US20190127656A1 - Lubricant compositions comprising polymeric diphenylamine antioxidants

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Abstract

Description

Claims

US20190127656A1

Publication number: US20190127656A1
Application number: US16/175,305
Authority: US
Inventors: Liehpao Oscar Farng; Graciela Sanchez Jimenez; Mary DERY; Paul Odorisio; Bridgett RAKESTRAW; Sai Shum; David Khoshabo; Michael L. Alessi; Rebecca Cristine Vieira; Andrew Edmund Taggi
Original assignee: Exxonmobil Research And Engineering Company
Current assignee: ExxonMobil Technology and Engineering Co
Priority date: 2017-10-31
Filing date: 2018-10-30
Publication date: 2019-05-02
Also published as: WO2019089723A1

Disclosed in certain embodiments is a lubricating oil composition comprising an antioxidant polymer (e.g., oligomer) composition comprising repeat units of diphenylamine monomers of formula I

wherein
R is H, C₁-C₁₈alkyl, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, —C(O)C₁-C₁₈alkyl, —C(O)aryl and R₁, R₂, R₃and R₄are each independently H or a linear or branched C₁-C₁₈alkyl, C₁-C₁₈alkoxy, C₁-C₁₈alkylamino, C₁-C₁₈dialkylamino, C₁-C₁₈alkylthio, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl or C₇-C₂₁aralkyl and
wherein
the number average molecular weight (Mn) of the polymer composition is from about 350 g/mol to about 5000 g/mol.

RELATED APPLICATION

This application claims priority to U.S. Provisional Patent Application No. 62/579,643, filed on Oct. 31, 2017, which is herein incorporated by reference in its entirety.

FIELD

This disclosure relates to engine lubricating oils with viscosity control and deposit control. In particular, this disclosure relates to lubricating oils, methods for improving viscosity control and deposit control of a lubricating oil in an engine or other mechanical component lubricated with the lubricating oil, and methods for improving oxidative stability and deposit control, of a lubricating oil in an engine or other mechanical component lubricated with the lubricating oil. The lubricating oils of this disclosure may be useful as passenger vehicle engine oil (PVEO) products or commercial vehicle engine oil (CVEO) products as well as industrial, aviation and marine lubricants and greases.

BACKGROUND

Lubricant oxidative stability is one of the key parameters controlling oil life, which translates to oil drain interval in practical terms. Additionally, deposit formation is an issue associated with the decomposition of the base stock molecules mostly propagated by oxidative chain reactions. There are several conventional approaches to improve the resistance to oxidation of a finished lubricant product, but most products are formulated using small molecules such as diphenylamine (DPA) or a phenolic antioxidant.
Improved oxidation stability is necessary to increase oil life and oil drain intervals, thus reducing the amount of used oil generated as a consequence of more frequent oil changes. Longer oil life and oil drain intervals are key benefits that are desirable to end customers. Traditional antioxidant packages provide standard protection leaving the main differentiation hinging on the quality of the base stock in the formulation.
What is needed are newly designed lubricants capable of controlling oxidation and oil thickening for longer periods of time as compared to conventional lubricants. Further, what are needed are newly designed lubricants that enable extended oil life in combination with desired deposit control and cleanliness performance.

SUMMARY

In certain embodiments, the present disclosure is directed to a lubricating oil composition comprising a base oil and an antioxidant polymer (e.g., oligomer) composition comprising repeat units of diphenylamine monomers of formula I
wherein

R is H, C₁-C₁₈alkyl, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, —C(O)C₁-C₁₈alkyl, —C(O)aryl and R₁, R₂, R₃and R₄are each independently H or a linear or branched C₁-C₁₈alkyl, C₁-C₁₈alkoxy, C₁-C₁₈alkylamino, C₁-C₁₈dialkylamino, C₁-C₁₈alkylthio, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl or C₇-C₂₁aralkyl. In certain embodiments, the number average molecular weight (Mn) of the antioxidant polymer (e.g., oligomer) composition is at least about 350 g/mol or from about 350 g/mol to about 5000 g/mol.

Also disclosed in certain embodiments is a lubricating oil composition comprising an antioxidant polymer (e.g., oligomer) composition comprising≤about 99 wt %, ≤about 90 wt %, ≤about 80 wt %, ≤about 70 wt %, ≤about 65 wt %, ≤about 60 wt %, ≤about 55 wt %, ≤about 50 wt %, ≤about 45 wt %, ≤about 40 wt %, ≤about 35 wt %, ≤about 30 wt %, <about 25 wt %, ≤about 20 wt %, ≤about 15 wt %, ≤about 10 wt %, ≤about 5 wt %, ≤about 1 wt %, ≤about 0.5 wt %, ≤about 0.1 wt %, ≤about 0.05 wt % or ≤about 0.01 wt % residual monomers of formula I. For example, in certain embodiments, disclosed is an antioxidant polymer (e.g., oligomer) composition comprising repeat units of diphenylamine monomers of formula I, wherein the composition comprises from any one of about 0.01 wt %, about 0.05 wt %, about 0.1 wt %, about 0.5 wt %, about 1 wt %, about 2 wt % , about 3 wt %, about 4 wt %, about 5 wt %, about 7 wt %, about 9 wt %, ab about 70 wt %out 11 wt % or about 13 wt % to any one of about 15 wt %, about 18 wt %, about 21 wt %, about 24 wt %, about 27 about 70 wt % wt %, about 30 wt %, about 35 wt %, about 40 wt %, about 45 wt %, about 50 wt %, about 55 wt %, about 60 wt %, about 65 wt %, about 70 wt %, about 80 wt % or about 99 wt % residual monomers of formula I, based on the total weight of the antioxidant composition.
In certain embodiments wherein the polymer (e.g., oligomer) composition comprises residual monomers, about 90 wt %, about 91 wt %, about 92 wt %, about 93 wt %, about 94 wt % or about 95 wt % to about 96 wt %, about 97 wt %, about 98 wt %, about 99 wt % or 100 wt % of the residual monomer(s) is of formula I wherein one or both of R₁and R₄are independently C₄-C₁₈alkyl, C₄-C₁₈alkenyl or C₇-C₂₁aralkyl, based on the total weight of residual monomer(s).
In certain other embodiments, the disclosure is directed to a method of extending an oil drain interval of an engine (e.g., by preventing oxidation of base stock and additives), the method comprising adding to the engine the lubricating oil composition as disclosed herein.
Also disclosed in certain embodiments is a process of manufacturing a lubricating oil composition protected against the deleterious effects of heat and oxygen, comprising adding an antioxidant polymer (e.g., oligomer) composition comprising repeat units of diphenylamine monomers of formula I (with or without residual monomer(s)) to a base oil.
Also disclosed are lubricating grease composition comprising a base oil and an antioxidant polymer (e.g., oligomer) composition comprising repeat units of diphenylamine monomers of formula I. The grease composition can be used in many industrial and consumer applications such as lubricating a bearing such as a rolling element bearing, e g. a spherical roller bearing, a taper roller bearing, a cylindrical roller bearing, a needle roller bearing, a ball bearing, and may also be used to lubricate a sliding or plain bearing. The grease composition can also be used in coupling and gearing applications.

