Lubricant Compositions Containing High C9 Disubstituted Diphenylamine Antioxidant Content

Abstract

This disclosure relates to the use of di(alkyl substituted phenyl)amine antioxidants as additives in lubricant compositions having good oxidation properties in engine crankcase applications, especially in compression ignited engine and or spark ignited engine applications, where the antioxidant comprises from 0 to 10 mass % mono-C9-alkyl substituted diphenyl amine, and 90 to 100 mass % di-C9-alkyl substituted phenyl amines based upon the weight of the mono- and di-C9-alkyl substituted phenyl amines, preferably where tri-C9-alkyl substituted phenyl amines are minimized and ortho substituted di-C9-alkyl substituted phenyl amines are minimized.

What is claimed is: 
     
         1 . A lubricating oil composition comprising diphenyl amine antioxidant comprising:
 1) 90 mass % or more of di(C 9 -alkyl substituted phenyl) amine, and   2) from 0 to less than 10 mass % of mono-C 9 -alkyl substituted diphenyl amine, based upon the mass of the mono-C 9 -alkyl substituted diphenyl amine and di-C 9 -alkyl substituted diphenyl amine present in the lubricating oil composition.   
     
     
         2 . The lubricating oil composition of  claim 1 , wherein the diphenyl amine antioxidant comprises:
 1) 99 mass % or more of di(C 9 -alkyl substituted phenyl) amine, and   2) from 0 to less than 1 mass % of mono-C 9 -alkyl substituted diphenyl amine, based upon the mass of the mono-C 9 -alkyl substituted diphenyl amine and di-C 9 -alkyl substituted diphenyl amine.   
     
     
         3 . A lubricating oil composition comprising diphenyl amine antioxidant comprising:
 1) 85 mass % or more of di(C 9 -alkyl substituted phenyl) amine,   2) from 0 to 5 mass % of mono-C 9 -alkyl substituted diphenyl amine, and   3) from 0 to 20 mass % of tri-C 9 -alkyl substituted diphenyl amine, based upon the weight of 1), 2) and 3) present in the lubricating oil composition.   
     
     
         4 . The lubricating oil composition of  claim 3 , comprising or resulting from the admixing of:
 1) 90 mass % or more of di(C 9 -alkyl substituted phenyl) amine,   2) from 0 to 5 mass % of mono-C 9 -alkyl substituted diphenyl amine, and   3) from 0 to 10 mass % of tri-C 9 -alkyl substituted diphenyl amine, based upon the weight of 1), 2) and 3) present in the lubricating oil composition.   
     
     
         5 . The lubricating oil composition of  claim 1 , comprising or resulting from the admixing of
 (i) at least 50 mass % of one or more base oils, based upon the weight of the lubricating oil composition;   (ii) one or more dispersants;   (iii) one or more detergents; and   (iv) diphenyl amine antioxidant composition comprising:
 a) from 0 to less than 10 mass % mono-C 9 -alkyl substituted diphenyl amine represented by the Formula (III) where n is 1, w is 0, and z is 0, 
 b) 90 mass % or more of di(C 9 -alkyl substituted diphenyl) amines represented by Formula (III), where w is 0, n is 1, and z is 1, 
 c) from 0 to less than 10 mass % tri-C 9 -alkyl substituted diphenyl amine represented by Formula (III), where w is 1, n is 1, and z is 1, 
 d) from 0 to 1 mass % of unsubstituted diphenyl amine represented by Formula (III) where w is 0, n is 0, and z is 0, 
   based upon the total weight of a), b), c) and d) present in the lubricating oil composition, where Formula (III) is:   
       
         
           
           
               
               
           
         
       
       where each R a  is independently a linear C 9  alkyl or branched C 9  alkyl group, n is 1 or 0, z is 0 or 1, and w is 0 or 1. 
     
     
         6 . The lubricating oil composition of  claim 5 , comprising:
 a) from 0 to less than 3 mass % mono-C 9 -alkyl substituted diphenyl amines represented by the Formula (III) where w is 0, n is 1, and z is 0,   b) 90 mass % or more of di-C 9 -alkyl substituted diphenyl amines represented by Formula (III), where w is 0, n is 1, and z is 1,   c) 10 mass % or less of tri-C 9 -alkyl substituted diphenyl amines represented by Formula (III), where w is 1, n is 1, and z is 1,   d) from 0 to 0.5 mass % or less of unsubstituted diphenyl amines represented by Formula (III) where w is 0, n is 0, and z is 0,   
       based upon the total weight of the diphenyl amines of a), b), c) and d) present in the lubricating oil composition. 
     
     
         7 . The lubricating oil composition of  claim 6 , wherein a) comprises from 0 to less than 1.0 mass %, mono-C 9 -alkyl substituted diphenyl amines represented by the Formula (III) where w is 0, n is 1, and z is 0, based upon the total weight of the diphenyl amines of a), b),
 c) and d) present in the lubricating oil composition.   
     
