference to friction modifiers means a carbon chain having 8 to 22 carbon atoms, typically a straight carbon chain. Alternatively, the fatty alkyl may be a mono-branched alkyl group, typically branched at the β position. Examples of mono-branched alkyl groups include 2-ethylhexyl, 2-propylheptyl, or 2-octyldodecyl.

[0276] Examples of suitable friction modifiers include long chain fatty acid derivatives of amines, fatty esters, or fatty epoxides, fatty imidazolines such as condensation products of carboxylic acids with polyalkylene-polyamines, amine salts of alkylphosphoric acids, fatty phosphonates, fatty phosphites, borated phospholipids, borated fatty epoxides, glycerol esters, borated glycerol esters, fatty amines, alkoxylated fatty amines, borated alkoxylated fatty amines, hydroxyl and polyhydroxy fatty amines, hydroxyalkylamides, metal salts of fatty acids, metal salts of alkyl salicylates, aliphatic oxazolines, fatty ethoxylated alcohols, condensation products of carboxylic acids with polyalkylenepolyamines, or reaction products of aliphatic carboxylic acids with guanidine, aminoguanidine, urea, or thiourea and their salts.

[0277] The amount of ashless friction modifier in the lubricant may be 0.1 to 3 weight percent (or 0.12 to 1.2 or 0.15 to 0.8 weight percent). The material may be present alone or with other additives, and in concentrates with smaller amounts of oil. In concentrates, the amount of material may be 2 to 10 times the amount of the concentrate described above.

[0278] The nitrogen-containing molybdenum compound may be present in the lubricant composition at 0.005 to 2 weight percent of the composition, or at 0.01 to 1.3 weight percent, or at 0.02 to 1.0 weight percent of the composition. The molybdenum compound may provide the lubricant composition with 0 to 1000 ppm, or 5 to 1000 ppm, or 10 to 750 ppm, 5 ppm to 300 ppm, or 20 ppm to 250 ppm of molybdenum.

[0279] The lubricant composition may include a friction modifier, typically at least two friction modifiers. Useful friction modifiers are described below. In one embodiment, the friction modifier is typically present at 0-4 wt%, or 0.1-4 wt%, 0.2-3 wt%, 0.3-3 wt%, 0.25-2.5 wt%. In one embodiment, a friction modifier is present, and in an alternative embodiment, no friction modifier is present.

[0280] Demulsifier Compositions prepared according to the present disclosure may include a demulsifier. Demulsifiers useful herein include trialkyl phosphates, and various polymers and copolymers of ethylene glycol, ethylene oxide, propylene oxide, and mixtures thereof.

[0281] Demulsifiers are known in the art and include propylene oxide, ethylene oxide, polyoxyalkylene alcohols, alkylamines, amino alcohols, derivatives of diamines, polyamines reacted in turn with ethylene oxide or substituted ethylene oxide, or mixtures thereof. Examples of demulsifiers include polyethylene glycols, polyethylene oxides, polypropylene oxides, (ethylene oxide-propylene oxide) polymers, and mixtures thereof. In some embodiments, the demulsifier is a polyether. In one embodiment, the demulsifier may be an oxyalkylated phenolic resin blend. Such a blend may include formaldehyde polymers with 4-nonylphenol, ethylene oxide, and propylene oxide, and formaldehyde polymers with 4-nonylphenol ethylene oxide. The demulsifier may be present in the composition at 0.002% to 0.012% by weight.

[0282] Seal swelling agent Seal swell agents may also be included in compositions prepared according to the present disclosure, including sulfolene derivatives such as Exxon Necton-37™ (FN 1380) and Exxon Mineral Seal Oil™ (FN 3200).

[0283] Other useful seal swell agents are the substituted sulfonyldibenzene compounds of the formula: [ka] In the formula, n is 0 or 1, R 1 and R 2 are each independently R 3 or R 4 P - a group represented by Y, R 3 is a hydrocarbyl group of about 4, or about 12 to about 20, about 6 to about 18, about 6 to about 14, or about 6 to about 8 carbon atoms; R 4 is an alkylene group of about 1 or 2 carbon atoms, p is 0 or 1, -Y, -ZR 5 In the formula, -Z- is -H-, -N(R 6 )-, wherein R 6 is a hydrocarbyl group of about 6 to about 18 carbon atoms, -N=CH-, -HC=N-, -OC(O)-, and -C(0)-0-; R 5 is hydrogen or an aliphatic hydrocarbyl group of about 4, or about 12 to about 20, about 6 to about 18, about 6 to about 14, or about 6 to about 8 carbon atoms; or -Y is represented by the formula: [ka] In the formula, R 7 is a hydrocarbyl group containing from about 8 to about 100, from about 12 to about 24, from about 8 to about 16, from about 14 to about 16, or from about 40 to about 70 carbon atoms.