DETAILED DESCRIPTION

In certain embodiments, the present disclosure is directed to a lubricating oil composition comprising a base oil and an antioxidant polymer (e.g., oligomer) composition comprising repeat units of diphenylamine monomers of formula I
wherein R is H, C₁-C₁₈alkyl, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, —C(O)C₁-C₁₈alkyl, —C(O)aryl; and R₁, R₂, R₃and R₄are each independently H or a linear or branched C₁-C₁₈alkyl, C₁-C₁₈alkoxy, C₁-C₁₈alkylamino, C₁-C₁₈dialkylamino, C₁-C₁₈alkylthio, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl or C₇-C₂₁aralkyl. In certain embodiments, the number average molecular weight (Mn) of the antioxidant polymer (e.g., oligomer) composition is at least about 350 g/mol or from about 350 g/mol to about 5000 g/mol.
In other embodiments, the antioxidant polymer (e.g., oligomer) compositions of the disclosure have an Mn of from about 900 g/mol or about 1000 g/mol to about 1200 g/mol or an Mn of any one of from about 400 g/mol, about 430 g/mol, about 460 g/mol, about 490 g/mol, about 520 g/mol, about 550 g/mol, about 580 g/mol, about 610 g/mol, about 640 g/mol, about 670 g/mol, about 700 g/mol or about 730 g/mol g/mol to any one of about 760 g/mol, about 790 g/mol, about 820 g/mol, about 850 g/mol, about 880 g/mol, about 910 g/mol, about 940 g/mol, about 970 g/mol, about 1000 g/mol, about 1030 g/mol, about 1060 g/mol, about 1090 g/mol, about 1120 g/mol, about 1150 g/mol, about 1180 g/mol, about 1210 g/mol, about 1240 g/mol, about 1270 g/mol, about 1300 g/mol, about 1400 g/mol, about 1500 g/mol, about 1600 g/mol, about 1700 g/mol, about 2000 g/mol, about 2100 g/mol, about 2200 g/mol, about 2300 g/mol, about 2400 g/mol, about 2500 g/mol, about 3000 g/mol, about 3500 g/mol, about 4000 g/mol or about 5000 g/mol.
The number average molecular weight can be determined, for example, by gel permeation chromatography (GPC) techniques with a polystyrene standard. GPC conditions may include testing relative to a set of polystyrene standards (EasiCal PS-1, low and high and PS162). Samples are prepared in tetrahydrofuran (THF) and duplicate injections of solutions are run. Similar conditions may also be employed.
In certain embodiments, less than about 25 percent by weight of the antioxidant composition contains molecules having a molecular weight of less than about 1000 g/mol.
In certain embodiments, the present disclosure is directed to a lubricating oil composition comprising a base oil and an antioxidant polymer (e.g., oligomer) composition comprising repeat units of diphenylamine monomers of formula II
wherein R and R′ are each independently H or a linear or branched C₁-C₁₈alkyl, C₂-C₁₈alkenyl or C₇-C₂₁aralkyl. In certain embodiments, R and R′ are each independently H, tert-butyl or tert-octyl.
Linear or branched alkyl includes methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, tert-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl. Alkyl groups mentioned herein are linear or branched.
The alkyl portion of alkoxy, alkylamine, dialkylamino and alkylthio groups are linear or branched and include the alkyl groups mentioned above.
Alkenyl is an unsaturated alkyl, for instance allyl. Alkynyl includes a triple bond.
Aralkyl includes benzyl, a-methylbenzyl, a,a-dimethylbenzyl and 2-phenylethyl.
Diphenylamine antioxidants are commercially available, for example under the trade names IRGANOX L57, IRGANOX L67 and IRGANOX L01.
In certain embodiments, the antioxidant polymer (e.g., oligomer) compositions of the disclosure can be prepared by a process comprising subjecting diphenylamine monomers of formula I
wherein R is H, C₁-C₁₈alkyl, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, —C(O)C₁-C₁₈alkyl, —C(O)aryl; and R₁, R₂, R₃and R₄are each independently H or a linear or branched C₁-C₁₈alkyl, C₁-C₁₈alkoxy, C₁-C₁₈alkylamino, C₁-C₁₈dialkylamino, C₁-C₁₈alkylthio, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl or C₇-C₂₁aralkyl to dehydrocondensation conditions.
Dehydrocondensation conditions comprise exposing monomers of formula Ito oxidative conditions, for example, by exposure to a compound capable of forming free radicals. Compounds capable of forming free radicals include inorganic and organic peroxides, such as di-t-butylperoxide and di-t-amylperoxide. The dehydrocondensation reaction may be performed neat, that is, without added solvent, or may be performed in the presence of a solvent. Suitable solvents include alkanes such as hexane, heptane, octane, nonane, decane, undecane or dodecane. Dehydrocondensation may be performed in the presence of a base stock (e.g., ester, mineral, synthetic, GTL or alkyl naphthalene base stocks).
In some embodiments, the dehydrocondensation conditions comprise reaction temperatures of any one of from about 40° C., about 60° C., about 80° C., about 100° C., about 120° C., about 140° C. or about 160° C. to any one of about 180° C., about 200° C., about 220° C., about 240° C. or about 250° C.
In certain embodiments, the dehydrocondensation conditions comprise a reaction time of any one of from about 0.3 hours, about 0.5 hour, about 1 hour, about 2 hours, about 3 hours, about 4 hours, about 5 hours or about 6 hours to any one of about 7 hours, about 8 hours, about 9 hours, about 10 hours, about 11 hours or about 12 hours. In other embodiments, the dehydrocondensation conditions may comprise a reaction time of from any one of about 12 hours, about 24 hours, about 36 hours, about 48 hours or about 60 hours to any one of about 72 hours, about 84 hours, about 96 hours, about 108 hours or about 120 hours.
The oxidative conditions remove hydrogen from the monomers, which subsequently couple through C—N, C—C or N—N bonds. When an alkane solvent is used, the solvent appears to be inert and to not be involved in the reaction. Therefore, the produced polymer (e.g., oligomer) may contain no alkane solvent fragments.
The term “oligomer comprising repeat units of diphenylamine monomers” means the oligomers contain “reacted in” monomers, that is, radicals of monomers.
In certain embodiments, the lubricating oil compositions of the present disclosure provide for an improvement in at least one of viscosity control and deposits prevention as compared to a lubricating oil composition that does not contain the oligomer compositions of the present disclosure.
Viscosity control and deposit prevention may be determined by industry standard tests, for instance a TEOST MHT 4 test (ASTM D7097) bench test or Sequence IITH Test (ASTM D8111) engine test. Tests may be modified to increase the severity, for example by increasing temperature and/or time of a test.
In some embodiments, the lubricating oil compositions of the present disclosure exhibits color according to ASTM D1500 of any one of about 3.5, about 4.0, about 4.5, about 5.0, about 5.5 or about 6.0. In certain embodiments, the lubricating oil compositions exhibit color according to ASTM D1500 of <6.0. In certain embodiments, the lubricating oil compositions of the present disclosure exhibit a lower color according to ASTM D1500 relative to compositions containing other polymeric aminic antioxidants, for example relative to compositions containing polymeric phenylnaphthylamine antioxidants.
The antioxidant polymer (e.g., oligomer) compositions of the present disclosure may contain a mixture of different chain lengths. For example, the composition may contain residual unreacted monomer as well as fragments or chains having molecular weights above or below the ranges mentioned above. Residual monomer means unreacted monomer. The polymer (e.g., oligomer) may be purified, for example by a step comprising chromatography or distillation. In one embodiment, the produced polymer (e.g., oligomer) composition may be subject to reduced pressure to remove residual monomer.
Accordingly, the polymer (e.g., oligomer) composition of the present disclosure may contain ≤about 99 wt %, ≤about 90 wt %, ≤about 80 wt %, ≤about 70 wt %, ≤about 65 wt %, ≤about 60 wt %, ≤about 55 wt %, ≤about 50 wt %, ≤about 45 wt %, ≤about 40 wt %, ≤about 35 wt %, ≤about 30 wt %, ≤about 25 wt %, ≤about 20 wt %, ≤about 15 wt %, ≤about 10 wt % ≤about 5 wt %, ≤about 1 wt %, ≤about 0.5 wt %, ≤about 0.1 wt %, ≤about 0.05 wt % or ≤about 0.01 wt % residual monomers of formula I, based on the weight of the composition. For example, in certain embodiments, disclosed is a polymer (e.g., oligomer) composition comprising repeat units of diphenylamine monomers of formula I, wherein the composition comprises from any one of about 0.01 wt %, about 0.05 wt %, about 0.1 wt %, about 0.5 wt %, about 1 wt %, about 2 wt % , about 3 wt %, about 4 wt %, about 5 wt %, about 7 wt %, about 9 wt %, about 11 wt % or about 13 wt % to any one of about 15 wt %, about 18 wt %, about 21 wt %, about 24 wt %, about 27 wt %, about 30 wt %, about 35 wt %, about 40 wt %, about 45 wt %, about 50 wt %, about 55 wt %, about 60 wt %, about 65 wt % about 70 wt %, about 80 wt % or about 99 wt % residual monomers of formula I, based on the total weight of the antioxidant composition.
In certain embodiments, the purification steps to remove residual monomers include subjecting the polymer (e.g., oligomer) composition to reduced pressure. In certain embodiments, the remaining monomer in the composition will include higher molecular weight monomers, e.g., di- or tri-alkyl substituted monomers. In some embodiments, wherein the polymer (e.g., oligomer) composition contains residual monomer, any one of from about 90 wt %, about 91 wt %, about 92 wt %, about 93 wt %, about 94 wt % or about 95 wt % to any one of about 96 wt %, about 97, about 98, about 99 or 100 wt % of the residual monomer is of formula I wherein R₁and R₄are independently C₄-C₁₈alkyl, C₄-C₁₈alkenyl or C₇-C₂₁aralkyl, based on the total weight of residual monomer.
In certain embodiments, the polymer (e.g., oligomer) composition may also be characterized by its viscosity. For example, the present polymer (e.g., oligomer) compositions of the disclosure may have a kinematic viscosity at 100° C. of from any one of about 10 cSt to about 2,500 cSt. In other embodiments, the kinematic viscosity at 100° C. may be from any one of about 10 cSt, about 20 cSt, about 30 cSt, about 40 cSt, about 50 cSt, about 60 cSt, about 70 cSt, about 80 cSt, about 81 cSt, about 82 cSt, about 83 cSt, about 84 cSt, about 85 cSt, about 86 cSt, about 87 cSt, about 88 cSt, about 89 cSt, about 90 cSt, about 91 cSt, about 92 cSt, about 93 cSt, about 94 cSt, about 95 cSt, about 96 cSt, about 97 cSt, about 98 cSt or about 99 cSt to any one of about 100 cSt, about 101 cSt, about 102 cSt, about 103 cSt, about 104 cSt, about 105 cSt, about 106 cSt, about 107 cSt, about 108 cSt, about 109 cSt, about 110 cSt, about 111 cSt, about 112 cSt, about 113 cSt, about 114 cSt, about 115 cSt, about 116 cSt, about 117 cSt, about 118 cSt, about 119 cSt , about 120 cSt, about 500 cSt, about 1,000 cSt, about 1,500 cSt, about 2,000 cSt or about 2,500 cSt.
In certain other embodiments of the disclosure, the antioxidant polymer (e.g., oligomer) compositions may have a kinematic viscosity 100° C. of from any one of about 120 cSt, about 140 cSt, about 170 cSt, about 190 cSt, about 210 cSt, about 230 cSt, about 260 cSt, about 310 cSt or about 360 cSt to any one of about 400 cSt, about 420 cSt, about 450 cSt, about 470 cSt, about 500 cSt, about 530 cSt, about 570 cSt or about 600 cSt. In certain other embodiments, the polymer (e.g., oligomer) compositions may be solids.
Viscosity may be determined according to ASTM D445 or equivalent or similar methods measured at 100° C.
In certain embodiments, further monomers may be included in the polymerization reaction. For example, present polymer (e.g., oligomer)s may contain one or more monomers selected from the group consisting of other diphenylamines, phenothiazines, phenoxazines, aminodiphenylamines, methylenedianiline, toluenediamine, aminophenols, alkylphenols, thiophenols, phenylenediamines, quinolines, phenyl pyridinediamines, pyridinepyrimidinediamines, naphthylphenylamines and phenylpyrimidinediamines.
In some embodiments, present polymer (e.g., oligomer) compositions comprise any one of from about 1 mol %, 10 mol %, about 20 mol %, about 30 mol %, about 40 mol % or about 50 mol % to any one of about 60 mol %, about 70 mol %, about 80 mol %, about 90 mol %, about 95 mol %, about 96 mol %, about 97 mol %, about 98 mol %, about 99 mol % or 100 mol % diphenylamine monomers of formula I.
In certain embodiments, the polymeric compositions disclosed herein are oligomeric compositions (i.e., dimers, trimers and tetramers).
In certain embodiments, the polymeric compositions disclosed herein comprise one or more of dimers, trimers, tetramers or higher repeating units (i.e. a polymer of 5 or more monomers).
In certain embodiments, the polymeric compositions have an amount of dimers that are greater than the amount of higher repeating units.
In certain embodiments, the polymeric compositions have an amount of trimers that are greater than the amount of higher repeating units.
In certain embodiments, the polymeric compositions have a combined amount of dimers and trimers that are greater than the amount of higher repeating units.
In certain embodiments, the polymeric compositions have at least 75% Mn of greater than 1000. In other embodiments, the polymeric compositions have about 20% to about 80%, about 25% to about 75%, about 30% to about 70% or about 40% to about 60% Mn of greater than 1000.
In certain embodiments, the polymeric compositions have at least 75% Mn of less than 1000. In other embodiments, the polymeric compositions have about 10% to about 100%, about 20% to about 80%, about 25% to about 75%, about 30% to about 70% or about 40% to about 60% Mn of less than 1000.
In certain embodiments, the polymeric compositions have an amount of dimers of from any one of about 5%, about 10%, about 15%, about 20%, about 25% or about 30% to any one of about 40%, about 45%, about 50%, about 55%, about 60%, about 70%, about 80%, about 90% or about 100%. In certain embodiments, the dimers have a number average molecular weight (Mn) of about 300 to about 850.
In certain embodiments, the polymeric compositions have an amount of trimers of from any one of about 10%, about 15%, about 20%, about 25%, about 30% or about 40% to any one of about 50%, about 55%, about 60%, about 65%, about 70%, about 80%, about 90% or about 100%. In certain embodiments, the trimers have a number average molecular weight (Mn) of about 400 to about 1200.
In certain embodiments, the polymeric compositions have an amount of tetramers of from any one of about 15%, about 20%, about 25%, about 30%, about 40% or about 50% to any one of about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 90% or about 100%. In certain embodiments, the tetramers have a number average molecular weight (Mn) of about 500 to about 1500.
In certain embodiments, the polymeric compositions have an amount of higher repeating units of from any one of about 5%, about 10%, about 25%, about 30%, about 40% to any one of about 50%, about 60%, about 70%, about 80%, about 90% or about 100%. In certain embodiments, the higher repeating units have a number average molecular weight (Mn) of greater than about 1000 or greater than about 1174.
In certain embodiments polymeric composition have m/z ions ranging from 300 to 1000. In certain embodiments, the above m/z ions include 838 Daltons, 894 Daltons or 911 Daltons.
In certain embodiments, the polymeric compositions have an m/z ion count from about 300 to about 1,000 of greater than about 50, greater than about 75, greater than about 100, greater than about 150, greater than about 200, greater than about 250, greater than about 300 or greater than about 350. In certain embodiments, the polymeric compositions have an m/z ion count from about 800 to about 1,000 of from any one of about 50, about 75, about 100 or about 150 to any one of about 200, about 250, about 300 or about 350.
In certain embodiments, the polymeric compositions exhibit a VIT(h) of greater than about 600, greater than about 650, greater than about 700, or greater than about 850. In certain embodiments, the polymeric compositions exhibit a VIT(h) of from any one of about 600, about 650, or about 700 to any one of about 900, about 1,200 or about 1,500. A comparator monomer composition provides a VIT(h) of 472. The VIT test is performed by placing a sample of formulated oil in a glass tube with a homogeneous catalyst consisting of iron, copper and lead. Air is bubbled through the sample at a rate of 8L/h and heated to 150 ° C. The kinematic viscosity (KV40) is monitored throughout the test, and the data fit to a power curve to calculate the time, in hours, it takes for the sample to reach 150% of its original KV40.
In certain embodiments, disclosed is a grease formulation that provides a value of greater than 100, greater than 110 or greater than 120 when tested according to DIN 51821 FAG FE9 AFAG FE9 A/1500/6000 @140 C (B50, hours) when the grease formulation comprises 1% of the disclosed polymer composition.
In certain embodiments, disclosed is an industrial oil formulation that provides a value of greater than 2000, greater than 2025 or greater than 2050 when tested according to ASTM D2272-RPVOT at 150 C (min) when the industrial oil formulation comprises 1% of the disclosed polymer composition.
In certain embodiments, disclosed is an industrial oil formulation that provides a value of greater than 2100, greater than 2200 or greater than 2500 when tested according to ASTM D2272-RPVOT at 150C (min) when the industrial oil formulation comprises 0.7% of the disclosed polymer composition.
In certain embodiments, disclosed is an industrial oil formulation that provides a value of greater than 225, greater than 230 or greater than 235 when tested according to High Pressure Differential Scanning calorimetry (min) when the industrial oil formulation comprises 1% of the disclosed polymer composition.
In certain embodiments, disclosed is an industrial oil formulation that provides a value of greater than 50, greater than 65 or greater than 80 when tested according to High Pressure Differential Scanning calorimetry (min) when the industrial oil formulation comprises 0.7% of the disclosed polymer composition.
In certain embodiments, disclosed is a passenger vehicle lubricant formulation that provides a value of less than 52, less than 46 or less than 40 when tested according to ASTM D7097-TEOST MHT4 (Total deposits, mg) when the passenger vehicle lubricant formulation comprises 2% of the disclosed polymer composition.
In certain embodiments, disclosed is a passenger vehicle lubricant formulation that provides a value of less than 35, less than 34 or less than 32 when tested according to ASTM D6335-TEOST 33 C (Total deposits, mg) when the passenger vehicle lubricant formulation comprises 2% of the disclosed polymer composition.
In certain embodiments, disclosed is a passenger vehicle lubricant formulation that provides a value of less than 400, less than 300, less than 200, less than 150 or less than 75 when tested according to ASTM D8111-Sequence IIIH, EOT % Viscosity increase when the passenger vehicle lubricant formulation comprises 2% of the disclosed polymer composition.
In certain embodiments, disclosed is a passenger vehicle lubricant formulation that provides a value of greater than 4.8, greater than 4.9, greater than 5.0 or greater than 5.1 when tested according to ASTM D8111-Sequence IIIH, Weighted Piston Deposit Merits when the passenger vehicle lubricant formulation comprises 2% of the disclosed polymer composition.
In certain embodiments, disclosed is a passenger vehicle lubricant formulation that provides a value of greater than 9.7, greater than 9.75 or greater than 9.8 when tested according to ASTM D8111-Sequence IIIH, Average Piston Varnish Merits when the passenger vehicle lubricant formulation comprises 2% of the disclosed polymer composition.
In certain embodiments, disclosed is a commercial vehicle lubricant formulation that provides a value of less than 145, less than 135 or less than 125 when tested according to ASTM D8048-Volvo T-13, IR Peak Increase when the commercial vehicle lubricant formulation comprises 1.4% of the disclosed polymer composition.
The lubricating oil formulations of the present disclosure include but are not limited to greases, gear oils, hydraulic oils, brake fluids, manual and automatic transmission fluids, other energy transferring fluids, tractor fluids, diesel compression ignition engine oils, gasoline spark ignition engine oils, turbine oils and the like. The lubricating base oil may be selected from the group consisting of natural oils, petroleum-derived mineral oils, synthetic oils and mixtures thereof. The lubricant to include in the disclosed formulations may be referred to as a “base fluid”, “base oil”, “lubricating oil” or “lubricant”.
A wide range of lubricating base oils is known in the art. Lubricating base oils that may be useful in the present disclosure are both natural oils, and synthetic oils, and unconventional oils (or mixtures thereof) can be used unrefined, refined, or rerefined (the latter is also known as reclaimed or reprocessed oil). Unrefined oils are those obtained directly from a natural or synthetic source and used without added purification. These include shale oil obtained directly from retorting operations, petroleum oil obtained directly from primary distillation, and ester oil obtained directly from an esterification process. Refined oils are similar to the oils discussed for unrefined oils except refined oils are subjected to one or more purification steps to improve at least one lubricating oil property. One skilled in the art is familiar with many purification processes. These processes include solvent extraction, secondary distillation, acid extraction, base extraction, filtration, and percolation. Rerefined oils are obtained by processes analogous to refined oils but using an oil that has been previously used as a feed stock.
Groups I, II, III, IV and V are broad base oil stock categories developed and defined by the American Petroleum Institute (API Publication 1509; www.API.org to create guidelines for lubricant base oils. Group I base stocks have a viscosity index of from 80 to 120 and contain greater than 0.03% sulfur and/or less than 90% saturates. Group II base stocks have a viscosity index of from 80 to 120, and contain less than or equal to 0.03% sulfur and greater than or equal to 90% saturates. Group III stocks have a viscosity index greater than 120 and contain less than or equal to 0.03% sulfur and greater than 90% saturates. Group IV includes polyalphaolefins (PAO). Group V base stock includes base stocks not included in Groups I-IV. The table below summarizes properties of each of these five groups.


saturates	sulfur	viscosity index

Group I	<90 and/or	>0.03% and	≥80 and <120
Group II	≥90 and	≤0.03% and	≥80 and <120
Group III	≥90 and	≤0.03% and	≥120

	Group IV	---- polyalphaolefins (PAO) ----
	Group V	--- all other base stocks not of Groups I-IV ----