     
         8 . The lubricating oil composition of  claim 6 , wherein one or more mono-C 9 -alkyl substituted diphenyl amines, represented by the Formula (III) where n is 1, w is 0, and z is 0 are absent or present at less than 0.1 mass %, based upon the weight of the diphenyl amine antioxidants represented by Formula (III), where n is 1 w is 0 and z is 0 or 1, present in the lubricating oil composition. 
     
     
         9 . The lubricating oil composition of  claim 6 , wherein the di-C 9 -alkyl substituted diphenyl amine represented by Formula (III), where w is 0, n is 1, and z is 1, comprises less than 5 mass % of the isomers shown below, where each R is independently a linear C 9  alkyl or branched C 9  alkyl group: 
       
         
           
           
               
               
           
         
       
       based upon the weight of di-C 9 -alkyl substituted diphenyl amine represented by Formula (III), where w is 0, n is 1, and z is 1. 
     
     
         10 . The lubricating oil composition of  claim 1 , wherein the lubricating oil composition has a percent viscosity increase between the initial KV100 and the KV100 at 216 hours of the CEC-L-109-14 Oxidation Test that is at least 2% less than the percent viscosity increase of the same lubricating oil composition except that the diphenyl amine antioxidant has been replaced with the same amount of diphenyl amine antioxidant having:
 1) about 68 mass % di-C 9 -alkyl substituted diphenyl amine,   2) about 29 mass % of mono-C 9 -alkyl substituted diphenyl amine, and   3) about 3 mass % of tri-C 9 -alkyl substituted diphenyl amine, based upon the weight of 1), 2) and 3), as determined by UPLC.   
     
     
         11 . The lubricating oil composition of  claim 5 , wherein the ratio of the amount of di-C 9 -alkyl substituted diphenyl amine represented by Formula (III), where w is 0, n is 1, and z is 1, to the amount of mono-C 9 -alkyl substituted diphenyl amine represented by Formula (III), where w is 0, n is 1, and z is 0, present in the lubricating oil composition is 9:1 or more. 
     
     
         12 . The lubricating oil composition of  claim 11 , wherein the amount of mono-C 9 -alkyl substituted diphenyl amine represented by Formula (III), where w is 0, n is 1, and z is 0, present in the lubricating oil composition is less than 0.3 mass % or less than 0.1 mass %, or less than 0.05 mass %. 
     
     
         13 . The lubricating oil composition of  claim 1 , having higher Sequence IIIH weighted piston deposits merits (such as 0.5 WPD higher, such as 0.8 WPD or higher, such as 0.85 WPD or higher) as compared to the same lubricating oil composition except that the diphenyl amine antioxidant has been replaced with the same amount of diphenyl amine antioxidant having:
 1) about 68 mass % di-C 9 -alkyl substituted diphenyl amine,   2) about 29 mass % of mono-C 9 -alkyl substituted diphenyl amine, and   3) about 3 mass % of tri-C 9 -alkyl substituted diphenyl amine, based upon the weight of 1), 2) and 3), as determined by UPLC.   
     
     
         14 . The lubricating oil composition of  claim 1 , wherein the oxidation (FTIR, CEC-L-109-14 Oxidation Test) of the lubricating oil composition is less than or within 10% of the oxidation of the same lubricating oil composition except that the diphenyl amine antioxidant has been replaced with the same amount of diphenyl amine antioxidant having
 1) about 68 mass % di-C 9 -alkyl diphenyl amine,   2) about 29 mass % of mono-C 9 -alkyl diphenyl amine, and   3) about 3 mass % of tri-C 9 -alkyl diphenyl amine, based upon the weight of 1), 2) and 3), as determined by UPLC.   
     
     
         15 . The lubricating oil composition of  claim 1 , further comprising zinc dialkyldithiophosphate, hindered phenolic antioxidant, molybdenum containing compound, and or ethoxylated alcohol. 
     
     
         16 . The lubricating oil composition of  claim 1  wherein the lubricating oil composition further comprises additional antioxidant comprising oil-soluble or oil-dispersible sulfur-containing antioxidant(s), sulfurized aliphatic (C 7  to C 29 ) hydrocarbyl fatty acid ester(s), sulfur-containing organo-molybdenum compound(s), and combinations thereof. 
     
     
         17 . The lubricating oil composition of  claim 5 , where the detergent comprises salicylate detergent, optionally having a TBN of 100 or less and or optionally providing from 1 to 30 mmol/kg soap. 
     