[0284] In some embodiments, the lubricants prepared according to the present process are formulated to lubricate mechanical devices, which may be associated with an automobile, such as driveline devices, including automatic transmissions, manual transmissions, dual clutch transmissions, or axles or differentials.

[0285] The driveline device lubricating composition in different embodiments may have a composition as disclosed in the following table. [Table 1]

[0286] The mechanical device may be, for example, an internal combustion engine, such as a spark ignition internal combustion engine or a compression ignition internal combustion engine. The engine lubricating composition in different embodiments may have a composition as disclosed in the following table. [Table 2]

[0287] The present disclosure is not limited with respect to the specific embodiments described in this application, but are intended as illustrative of various aspects. As will be apparent to those skilled in the art, many modifications and variations can be made without departing from the spirit and scope thereof. In addition to those enumerated herein, functionally equivalent methods and components within the scope of the present disclosure will be apparent to those skilled in the art from the foregoing description. Such modifications and variations are intended to be included within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that the present disclosure is not limited to specific methods, reagents, compounds, or compositions, which may of course vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0288] As used herein, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Nothing in this disclosure should be construed as an admission that the embodiments described in this disclosure are not entitled to antedate such disclosure by prior invention. As used herein, the term "including" means "including, but not limited to."

[0289] Although various compositions, methods, and apparatus are described with the term "comprising" various components or steps (which is interpreted to mean "including, but not limited to"), the compositions, methods, and apparatus may also "consist essentially of" or "consist of" the various components and steps, and such terms should be interpreted as defining an essentially closed group of elements.

[0290] With respect to the use of substantially any plural and / or singular term herein, those skilled in the art can convert from plural to singular and / or from singular to plural as appropriate to the context and / or application. For clarity, various singular / plural permutations may be expressly described herein.

[0291] In general, it will be understood by those skilled in the art that the terms used in this specification, and particularly in the appended claims (e.g., the body of the appended claims), are generally intended as "open" terms (e.g., the term "including" should be interpreted as "including, but not limited to," the term "having" should be interpreted as "having at least," and the term "including" should be interpreted as "including, but not limited to"). If a specific number of introduced claim recitations are intended, such intent will be explicitly set forth in the claims, and those skilled in the art will further understand that, in the absence of such recitation, no such intent exists. For example, to aid in understanding, the appended claims below may include the use of the introductory phrases "at least one" and "one or more" to introduce the claim recitations. However, the use of such phrases should not be interpreted as meaning that a claim recitation introduced with the indefinite article "a" or "an" limits any particular claim that includes the introduced recitation to embodiments that include only one of such recitations, even if the same claim includes the introductory phrase "one or more" or "at least one" and an indefinite article such as "a" or "an" (e.g., "a" and / or "an" should be interpreted to mean "at least one" or "one or more"). The same applies to the use of definite articles used to introduce claim recitations. Moreover, even if a specific number of introduced claim recitations is explicitly recited, one of ordinary skill in the art will recognize that such recitation should be interpreted to mean at least the recited number (e.g., the recitation "two recitations" without any other modifiers means at least two recitations or more than two recitations).Furthermore, when an idiomatic expression similar to "at least one of A, B, and C" is used, such configuration is generally intended in the sense of that idiomatic expression as one of ordinary skill in the art would understand (e.g., "a system having at least one of A, B, and C" includes, but is not limited to, a system having only A, a system having only B, a system having only C, a system having both A and B, a system having both A and C, a system having both B and C, and / or a system having both A, B, and C, etc.). When a phrase similar to "at least one of A, B, or C" is used, such configuration is generally intended in the sense of that phrase as one of ordinary skill in the art would understand it (e.g., "a system having at least one of A, B, or C" includes, but is not limited to, a system having only A, a system having only B, a system having only C, a system having both A and B, a system having both A and C, a system having both B and C, and / or a system having both A, B, and C, etc.). It will be further understood by one of ordinary skill in the art that substantially any disjunctive word and / or phrase presenting two or more alternative items, whether in the specification, claims, or drawings, should be understood to contemplate the possibility of including one of those items, the possibility of including either of those items, or the possibility of including both of those items. For example, the phrase "A or B" is understood to include the possibilities of "A" or "B" or "A and B."