Natural oils include animal oils, vegetable oils (castor oil and lard oil, for example), and mineral oils. Animal and vegetable oils possessing favorable thermal oxidative stability can be used. Of the natural oils, mineral oils are preferred. Mineral oils vary widely as to their crude source, for example, as to whether they are paraffinic, naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal or shale are also useful. Natural oils vary also as to the method used for their production and purification, for example, their distillation range and whether they are straight run or cracked, hydrorefined, or solvent extracted.
Group II and/or Group III hydroprocessed or hydrocracked base stocks, including synthetic oils such as polyalphaolefins, alkyl aromatics and synthetic esters are also well known base stock oils.
Synthetic oils include hydrocarbon oil. Hydrocarbon oils include oils such as polymerized and interpolymerized olefins (polybutylenes, polypropylenes, propylene isobutylene copolymers, ethylene-olefin copolymers, and ethylene-alphaolefin copolymers, for example). Polyalphaolefin (PAO) oil base stocks are commonly used synthetic hydrocarbon oil. By way of example, PAOs derived from C₆, C₈, C₁₀, C₁₂, C₁₄olefins or mixtures thereof may be utilized. See U.S. Pat. Nos. 4,956,122; 4,827,064; and 4,827,073.
The number average molecular weights of the PAOs, which are known materials and generally available on a major commercial scale from suppliers such as ExxonMobil Chemical Company, Chevron Phillips Chemical Company, BP, and others, typically vary from 250 to 3,000, although PAO's may be made in viscosities up to 100 cSt (100° C.). The PAOs are typically comprised of relatively low molecular weight hydrogenated polymers or oligomers of alphaolefins which include, but are not limited to, C₂to C₃₂alphaolefins with the C₈to C₁₆alphaolefins, such as 1-hexene, 1-octene, 1-decene, 1-dodecene and the like, being preferred. The preferred polyalphaolefins are poly-1-hexene, poly-1-octene, poly-l-decene and poly-1-dodecene and mixtures thereof and mixed olefin-derived polyolefins. However, the dimers of higher olefins in the range of C₁₄to C₁₈may be used to provide low viscosity base stocks of acceptably low volatility. Depending on the viscosity grade and the starting polymer (e.g., oligomer), the PAOs may be predominantly trimers and tetramers of the starting olefins, with minor amounts of the higher polymers, having a viscosity range of 1.5 to 12 cSt. PAO fluids of particular use may include 3.0 cSt, 3.4 cSt, and/or 3.6 cSt and combinations thereof. Bi-modal mixtures of PAO fluids having a viscosity range of 1.5 to about 100 cSt or to about 300 cSt may be used if desired.
The PAO fluids may be conveniently made by the polymerization of an alphaolefin in the presence of a polymerization catalyst such as the Friedel-Crafts catalysts including, for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate. For example the methods disclosed by U.S. Pat. No. 4,149,178 or 3,382,291 may be conveniently used herein. Other descriptions of PAO synthesis are found in the following U.S. Pat. Nos. 3,742,082; 3,769,363; 3,876,720; 4,239,930; 4,367,352; 4,413,156; 4,434,408; 4,910,355; 4,956,122; and 5,068,487. The dimers of the C₁₄to C₁₈olefins are described in U.S. Pat. No. 4,218,330.
Other useful lubricant oil base stocks include wax isomerate base stocks and base oils, comprising hydroisomerized waxy stocks (e.g. waxy stocks such as gas oils, slack waxes, fuels hydrocracker bottoms, etc.), hydroisomerized Fischer-Tropsch waxes, Gas-to-Liquids (GTL) base stocks and base oils, and other wax isomerate hydroisomerized base stocks and base oils, or mixtures thereof Fischer-Tropsch waxes, the high boiling point residues of Fischer-Tropsch synthesis, are highly paraffinic hydrocarbons with very low sulfur content. The hydroprocessing used for the production of such base stocks may use an amorphous hydrocracking/hydroisomerization catalyst, such as one of the specialized lube hydrocracking (LHDC) catalysts or a crystalline hydrocracking/hydroisomerization catalyst, preferably a zeolitic catalyst. For example, one useful catalyst is ZSM-48 as described in U.S. Pat. No. 5,075,269, the disclosure of which is incorporated herein by reference in its entirety. Processes for making hydrocracked/hydroisomerized distillates and hydrocracked/hydroisomerized waxes are described, for example, in U.S. Pat. Nos. 2,817,693; 4,975,177; 4,921,594 and 4,897,178 as well as in British Patent Nos. 1,429,494; 1,350,257; 1,440,230 and 1,390,359. Each of the aforementioned patents is incorporated herein in their entirety. Particularly favorable processes are described in European Patent Application Nos. 464546 and 464547, also incorporated herein by reference. Processes using Fischer-Tropsch wax feeds are described in U.S. Pat. Nos. 4,594,172 and 4,943,672, the disclosures of which are incorporated herein by reference in their entirety.
Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils, and other wax-derived hydroisomerized (wax isomerate) base oils be advantageously used in the instant disclosure, and may have useful kinematic viscosities at 100° C. of 3 cSt to 50 cSt, preferably 3 cSt to 30 cSt, more preferably 3.5 cSt to 25 cSt, as exemplified by GTL 4 with kinematic viscosity of 4.0 cSt at 100° C. and a viscosity index of 141. These Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils, and other wax-derived hydroisomerized base oils may have useful pour points of −20° C. or lower, and under some conditions may have advantageous pour points of −25° C. or lower, with useful pour points of −30° C. to −40° C. or lower. Useful compositions of Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils, and wax-derived hydroisomerized base oils are recited in U.S. Pat. Nos. 6,080,301; 6,090,989, and 6,165,949 for example, and are incorporated herein in their entirety by reference.
The hydrocarbyl aromatics can be used as base oil or base oil component and can be any hydrocarbyl molecule that contains at least 5% of its weight derived from an aromatic moiety such as a benzenoid moiety or naphthenoid moiety, or their derivatives. These hydrocarbyl aromatics include alkyl benzenes, alkyl naphthalenes, alkyl diphenyl oxides, alkyl naphthols, alkyl diphenyl sulfides, alkylated bis-phenol A, alkylated thiodiphenol, and the like. The aromatic can be mono-alkylated, dialkylated, polyalkylated, and the like. The aromatic can be mono- or poly-functionalized. The hydrocarbyl groups can also be comprised of mixtures of alkyl groups, alkenyl groups, alkynyl, cycloalkyl groups, cycloalkenyl groups and other related hydrocarbyl groups. The hydrocarbyl groups can range from C₆up to C₆₀with a range of C₈to C₂₀often being preferred. A mixture of hydrocarbyl groups is often preferred, and up to three such substituents may be present.
The hydrocarbyl group can optionally contain sulfur, oxygen, and/or nitrogen containing substituents. The aromatic group can also be derived from natural (petroleum) sources, provided at least 5% of the molecule is comprised of an above-type aromatic moiety. Viscosities at 100° C. of about 3 cSt to about 50 cSt are preferred, with viscosities of about 3.4 cSt to about 20 cSt often being more preferred for the hydrocarbyl aromatic component. In one embodiment, an alkyl naphthalene where the alkyl group is primarily comprised of 1-hexadecene is used. Other alkylates of aromatics can be advantageously used. Naphthalene or methyl naphthalene, for example, can be alkylated with olefins such as octene, decene, dodecene, tetradecene or higher, mixtures of similar olefins, and the like. Useful concentrations of hydrocarbyl aromatic in a lubricant oil composition can be 2% to 25%, preferably 4% to 20%, and more preferably 4% to 15%, depending on the application.
Alkylated aromatics such as the hydrocarbyl aromatics of the present disclosure may be produced by well-known Friedel-Crafts alkylation of aromatic compounds. See Friedel-Crafts and Related Reactions, Olah, G. A. (ed.), Inter-science Publishers, New York, 1963. For example, an aromatic compound, such as benzene or naphthalene, is alkylated by an olefin, alkyl halide or alcohol in the presence of a Friedel-Crafts catalyst. See Friedel-Crafts and Related Reactions, Vol. 2, part 1, chapters 14, 17, and 18, See Olah, G. A. (ed.), Inter-science Publishers, New York, 1964. Many homogeneous or heterogeneous, solid catalysts are known to one skilled in the art. The choice of catalyst depends on the reactivity of the starting materials and product quality requirements. For example, strong acids such as AlCl₃, BF3, or HF may be used. In some cases, milder catalysts such as FeCl₃or SnCl₄are preferred. Newer alkylation technology uses zeolites or solid super acids.
Esters comprise a useful base stock. Additive solvency and seal compatibility characteristics may be secured by the use of esters such as the esters of dibasic acids with monoalkanols and the polyol esters of monocarboxylic acids. Esters of the former type include, for example, the esters of dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc., with a variety of alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, etc. Specific examples of these types of esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, etc.
Particularly useful synthetic esters may be those which are obtained by reacting one or more polyhydric alcohols, preferably the hindered polyols (such as the neopentyl polyols, e.g., neopentyl glycol, trimethylol ethane, 2-methyl-2-propyl-1,3-propanediol, trimethylol propane, pentaerythritol and dipentaerythritol) with alkanoic acids containing at least 4 carbon atoms, preferably C₅to C₃₀acids such as saturated straight chain fatty acids including caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, and behenic acid, or the corresponding branched chain fatty acids or unsaturated fatty acids such as oleic acid, or mixtures of any of these materials.
Suitable synthetic ester components include the esters of trimethylol propane, trimethylol butane, trimethylol ethane, pentaerythritol and/or dipentaerythritol with one or more monocarboxylic acids containing from 5 to 10 carbon atoms. These esters are widely available commercially, for example, the Mobil P-41 and P-51 esters of ExxonMobil Chemical Company.
Also useful are esters derived from renewable material such as coconut, palm, rapeseed, soy, sunflower and the like. These esters may be monoesters, di-esters, polyol esters, complex esters, or mixtures thereof. These esters are widely available commercially, for example, the Mobil P-51 ester of ExxonMobil Chemical Company.
Engine oil formulations containing renewable esters are included in this disclosure. For such formulations, the renewable content of the ester is typically greater than 70 weight percent, preferably more than 80 weight percent and most preferably more than 90 weight percent. Renewable esters can be preferred in combination with the friction modifier mixture.
Other useful fluids of lubricating viscosity include non-conventional or unconventional base stocks that have been processed, preferably catalytically, or synthesized to provide high performance lubrication characteristics.
Non-conventional or unconventional base stocks/base oils include one or more of a mixture of base stock(s) derived from one or more Gas-to-Liquids (GTL) materials, as well as isomerate/isodewaxate base stock(s) derived from natural wax or waxy feeds, mineral and or non-mineral oil waxy feed stocks such as slack waxes, natural waxes, and waxy stocks such as gas oils, waxy fuels hydrocracker bottoms, waxy raffinate, hydrocrackate, thermal crackates, or other mineral, mineral oil, or even non-petroleum oil derived waxy materials such as waxy materials received from coal liquefaction or shale oil, and mixtures of such base stocks.
GTL materials are materials that are derived via one or more synthesis, combination, transformation, rearrangement, and/or degradation/deconstructive processes from gaseous carbon-containing compounds, hydrogen-containing compounds and/or elements as feed stocks such as hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butylenes, and butynes. GTL base stocks and/or base oils are GTL materials of lubricating viscosity that are generally derived from hydrocarbons; for example, waxy synthesized hydrocarbons, that are themselves derived from simpler gaseous carbon-containing compounds, hydrogen-containing compounds and/or elements as feed stocks. GTL base stock(s) and/or base oil(s) include oils boiling in the lube oil boiling range (1) separated/fractionated from synthesized GTL materials such as, for example, by distillation and subsequently subjected to a final wax processing step which involves either or both of a catalytic dewaxing process, or a solvent dewaxing process, to produce lube oils of reduced/low pour point; (2) synthesized wax isomerates, comprising, for example, hydrodewaxed or hydroisomerized cat and/or solvent dewaxed synthesized wax or waxy hydrocarbons; (3) hydrodewaxed or hydroisomerized cat and/or solvent dewaxed Fischer-Tropsch (F-T) material (i.e., hydrocarbons, waxy hydrocarbons, waxes and possible analogous oxygenates); preferably hydrodewaxed or hydroisomerized/followed by cat and/or solvent dewaxing dewaxed F-T waxy hydrocarbons, or hydrodewaxed or hydroisomerized/followed by cat (or solvent) dewaxing dewaxed, F-T waxes, or mixtures thereof.
GTL base stock(s) and/or base oil(s) derived from GTL materials, especially, hydrodewaxed or hydroisomerized/followed by cat and/or solvent dewaxed wax or waxy feed, preferably F-T material derived base stock(s) and/or base oil(s), are characterized typically as having kinematic viscosities at 100° C. of from 2 mm²/s to 50 mm²/s (ASTM D445). They are further characterized typically as having pour points of −5° C. to −40° C. or lower (ASTM D97). They are also characterized typically as having viscosity indices of 80 to 140 or greater (ASTM D2270).
In addition, the GTL base stock(s) and/or base oil(s) are typically highly paraffinic (>90% saturates), and may contain mixtures of monocycloparaffins and multicycloparaffins in combination with non-cyclic isoparaffins. The ratio of the naphthenic (i.e., cycloparaffin) content in such combinations varies with the catalyst and temperature used. Further, GTL base stock(s) and/or base oil(s) typically have very low sulfur and nitrogen content, generally containing less than 10 ppm, and more typically less than 5 ppm of each of these elements. The sulfur and nitrogen content of GTL base stock(s) and/or base oil(s) obtained from F-T material, especially F-T wax, is essentially nil. In addition, the absence of phosphorous and aromatics make this materially especially suitable for the formulation of low SAP products.
The term GTL base stock and/or base oil and/or wax isomerate base stock and/or base oil is to be understood as embracing individual fractions of such materials of wide viscosity range as recovered in the production process, mixtures of two or more of such fractions, as well as mixtures of one or two or more low viscosity fractions with one, two or more higher viscosity fractions to produce a blend wherein the blend exhibits a target kinematic viscosity.
The GTL material, from which the GTL base stock(s) and/or base oil(s) is/are derived is preferably an F-T material (i.e., hydrocarbons, waxy hydrocarbons, wax).
In addition, the GTL base stock(s) and/or base oil(s) are typically highly paraffinic (>90% saturates), and may contain mixtures of monocycloparaffins and multicycloparaffins in combination with non-cyclic isoparaffins. The ratio of the naphthenic (i.e., cycloparaffin) content in such combinations varies with the catalyst and temperature used. Further, GTL base stock(s) and/or base oil(s) and hydrodewaxed, or hydroisomerized/cat (and/or solvent) dewaxed base stock(s) and/or base oil(s) typically have very low sulfur and nitrogen content, generally containing less than 10 ppm, and more typically less than 5 ppm of each of these elements. The sulfur and nitrogen content of GTL base stock(s) and/or base oil(s) obtained from F-T material, especially F-T wax, is essentially nil. In addition, the absence of phosphorous and aromatics make this material especially suitable for the formulation of low sulfur, sulfated ash, and phosphorus (low SAP) products.
Base oils for use in the formulated lubricating oils useful in the present disclosure are any of the variety of oils corresponding to API Group I, Group II, Group III, Group IV, and Group V oils and mixtures thereof, preferably API Group II, Group III, Group IV, and Group V oils and mixtures thereof, more preferably the Group III to Group V base oils due to their exceptional volatility, stability, viscometric and cleanliness features. Minor quantities of Group I stock, such as the amount used to dilute additives for blending into formulated lube oil products, can be tolerated but should be kept to a minimum, i.e. amounts only associated with their use as diluent/carrier oil for additives used on an “as-received” basis. Even in regard to the Group II stocks, it is preferred that the Group II stock be in the higher quality range associated with that stock, i.e. a Group II stock having a viscosity index in the range 100<VI<120.
The lubricating base oil or base stock constitutes the major component of the engine oil lubricant composition of the present disclosure. One particularly preferred lubricating oil base stock for the inventive lubricating engine oil and the inventive method for improving fuel efficiency, frictional properties and deposit control is a Group I base stock that is included in the formulated oil at from 75 to 95 wt %, or from 80 to 90 wt %, or from 82 to 88 wt %. Another particularly preferred lubricating oil base stock for the inventive lubricating engine oil and the inventive method for improving fuel efficiency, frictional properties and deposit control is a combination of a Group III, Group IV and Group V base stock wherein the combination is included in the formulated oil at from 75 to 95 wt %, or from 80 to 90 wt %, or from 82 to 88 wt %. In this form, the Group III base stock is included at from 30 to 35 wt % or from 32 to 33 wt %, the Group IV base stock at from 45 to 55 wt % or from 48 to 52 wt %, and the Group V base stock at from 0 to 5 wt %, or from 2 to 4 wt %.
Preferred Group III base stocks are GTL and Yubase Plus (hydroprocessed base stock). Preferred Group V base stocks include alkylated naphthalene, synthetic esters and combinations thereof.
In some embodiments, the base oils or base stocks described above have a kinematic viscosity, according to ASTM standards, of about 2.5 cSt to about 12 cSt (or mm²/s) at 100° C., preferably of about 2.5 cSt to about 9 cSt (or mm²/s) at 100° C., more preferably of about 4 cSt to about 8 cSt (or mm²/s) at 100° C., and even more preferably of about 4 cSt to about 6 cSt (or mm²/s) at 100° C. In other embodiments, base stocks may have a kinematic viscosity of up to about 100 cSt, about 150 cSt, about 200 cSt, about 250 cSt or about 300 cSt at 100° C.
Lubricating oils and base stocks are disclosed for example In US. Pub. Nos. 20170211007, 20150344805 and 2015322367.
The lubricating oils of the disclosure may contain one or more further additives. Further additives may be present, in each case, from about 0.01 wt %, about 0.1, about 0.5 or about 1 wt % to about 2 wt %, about 5, about 7, about 8, about 10, about 14, about 17, about 20, about 22 or about 25 wt %, based on the total weight of the lubricating oil formulation.
The formulated lubricating oil useful in the present disclosure may additionally contain one or more of the other commonly used lubricating oil performance additives including but not limited to antiwear agents, dispersants, other detergents, corrosion inhibitors, rust inhibitors, metal deactivators, extreme pressure additives, anti-seizure agents, wax modifiers, viscosity index improvers, viscosity modifiers, fluid-loss additives, seal compatibility agents, organic metallic friction modifiers, lubricity agents, anti-staining agents, chromophoric agents, defoamants, demulsifiers, emulsifiers, densifiers, wetting agents, gelling agents, tackiness agents, colorants, and others. For a review of many commonly used additives, see Klamann in Lubricants and Related Products, Verlag Chemie, Deerfield Beach, Fla.; ISBN 0-89573-177-0.
Reference is also made to “Lubricant Additives” by M. W. Ranney, published by Noyes Data Corporation of Parkridge, N.J. (1973); see also U.S. Pat. No. 7,704,930, the disclosure of which is incorporated herein in its entirety. These additives are commonly delivered with varying amounts of diluent oil that may range from 5 weight percent to 50 weight percent.
The types and quantities of performance additives used in combination with the instant disclosure in lubricant compositions are not limited by the examples shown herein as illustrations.