     
         18 . The lubricating oil composition of  claim 5 , further comprising one or more of the following components.
 D) optionally, one or more friction modifiers;   E) optionally, one or more antioxidants, other than the antioxidants represented by Formula (III), such as Formula (I);   F) optionally, one or more pour point depressants;   G) optionally, one or more anti-foaming agents;   H) optionally, one or more viscosity modifiers;   J) optionally, one or more inhibitors and/or antirust agents; and/or   K) optionally, one or more anti-wear agents.   
     
     
         19 . The lubricating oil composition of  claim 5 , wherein further comprising one or more functionalized polymers comprising an amide, imide, and/or ester functionalized partially or fully saturated polymer comprising C 4-5  olefins having:
 i) an Mw/Mn of less than 2,   ii) a Functionality Distribution (Fd) value of 3.5 or less, and   iii) an Mn of 10,000 g/mol or more (GPC-PS) of the polymer prior to functionalization, provided that, if the polymer prior to functionalization is a copolymer of isoprene and butadiene, then the Mn of the copolymer is greater than 25,000 g/mol.   
     
     
         20 . The lubricating oil composition of  claim 1 , wherein phosphorus is present at 0.08 mass % or less, based upon the weight of the lubricating oil composition. 
     
     
         21 . The lubricating oil composition of  claim 1 , wherein the di(C 9 -alkyl substituted phenyl) amine is obtained from a reaction of para-nonyl phenol with ammonia in the presence of a hydrogen transfer catalyst. 
     
     
         22 . The lubricating oil composition of  claim 1 , wherein the 90 mass % or more of di(C 9 -alkyl substituted phenyl) amine is obtained by distillation of the reaction product of nonene with diphenylamine in the presence of Lewis acid catalyst. 
     
     
         23 . The lubricating oil composition of  claim 11 , wherein the amount of di-C 9 -alkyl substituted diphenyl amine represented by Formula (III), where w is 0, n is 1, and z is 1, present in the lubricating oil composition is 0.5 mass % or more, or 0.75 mass % or more, or 0.9 mass % or more. 
     
     
         24 . The lubricating oil composition of  claim 1 , comprising or resulting from the admixing of:
 A) at least 50 mass % of one or more base oils, based upon the weight of the lubricating oil composition;   B) one or more dispersants;   C) one or more detergents; and   D) diphenyl amine antioxidant composition comprising:
 a) from 0 to less than 10 mass % mono-C 9 -alkyl substituted diphenyl amine represented by the Formula (III) where n is 1, w is 0, and z is 0, 
 b) 90 mass % or more of di(C 9 -alkyl substituted diphenyl) amines represented by Formula (III), where w is 0, n is 1, and z is 1, 
   based upon the total weight of a) and b) present in the lubricating oil composition, where Formula (III) is:   
       
         
           
           
               
               
           
         
       
       where each R a  is independently a linear C 9  alkyl or branched C 9  alkyl group, n is 1 or 0, z is 0 or 1, and w is 0 or 1;
 E) optionally, one or more antioxidants, other than the antioxidants represented by Formula (III); 
 F) optionally, one or more pour point depressants; 
 G) optionally, one or more anti-foaming agents; 
 H) optionally, one or more viscosity modifiers; 
 J) optionally, one or more inhibitors and/or antirust agents; and/or 
 K) optionally, one or more anti-wear agents; and/or 
 L) optionally, one or more friction modifiers. 
 
     
     
         25 . The lubricating oil composition of  claim 24 , where in the diphenyl amine antioxidant composition comprises:
 a) from 0 to less than 10 mass % mono-C 9 -alkyl substituted diphenyl amine represented by the Formula (III) where n is 1, w is 0, and z is 0,   b) 90 mass % or more of di(C 9 -alkyl substituted diphenyl) amines represented by Formula (III), where w is 0, n is 1, and z is 1,   c) from 0 to less than 10 mass % tri-C 9 -alkyl substituted diphenyl amines represented by Formula (III), where w is 1, n is 1, and z is 1,   d) from 0 to 1 mass % of unsubstituted diphenyl amine represented by Formula (III) where w is 0, n is 0, and z is 0,   based upon the total weight of a), b), c) and d) present in the lubricating oil composition.   
     
     
         26 . The lubricating oil composition of  claim 24 , wherein: the dispersant comprises one or more PIBSA-PAMs, the detergent comprises one or more calcium and or magnesium sulfonate detergents, the friction modifier comprises one or more polyol fatty acid esters and or one or more molybdenum compounds. 
     
     
         27 . Diphenyl amine antioxidant, for use in a lubricating oil composition or a concentrate, comprising:
 a) mono-C 9 -alkyl substituted diphenyl amines represented by the Formula (III) where n is 1, z is 0 and w is 0, that are absent or present at less than 10 mass %,   b) di-C 9 -alkyl substituted diphenyl amines represented by Formula (III), where n is 1 and z is 1, that are present at 90 mass % or more,   c) tri-C 9 -alkyl substituted diphenyl amines represented by Formula (III), where n is 1, z is 1 and w is 1, are present at 0.01 to less than 10 mass %,   based upon the total weight of the phenyl amines of a)+b)+c),   where Formula (III) is:   
       
         
           
           
               
               
           
         
       
       where each R a  is independently a linear C 9  alkyl or branched C 9  alkyl group, n is 1, z is 0 or 1, and w is 0 or 1. 
     