[0292] Furthermore, where features or aspects of the disclosure can be described in terms of Markush groups, those skilled in the art will recognize that the disclosure also can be described in terms of any individual element or subgroup of elements of the Markush group.

[0293] As will be understood by those of skill in the art, for any and all purposes, e.g., with respect to providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any recited range can be readily recognized as fully describing and allowing for division of that same range into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily divided into a lower third, a middle third, an upper third, etc. Also, as will be understood by those of skill in the art, all language such as "up to," "at least," etc., includes the recited number and refers to a range that can be subsequently divided into subranges as discussed above. Finally, as will be understood by those of skill in the art, a range includes each individual element. Thus, for example, a group having 1-3% by weight refers to the group having 1, 2, or 3% by weight. Similarly, a group having 1-5% by weight refers to the group having 1, 2, 3, 4, or 5% by weight, etc., including all points in between.

[0294] As used herein, the term "about" means that the value of a given quantity is within ±20% of the stated value. In other embodiments, the value is within ±15% of the stated value. In other embodiments, the value is within ±10% of the stated value. In other embodiments, the value is within ±5% of the stated value. In other embodiments, the value is within ±2.5% of the stated value. In other embodiments, the value is within ±1% of the stated value.

[0295] Unless otherwise specified, "wt %" as used herein shall refer to weight percent based on the total weight of the composition. EXAMPLES

[0296] Methods for preparing branched olefin copolymers Functionalization with carboxylic acid moieties and subsequent reaction with amines is well known and disclosed above. Illustrative examples of branched olefins, polymers, and polymeric surfactants are provided in the table below. [Table 3] [Table 4] [Table 5]

Claims

1. 1. A lubricating oil composition comprising: a. an oil of lubricating viscosity; b. 0.1-20% by weight of a polymeric surfactant compound comprising an acylated polymer, said polymer comprising a branched olefin containing 8-30 carbon atoms, and combinations thereof, said polymer having a number average molecular weight (Mn) of 500-50,000 Da; The branched olefin has the formula: 【Chemistry 3】 (2E,5E,7E,10E)-3,6,10-trimethyldodeca-2,5,7,10-tetraene 【Chemistry 4】 (3E,7E,10E)-2,7,10-trimethyldodeca-1,3,7,10-tetraene 【Chemistry 5】 (E)-2,9-Dimethyl-5-(prop-1-en-2-yl)deca-1,3,8-triene 【Chemistry 6】 (3E,6E,10E)-2,6,10-trimethyldodeca-1,3,6,10-thretolane 【Chemistry 7】 (E)-7,11-dimethyl-3-methylenedodeca-1,6,10-triene or The branched olefin has the formula: 【Chemistry 8】 (6E,10E)-7,11,15-trimethyl-3-methylenehexadeca-1,6,10,14-tetraene 【Chemistry 9】 (3E,10E,14E)-3,7,11,15-tetramethylhexadeca-1,3,6,10,14-pentaene 【Chemistry 10】 (6E,10E,14E)-7,11,14-trimethyl-3-methylenehexadeca-1,6,10,14-tetraene 【Chemistry 11】 (6E,9E,13E)-2,10,13-trimethyl-6-(prop-1-en-2-yl)pentadeca-1,3,9,13-tetraene The lubricating oil composition according to claim 1,

2. 10. The lubricating composition of claim 1, wherein the acylated polymer is further reacted with an amine or an alcohol to form imides, amides, esters, and combinations thereof.

3. The polymer is represented by the formula: -[T] ｎ -[Z] ｍ - During the ceremony, [T] is the branched olefin, [Z] is a vinyl monomer capable of polymerizing with the branched olefin, 2. The lubricating composition of claim 1, wherein m is 0 to 100, and when m=0, n is at least 1, or at least 2.