Antiwear Additives

A metal alkylthiophosphate and more particularly a metal dialkyl dithio phosphate in which the metal constituent is zinc, or zinc dialkyl dithio phosphate (ZDDP) is a useful component of the lubricating oils of this disclosure. ZDDP can be derived from primary alcohols, secondary alcohols or mixtures thereof. ZDDP compounds generally are of the formula Zn[SP(S)(OR¹)(OR²)]₂where R¹and R²are C₁-C₁₈alkyl groups, preferably C₂-C₁₂alkyl groups. These alkyl groups may be straight chain or branched. Alcohols used in the ZDDP can be 2-propanol, butanol, secondary butanol, pentanols, hexanols such as 4-methyl-2-pentanol, n-hexanol, n-octanol, 2-ethyl hexanol, alkylated phenols, and the like. Mixtures of secondary alcohols or of primary and secondary alcohol can be preferred. Alkyl aryl groups may also be used.
Preferable zinc dithiophosphates which are commercially available include secondary zinc dithiophosphates such as those available from for example, The Lubrizol Corporation under the trade designations “LZ 677A”, “LZ 1095” and “LZ 1371”, from for example Chevron Oronite under the trade designation “OLOA 262” and from for example Afton Chemical under the trade designation “HiTEC 7169”.
The ZDDP is typically used in amounts of from 0.4 weight percent to 1.2 weight percent, preferably from 0.5 weight percent to 1.0 weight percent, and more preferably from 0.6 weight percent to 0.8 weight percent, based on the total weight of the lubricating oil, although more or less can often be used advantageously. Preferably, the ZDDP is a secondary ZDDP and present in an amount of from 0.6 to 1.0 weight percent of the total weight of the lubricating oil.
Low phosphorus engine oil formulations are included in this disclosure. For such formulations, the phosphorus content is typically less than 0.12 weight percent preferably less than 0.10 weight percent and most preferably less than 0.085 weight percent. Low phosphorus can be preferred in combination with the friction modifier mixture.

Viscosity Index Improvers

Viscosity index improvers (also known as VI improvers, viscosity modifiers, and viscosity improvers) can be included in the lubricant compositions of this disclosure.
Viscosity index improvers provide lubricants with high and low temperature operability. These additives impart shear stability at elevated temperatures and acceptable viscosity at low temperatures.
Suitable viscosity index improvers include high molecular weight hydrocarbons, polyesters and viscosity index improver dispersants that function as both a viscosity index improver and a dispersant. Typical molecular weights of these polymers are between 10,000 to 1,500,000, more typically 20,000 to 1,200,000, and even more typically between 50,000 and 1,000,000.
Examples of suitable viscosity index improvers are linear or star-shaped polymers and copolymers of methacrylate, butadiene, olefins, or alkylated styrenes. Polyisobutylene is a commonly used viscosity index improver. Another suitable viscosity index improver is polymethacrylate (copolymers of various chain length alkyl methacrylates, for example), some formulations of which also serve as pour point depressants. Other suitable viscosity index improvers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (copolymers of various chain length acrylates, for example). Specific examples include styrene-isoprene or styrene-butadiene based polymers of 50,000 to 200,000 molecular weight.
Olefin copolymers, are commercially available from Chevron Oronite Company LLC under the trade designation “PARATONE®” (such as “PARATONE® 8921” and “PARATONE® 8941”); from Afton Chemical Corporation under the trade designation “HiTEC®” (such as “HiTEC® 5850B”; and from The Lubrizol Corporation under the trade designation “Lubrizol® 7067C”. Polyisoprene polymers are commercially available from Infineum International Limited, e.g. under the trade designation “SV200”; diene-styrene copolymers are commercially available from Infineum International Limited, e.g. under the trade designation “SV 260”.
In an embodiment of this disclosure, the viscosity index improvers may be used in an amount of less than 2.0 weight percent, preferably less than 1.0 weight percent, and more preferably less than 0.5 weight percent, based on the total weight of the formulated oil or lubricating engine oil. Viscosity improvers are typically added as concentrates, in large amounts of diluent oil.
In another embodiment of this disclosure, the viscosity index improvers may be used in an amount of from 0.25 to 2.0 weight percent, preferably 0.15 to 1.0 weight percent, and more preferably 0.05 to 0.5 weight percent, based on the total weight of the formulated oil or lubricating engine oil.

Detergents

Illustrative detergents useful in this disclosure include, for example, alkali metal detergents, alkaline earth metal detergents, or mixtures of one or more alkali metal detergents and one or more alkaline earth metal detergents. A typical detergent is an anionic material that contains a long chain hydrophobic portion of the molecule and a smaller anionic or oleophobic hydrophilic portion of the molecule. The anionic portion of the detergent is typically derived from an organic acid such as a sulfur acid, carboxylic acid, phosphorous acid, phenol, or mixtures thereof. The counterion is typically an alkaline earth or alkali metal.
Salts that contain a substantially stochiometric amount of the metal are described as neutral salts and have a total base number (TBN, as measured by ASTM D2896) of from 0 to 80. Many compositions are overbased, containing large amounts of a metal base that is achieved by reacting an excess of a metal compound (a metal hydroxide or oxide, for example) with an acidic gas (such as carbon dioxide). Useful detergents can be neutral, mildly overbased, or highly overbased. These detergents can be used in mixtures of neutral, overbased, highly overbased calcium salicylate, sulfonates, phenates and/or magnesium salicylate, sulfonates, phenates. The TBN ranges can vary from low, medium to high TBN products, including as low as 0 to as high as 600. Mixtures of low, medium, high TBN can be used, along with mixtures of calcium and magnesium metal based detergents, and including sulfonates, phenates, salicylates, and carboxylates. A detergent mixture with a metal ratio of 1, in conjunction of a detergent with a metal ratio of 2, and as high as a detergent with a metal ratio of 5, can be used. Borated detergents can also be used.
Alkaline earth phenates are another useful class of detergent. These detergents can be made by reacting alkaline earth metal hydroxide or oxide (CaO, Ca(OH)₂, BaO, Ba(OH)₂, MgO, Mg(OH)₂, for example) with an alkyl phenol or sulfurized alkylphenol. Useful alkyl groups include straight chain or branched C₁-C₃₀alkyl groups, preferably, C₄-C₂₀or mixtures thereof. Examples of suitable phenols include isobutylphenol, 2-ethylhexylphenol, nonylphenol, dodecyl phenol, and the like. It should be noted that starting alkylphenols may contain more than one alkyl substituent that are each independently straight chain or branched and can be used from 0.5 to 6 weight percent. When a non-sulfurized alkylphenol is used, the sulfurized product may be obtained by methods well known in the art. These methods include heating a mixture of alkylphenol and sulfurizing agent (including elemental sulfur, sulfur halides such as sulfur dichloride, and the like) and then reacting the sulfurized phenol with an alkaline earth metal base.
Metal salts of carboxylic acids are also useful as detergents. These carboxylic acid detergents may be prepared by reacting a basic metal compound with at least one carboxylic acid and removing free water from the reaction product. These compounds may be overbased to produce the desired TBN level. Detergents made from salicylic acid are one preferred class of detergents derived from carboxylic acids. Useful salicylates include long chain alkyl salicylates. One useful family of compositions is of the formula
where R is an alkyl group having 1 to 30 carbon atoms, n is an integer from 1 to 4, and M is an alkaline earth metal. Preferred R groups are alkyl chains of at least C₁₁, preferably C₁₃or greater.
R may be optionally substituted with substituents that do not interfere with the detergent's function. M is preferably, calcium, magnesium, or barium. More preferably, M is calcium.
Hydrocarbyl-substituted salicylic acids may be prepared from phenols by the Kolbe reaction (see U.S. Pat. No. 3,595,791). The metal salts of the hydrocarbyl-substituted salicylic acids may be prepared by double decomposition of a metal salt in a polar solvent such as water or alcohol.
Alkaline earth metal phosphates are also used as detergents and are known in the art.
Detergents may be simple detergents or what is known as hybrid or complex detergents. The latter detergents can provide the properties of two detergents without the need to blend separate materials. See U.S. Pat. No. 6,034,039.
Preferred detergents include calcium phenates, calcium sulfonates, calcium salicylates, magnesium phenates, magnesium sulfonates, magnesium salicylates and other related components (including borated detergents), and mixtures thereof. Preferred mixtures of detergents include magnesium sulfonate and calcium salicylate, magnesium sulfonate and calcium sulfonate, magnesium sulfonate and calcium phenate, calcium phenate and calcium salicylate, calcium phenate and calcium sulfonate, calcium phenate and magnesium salicylate, calcium phenate and magnesium phenate.
The detergent concentration in the lubricating oils of this disclosure can range from 1.0 to 6.0 weight percent, preferably 2.0 to 5.0 weight percent, and more preferably from 2.0 weight percent to 4.0 weight percent, based on the total weight of the lubricating oil.
One particularly preferred detergent mixture for the inventive lubricating engine oil and the inventive method for improving fuel efficiency, frictional properties and deposit control is a combination of an overbased calcium salicylate detergent and a magnesium sulfonate or a calcium sulfonate detergent. The overbased calcium salicylate detergent may be included in the formulated oil at from 0.5 to 2.5 wt %, or 1.0 to 2.0 wt %, or 1.2 to 1.8 wt %. The magnesium sulfonate or a calcium sulfonate detergent may also be included in the formulated oil at from 0.5 to 2.5 wt %, or 1.0 to 2.0 wt %, or 1.2 to 1.8 wt %.
As used herein, the detergent concentrations are given on an “as delivered” basis. Typically, the active detergent is delivered with a process oil. The “as delivered” detergent typically contains from 20 weight percent to 80 weight percent, or from 40 weight percent to 60 weight percent, of active detergent in the “as delivered” detergent product.

Dispersants

During engine operation, oil-insoluble oxidation byproducts are produced. Dispersants help keep these byproducts in solution, thus diminishing their deposition on metal surfaces. Dispersants used in the formulation of the lubricating oil may be ashless or ash-forming in nature. Preferably, the dispersant is ashless. So-called ashless dispersants are organic materials that form substantially no ash upon combustion. For example, non-metal-containing or borated metal-free dispersants are considered ashless. In contrast, metal-containing detergents discussed above form ash upon combustion.
Suitable dispersants typically contain a polar group attached to a relatively high molecular weight hydrocarbon chain. The polar group typically contains at least one element of nitrogen, oxygen, or phosphorus. Typical hydrocarbon chains contain 50 to 400 carbon atoms.
A particularly useful class of dispersants are the alkenylsuccinic derivatives, typically produced by the reaction of a long chain hydrocarbyl substituted succinic compound, usually a hydrocarbyl substituted succinic anhydride, with a polyhydroxy or polyamino compound. The long chain hydrocarbyl group constituting the oleophilic portion of the molecule which confers solubility in the oil, is normally a polyisobutylene group. Many examples of this type of dispersant are well known commercially and in the literature. Exemplary U.S. patents describing such dispersants are U.S. Pat. Nos. 3,172,892; 3,215,707; 3,219,666; 3,316,177; 3,341,542; 3,444,170; 3,454,607; 3,541,012; 3,630,904; 3,632,511; 3,787,374 and 4,234,435. Other types of dispersant are described in U.S. Pat. Nos. 3,036,003; 3,200,107; 3,254,025; 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,413,347; 3,697,574; 3,725,277; 3,725,480; 3,726,882; 4,454,059; 3,329,658; 3,449,250; 3,519,565; 3,666,730; 3,687,849; 3,702,300; 4,100,082; 5,705,458. A further description of dispersants may be found, for example, in European Patent Application No. 471 071, to which reference is made for this purpose.
Hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride derivatives are useful dispersants. In particular, succinimide, succinate esters, or succinate ester amides prepared by the reaction of a hydrocarbon-substituted succinic acid compound preferably having at least 50 carbon atoms in the hydrocarbon substituent, with at least one equivalent of an alkylene amine are particularly useful, although on occasion, having a hydrocarbon substituent between 20-50 carbon atoms can be useful.
Succinimides are formed by the condensation reaction between hydrocarbyl substituted succinic anhydrides and amines. Molar ratios can vary depending on the polyamine. For example, the molar ratio of hydrocarbyl substituted succinic anhydride to TEPA can vary from 1:1 to 5:1. Representative examples are shown in U.S. Pat. Nos. 3,087,936; 3,172,892; 3,219,666; 3,272,746; 3,322,670; and U.S. Pat. Nos. 3,652,616, 3,948,800; and Canada Patent No. 1,094,044.
Succinate esters are formed by the condensation reaction between hydrocarbyl substituted succinic anhydrides and alcohols or polyols. Molar ratios can vary depending on the alcohol or polyol used. For example, the condensation product of a hydrocarbyl substituted succinic anhydride and pentaerythritol is a useful dispersant.
Succinate ester amides are formed by condensation reaction between hydrocarbyl substituted succinic anhydrides and alkanol amines. For example, suitable alkanol amines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines and polyalkenylpolyamines such as polyethylene polyamines. One example is propoxylated hexamethylenediamine. Representative examples are shown in U.S. Pat. No. 4,426,305.
The molecular weight of the hydrocarbyl substituted succinic anhydrides used in the preceding paragraphs will typically range between 800 and 2,500 or more. The above products can be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid. The above products can also be post reacted with boron compounds such as boric acid, borate esters or highly borated dispersants, to form borated dispersants generally having from 0.1 to 5 moles of boron per mole of dispersant reaction product.
Mannich base dispersants are made from the reaction of alkylphenols, formaldehyde, and amines. See U.S. Pat. No. 4,767,551, which is incorporated herein by reference. Process aids and catalysts, such as oleic acid and sulfonic acids, can also be part of the reaction mixture. Molecular weights of the alkylphenols range from 800 to 2,500. Representative examples are shown in U.S. Pat. Nos. 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,798,165; and 3,803,039.
Typical high molecular weight aliphatic acid modified Mannich condensation products useful in this disclosure can be prepared from high molecular weight alkyl-substituted hydroxyaromatics or HNR₂group-containing reactants.
Hydrocarbyl substituted amine ashless dispersant additives are well known to one skilled in the art; see, for example, U.S. Pat. Nos. 3,275,554; 3,438,757; 3,565,804; 3,755,433, 3,822,209, and 5,084,197.
Preferred dispersants include borated and non-borated succinimides, including those derivatives from mono-succinimides, bis-succinimides, and/or mixtures of mono- and bis-succinimides, wherein the hydrocarbyl succinimide is derived from a hydrocarbylene group such as polyisobutylene having a Mn of from 500 to 5000, or from 1000 to 3000, or 1000 to 2000, or a mixture of such hydrocarbylene groups, often with high terminal vinylic groups. Other preferred dispersants include succinic acid-esters and amides, alkylphenol-polyamine-coupled Mannich adducts, their capped derivatives, and other related components. Such additives may be used in an amount of 0.1 to 20 weight percent, preferably 0.5 to 8 weight percent, or more preferably 0.5 to 4 weight percent. On an active ingredient basis, such additives may be used in an amount of 0.06 to 14 weight percent, preferably 0.3 to 6 weight percent. The hydrocarbon portion of the dispersant atoms can range from C₆₀to C₄₀₀, or from C₇₀to C₃₀₀, or from C₇₀to C₂₀₀. These dispersants may contain both neutral and basic nitrogen, and mixtures of both. Dispersants can be end-capped by borates and/or cyclic carbonates.
One particularly preferred dispersant for the inventive lubricating engine oil and the inventive method for improving fuel efficiency, frictional properties and deposit control is a non-borated polyisobutenyl bis-succinimide (PIBSA) dispersant. The non-borated PIBSA dispersant may be included in the formulated oil at from 2.0 to 6.0 wt %, or 3.0 to 5.0 wt %, or 3.5 to 4.5 wt %.
As used herein, the dispersant concentrations are given on an “as delivered” basis. Typically, the active dispersant is delivered with a process oil. The “as delivered” dispersant typically contains from 20 weight percent to 80 weight percent, or from 40 weight percent to 60 weight percent, of active dispersant in the “as delivered” dispersant product.