     
         28 . Diphenyl amine antioxidant comprising:
 a) less than 0.50 mass % of mono-C 9 -alkyl substituted diphenyl amines,   b) greater than 99.50 mass % di-C 9 -alkyl substituted diphenyl amines,   
       based upon the total weight of mono-C 9 -alkyl substituted diphenyl amines and the di-C 9 -alkyl substituted diphenyl amines. 
     
     
         29 . A concentrate composition comprising or resulting from the admixing of:
 (i) less than 50 mass % of one or more base oils, based upon the weight of the concentrate composition;   (ii) one or more dispersants;   (iii) one or more detergents; and   (iv) diphenyl amine antioxidant comprising:
 1) more than 90 mass % di-C 9 -alkyl substituted diphenyl amine and 
 2) from 0 to 10 mass % of mono-C 9 -alkyl substituted diphenyl amine, based upon the weight of the mono-C 9 -alkyl substituted diphenyl amine and di-C 9 -alkyl substituted diphenyl amine present in the concentrate. 
   
     
     
         30 . The concentrate of  claim 29 , wherein the concentrate comprises:
 1) 95 mass % or more of diphenyl amine antioxidant comprising:   a) di-C 9 -alkyl substituted diphenyl amine and b) from 0 to less than 5 mass % of mono-C 9 -alkyl substituted diphenyl amine, based upon the weight of the mono- and di-phenyl amines present in the concentrate; and   2) salicylate detergent, such as calcium salicylate.   
     
     
         31 . The concentrate of  claim 29 , wherein the concentrate comprises:
 1) 95 mass % or more of diphenyl amine antioxidant comprising:   a) di-C 9 -alkyl substituted diphenyl amine and b) from 0 to less than 5 mass % of mono-C 9 -alkyl substituted diphenyl amine, based upon the weight of the mono- and di-phenyl amines present in the concentrate; and   2) one or more of magnesium salicylate detergent, magnesium sulfonate detergent, calcium salicylate detergent, and calcium sulfonate detergent,   3) optional zinc dialkyldithiophosphate, a portion of which is derived from primary alcohol, secondary alcohol, or a combination of primary and secondary alcohol,   4) optional organic friction modifier, such as glycerol monooleate and or organomolybdenum-based friction modifier.   
     
     
         32 . The concentrate of  claim 31  wherein a portion of the zinc dialkyldithiophosphate is derived from iso-octanol and/or 4-methyl-pentan-2-ol and/or 2-butanol. 
     
     
         33 . The concentrate of  claim 29  wherein the diphenyl amine antioxidant comprises:
 1) 99 mass % or more of di-C 9 -alkyl substituted diphenyl amine and 
 2) from 0 to less than 1 mass % of mono-C 9 -alkyl substituted diphenyl amine, based upon the weight of 1) and 2) present in the concentrate composition. 
 
     
     
         34 . The concentrate of  claim 29 , further comprising:
 D) optionally, one or more friction modifiers;   E) optionally, one or more antioxidants, other than the antioxidants of (iv);   F) optionally, one or more pour point depressants;   G) optionally, one or more anti-foaming agents;   H) optionally, one or more viscosity modifiers;   J) optionally, one or more inhibitors and/or antirust agents; and/or   K) optionally, one or more anti-wear agents.   
     
     
         35 . A concentrate, comprising 0.1 to 50 mass % base oil, based the weight of concentrate, and 0.1 to 99.9 mass %, based on total weight of the concentrate, of diphenyl amine antioxidant comprising 90 mass % or more of bis(nonylphenyl)amine and 10 mass % or less of (nonylphenyl)(phenyl)amine based on the weight of the bis(nonylphenyl)amine and (nonylphenyl)(phenyl)amine. 
     
     
         36 . A method of lubricating an internal combustion engine during operation of the engine comprising:
 (i) providing to a crankcase of the internal combustion engine an automotive crankcase the lubricating oil composition  claim 1 ;   (ii) providing a hydrocarbon fuel in the internal combustion engine; and   (iii) combusting the fuel in the internal combustion engine.   
     
     
         37 . The method of  claim 36 , wherein the temperature of the oil sump of the internal combustion engine is greater than 100° C. 
     
     
         38 . A composition comprising: 1) diphenyl amine antioxidant comprising 90 mass % or more of bis(nonylphenyl)amine and 10 mass % or less of (nonylphenyl)(phenyl)amine based on the weight of the bis(nonylphenyl)amine and (nonylphenyl)(phenyl)amine, and 2) one or more of dinuclear organomolybdenum-based friction modifier, magnesium-based detergents optionally providing 400 ppm or more of Mg to the composition, and or sulfonate based detergents. 
     