4. 4. The lubricating composition according to claim 1, wherein the branched olefin is a trimer of isoprene represented by the formula: 【Chemistry 3】 (2E,5E,7E,10E)-3,6,10-trimethyldodeca-2,5,7,10-tetraene 【Chemistry 4】 (3E,7E,10E)-2,7,10-trimethyldodeca-1,3,7,10-tetraene 【Chemistry 5】 (E)-2,9-Dimethyl-5-(prop-1-en-2-yl)deca-1,3,8-triene 【Chemistry 6】 (3E,6E,10E)-2,6,10-trimethyldodeca-1,3,6,10-thretolane 【Chemistry 7】 (E)-7,11-dimethyl-3-methylenedodeca-1,6,10-triene

5. The lubricating composition of any one of claims 1 to 3, wherein the branched olefin may be a tetramer of the following formula: 【Chemistry 8】 (6E,10E)-7,11,15-trimethyl-3-methylenehexadeca-1,6,10,14-tetraene 【Chemistry 9】 (3E,10E,14E)-3,7,11,15-tetramethylhexadeca-1,3,6,10, 14-Pentaene 【Chemistry 10】 (6E,10E,14E)-7,11,14-trimethyl-3-methylenehexadeca-1,6, 10,14-Tetraene 【Chemistry 11】 (6E,9E,13E)-2,10,13-trimethyl-6-(prop-1-en-2-yl)pentadeca-1,3,9,13-tetraene

6. The lubricating composition of claim 3, wherein m is at least 1.

7. The vinyl monomer is represented by formula (13): 【Chemistry 17】 During the ceremony, R ５ , R ６ , R ７ , and R ８ The lubricating composition of any one of claims 3 to 6, wherein each is independently H, alkyl, cycloalkyl, aryl, cycloalkenyl, and alkynyl.

8. The lubricating composition of any one of claims 3 to 6, wherein the vinyl monomer is one or more of ethylene, an α-olefin, and styrene.

9. The lubricating composition of any one of claims 1 to 8, wherein the acylated polymer has acyl groups composed of carboxylic acids.

10. The lubricating composition of any one of claims 1 to 9, wherein the acylated polymer is a reaction product of the polymer with an ethylenically unsaturated carboxylic acid.

11. 11. The lubricating composition of claim 10, wherein the ethylenically unsaturated carboxylic acid is maleic anhydride or a reactive equivalent thereof.

12. 12. The lubricating composition of claim 10 or 11, wherein the ethylenically unsaturated carboxylic acid is grafted onto the polymer in solution or in molten form, and optionally in the presence of a free radical initiator.

13. 13. The lubricating composition of claim 12, wherein the free radical initiator is selected from one or more of peroxides, hydroperoxides, and azo compounds.

14. The lubricating composition of any one of claims 2 to 13, wherein the amine is selected from one or more of aromatic amines, aliphatic amines, and combinations thereof.

15. The aromatic amine is an N-arylphenylenediamine represented by the following formula: 【Chemistry 18】 During the ceremony, R ７ is H, -NHaryl, -NHalkaryl, or a branched or linear hydrocarbyl radical having 4 to 24 carbon atoms selected from alkyl, alkenyl, alkoxyl, aralkyl, or analcaryl; R ９ is -NH ２ .-(NH(CH ２ ) ｎ ) ｍ N.H. ２ , -NHalkyl, -NHaralkyl, -CH2-aryl-NH2, where n and m each have a value of 1 to 10; R ８ The lubricating composition of claim 14, wherein is H, alkyl, alkenyl, alkoxyl, aralkyl, or alkaryl having 4 to 24 carbon atoms.

16. The N-arylphenylenediamine is N-phenyl-1,4-phenylenediamine, N-phenyl-1,3-phenylenediamine, N-phenyl-1,2-phenylenediamine, and The lubricating composition of claim 15, wherein the N-naphthyl-1,4-phenylenediamine is selected from N-naphthyl-1,4-phenylenediamine.

17. 15. The lubricating composition of claim 14, wherein the aromatic amine is selected from aniline, N-methylaniline, N-butylaniline, di-(para-methylphenyl)amine, naphthylamine, 4-aminodiphenylamine, N,N-dimethylphenylenediamine, 4-(4-nitro-phenylazo)aniline (Disperse Orange 3), sulfamethazine, 4-phenoxyaniline, 3-nitroaniline, 4-aminoacetanilide, 4-amino-2-hydroxy-benzoic acid phenyl ester (phenyl aminosalicylate), 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.