Further Antioxidants

Antioxidants retard the oxidative degradation of base oils and additives during service. Such degradation may result in deposits on metal surfaces, the presence of sludge, or a viscosity increase in the lubricant. One skilled in the art knows a wide variety of oxidation inhibitors that are useful in lubricating oil compositions. See, Klamann in Lubricants and Related Products, op cite, and U.S. Pat. Nos. 4,798,684 and 5,084,197, for example.
Useful antioxidants may include hindered phenols. These phenolic antioxidants may be ashless (metal-free) phenolic compounds or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are the hindered phenolics which are the ones which contain a sterically hindered hydroxyl group, and these include those derivatives of dihydroxy aryl compounds in which the hydroxyl groups are in the o- or p-position to each other. Typical phenolic antioxidants may include the hindered phenols substituted with C₆+alkyl groups and the alkylene coupled derivatives of these hindered phenols. Examples of phenolic materials of this type 2-t-butyl-4-heptyl phenol; 2-t-butyl-4-octyl phenol; 2-t-butyl-4-dodecyl phenol; 2,6-di-t-butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol; 2-methyl-6-t-butyl-4-heptyl phenol; and 2-methyl-6-t-butyl-4-dodecyl phenol. Other useful hindered mono-phenolic antioxidants may include for example hindered 2,6-di-alkyl-phenolic propionic ester derivatives. Bis-phenolic antioxidants may also be advantageously used in combination with the instant disclosure. Examples of ortho-coupled phenols include: 2,2′-bis(4-heptyl-6-t-butyl-phenol); 2,2′-bis(4-octyl-6-t-butyl-phenol); and 2,2′-bis(4-dodecyl-6-t-butyl-phenol). Para-coupled bisphenols include for example 4,4′-bis(2,6-di-t-butyl phenol) and 4,4′-methylene-bis(2,6-di-t-butyl phenol).
Effective amounts of one or more catalytic antioxidants may also be used. The catalytic antioxidants comprise an effective amount of a) one or more oil soluble polymetal organic compounds; and, effective amounts of b) one or more substituted N,N′-diaryl-o- phenylenediamine compounds or c) one or more hindered phenol compounds; or a combination of both b) and c). Catalytic antioxidants are more fully described in U.S. Pat. No. 8,048,833, herein incorporated by reference in its entirety.
Non-phenolic oxidation inhibitors which may be used include aromatic amine antioxidants and these may be used either as such or in combination with phenolics. Typical examples of non-phenolic antioxidants may include: alkylated and non-alkylated aromatic amines such as aromatic monoamines of the formula R⁸R⁹R¹⁰N where R⁸is an aliphatic, aromatic or substituted aromatic group, R⁹is an aromatic or a substituted aromatic group, and R¹° is H, alkyl, aryl or R11S(O)_XR¹²where R¹¹is an alkylene, alkenylene, or aralkylene group, R¹²is a higher alkyl group, or an alkenyl, aryl, or alkaryl group, and x is 0, 1 or 2. The aliphatic group R⁸may contain from 1 to 20 carbon atoms, and preferably contains from 6 to 12 carbon atoms. The aliphatic group is a saturated aliphatic group. Preferably, both R⁸and R⁹are aromatic or substituted aromatic groups, and the aromatic group may be a fused ring aromatic group such as naphthyl. Aromatic groups R⁸and R⁹may be joined together with other groups such as S.
Typical aromatic amines antioxidants have alkyl substituent groups of at least 6 carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally, the aliphatic groups will not contain more than 14 carbon atoms. The general types of amine antioxidants useful in the present compositions include diphenylamines, phenyl naphthylamines, phenothiazines, imidodibenzyls and diphenyl phenylene diamines. Mixtures of two or more aromatic amines are also useful. Polymeric amine antioxidants can also be used. Particular examples of aromatic amine antioxidants useful in the present disclosure include: p,p′-dioctyldiphenylamine; t-octylphenyl-alpha-naphthylamine; phenyl-alphanaphthylamine; and p-octylphenyl-alpha-naphthylamine.
Sulfurized alkyl phenols and alkali or alkaline earth metal salts thereof also are useful antioxidants.
Preferred antioxidants may include hindered phenols, arylamines. These antioxidants may be used individually by type or in combination with one another. Such additives may be used in an amount of 0.01 to 5 weight percent, preferably 0.01 to 1.5 weight percent, more preferably zero to less than 1.5 weight percent, more preferably zero to less than 1 weight percent.

Pour Point Depressants (PPDs)

Conventional pour point depressants (also known as lube oil flow improvers) may be added to the compositions of the present disclosure if desired. These pour point depressant may be added to lubricating compositions of the present disclosure to lower the minimum temperature at which the fluid will flow or can be poured. Examples of suitable pour point depressants include polymethacrylates, polyacrylates, polyarylamides, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, and terpolymers of dialkylfumarates, vinyl esters of fatty acids and allyl vinyl ethers. U.S. Pat. Nos. 1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,655, 479; 2,666,746; 2,721,877; 2,721,878; and 3,250,715 describe useful pour point depressants and/or the preparation thereof. Such additives may be used in an amount of 0.01 to 5 weight percent, preferably 0.01 to 1.5 weight percent.

Seal Compatibility Agents

Seal compatibility agents help to swell elastomeric seals by causing a chemical reaction in the fluid or physical change in the elastomer. Suitable seal compatibility agents for lubricating oils include organic phosphates, alkoxysulfonlanes (C₁₀alcohol, for example), aromatic esters, aromatic hydrocarbons, esters (butylbenzyl phthalate, for example), and polybutenyl succinic anhydride. Such additives may be used in an amount of 0.01 to 3 weight percent, preferably 0.01 to 2 weight percent.

Antifoam Agents

Antifoam agents may advantageously be added to lubricant compositions. These agents retard the formation of stable foams. Silicones and organic polymers are typical antifoam agents. For example, polysiloxanes, such as silicon oil or polydimethyl siloxane, provide antifoam properties. Antifoam agents are commercially available and may be used in conventional minor amounts along with other additives such as demulsifiers; usually the amount of these additives combined is less than 1 weight percent and often less than 0.1 weight percent.

Inhibitors and Antirust Additives

Antirust additives (or corrosion inhibitors) are additives that protect lubricated metal surfaces against chemical attack by water or other contaminants. A wide variety of these are commercially available.
One type of antirust additive is a polar compound that wets the metal surface preferentially, protecting it with a film of oil. Another type of antirust additive absorbs water by incorporating it in a water-in-oil emulsion so that only the oil touches the metal surface. Yet another type of antirust additive chemically adheres to the metal to produce a non-reactive surface. Examples of suitable additives include zinc dithiophosphates, metal phenolates, basic metal sulfonates, fatty acids and amines. Such additives may be used in an amount of 0.01 to 5 weight percent, preferably 0.01 to 1.5 weight percent.

Friction Modifiers

A friction modifier is any material or materials that can alter the coefficient of friction of a surface lubricated by any lubricant or fluid containing such material(s). Friction modifiers, also known as friction reducers, or lubricity agents or oiliness agents, and other such agents that change the ability of base oils, formulated lubricant compositions, or functional fluids, to modify the coefficient of friction of a lubricated surface may be effectively used in combination with the base oils or lubricant compositions of the present disclosure if desired. Friction modifiers that lower the coefficient of friction are particularly advantageous in combination with the base oils and lube compositions of this disclosure.
Illustrative friction modifiers may include, for example, organometallic compounds or materials, or mixtures thereof. Illustrative organometallic friction modifiers useful in the lubricating engine oil formulations of this disclosure include, for example, molybdenum amine, molybdenum diamine, an organotungstenate, a molybdenum dithiocarbamate, molybdenum dithiophosphates, molybdenum amine complexes, molybdenum carboxylates, and the like, and mixtures thereof. Similar tungsten based compounds may be preferable. [00152] Other illustrative friction modifiers useful in the lubricating engine oil formulations of this disclosure include, for example, alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, borated glycerol fatty acid esters, fatty alcohol ethers, and mixtures thereof.
Illustrative alkoxylated fatty acid esters include, for example, polyoxyethylene stearate, fatty acid polyglycol ester, and the like. These can include polyoxypropylene stearate, polyoxybutylene stearate, polyoxyethylene isosterate, polyoxypropylene isostearate, polyoxyethylene palmitate, and the like.
Illustrative alkanolamides include, for example, lauric acid diethylalkanolamide, palmic acid diethylalkanolamide, and the like. These can include oleic acid diethyalkanolamide, stearic acid diethylalkanolamide, oleic acid diethylalkanolamide, polyethoxylated hydrocarbylamides, polypropoxylated hydrocarbylamides, and the like.
Illustrative polyol fatty acid esters include, for example, glycerol mono-oleate, saturated mono-, di-, and tri-glyceride esters, glycerol mono-stearate, and the like. These can include polyol esters, hydroxyl-containing polyol esters, and the like.
Illustrative borated glycerol fatty acid esters include, for example, borated glycerol mono-oleate, borated saturated mono-, di-, and tri-glyceride esters, borated glycerol mono-stearate, and the like. In addition to glycerol polyols, these can include trimethylolpropane, pentaerythritol, sorbitan, and the like. These esters can be polyol monocarboxylate esters, polyol dicarboxylate esters, and on occasion polyoltricarboxylate esters. Preferred can be the glycerol mono-oleates, glycerol dioleates, glycerol trioleates, glycerol monostearates, glycerol distearates, and glycerol tristearates and the corresponding glycerol monopalmitates, glycerol dipalmitates, and glycerol tripalmitates, and the respective isostearates, linoleates, and the like. On occasion the glycerol esters can be preferred as well as mixtures containing any of these. Ethoxylated, propoxylated, butoxylated fatty acid esters of polyols, especially using glycerol as underlying polyol can be preferred.
Illustrative fatty alcohol ethers include, for example, stearyl ether, myristyl ether, and the like. Alcohols, including those that have carbon numbers from C₃to C₅₀, can be ethoxylated, propoxylated, or butoxylated to form the corresponding fatty alkyl ethers. The underlying alcohol portion can preferably be stearyl, myristyl, C₁₁-C₁₃hydrocarbon, oleyl, isosteryl, and the like.
Useful concentrations of friction modifiers may range from 0.01 weight percent to 5 weight percent, or about 0.1 weight percent to about 2.5 weight percent, or about 0.1 weight percent to about 1.5 weight percent, or about 0.1 weight percent to about 1 weight percent.
Concentrations of molybdenum-containing materials are often described in terms of Mo metal concentration. Advantageous concentrations of Mo may range from 25 ppm to 700 ppm or more, and often with a preferred range of 50-200 ppm. Friction modifiers of all types may be used alone or in mixtures with the materials of this disclosure. Often mixtures of two or more friction modifiers, or mixtures of friction modifier(s) with alternate surface active material(s), are also desirable.
When lubricating oil compositions contain one or more of the additives discussed above, the additive(s) are blended into the composition in an amount sufficient for it to perform its intended function. Typical amounts of such additives useful in the present disclosure are shown in the table below.
It is noted that many of the additives are shipped from the additive manufacturer as a concentrate, containing one or more additives together, with a certain amount of base oil diluents. Accordingly, the weight amounts in the table below, as well as other amounts mentioned herein, are directed to the amount of active ingredient (that is the non-diluent portion of the ingredient). The weight percent (wt %) indicated below is based on the total weight of the lubricating oil composition.


compound	useful amount	typical amount

dispersant	0.1-20	0.1-8
detergent	0.1-20	0.1-8
friction modifier	0.01-5	0.01-1.5
antioxidant	0.1-5	0.1-1.5
pour point depressant	0-5	0.01-1.5
anti-foam agent	0.001-3	0.001-0.15
viscosity index improver	0.1-2	0.1-1
anti-wear	0.1-2	0.5-1
inhibitor and antirust	0.01-5	0.01-1.5

The foregoing additives are all commercially available materials. These additives may be added independently but are usually precombined in packages which can be obtained from suppliers of lubricant oil additives. Additive packages with a variety of ingredients, proportions and characteristics are available and selection of the appropriate package will take the requisite use of the ultimate composition into account.
The present antioxidant compositions can be introduced into the lubricating oil in manners known per se. The compounds are readily soluble in oils. They may be added directly to the lubricating oil or they can be diluted with a substantially inert, normally liquid organic diluent such as naphtha, benzene, toluene, xylene or a normally liquid oil or fuel to form an additive concentrate or masterbatch. Antioxidant concentrates may include base stocks, such as ester base stocks, as a diluent. In certain embodiments, antioxidant concentrates include solvents such as glymes, such as monomethyl tetraglyme. These concentrates generally contain from about 10% to about 90% by weight additive and may contain one or more other additional additives. The present antioxidant compositions may be introduced as part of an additive package in liquid or solid form.
The antioxidant polymer (e.g., oligomer) compositions of this disclosure may advantageously be diluted with one or more liquid additives disclosed herein, for instance one or more liquid dispersants, detergents, antiwear additives, corrosion inhibitors or antioxidants mentioned herein to prepare an antioxidant additive package. Liquid antioxidants may include certain aminic and phenolic antioxidants. Further aminic and phenolic antioxidants may include one or more of N,N-di-(p-tert-butylphenyl)amine, N,N-di-(p-tert-octylphenyl)amine, N-(p-tert-butylphenyl)-N-phenylamine, N-(p-tert-octylphenyl)-N-phenylamine and N-(p-tert-butylphenyl)-N-(p-tert-octylphenyl)amine, bis-nonylphenyldiphenylamine, N-(tert-C₁-C₂₀alkylphenyl)-1-naphthylamine and 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid octyl ester.
In some embodiments, the amount of polymer (e.g., oligomer) to be added to a base oil is that to provide a desired good balance of deposits performance, good color and viscosity control. For instance, an effective amount of polymer (e.g., oligomer) is from about 0.01 wt %, about 0.05, about 0.1, about 0.3, about 0.5, about 0.7, about 1.0, about 1.5, about 2.0, about 2.5, about 3.0, about 3.5, about 4.0, about 4.5, about 5.0, about 5.5, about 6.0, about 6.5, about 7.0, about 7.5, about 8.0, about 8.5 or about 9.0 wt % to about 10, about 11, about 12, about 13, about 14, about 15, about 16, about 17, about 18, about 19 or about 20 wt % of the polymer (e.g., oligomer), based on the total weight of the lubricating oil composition.
The lubricating oil compositions are in some embodiments engine oils having a kinematic viscosity at 100° C. of from any one of about 2 cSt, about 3 cSt, about 4 cSt, about 5 cSt, about 6 cSt or about 7 cSt to any one of about 8 cSt, about 9 cSt, about 10 cSt, about 11 cSt, about 12 cSt, about 13 cSt, about 14 cSt, about 15 cSt, about 16 cSt, about 17 cSt, about 18 cSt, about 19 cSt or about 20 cSt.