     
         39 . A method to reduce one or more of: piston deposits (Sequence III), and or rod deposits (MHT4 TEOST), and or friction (such as HFRR friction coefficient at 140° C., and or MTM friction coefficient, 135° C., 0.02 m/s and or MTM-R: Traction Coefficient at 100° C.), and or wear (such as HFRR: wear scar diameter and or MTM-R: wear scar volume), and or viscometric growth (such as CEC-L109-14), in a lubricating oil composition lubricating internal combustion engine, comprising: providing the lubricating oil comprising 1) di(C 9 -alkyl substituted diphenyl) amine and 2) from 0 to less than 10 mass % of mono-C 9 -alkyl substituted diphenyl amine to the internal combustion engine (where the reduction is determined by comparison to the same lubricating oil composition except that the diphenyl amine antioxidant has been replaced with the same amount of diphenyl amine antioxidant having: 1) about 68 mass % di-C 9 -alkyl diphenyl amine, 2) about 29 mass % of mono-C 9 -alkyl diphenyl amine, and 3) about 3 mass % of tri-C 9 -alkyl diphenyl amine, based on the weight of 1), 2) and 3), as determined by UPLC, “Comparative LOC”). 
     
     
         40 . The method of  claim 39  where in the lubricating oil composition further comprises: one or more additives selected from the group consisting of:
 1) glycerol-based friction modifiers, 
 2) sulfonate-based detergents, 
 3) organomolybdenum-based friction modifiers, 
 4) magnesium-based detergents providing 400 ppm or more of Mg to the composition, 
 5) salicylate based detergents (such as Ca salicylate based detergents, such as blends of Ca salicylate based detergents and Mg salicylate based detergents), and or 
 6) zinc-based antiwear agents (such as derived ZDDP from primary alcohol). and/or 
 7) base oil comprising a combination of refined and renewable base oils and or a combination of Group III and Group II base oils. 
 
     
     
         41 . The method of  claim 39  wherein:
 1) the lubricating oil composition further comprises sulfonate based detergents (such as solely sulfonate based detergents) and has at least 5% less (such as at least 10% less, such as at least 20% less, such as at least 25% less) MHT4 TEOST: Total rod deposits (mg); and or 
 2) the lubricating oil composition further comprises: 1) salicylate based detergents (such calcium salicylate based detergents), and 2) optionally dispersant (such as PIBSA-PAM) derived from polymer having an Mn of less than 1600 g/mol); and has at least 5% less (such as at least 10% less, such as at least 20% less, such as at least 30% less, such as at least 40% less) MHT4 TEOST: total rod deposits (mg); and or 
 3) the lubricating oil composition further comprises: 1) magnesium based detergents (such magnesium sulfonate and or magnesium salicylate based detergents providing at least 600 ppm Mg to the lubricating oil composition); and has at least 5% less (such as at least 10% less, such as at least 20% less, such as at least 30% less, such as at least 40% less, such as at least 50% less, such as at least 60% less, such as at least 70% less)) MHT4 TEOST: Total rod deposits (mg); and or 
 4) the lubricating oil composition further comprises: 1) magnesium and calcium based detergents (such magnesium sulfonate and/or salicylate detergents and calcium sulfonate and/or salicylate detergents present in the lubricating oil composition at a mass % ratio of Mg:Ca of 1:2 to 2:1); and has at least 5% less (such as at least 10% less, such as at least 20% less, such as at least 30% less, such as at least 40% less, such as at least 50% less, such as at least 60% less, such as at least 70% less) MHT4 TEOST: Total rod deposits (mg). 
 
     
     