18. The aromatic amine is an amine having at least three or at least four aromatic groups and is represented by the formula: 【Chemistry 19】 During the ceremony, R1 is H or C １ ~C ５ is an alkyl group, R2 is H or C １ ~C ５ is an alkyl group, U is an aliphatic, alicyclic, or aromatic group, with the proviso that if U is aliphatic, said aliphatic group is a straight or branched alkylene group containing 1 to 5 carbon atoms; The lubricating composition of claim 14, wherein w is 1 to 10.

19. 15. The lubricating composition of claim 14, wherein the aliphatic amine is a monoamine, diamine, or polyamine, the diamines and polyamines having a single primary amino group.

20. 20. The lubricating composition of claim 19, wherein the diamine or polyamine has a single primary amino group.

21. 21. The lubricating composition of claim 19 or 20, wherein the diamine or polyamine is selected from dimethylaminopropylamine, diethylaminopropylamine, dibutylamine-propylamine, dimethylaminoethylamine, diethylaminoethylamine, dibutylaminoethylamine, 1-(2-aminoethyl)piperidine, 1-(2-aminoethyl)pyrrolidone, N,N-dimethylethylamine; 3-(dimethylamino)-1-propylamine; N,N-dimethyldipropylenetriamine; aminoethylmorpholine; aminoethylethyleneurea; and aminopropylmorpholine.

22. The amine or alcohol is represented by the formula: 【Chemistry 20】 During the ceremony, X is an alkylene group containing 1 to 4 carbon atoms; The lubricating composition of any one of claims 2 to 14, wherein R2, R3, and R4 are each independently a hydrocarbyl group.

23. The lubricating composition of any one of claims 2 to 14, wherein the amine is a polyetheramine or a polyetherpolyamine.

24. 24. The lubricating composition of claim 23, wherein the polyetheramine contains at least one ether unit and is chain terminated with at least one amine moiety.

25. The polyetheramine is a C amine such as ethylene oxide, propylene oxide, and butylene oxide. ２ ~C ６ 25. The lubricating composition of claim 23 or 24, comprising an epoxide-derived polymer.

26. 24. The lubricating composition of claim 23, wherein the polyether amine is a polyether aromatic amine.

27. The polyether aromatic amine is represented by the formula: 【Chemistry 21】 During the ceremony, A is an aromatic amine moiety to which the ether group is linked through at least one amine group on the aromatic moiety; R １ and R ６ are each independently H, alkyl, alkaryl, aralkyl, or aryl, or mixtures thereof; R ２ , R ３ , R ４ , and R ５ are each independently H, or alkyl containing 1 to 6 carbon atoms, mixtures thereof; 27. The lubricating composition of claim 26, wherein a and x are each independently an integer from 1 to 50.

28. A lubricating composition according to any one of claims 2 to 14, wherein the acylated polymer and the amine are reacted in a CO:N ratio of from 5:1 to 1:

10.

29. 29. The lubricating composition of any one of claims 1 to 28, wherein the composition further comprises one or more additives selected from the group consisting of antifoam agents, antiwear agents, antioxidants, demulsifiers, detergents, dispersants, extreme pressure agents, friction modifiers, metal deactivators, pour point depressants, rust and corrosion inhibitors, viscosity modifiers, and combinations thereof.

30. 30. The lubricating composition of any one of claims 1 to 29, wherein the composition contains up to 2 wt.% of a polyisobutylene based dispersant.

31. The lubricating composition of any one of claims 1 to 30, wherein the composition contains up to 1 wt% of an ethylene / propylene based viscosity modifier dispersant.

32. 32. The lubricating composition of any one of claims 1 to 31, wherein the oil of lubricating viscosity comprises a base oil having a kinematic viscosity at 100°C of from 2 cSt to 8 cSt.

33. The lubricating composition of any one of claims 1 to 32, wherein the lubricating composition has a High Temperature High Shear (HTHS) of less than 3.5 cP as measured by ASTM D4683.

34. The lubricating composition of any one of claims 1 to 33, wherein the lubricating composition has a sulfur content of not more than 1 wt%.

35. The lubricating composition of any one of claims 1 to 34, wherein the lubricating composition has a phosphorus content of not more than 0.2 wt%.

36. The lubricating composition of any one of claims 1 to 35, wherein the lubricating composition has a total sulfated ash content of not more than 2 wt%.

37. 37. The lubricating composition of any one of claims 1 to 36, wherein the lubricating composition is an engine oil having at least one of: (i) a sulfur content of 0.5 wt. % or less; (ii) a phosphorus content of 0.1 wt. % or less; (iii) a sulfated ash content of 1.5 wt. % or less; or a combination thereof.