Greases

The compositions of the present disclosure may include a thickener (e.g., a water-insoluble thickener) in a range from about 0.5 to about 20 wt. % (e.g., about 0.5 to about 10 wt. %. For example, the grease composition of the present disclosure may have thickener present in an amount of about 0.5 wt. % to about 20 wt. %, about 0.5 wt. % to about 17.5 wt. %, about 0.5 wt. % to about 15 wt. %, about 0.5 wt. % to about 12.5 wt. %, about 0.5 wt. % to about 10 wt. %, about 0.5 wt. % to about 7.5 wt. %, about 0.5 wt. % to about 5 wt. %, about 1 wt. % to about 20 wt. %, about 1 wt. % to about 17.5 wt. %, about 1 wt. % to about 15 wt. %, about 1 wt. % to about 12.5 wt. %, about 1 wt. % to about 10 wt. %, about 1 wt. % to about 7.5 wt. %, about 1 wt. % to about 5 wt. %, about 2.5 wt. % to about 20 wt. %, about 2.5 wt. % to about 17.5 wt. %, about 2.5 wt. % to about 15 wt. %, about 2.5 wt. % to about 12.5 wt. %, about 2.5 wt. % to about 10 wt. %, about 2.5 wt. % to about 7.5 wt. %, about 5 wt. % to about 20 wt. %, about 5 wt. % to about 17.5 wt. %, about 5 wt. % to about 15 wt. %, about 5 wt. % to about 12.5 wt. %, about 5 wt. % to about 10 wt. %, about 7.5 wt. % to about 20 wt. %, about 7.5 wt. % to about 17.5 wt. %, about 7.5 wt. % to about 15 wt. %, about 7.5 wt. % to about 12.5 wt. %, about 10 wt. % to about 20 wt. %, about 10 wt. % to about 17.5 wt. %, about 10 wt. % to about 15 wt. %, about 12.5 wt. % to about 20 wt. %, about 12.5 wt. % to about 17.5 wt. %, or about 15 wt. % to about 20 wt. %.
The grease will contain an essentially water- and oil-insoluble thickener to provide the desired grease consistency and structure (cone penetration, dropping point, etc.). Thickeners may be of the soap or non-soap types. Non-soaps are based on organic or non-organic solids such as bentonite clay, polymers such as the polyureas or silica aerogels and may be used where their particular properties so indicate. For example, thickeners for the present greases are the metal salt/soap thickeners, including the complex soap thickeners based on metals including aluminum, barium, calcium, lithium, sodium. These types of thickeners are well established and are described in numerous publications. See, for example, Boner op cit, Lubricants and Related Products, Klamann, Verlag Chemie, 1984, ISBN 3-527-26022-6, ISBN 0-89573-177-0 to which reference is made for a description of suitable thickeners and the manufacture of grease incorporating them.
Complex grease thickeners are made by combining the conventional metallic soaps with a complexing agent. The soaps may be a metal salt of a long chain fatty acid having from 8 to 24 carbon atoms such as decanoic acid, myristic acid, palmitic acid or stearic acid. The thickener may be a lithium or lithium complex thickener that incorporates a hydroxy fatty acid having from 12 to 24 (e.g., from 16 to 20) carbon atoms. For example, the hydroxy fatty acid may be an hydroxy stearic acid, e.g., 9-hydroxy or 10-hydroxy stearic acid, or 12-hydroxy stearic acid. Other hydroxyl fatty acids which may be used include ricinoleic acid (12-hydoxystearic acid unsaturated at the 9,10 position), 12-hydroxybehenic acid and 10-hydroxypalmitic acid. The complex salt/soap thickeners are made with a combination of conventional lithium soap such as lithium 12-hydroxystearate and a complexing agent which may vary with the type of thickener, e.g. calcium complex thickeners may be formulated with acetic acid and hydroxy-substituted acids; boric acid may be used with lithium soaps. Low molecular-weight organic acid, typically C₄to C₁₂dibasic acids such as glutaric, azelaic, pimelic, suberic, adipic or sebacic acids, are generally favored as the complexing agents with lithium greases. The complexes are formed by the introduction of the complexing agent or its metal salt into the lattice of the metal salt. Examples of metal salt/soap complex thickeners are described in U.S. Pat. No. 3,929,651; 3,940,339; 4,410,435; 4,444,669 and 5,731,274. The complexing agent may be added as the free acid, a salt e.g., the lithium salt or as an ester such as an alkyl ester, e.g. methyl glutarate or methyl adipate, which will undergo hydrolysis to the acid in the presence of the added alkali, e.g. lithium hydroxide, to form the complexing agent. PAO bases may require a higher proportion of thickener than mineral oil base stocks.
The lithium complex thickener used in the grease of the present disclosure is not particularly limited and can be any lithium complex thickener that is known or that becomes known. For example, the lithium complex thickener can comprise a lithium soap derived from a fatty acid having: (a) (i) at least one of an epoxy group, ethylenic unsaturation, or a combination thereof, and (ii) a dilithium salt derived from a straight chain dicarboxylic acid; and/or (b) a lithium salt derived from a hydroxy-substituted carboxylic acid, e.g. salicylic acid.
For example, the lithium complex thickener can comprise at least one of: a complex of a lithium soap of a C₁₂to C₂₄hydroxy fatty acid and a monolithium salt of boric acid; a lithium salt of a second hydroxy carboxylic acid, such as salicylic acid; or a combination thereof.
The lithium complex thickener can comprise a lithium soap of a C₁₂to C₂₄hydroxy fatty acid thickener antioxidant having an alkali metal salt of hydroxy benzoic acid and a diozime compound. In certain embodiments, the alkali metal salt of hydroxy benzoic acid includes dilithium salicylate.
The lithium complex thickener can be a lithium soap comprising at least one of: a dilithium salt of a C₄to C₁₂dicarboxylic acid, e.g., dilithium azelate; a lithium soap of a 9-, 10- or 12-hydroxy C₁₂to C₂₄fatty acid, e.g., lithium 12-hydroxy stearate; and a lithium salt formed in-situ in the grease from a second hydroxy carboxylic acid, wherein the —OH group is attached to a carbon atom not more than 6 carbons removed from the carboxyl group and either of those groups can be attached to aliphatic portions of the materials or aromatic portions of the materials.
In any aspect or embodiment described herein, the lithium complex thickener can comprise a complex lithium thickener and at least one of a lithium salt of a C₃to C₁₄hydroxycarboxylic acid, a thiadiazole, or a combination thereof.
In any aspect or embodiment described herein, the water insoluble thickener may include at least one of an aluminum soap, a barium soap, a calcium soap, a lithium soap, an aluminum salt/soap complex, a barium salt/soap complex, a calcium salt/soap complex, a lithium salt/soap complex, or a combination thereof.
The grease composition of the present disclosure comprises a low molecular weight thixotropic polyamide composition as a co-thickener, which contributes to the formation of the thickener matrix. The thixotrope is essentially insoluble in water and oil in order to maintain the grease structure and the desired resistance to water wash out. Thixotropes create a viscosity increase that is reversed during shearing, but then reforms when the shear forces are removed. This characteristic has been found to provide advantageous properties when used in combination with the remaining grease components.
In any aspect or embodiment described herein, the composition of the present disclosure comprises less than or equal to about 1.25 wt. % of the low molecular weight thixotropic polyamide composition. For example, the low molecular weight thixotropic polyamide composition may be present in an amount of less than or equal to about 1.10 wt. %, less than or equal to about 1 wt. %, less than or equal to about 0.75 wt. %, less than or equal to about 0.50 wt. %, or less than or equal to about 0.25 wt. %.
In any aspect or embodiment described herein, the thixotropic polyamide composition of the present disclosure may have a (O—H+N—H) to C—H peak intensity ratio of ≥ about 0.5. For example, the (O—H+N—H) to C—H peak intensity ratio of the low molecular weight thixotropic polyamide may be ≥ about 0.55, ≥ about 0.6, ≥ about 0.65, ≥ about 0.7, or ≥ about 0.75. In any aspect or embodiment described herein, the thixotropic polyamide composition of the present disclosure may have at least one of:
≤ about 8 wt. % (e.g., about 5 wt. % or ≤ about 4 wt. %) of amide material having a molecular weight of at least about 1700;
≤ about 25 wt. % (e.g., ≤ about 20 wt. % or ≤ about 17.5 wt. %) of amide material having a molecular weight of about 1100 to about 1300;
≥ about 70 wt. % (e.g., ≥ about 75 wt. % or ≥ about 80 wt. %) of amide material having a molecular weight of about 1000 or less (e.g., about 50 wt. % to about 80 wt. % of the amide material having a molecular weight of about 700 to about 1000); or a combination thereof.
In any aspect or embodiment described here, the low molecular weight thixotropic polyamide composition has amide material with a molecular weight of about 700 to about 1000 present in an amount of about 50 wt. % to about 80 wt. %, about 50 wt. % to about 70 wt. %, about 50 wt. % to about 60 wt. %, about 60 wt. % to about 80 wt. %, about 60 wt. % to about 70 wt. %, or about 70 wt. % to about 80 wt. %.
The composition of the present disclosure may include small amounts of at least one (e.g., 1, 2, 3, 4, 5, or 6, or more) performance additive. For example, the composition of the present disclosure may include at least one of anticorrosive agent or corrosion inhibitor, an extreme pressure additive, an antiwear agent, a pour point depressants, an antioxidant or oxidation inhibitor, a rust inhibitor, a metal deactivator, a dispersant, a demulsifier, a dye or colorant/chromophoric agent, a seal compatibility agent, a friction modifier, a viscosity modifier/improver, a viscosity index improver, or combinations thereof. For example, solid lubricants such as molybdenum disulfide and graphite may be present in the composition of the present disclosure, such as from about 1 to about 5 wt. % (e.g., from about 1.5 to about 3 wt. %) for molybdenum disulfide and from about 3 to about 15.wt. % (e.g., from about 6 to about 12 wt. %) for graphite.
The amounts of individual additives will vary according to the additive and the level of functionality to be provided by it.
The presence or absence of these lubricating oil performance additives does not adversely affect the compositions of the present disclosure. For a review of many commonly used additives, see Klamann in Lubricants and Related Products, Verlag Chemie, Deerfield Beach, Fla.; ISBN 0 89573 177 0. Reference is also made to “Lubricant Additives” by M. W. Ranney, published by Noyes Data Corporation of Parkridge, N.J. (1973) and “Lubricant Additives: Chemistry and Applications” edited by L. R. Rudnick, published by CRC Press of Boca Raton, Fla. (2009). The performance additives useful in the present disclosure do not have to be soluble in the lubricating oils. Insoluble additives in oil can be dispersed in the lubricating oils of the present disclosure. The types and quantities of performance additives used in combination with the compositions of the present disclosure are not limited by the examples shown herein as illustrations.
As such, in any aspect or embodiment described herein, the composition further comprises at least one of anticorrosive agent or corrosion inhibitor, an extreme pressure additive, an antiwear agent, a pour point depressants, an antioxidant or oxidation inhibitor, a rust inhibitor, a metal deactivator, a dispersant, a demulsifier, a dye or colorant/chromophoric agent, a seal compatibility agent, a friction modifier, a viscosity modifier/improver, a viscosity index improver, or combinations thereof. In any aspect or embodiment described herein, the dispersant includes succinimide-type dispersant. Unless specified otherwise, the performance additive or performance additives listed above are present in a total amount equal to or less than about 10 wt. %, equal to or less than about 9.5 wt. %, equal to or less than about 9 wt. %, equal to or less than about 8.5 wt. %, equal to or less than about 8 wt. %, equal to or less than about 7.5 wt. %, equal to or less than about 7 wt. %, equal to or less than about 6.5 wt. %, equal to or less than about 6 wt. %, equal to or less than about 5.5 wt. %, equal to or less than about 5 wt. %, equal to or less than about 4.5 wt. %, equal to or less than about 4 wt. %, equal to or less than about 3.5 wt. %, equal to or less than about 3 wt. %, equal to or less than about 2.5 wt. %, equal to or less than about 2 wt. %, equal to or less than about 1.5 wt. %, or equal to or less than about 0.5 wt. %. For example, the performance additive or performance additives are present in a total amount of about 0.1 to about 10 wt. %, about 0.1 to about 9 wt. %, about 0.1 to about 8 wt. %, about 0.1 to about 7 wt. %, about 0.1 to about 6 wt. %, about 0.1 to about 5 wt. %, about 0.1 to about 4 wt. %, about 0.1 to about 3 wt. %, about 0.1 to about 2 wt. %, about 0.1 to about 1 wt. %, about 0.5 to about 10 wt. %, about 0.5 to about 9 wt. %, about 0.5 to about 8 wt. %, about 0.5 to about 7 wt. %, about 0.5 to about 6 wt. %, about 0.5 to about 5 wt. %, about 0.5 to about 4 wt. %, about 0.5 to about 3 wt. %, about 0.5 to about 2 wt. %, about 1 to about 10 wt. %, about 1 to about 9 wt. %, about 1 to about 8 wt. %, about 1 to about 7 wt. %, about 1 to about 6 wt. %, about 1 to about 5 wt. %, about 1 to about 4 wt. %, about 1 to about 3 wt. %, about 2 to about 10 wt. %, about 2 to about 9 wt. %, about 2 to about 8 wt. %, about 2 to about 7 wt. %, about 2 to about 6 wt. %, about 2 to about 5 wt. %, about 2 to about 4 wt. %, about 3 to about 10 wt. %, about 3 to about 9 wt. %, about 3 to about 8 wt. %, about 3 to about 7 wt. %, about 3 to about 6 wt. %, about 3 to about 5 wt. %, about 4 to about 10 wt. %, about 4 to about 9 wt. %, about 4 to about 8 wt. %, about 4 to about 7 wt. %, about 4 to about 6 wt. %, about 5 to about 10 wt. %, about 5 to about 9 wt. %, about 5 to about 8 wt. %, about 5 to about 7 wt. %, about 6 to about 10 wt. %, about 6 to about 9 wt. %, about 6 to about 8 wt. %, about 7 to about 10 wt. %, about 7 to about 9 wt. %, or about 8 to about 10 wt. %.
When the additives are described below by reference to individual components used in the formulation, they will not necessarily be present or identifiable as discrete entities in the final product but may be present as reaction products which are formed during the grease manufacture or even its use. This will depend on the respective chemistries of the ingredients, their stoichiometry, and the temperatures encountered in the grease making process or during its use. It will also depend, naturally enough, on whether or not the species are added as a pre-reacted additive package. For example, the acid amine phosphates may be added as discrete amines and acid phosphates but these may react to form a new entity in the final grease composition under the processing conditions used in the grease manufacture.
Viscosity Improver(s) or Modifier(s). In any aspect or embodiment described herein, the composition of the present disclosure comprises at least one viscosity improver or modifier (e.g., 1, 2, 3, 4, 5, 6, or more viscosity improver or modifier). The viscosity improver, viscosity modifier, or Viscosity Index (VI) modifier increases the viscosity of the composition of the present disclosure at elevated temperatures, thereby increasing film thickness, and having limited effects on the viscosity of the composition of the present disclosure at low temperatures. In certain embodiments, the composition of the present disclosure comprises at least one viscosity improver (e.g., 1, 2, 3, 4, 5, 6, or more viscosity improver(s)). Any viscosity improver that is known or that becomes known in the art may be utilized in the composition of the present disclosure. Exemplary viscosity improvers include high molecular weight hydrocarbons, polyesters and viscosity index improver dispersants that function as both a viscosity index improver and a dispersant. The molecular weight of these polymers can range from about 1,000 to about 1,500,000 (e.g., about 20,000 to about 1,200,000 or about 50,000 to about 1,000,000). In a particular embodiment, the molecular weights of these polymers can range from about 1,000 to about 1,000,000 (e.g., about 1,200 to about 500,000 or about 1,200 to about 5,000).
In certain embodiments, the viscosity improver is at least one of linear or star-shaped polymers of methacrylate, linear or star-shaped copolymers of methacrylate, butadiene, olefins, alkylated styrenes, polyisobutylene, polymethacrylate (e.g., copolymers of various chain length alkyl methacrylates), copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, or combinations thereof. For example, the viscosity improver may include styrene-isoprene or styrene-butadiene based polymers of about 50,000 to about 200,000 molecular weight.
Olefin copolymers are commercially available from Chevron Oronite Company LLC under the trade designation “PARATONE®” (such as “PARATONE® 8921” and “PARATONE® 8941”); from Afton Chemical Corporation under the trade designation “HiTEC®” (such as “HiTEC® 5850B”); and from The Lubrizol Corporation under the trade designation “Lubrizol® 7067C”. Hydrogenated polyisoprene star polymers are commercially available from Infineum International Limited, e.g., under the trade designation “SV200” and “SV600”. Hydrogenated diene-styrene block copolymers are commercially available from Infineum International Limited, e.g., under the trade designation “SV 50”.
The polymethacrylate or polyacrylate polymers can be linear polymers which are available from Evnoik Industries under the trade designation “Viscoplex®” (e.g., Viscoplex 6-954) or star polymers which are available from Lubrizol Corporation under the trade designation Asteric™ (e.g., Lubrizol 87708 and Lubrizol 87725).
Illustrative vinyl aromatic-containing polymers useful in the present disclosure may be derived predominantly from vinyl aromatic hydrocarbon monomer. Illustrative vinyl aromatic-containing copolymers useful in the present disclosure may be represented by the following formula:
A-B,
wherein:
A is a polymeric block derived predominantly from vinyl aromatic hydrocarbon monomer, and
B is a polymeric block derived predominantly from conjugated diene monomer.
Although their presence is not required to obtain the benefit of the composition of the present disclosure, viscosity modifiers may be used in an amount of less than about 10 weight percent (e.g. less than about 7 weight percent or less than about 4 weight percent). In certain embodiments, the viscosity improver is present in an amount less than 2 weight percent, less than about 1 weight percent, or less than about 0.5 weight percent, based on the total weight of the composition of the present disclosure. Viscosity modifiers are generally added as concentrates, in large amounts of diluent oil.