         42 . The method of  claim 39  wherein:
 1) the lubricating oil composition further comprises glycerol-based friction modifier (such as glycerol mono-oleate) and or magnesium based detergents (such magnesium sulfonate and or magnesium salicylate based detergents, optionally providing at least 600 ppm Mg to the lubricating oil composition) and has at least 5% less (such as at least 3% less) viscosity growth; and or 
 2) the lubricating oil composition further comprises dinuclear organo-molybdenum compound (such as one or more molybdenum dithiocarbamate dimers) and has at has at least 5% less (such as at least 10% less, such as at least 20% less, such as at least 30% less, such as at least 40% less, such as at least 50% less, such as at least 60% less, such as at least 70% less, such as such as at least 75% less, such as at least 77% less) viscosity growth; and or 
 3) the lubricating oil composition further comprises trinuclear organo-molybdenum compound (such as one or more molybdenum dithiocarbamate trimers) and has at has at least 5% less (such as at least 10% less, such as at least 13% less, such as at least 15% less, such as at least 17% less) viscosity growth; and or 
 4) the lubricating oil composition further comprises renewable base oil (such as refined Group II and or Group III base oil combined with Group III renewable base oil, and optionally Group IV base oil) and has at has at least 5% less (such as at least 10% less, such as at least 15% less) viscosity growth; and or 
 5) the lubricating oil composition further comprises Group II and Group III base oil, and optionally Group IV base oil and has at has at least 5% less (such as at least 10% less, such as at least 15% less, such as at least 20% less, such as at least 30% less, such as at least 33% less) viscosity growth; and or 
 6) the lubricating oil composition further comprises magnesium based detergents (such magnesium sulfonate and or magnesium salicylate based detergents providing at least 600 ppm Mg, such s at least 700 ppm, such as at least 800 ppm to the lubricating oil composition) and has at least 5% less (such as at least 10% less, such as at least 15% less, such as at least 20% less, such as at least 25% less, such as at least 30% less, such as at least 55% less, such as at least 40% less) viscosity growth; and or 
 7) the lubricating oil composition further comprises salicylate based detergents (such calcium and or magnesium salicylate based detergents) and has at least 5% less (such as at least 10% less, such as at least 14% less) viscosity growth; and or 
 8) the lubricating oil composition further comprises zero mass % glycerol based friction modifier (such as glycerol mono-oleate) and has at least 5% less (such as at least 10% less, such as at least 15% less) viscosity growth; and or 
 9) the lubricating oil composition further comprises zinc based antiwear agents derived from one or more primary alcohols (such as zinc dialkyldithiophosphates where the alkyl is derived from one or more primary alcohols) and has at least 5% less (such as at least 10% less, such as at least 15% less, such as at least 20% less) viscosity growth as compared to the same lubricating oil composition except that the Comparative LOC additionally contains the same amount of a ZDDP derived from a combination of isooctanol and 2-butanol. 
 
     
     
         43 . The method  claim 39  wherein:
 1) the lubricating oil composition further comprises dinuclear organo-molybdenum compound (such as molybdenum dithiocarbamate dimer and has at has at least 5% less (such as at least 10% less, such as at least 20% less, such as at least 30% less, such as at least 40% less, such as at least 50% less, such as at least 60% less, such as at least 65% less) wear scar volume (MTM-R), and or 
 2) the lubricating oil composition further comprises magnesium and calcium based detergents (such magnesium sulfonate and/or salicylate detergents and calcium sulfonate and/or salicylate detergents present in the lubricating oil composition at a mass % ratio of Mg:Ca of 1:2 to 2:1, providing at least 400 ppm Mg to the lubricating oil composition); and has at least 5% less (such as at least 10% less, such as at least 15% less, such as at least 19% less) avg traction coefficient at 100° C. (MTM-R); and or 
 3) the lubricating oil composition further comprises zinc based antiwear agents derived from one or more primary alcohols (such as zinc dialkyldithiophosphates where the alkyl is derived from one or more primary alcohols) and has at has at least 5% less (such as at least 9% less) avg traction coefficient at 100° C. (MTM-R), except that the Comparative LOC additionally contains the same amount of a ZDDP derived from a combination of isooctanol and 2-butanol, and or 
 4) the lubricating oil composition further comprises trinuclear organo-molybdenum compound and has at has at least 5% less (such as at least 10% less, such as at least 20% less, such as at least 30% less, such as at least 40% less, such as at least 50% less, such as at least 60% less, such as at least 65% less) wear scar volume (MTM-R); and or 
 5) the lubricating oil composition further comprises trinuclear organo-molybdenum compound and has at has at least 5% less (such as at least 10% less, such as at least 20% less, such as at least 30% less, such as at least 40% less, such as at least 50% less, such as at least 60% less, such as at least 65% less) avg traction coefficient at 100° C. (MTM-R); and or 
 6) the lubricating oil composition further comprises glycerol based friction modifier (such as glycerol mono-oleate) and has at least 5% less (such as at least 10% less, such as at least 13% less) avg traction coefficient at 100° C. (MTM-R), and or 
 7) the lubricating oil composition further comprises dinuclear organo-molybdenum compound (such as molybdenum dithiocarbamate dimer and has at has at least 5% less (such as at least 10% less, such as at least 20% less, such as at least 30% less, such as at least 40% less, such as at least 50% less, such as at least 60% less, such as at least 65% less) wear scar area (HFRR), and or 
 8) the lubricating oil composition further comprises trinuclear organo-molybdenum compound and has at has at least 5% less (such as at least 10% less, such as at least 20% less, such as at least 30% less, such as at least 40% less, such as at least 50% less, such as at least 60% less, such as at least 65% less) wear scar area (HFRR). 
 