38. The lubricating composition comprises: One or more additives selected from the group consisting of antifoam agents, antiwear agents, antioxidants, demulsifiers, detergents, dispersants, extreme pressure agents, friction modifiers, metal deactivators, pour point depressants, rust and corrosion inhibitors, viscosity modifiers, and combinations thereof, and additive mixtures without variations in the combination of additives, or relative proportions thereof within the additive mixture that meet or exceed the performance requirements of one or more of the following engine oil certification programs: ILSAC GF-5, ILSAC GF-6, API SN, dexos, CJ-4, ACEA-A1, ACEA-A2, ACE A-A3, ACEA-B1, ACEA-B2, ACEA-B3, ACEA-B4, ACEA-E1, ACEA-E2, ACEA-E3, ACEA-E4, and PC-11.

38. The lubricating composition of claim 37, further comprising:

39. The lubricating composition is a gear oil, One or more additives selected from the group consisting of antifoam agents, antiwear agents, antioxidants, demulsifiers, detergents, dispersants, extreme pressure agents, friction modifiers, metal deactivators, pour point depressants, rust and corrosion inhibitors, viscosity modifiers, and combinations thereof, and additive mixtures without variations in the combination of additives, or relative proportions thereof within the additive mixture that meet or exceed the performance requirements of one or more of the following API gear oil categories: API GL-4, GL-5, MIL-L-2105D, MIL-PRF-2105E, MT-1, and SAE Standard J2360. The lubricating composition of any one of claims 1 to 36, further comprising:

40. The lubricating composition is an automatic transmission fluid, the lubricating composition comprising: One or more additives selected from the group consisting of antifoam agents, antiwear agents, antioxidants, demulsifiers, detergents, dispersants, extreme pressure agents, friction modifiers, metal deactivators, pour point depressants, rust and corrosion inhibitors, viscosity modifiers, and combinations thereof, as well as additive mixtures with no variations in combinations of additives, or in the following performance categories: DEXRON ULV, MERCON ULV, Mopar ATF+4, DEXRON III / MERCON, DEXRON VI / MERCON V, MERCON V-Most Ford, Mercury, Lincoln, Mazda B-Series, 2001-08 Mazda Tribute, MERCON LV, MERCON SP, Toyota ATF Type T-IV (T4), and their relative proportions within the additive mixture that meet or exceed the performance requirements of one or more of Toyota ATF WS. The lubricating composition of any one of claims 1 to 36, further comprising:

41. 37. A method of operating an automatic transmission having a continuously variable transmission (CVT), or an infinitely variable transmission (IVT), or a toroidal transmission, or a continuous slip torque converter clutch (CSTCC), a stepped automatic transmission, or a dual clutch transmission (DCT), the method comprising operating the automatic transmission with a lubricating composition according to any one of claims 1 to 36, the lubricating composition comprising: The method further comprising one or more additives selected from the group consisting of antifoam agents, antiwear agents, antioxidants, demulsifiers, detergents, dispersants, extreme pressure agents, friction modifiers, metal deactivators, pour point depressants, rust and corrosion inhibitors, viscosity modifiers, and combinations thereof.

42. 37. A method of operating an internal combustion engine equipped with an emission control system such as a diesel particulate filter (DPF) or a system employing selective catalytic reduction (SCR), the method comprising operating the engine with the lubricating composition of any one of claims 1 to 36, the lubricating composition further comprising one or more additives selected from the group consisting of antifoam agents, antiwear agents, antioxidants, demulsifiers, detergents, dispersants, extreme pressure agents, friction modifiers, metal deactivators, pour point depressants, rust and corrosion inhibitors, viscosity modifiers, and combinations thereof.

43. 37. A method of operating a turbocharged internal combustion engine, the method comprising operating the engine with the lubricating composition of any one of claims 1 to 36, the lubricating composition further comprising one or more additives selected from the group consisting of antifoam agents, antiwear agents, antioxidants, demulsifiers, detergents, dispersants, extreme pressure agents, friction modifiers, metal deactivators, pour point depressants, rust and corrosion inhibitors, viscosity modifiers, and combinations thereof.

44. 44. The method of claim 42 or 43, wherein the internal combustion engine is selected from a spark ignition engine and a compression ignition engine.

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