As used herein, the viscosity modifier concentrations are given on an “as delivered” basis. The active polymer may be delivered with a diluent oil. The “as delivered” viscosity modifier may contain from about 20 weight percent to about 75 weight percent of an active polymer for polymethacrylate or polyacrylate polymers, or from about 8 weight percent to about 20 weight percent of an active polymer for olefin copolymers, hydrogenated polyisoprene star polymers, or hydrogenated diene-styrene block copolymers, in the “as delivered” polymer concentrate.
Demulsifier(s). In any aspect or embodiment described herein, the composition of the present disclosure comprises at least one (e.g., 1, 2, 3, or 4, or more) demulsifier. The demulsifier may be added to separate emulsions (e.g., water-in-oil). Any demulsifier that is known or that becomes know may be utilized in the composition of the present disclosure. An illustrative demulsifying component is described in EP-A-330,522. This exemplary demulsifying agent is obtained by reacting an alkylene oxide with an adduct obtained by reaction of a bis-epoxide with a polyhydric alcohol. Demulsifiers are commercially available and may be used in conventional minor amounts along with other additives such as antifoam agents. Although their presence is not required to obtain the benefit of the present disclosure, the emulsifier or emulsifiers may be present a combined amount less than 1 weight percent (e.g. less than 0.1 weight percent).
In certain embodiments, the demulsifying agent includes at least one of alkoxylated phenols, phenol-formaldehyde resins, synthetic alkylaryl sulfonates (such as metallic dinonylnaphthalene sulfonates), or a combination thereof. In an embodiment, a demulsifing agent is a predominant amount of a water-soluble polyoxyalkylene glycol having a pre-selected molecular weight of any value in the range of between about 450 and about 5000 or more. In an embodiment, the water soluble polyoxyalkylene glycol demulsifier may also be one produced from alkoxylation of n-butanol with a mixture of alkylene oxides to form a random alkoxylated product.
Polyoxyalkylene glycols useful in the present disclosure may be produced by a well- known process for preparing polyalkylene oxide having hydroxyl end-groups by subjecting an alcohol or a glycol ether and one or more alkylene oxide monomers, such as ethylene oxide, butylene oxide, or propylene oxide, to form block copolymers in addition polymerization, while employing a strong base, such as potassium hydroxide as a catalyst. In such a process, the polymerization is commonly carried out under a catalytic concentration of about 0.3 to about 1.0% by mole of potassium hydroxide to the monomer(s) and at high temperature of about 100° C. to about 160° C. It is well known that the catalyst potassium hydroxide is, for the most part, bonded to the chain-end of the produced polyalkylene oxide in a form of alkoxide in the polymer solution so obtained.
The soluble polyoxyalkylene glycol emulsifier(s) useful in the compositions of the present disclosure may also be one produced from alkoxylation of n-butanol with a mixture of alkylene oxides to form a random alkoxylated product.
Extreme Pressure Agent(s). In any aspect or embodiment described herein, the composition of the present disclosure comprises at least one (e.g., 1, 2, 3, or 4, or more) extreme pressure agent. Any extreme pressure agent that is known or that becomes know may be utilized in the composition of the present disclosure.
The extreme pressure agents can be at least one sulfur-based extreme pressure agents, such as sulfides, sulfoxides, sulfones, thiophosphinates, thiocarbonates, sulfurized fats and oils, sulfurized olefins, the like, or combinations thereof; at least one phosphorus-based extreme pressure agents, such as phosphoric acid esters (e.g., tricresyl phosphate (TCP) and the like), phosphorous acid esters, phosphoric acid ester amine salts, phosphorous acid ester amine salts, the like, or combinations thereof; halogen-based extreme pressure agents, such as chlorinated hydrocarbons, the like, or combinations thereof; organometallic extreme pressure agents, such as thiophosphoric acid salts (e.g., zinc dithiophosphate (ZnDTP) and the like), thiocarbamic acid salts, or combinations thereof; and the like.
The phosphoric acid ester, thiophosphoric acid ester, and amine salts thereof functions to enhance the lubricating performances, and can be selected from known compounds conventionally employed as extreme pressure agents. For example, phosphoric acid esters, a thiophosphoric acid ester, or an amine salt thereof which has an alkyl group, an alkenyl group, an alkylaryl group, or an aralkyl group, any of which contains approximately 3 to 30 carbon atoms, may be employed.
Examples of the phosphoric acid esters include aliphatic phosphoric acid esters such as triisopropyl phosphate, tributyl phosphate, ethyl dibutyl phosphate, trihexyl phosphate, tri-2-ethylhexyl phosphate, trilauryl phosphate, tristearyl phosphate, and trioleyl phosphate; and aromatic phosphoric acid esters such as benzyl phenyl phosphate, allyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, ethyl diphenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, ethylphenyl diphenyl phosphate, diethylphenyl phenyl phosphate, propylphenyl diphenyl phosphate, dipropylphenyl phenyl phosphate, triethylphenyl phosphate, tripropylphenyl phosphate, butylphenyl diphenyl phosphate, dibutylphenyl phenyl phosphate, and tributylphenyl phosphate. In an embodiment, the phosphoric acid ester is a trialkylphenyl phosphate.
Examples of the thiophosphoric acid esters include aliphatic thiophosphoric acid esters such as triisopropyl thiophosphate, tributyl thiophosphate, ethyl dibutyl thiophosphate, trihexyl thiophosphate, tri-2-ethylhexyl thiophosphate, trilauryl thiophosphate, tristearyl thiophosphate, and trioleyl thiophosphate; and aromatic thiophosphoric acid esters such as benzyl phenyl thiophosphate, allyl diphenyl thiophosphate, triphenyl thiophosphate, tricresyl thiophosphate, ethyl diphenyl thiophosphate, cresyl diphenyl thiophosphate, dicresyl phenyl thiophosphate, ethylphenyl diphenyl thiophosphate, diethylphenyl phenyl thiophosphate, propylphenyl diphenyl thiophosphate, dipropylphenyl phenyl thiophosphate, triethylphenyl thiophosphate, tripropylphenyl thiophosphate, butylphenyl diphenyl thiophosphate, dibutylphenyl phenyl thiophosphate, and tributylphenyl thiophosphate. In an embodiment, the thiophosphoric acid ester is a trialkylphenyl thiophosphate.
Also employable are amine salts of the above-mentioned phosphates and thiophosphates. Amine salts of acidic alkyl or aryl esters of the phosphoric acid and thiophosphoric acid are also employable. In an embodiment, the amine salt is an amine salt of trialkylphenyl phosphate or an amine salt of alkyl phosphate.
One or any combination of the compounds selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and an amine salt thereof may be used.
The phosphorus acid ester and/or its amine salt function to enhance the lubricating performance of the composition, and can be selected from known compounds conventionally employed as extreme pressure agents. For example, the extreme pressure agent can be a phosphorus acid ester or an amine salt thereof, which has an alkyl group, an alkenyl group, an alkylaryl group, or an aralkyl group, any of which contains approximately 3 to 30 carbon atoms.
Examples of phosphorus acid esters that may be used includes aliphatic phosphorus acid esters, such as triisopropyl phosphite, tributyl phosphite, ethyl dibutyl phosphite, trihexyl phosphite, tri-2-ethylhexylphosphite, trilauryl phosphite, tristearyl phosphite, and trioleyl phosphite; and aromatic phosphorus acid esters such as benzyl phenyl phosphite, allyl diphenylphosphite, triphenyl phosphite, tricresyl phosphite, ethyl diphenyl phosphite, tributyl phosphite, ethyl dibutyl phosphite, cresyl diphenyl phosphite, dicresyl phenyl phosphite, ethylphenyl diphenyl phosphite, diethylphenyl phenyl phosphite, propylphenyl diphenyl phosphite, dipropylphenyl phenyl phosphite, triethylphenyl phosphite, tripropylphenyl phosphite, butylphenyl diphenyl phosphite, dibutylphenyl phenyl phosphite, and tributylphenyl phosphite. Also favorably employed are dilauryl phosphite, dioleyl phosphite, dialkyl phosphites, and diphenyl phosphite. In certain embodiments, the phosphorus acid ester is a dialkyl phosphite or a trialkyl phosphite.
The phosphate salt may be derived from a polyamine, such as alkoxylated diamines, fatty polyamine diamines, alkylenepolyamines, hydroxy containing polyamines, condensed polyamines arylpolyamines, and heterocyclic polyamines. Examples of these amines include Ethoduomeen T/13 and T/20, which are ethylene oxide condensation products of N-tallowtrimethylenediamine containing 3 and 10 moles of ethylene oxide per mole of diamine, respectively.
In another embodiment, the polyamine is a fatty diamine. The fatty diamine may include mono- or dialkyl, symmetrical or asymmetrical ethylene diamines, propane diamines (1,2 or 1,3), and polyamine analogs of the above. Suitable commercial fatty polyamines are Duomeen C (N-coco-1,3-diaminopropane), Duomeen S (N-soya-1,3-diaminopropane), Duomeen T (N-tallow-1,3-diaminopropane), and Duomeen O (N-oleyl-1,3-diaminopropane). “Duomeens” are commercially available from Armak Chemical Co., Chicago, Ill.
Such alkylenepolyamines include methylenepolyamines, ethylenepolyamines, butylenepolyamines, propylenepolyamines, pentylenepolyamines, etc. The higher homologs and related heterocyclic amines, such as piperazines and N-amino alkyl-substituted piperazines, are also included. Specific examples of such polyamines are ethylenediamine, triethylenetetramine, tris-(2-aminoethyl)amine, propylenediamine, trimethylenediamine, tripropylenetetramine, tetraethylenepentamine, hexaethyleneheptamine, pentaethylenehexamine, etc. Higher homologs obtained by condensing two or more of the above-noted alkyleneamines are similarly useful as are mixtures of two or more of the aforedescribed polyamines.
In one embodiment the polyamine is an ethylenepolyamine. Such polyamines are described in detail under the heading Ethylene Amines in Kirk Othmer's “Encyclopedia of Chemical Technology”, 2nd Edition, Vol. 7, pages 22-37, Interscience Publishers, New York (1965). Ethylenepolyamines can be a complex mixture of polyalkylenepolyamines, including cyclic condensation products.
Other useful types of polyamine mixtures are those resulting from stripping of the above-described polyamine mixtures to leave, as residue, what is often termed “polyamine bottoms”. The alkylenepolyamine bottoms can be characterized as having less than 2%, usually less than 1% (by weight) material boiling below about 200° C. An exemplary sample of such ethylene polyamine bottoms obtained from the Dow Chemical Company of Freeport, Tex. designated “E-100”. These alkylenepolyamine bottoms include cyclic condensation products, such as piperazine, and higher analogs of diethylenetriamine, triethylenetetramine and the like. These alkylenepolyamine bottoms can be reacted solely with the acylating agent or they can be used with other amines, polyamines, or mixtures thereof. Another useful polyamine is a condensation reaction between at least one hydroxy compound with at least one polyamine reactant containing at least one primary or secondary amino group. In an embodiment, the hydroxy compounds are alcohols and amines. The polyhydric alcohols are described below. In one embodiment, the hydroxy compounds are polyhydric amines. Polyhydric amines include any of the above-described monoamines reacted with an alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene oxide, etc.) having from two to about 20 carbon atoms, or from two to about four. Examples of polyhydric amines include tri-(hydroxypropyl)amine, tris- (hydroxymethyl)amino methane, 2-amino-2-methyl-1,3-propanediol, N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine, and N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine. IN an embodiment, the polyhydric amin is tris(hydroxymethyl)aminomethane (THAM).
Polyamines which react with the polyhydric alcohol or amine to form the condensation products or condensed amines, are described above. In an embodiment, the polyamine include at least one of triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), and mixtures of polyamines, such as the above-described “amine bottoms”.
In some embodiments, the extreme pressure additive or additives includes sulphur-based extreme pressure additives, such as dialkyl sulphides, dibenzyl sulphide, dialkyl polysulphides, dibenzyl disulphide, alkyl mercaptans, dibenzothiophene, 2,2′-dithiobis(benzothiazole), or combinations thereof; phosphorus-based extreme pressure additives, such as trialkyl phosphates, triaryl phosphates, trialkyl phosphonates, trialkyl phosphites, triaryl phosphites, dialkylhydrozine phosphites, or combinations thereof; and/or phosphorus- and sulphur-based extreme pressure additives, such as zinc dialkyldithiophosphates, dialkylthiophosphoric acid, trialkyl thiophosphate esters, acidic thiophosphate esters, trialkyl trithiophosphates, or combinations thereof. Extreme pressure additives can be used individually or in the form of mixtures, conveniently in an amount within the range from zero to about 2% by weight of the composition of the present disclosure.
Molybdenum-Containing Compounds (Friction Reducers). Illustrative molybdenum-containing friction reducers useful in the disclosure include, for example, an oil-soluble decomposable organo molybdenum compound, such as Molyvan™ 855 which is an oil soluble secondary diarylamine defined as substantially free of active phosphorus and active sulfur. The Molyvan™ 855 is described in Vanderbilt's Material Data and Safety Sheet as a organomolybdenum compound having a density of 1.04 and viscosity at 100° C. of 47.12 cSt. The organo molybdenum compounds may be useful because of their superior solubility and effectiveness.
Another illustrative molybdenum-containing compound is Molyvan™ L, which is sulfonated oxymolybdenum dialkyldithiophosphate described in U.S. Pat. No. 5,055,174 hereby incorporated by reference.
Molyvan™ A made by R. T. Vanderbilt Company, Inc., New York, N.Y., USA, is also an illustrative molybdenum-containing compound, which contains about 28.8 wt. % Mo, 31.6 wt. % C, 5.4 wt. % H., and 25.9 wt. % S. Also useful are Molyvan™ 855, Molyvan™ 822, Molyvan™ 856, and Molyvan™ 807.
Also useful is Sakura Lube™ 500, which is more soluble Mo dithiocarbamate containing lubricant additive obtained from Asahi Denki Corporation and comprised of about 20.2 wt. % Mo, 43.8 wt. % C, 7.4 wt. % H, and 22.4 wt. % S. Sakura LubeTM 300, a low sulfur molybdenum dithiophosphate having a molybdenum to sulfur ratio of 1:1.07, is a molybdenum- containing compound useful in this disclosure.
Also useful is Molyvan™ 807, a mixture of about 50 wt. % molybdenum ditridecyldithyocarbonate, and about 50 wt. % of an aromatic oil having a specific gravity of about 38.4 SUS and containing about 4.6 wt. % molybdenum, also manufactured by R. T. Vanderbilt and marketed as an antioxidant and antiwear additive.
Other sources are molybdenum Mo(Co)₆, and molybdenum octoate, MoO(C₇H₁₅CO₂)₂containing about 8 wt- % Mo marketed by Aldrich Chemical Company, Milwaukee, Wis. and molybdenum naphthenethioctoate marketed by Shephard Chemical Company, Cincinnati, Ohio.
Inorganic molybdenum compounds, such as molybdenum sulfide and molybdenum oxide, are substantially less preferred than the organic compounds as described in Molyvan™ 855, Molyvan™ 822, Molyvan™ 856, and Molyvan™ 807.
Illustrative molybdenum-containing compounds useful in this disclosure are disclosed, for example, in U.S. Patent Application Publication No. 2003/0119682, which is incorporated herein by reference.
Organo molybdenum-nitrogen complexes may also be included in the formulations of the present disclosure. The term “organo molybdenum nitrogen complexes” embraces the organo molybdenum nitrogen complexes described in U.S. Pat. No. 4,889,647. The complexes are reaction products of a fatty oil, dithanolamine and a molybdenum source. Specific chemical structures have not been assigned to the complexes. U.S. Pat. No. 4,889,647 reports an infrared spectrum for an exemplary reaction product of that disclosure; the spectrum identifies an ester carbonyl band at 1740 cm 1 and an amide carbonyl band at 1620 cm 1. The fatty oils are glyceryl esters of higher fatty acids containing at least 12 carbon atoms up to 22 carbon atoms or more. The molybdenum source is an oxygen-containing compound such as ammonium molybdates, molybdenum oxides and mixtures.
Other organo molybdenum complexes which can be used in the present disclosure are tri nuclear molybdenum sulfur compounds described in EP 1 040 115 and WO 99/31113, and the molybdenum complexes described in U.S. Pat. No. 4,978,464.
Although their presence is not required to obtain the benefit of the present disclosure, molybdenum-containing additives may be used in an amount of from zero to about 5.0 (e.g., <about 5, ≤ about 4, ≤ about 3, ≤ about 2, or ≤ about 1) percent by mass of the composition of the present disclosure. For example, the dosage may be up to about 3,000 ppm by mass, such as from about about 100 ppm to about about 2,500 ppm by mass, from about 300 to about 2,000 ppm by mass, or from about 300 to about 1,500 ppm by mass of molybdenum.
The articles “a” and “an” herein refer to one or to more than one (e.g. at least one) of the grammatical object. Any ranges cited herein are inclusive. The term “about” used throughout is used to describe and account for small fluctuations. For instance, “about” may mean the numeric value may be modified by ±5%, ±4%, ±3%, ±2%, ±1%, ±0.5%, ±0.4%, ±0.3%, ±0.2%, ±0.1% or ±0.05%. All numeric values are modified by the term “about” whether or not explicitly indicated. Numeric values modified by the term “about” include the specific identified value. For example “about 5.0” includes 5.0.
U.S. patents, U.S. patent applications and published U.S. patent applications discussed herein are hereby incorporated by reference.
Unless otherwise indicated, all parts and percentages are by weight. Weight percent (wt %), if not otherwise indicated, is based on an entire composition free of any volatiles.