     
     
         44 . The method  claim 39  wherein the lubricating oil composition further comprises magnesium based detergents (optionally magnesium sulfonate and or magnesium salicylate based detergents providing at least 600 ppm Mg, optionally at least 700 ppm, optionally at least 800 ppm Mg to the lubricating oil composition) and has at least 5% less (optionally at least 10% less, optionally at least 15% less, optionally at least 17% less) friction coefficient at 135° C. (MTM). 
     
     
         45 . A composition, comprising,
 a) 0.1 to 99.9 mass %, based on total weight of the composition, of diphenylamine amine antioxidant comprising 90 mass % or more of bis(nonylphenyl)amine and 10 mass % or less of (nonylphenyl)(phenyl)amine based on the weight of the bis(nonylphenyl)amine and (nonylphenyl)(phenyl)amine, and   b) 99.9 to 0.1 mass %, based on total weight of the composition, of one, two, three, four, five, six or more additives selected from the group consisting of:
 1) glycerol-based friction modifiers (optionally 0.6 mass % or less glycerol-based friction modifier, based upon the weight of the composition), 
 2) sulfonate-based detergents, 
 3) organomolybdenum-based friction modifiers, 
 4) magnesium-based detergents providing 400 ppm or more of Mg to the composition, 
 5) salicylate based detergents, and or 
 6) zinc-based antiwear agents (such as derived ZDDP from primary alcohol). and/or 
 7) base oil comprising a combination of refined and renewable base oils and or a combination of Group III and Group II base oils. 
   
     
     
         46 . A lubricating oil composition comprising,
 a) 0.1 to 99.9 mass %, based on total weight of the composition, of diphenylamine amine antioxidant comprising 90 mass % or more of bis(nonylphenyl)amine and 10 mass % or less of (nonylphenyl)(phenyl)amine based on the weight of the bis(nonylphenyl)amine and (nonylphenyl)(phenyl)amine, and   b) 99.9 to 0.1 mass %, based on total weight of the composition, of one, two, three, four, five, six or more additives selected from the group consisting of:
 1) glycerol-based friction modifiers, 
 2) sulfonate-based detergents, 
 3) organomolybdenum-based friction modifiers, 
 4) magnesium-based detergents providing 400 ppm or more of Mg to the composition, 
 5) salicylate based detergents, and or 
 6) zinc-based antiwear agents (such as derived ZDDP from primary alcohol); and 
   c) from 50 mass % or more of base oil, optionally comprising a combination of refined and renewable base oils and or a combination of Group III and Group II base oils and or a combination of Group IV base oil, refined base oil and renewable base oil, and or a combination of Group IV base oil, Group III base oil and Group II base oil.   
     
     
         47 . The lubricating oil composition of  claim 46 , wherein the viscometric growth (CEC-L-109-14, 216 hr., 150° C.) of the lubricating oil composition is at least 5% (preferably at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 75%, at least 80%) lower relative to a lubricating oil composition of the same formulation except that the diphenylamine amine antioxidant is replaced at the same mass percentage by nonylphenyl amine antioxidant comprising about 68 mass % of bis(nonylphenyl)amine, about 29 mass % of (nonylphenyl)(phenyl)amine and about 3 mass % of tri(nonylphenyl)amine based upon the weight of the mono-(nonylphenyl)amine, bis(nonylphenyl)amine, and tri(nonylphenyl)amine, as determined by UPLC. 
     
     
         48 . A method of reducing friction in a crankcase of an internal combustion engine comprising providing to the crankcase a lubricating oil composition comprising,
 a) 0.5 to 15 mass %, based on total weight of the lubricating oil composition, of a diphenylamine amine antioxidant comprising, based on the weight of the aminic antioxidant, wherein the diphenylamine amine antioxidant comprises,
 i) 90 mass % or more of bis(nonylphenyl) amine, 
 ii) from 0 to less than 10 mass % of mono(nonylphenyl) amine, based upon the mass of the (nonylphenyl)(phenyl)amine and bis(nonylphenyl)amine present in the lubricating oil composition, and 
   b) 0.01 to 30 mass %, based on total weight of the lubricating oil composition, of one or more additives selected from the group consisting of glycerol-based friction modifiers, sulfonate-based detergents, organomolybdenum-based friction modifier, calcium/magnesium-based detergents, zinc-based antiwear agents, and combinations thereof, and variants thereof,   wherein the amount of any one additive can be synergistically increased in the presence of the diphenylamine amine antioxidant to maintaining or decrease the friction (CEC-L-109-14, 216 hr., 150° C.) relative to the friction in the presence of a diphenylamine amine antioxidant comprising a baseline antioxidant of nonylphenyl amine antioxidant comprising about 68 mass % of bis(nonylphenyl)amine, about 29 mass % of (nonylphenyl)(phenyl)amine and about 3 mass % of tri(nonylphenyl)amine, based upon the weight of the (nonylphenyl)(phenyl)amine, bis(nonylphenyl)amine, and tri(nonylphenyl)amine, as determined by UPLC.   
     
     
         49 . A method to lubricate an internal combustion engine comprising introducing a lubricating oil composition comprising base oil and a composition comprising the composition of  claim 38  into an internal combustion engine, wherein the (CEC L-109-14) viscosity growth of the lubricating oil composition is at least 5% less (such as at least 10% less, such as at least 20% less, such as at least 30% less, such as at least 40% less, such as at least 50% less, such as at least 60% less, such as at least 70% less, such as such as at least 75% less, such as at least 77% less) than the (CEC L-109-14) viscosity growth of a comparative lubricating oil composition having the same lubricating oil composition except that the diphenyl amine antioxidant has been replaced with the same amount of diphenyl amine antioxidant having: 1) about 68 mass % di-C 9 -alkyl diphenyl amine, 2) about 29 mass % of mono-C 9 -alkyl diphenyl amine, and 3) about 3 mass % of tri-C 9 -alkyl diphenyl amine, based on the weight of 1), 2) and 3), as determined by UPLC). 
     
     
         50 . The composition of  claim 46  wherein the di-C 9 -alkyl substituted diphenyl amine comprises less than 5 mass % of the isomers shown below, where each R is independently a linear C 9  alkyl or branched C 9  alkyl group: 
       
         
           
           
               
               
           
         
       
       based upon the weight of di-C 9 -alkyl substituted diphenyl amine. 
     
     
         51 . The composition of  claim 45  wherein two or more lubricating oil compositions each comprising: a) diphenylamine amine antioxidant comprising 90 mass % or more of bis(nonylphenyl)amine and 10 mass % or less of (nonylphenyl)(phenyl)amine based on the weight of the bis(nonylphenyl)amine and (nonylphenyl)(phenyl)amine, and b) at least one different component selected from the group consisting of:
 1) glycerol-based friction modifiers, (optionally 0.6 mass % or less glycerol-based friction modifier, based upon the weight of the composition) 
 2) sulfonate-based detergents, 
 3) organomolybdenum-based friction modifiers, 
 4) magnesium-based detergents, optionally providing 400 ppm or more of Mg to the composition, 
 5) salicylate based detergents (optionally calcium salicylate based detergents, such as combinations of calcium and magnesium based detergents), 
 6) zinc dialkyldithiphosphates derived from primary alcohol(s), 
 7) dispersants (such as PIBSA-PAM) derived from a polymer (such as polyisobutylene) having an Mn of less than 1600 g/mol, 
 8) calcium based detergents, 
 
       where: i) the viscometric growth (CEC-L-109-14, 216 hr., 150° C.) for each of two or more lubricating oil compositions is at least 5% (optionally at least 10%, at least 15%, at least 20%, at least 25%, at least 30% at least 35%, at least 40%, at least 55%, at least 60%, such as at least 70%, such as at least 75%, such as at least 77%) less than the viscometric growth of their respective reference formulations, and ii) where the reference lubricating oil composition for a formulation is the same as that formulation as the except that the diphenylamine antioxidant is replaced at the same mass percentage by diphenylamine antioxidant comprising about 68 mass % of bis(nonylphenyl)amine, about 29 mass % of (nonylphenyl)(phenyl)amine and about 3 mass % of tri(nonylphenyl)amine, based upon the weight of the (nonylphenyl)(phenyl)amine, bis(nonylphenyl)amine, and tri(nonylphenyl)amine, as determined by UPLC. 
     
     
         52 . The composition of  claim 51 , wherein the a) diphenylamine amine antioxidant comprises 95 mass % or more of bis(nonylphenyl)amine and 5 mass % or less of (nonylphenyl)(phenyl)amine based on the weight of the bis(nonylphenyl)amine and (nonylphenyl)(phenyl)amine. 
     
     
         53 . A method of using diphenylamine amine antioxidant to reduce wear scar volume μm 3  (MTM-R) and or wear scar area (HFRR) of the lubricating oil composition of  claim 46 , wherein organomolybdenum-based friction modifier comprises trinuclear organo-molybdenum compound (optionally as molybdenum dithiocarbamate trimer providing at least 100 ppm, such as at least 200 ppm Mo to the lubricating oil composition) and has: 1) at least 5% less (such as at least 10% less, such as at least 15% less, such as at least 20% less) wear scar volume μm 3  and or 2) at least 5% less (such as at least 10% less, such as at least 20% less, such as at least 30% less, such as at least 40% less, such as at least 50% less, such as at least 60% less, such as at least 65% less) wear scar area μm 3 , where the reduction is determined by comparison to the same lubricating oil composition except that the trinuclear organo-molybdenum compound has been replaced by dinuclear organo-molybdenum compound providing the same amount of molybdenum to the lubricating oil composition.