EXAMPLE 1

Polymer Preparation

An antioxidant diphenyl amine monomer mixture containing N,N-diphenylamine, N,N-di-(p-tert-butylphenyl)amine, N,N-di-(p-tert-octylphenyl)amine, N-(p-tert-butylphenyl)-N-phenylamine, N-(p-tert-octylphenyl)-N-phenylamine and N-(p-tert-butylphenyl)-N-(p-tert-octylphenyl)amine is charged together with n-decane to a 3 L glass reactor connected to a Dean-Stark head with a reflux condenser. The mixture is heated to 135° C. and t-butylperoxide is added dropwise with stirring. The temperature is maintained at 135° C. to 140° C. with stirring and t-butanol is distilled off. Samples are removed and tested for viscosity. Upon reaching a desired viscosity, unreacted peroxide is removed under reduced pressure, then the mixture is heated under reduced pressure to remove remaining volatiles. The diphenyl amine monomer mixture is CAS number 68411-46-1; N-phenyl-benzenamine reaction products with 2,4,4-trimethylpentene.
The monomer mixture exhibits a viscosity of 9.1 cSt (monomer). Polymers or oligomers are prepared having viscosities of 21 cSt (inventive sample 1), 81 cSt (inventive sample 2) and 100 cSt (inventive sample 3). Viscosity is kinematic viscosity at 100° C. determined according to ASTM D445.
The viscosity and Mn of the samples can be controlled by, e.g., the length of the reaction or the feed of the peroxide.

EXAMPLE 2

Bench Testing

Fully formulated oils are prepared containing 81.8% base stock, 16.2% additives and 2%, each by weight, of the samples of Example 1. All formulated oils exhibit a viscosity at 40° C. of from 52-53 cSt according to ASTM D445. The samples are tested for total deposits according to TEOST MHT 4 test (ASTM D7097), a bench test used to evaluate oil performance relative to forming moderately high temperature piston deposits when subjected to high power and temperature operating conditions. The samples are also tested for total deposits according to TEOST 33C (ASTM D6335), a test that simulates the effect of engine operating conditions on the oxidation and deposit-forming tendencies of engine oils, especially in the high temperature turbocharger area. Total deposits results (mg) are below.


sample	TEOST MHT 4	TEOST 33C

monomer	55	36
inventive 1	45	36
inventive 2	41	33
inventive 3	35	31

Inventive samples are superior regarding deposits formation.

EXAMPLE 3

Engine Testing

The formulated oils containing inventive sample 3 and the monomer mixture are tested according to a modified Sequence IIIH engine test. The additives are each added to an engine oil at 2 wt %. The Sequence IIIH Test (ASTM D8111) is a fired-engine, dynamometer lubricant test for evaluating automotive engine oils for certain high-temperature performance characteristics, including oil thickening, varnish deposition and oil consumption. Results are below.


	monomer	inventive 3

EOT % viscosity increase	432%	68%
weighted piston deposit merits	4.72	5.06
average piston varnish merits	9.61	9.87

EOT % viscosity increase is “end of test” viscosity increase. The inventive 3 sample provides for outstanding viscosity performance while maintaining improved deposits performance. Higher “merits” is better.

EXAMPLE 4

Color

The formulated oils containing inventive sample 3 and the monomer mixture exhibit an ASTM D1500 color rating of 4.0 and 3.5, respectively.

EXAMPLE 5

It is demonstrated that m/z ions in the isolated polymers and oligomers show a correlation to increased performance in a VIT test.
The table below shows that the m/z ion counts at 838, 984 and 911 Daltons are significantly higher than the #4 residue which has a lower VIT result. The higher the VIT value, the better the antioxidant

Reference	470	0	0	0
Sample 1	830	296	225	65
Sample 2	797	386	179	65
Sample 3	533	49	65	8

FIG. 1 shows a trend that VIT performance is better when there is a greater amount of dimers and trimers as compared to the amount of higher polymers (4+) in conjunction with the LC/MS data that yields the 838 and 894 (which corresponds to 837 and 893 Daltons)

EXAMPLE 6

A polymeric composition of the present disclosure is included as a component in a grease formulation as shown below.


	Formulation Details (wt %)

Base Stocks	71.5-73%	71.5-73%	71.5-73%
Thickener	7-8.5	7-8.5	7-8.5
Additives	13.37	13.37	13.37
(Standard) IRGANOX L57	1.00	2.00	0.00
Inventive 3	0.00	0.00	1.00
Total	100	100	100

Testing Results

ASTM D445 - Kinematic Viscosity	220.0	220.0	220.0
at 40° C. (cSt)
ASTM D217 - Penetration, Worked	287.0	287.0	294.0
(0.1 mm)
ASTM D5483 PDSC of Greases	23	N/A	17.3
(Isothermal at 210 C.)
ASTM D942 - Pressure Vessel	1.1	N/A	2.4
Oxidation Test @ 100 hrs
(psi drop)
ASTM D942 - Pressure Vessel	8	N/A	10.4
Oxidation Test @ 100 hrs
(psi drop)
DIN 51821 FAG FE9 FE9	84.0		135.0
A/1500/6000 @ 140 C.
(B50, hours)

All of the formulations in the above Table are Lithium complex (thickner type) greases, with ISO Viscosity grades of 220 and an NLGI consistency grade of 2. Common grease thickener types are simple lithium soap, lithium complex soap, polyurea, calcium sulfonate, aluminum soap, calcium soap, mixed aluminum/calcium, clay and polymer thickened. Greases contain, e.g., 70-80% basestock, 0.1-20% thickener, and 0-20% additives. The data demonstrates that the inventive example treated at 1% has the same oxidative performance as the commercial example treated at 1% in grease bench oxidation tests (ASTM D5483 and D942). However, when the same greases were tested in the DIN 51821 FAG FE9 test (rig test-high temperature bearing performance of a grease) the grease with the inventive example demonstrated superior performance compare to the grease that contained 1% commercial example and the grease that contained 2% of the commercial example. This is unexpected given the equivalent performance in the bench oxidation testing. According to the above data, the inventive polymer composition can be utilized in the preparation of a grease to improve high temperature bearing performance.

EXAMPLE 7

A polymeric composition of the present invention is included as a component in an industrial oil formulation as shown below.


Base Stocks	97.94	97.94	97.94	97.94	97.94	97.94
Additives	13.37	13.37	13.37	13.37	13.37	13.37
(Standard)	1.00	0.00	0.00	0.70	0.00	0.00
IRGANOX L57
Inventive 3	0.00	1.00	0.00	0.00	0.00	0.00
Inventive 7	0.00	0.00	1.00	0.00	0.70	0.00
Inventive 8	0.00	0.00	0.00	0.00	0.00	0.70
Total	100	100	100	100	100	100

Testing Results

ASTM	30.4	30.8	31.1	30.6	30.9	31
Viscosity
D445-Kinematic
at 40° C. (cSt)
ASTM D2272-	1974.0	2119.0	2036	2207	2611	2027
RPVOT
at 150 C. (min)
High Pressure	222.2	193.1	236.58	47.3	94.03	20
Differential
Scanning
Calorimetry
(min)

EXAMPLE 8

A polymeric composition of the present invention is included as a component in a passenger vehicle lubricant formulation as shown below.


	Formulation Details (wt %)

Base Stocks	81.76	81.76	81.76	81.76	81.76	81.76	81.76
Additives	16.24	16.24	16.24	16.24	16.24	16.24	16.24
(Standard) IRGANOX L57	2.00	0.00	0.00	0.00	0.00	0.00	0.00
Inventive 2	0.00	2.00	0.00	0.00	0.00	0.00	0.00
Inventive 1	0.00	0.00	2.00	0.00	0.00	0.00	0.00
Inventive 3	0.00	0.00	0.00	2.00	0.00	0.00	0.00
Inventive 7	0.00	0.00	0.00	0.00	2.00	0.00	0.00
Inventive 8	0.00	0.00	0.00	0.00	0.00	2.00	0.00
Inventive 9	0.00	0.00	0.00	0.00	0.00	0.00	2.00
Total	100	100	100	100	100	100	100

Testing Results

ASTM D445-Kinematic	51.9	52.6	53.2	53.2	53.7	53.4	54.4
Viscosity at 40° C. (cSt)
ASTM D7097-TEOST MHT4	55.0	45.2	41.0	34.8	—	—	—
(Total deposits, mg)
ASTM D6335-TEOST 33 C.	35.8	36.2	33.0	30.8	—	—	—
(Total deposits, mg)
ASTM D1500-Color	3.5	TBD	TBD	4.0	5.5	6	5
ASTM D8111-Sequence IIIH,	432%	—	—	68%	114.6	240.3	172.2
EOT % Viscosity increase
ASTM D8111-Sequence IIIH,	4.72	—	—	5.06	5.15	4.27	4.87
Weighted Piston Deposit Merits
ASTM D8111-Sequence IIIH,	9.61	—	—	9.87	9.68	9.47	9.68
Average Piston Varnish Merits

EXAMPLE 9

A polymeric composition of the present invention is included as a component in a commercial vehicle lubricant formulation as shown below.


	Formulation Details (wt %)

Base Stocks	80.38	80.38
Additives	18.22	18.22
(Standard) IRGANOX L57	1.40	0.00
Inventive 3	0.00	1.40
Total	100	100

Testing Results

ASTM D445 - Kinematic Viscosity	56.7	54.4
at 40° C. (cSt)
ASTM D8048 - Volvo T-13,	70.6	78.9
EOT % Viscosity Increase
ASTM D8048 - Volvo T-13,	148.0	127.0
IR Peak Increase

Legend for the above Examples


Inventive Antioxidant
Polymers#

Inventive 1	Lower molecular weight oligomeric material
Inventive 2	Lower molecular weight oligomeric material
Inventive 3	Lower molecular weight oligomeric material
Inventive 4	Oligomers no diluent
Inventive 5	Oligomers no diluent
Inventive 6	Isolated Substance, OECD polymer
	75% Mn > 1000
Inventive 7	75% Mn > 1000 plus L57 as diluent
Inventive 8	75% Mn > 1000 plus L57 as diluent
Inventive 9	75% Mn > 1000 plus L57 as diluent

VIT (h to pvisc 150)

1. A lubricating oil composition comprising

a base oil; and

from about 0.01 wt % to about 20 wt %, based on the total weight of the lubricating oil composition, of an antioxidant polymer composition comprising repeat units of diphenylamine monomers of formula I

wherein

R is H, C₁-C₁₈alkyl, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, —C(O)C₁-C₁₈alkyl, —C(O)aryl and R₁, R₂, R₃and R₄are each independently H or a linear or branched C₁-C₁₈alkyl, C₁-C₁₈alkoxy, C₁-C₁₈alkylamino, C₁-C₁₈dialkylamino, C₁-C₁₈alkylthio, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl or C₇-C₂₁aralkyl and

wherein

the number average molecular weight (Mn) of the polymer composition is from about 350 g/mol to about 5000 g/mol.

2. The lubricating oil composition according to claim 1, comprising one or more components selected from the group consisting of other antioxidants, antiwear additives, viscosity index improvers, detergents, dispersants, pour point depressants, corrosion inhibitors, metal deactivators, seal compatibility additives, antifoam agents, inhibitors, antirust additives, and friction modifiers.

3. The lubricating oil composition according to claim 1, wherein the Mn of the polymer composition is from about 400 g/mol to about 5000 g/mol.

4. The lubricating oil composition according to claim 1, wherein R₁, R₂, R₃and R₄are each independently H or a linear or branched C₄-C₁₀alkyl.

5. The lubricating oil composition according to claim 1, wherein R is H.

6. The lubricating oil composition according to claim 1, wherein the polymer composition further comprises one or more monomers selected from the group consisting of other diphenylamines, phenothiazines, phenoxazines, aminodiphenylamines, methylenedianiline, toluenediamine, aminophenols, alkylphenols, thiophenols, phenylenediamines, quinolines, phenyl pyridinediamines, pyridinepyrimidinediamines and phenylpyrimidinediamines.

7. The lubricating oil composition according to claim 1, wherein the polymer composition comprises from about 10 mol % to about 99 mol % diphenylamine monomers.

8. The lubricating oil composition according to claim 1, wherein the polymer composition comprises <70 wt % residual monomers of formula I.

9. The lubricating oil composition according to claim 1, wherein the polymer composition comprises from about 1 wt % to about 70 wt % residual monomers of formula I, based on the total weight of the polymer composition.

10. The lubricating oil composition according to claim 1, wherein the viscosity of the polymer composition is from about 20 cSt to about 600 cSt.

11. The lubricating oil composition according to claim 1, wherein the polymer composition is a solid.

12. The lubricating oil composition according to claim 1, wherein the base oil comprises a natural oil or a synthetic oil.

13. The lubricating oil composition according to claim 1, wherein the base oil comprises a mineral oil, a polyalphaolefin, an alkyl naphthalene or a gas-to-liquid base stock.

14. The lubricating oil composition according to claim 1, comprising from about 50 wt % to about 90 wt % base oil, based on the total weight of the lubricating oil composition.

15. The lubricating oil composition according to claim 1, which exhibits color of <about 5.5according to ASTM D1500.

16. The lubricating oil composition according to claim 1, comprising an antioxidant combination of the polymer composition and one or more antioxidants selected from the group consisting of further aminic and phenolic antioxidants.

17. The lubricating oil composition according to claim 1, comprising an antioxidant combination of the polymer composition and one or more further compounds selected from the group consisting of N,N-di-(p-tert-butylphenyl)amine, N,N-di-(p-tert-octylphenyl)amine, N-(p-tert-butylphenyl)-N-phenylamine, N-(p-tert-octylphenyl)-N-phenylamine and N-(p-tert-butylphenyl)-N-(p-tert-octylphenyl)amine, bis-nonylphenyldiphenylamine, N-(tert-C₁-C₂₀alkylphenyl)-1-naphthylamine and 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid octyl ester.

18. A lubricating oil composition comprising

a base oil; and

from about 0.01 wt % to about 20 wt %, based on the total weight of the lubricating oil composition, of a polymer composition comprising repeat units of diphenylamine monomers of formula I

wherein

R is H, C₁-C₁₈alkyl, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, —C(O)C₁-C₁₈alkyl, —C(O)aryl and R₁, R₂, R₃and R₄are each independently H or a linear or branched C₁-C₁₈alkyl, C₁-C₁₈alkoxy, C₁-C₁₈alkylamino, C₁-C₁₈dialkylamino, C₁-C₁₈alkylthio, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl or C₇-C₂₁aralkyl, and

wherein the polymer composition comprises ≤70 wt % residual monomers of formula I.

19. The lubrication oil composition according to claim 18, wherein the polymer composition comprises ≤30 wt % residual monomers of formula I.

20. The lubricating oil composition according to claim 18, wherein the polymer composition comprises from about 1 wt % to about 70 wt % residual monomers of formula I, based on the total weight of the polymer composition.

21. A method of reducing extending an oil drain interval, the method comprising adding to the engine the lubricating oil composition of claim 1.

22. A method of improving oxidative stability of a lubricating oil in an engine, the method comprising adding to the engine the lubricating oil composition of claim 1.

23. A process of providing a lubricating oil composition oxidative stability, deposits control and viscosity control, the process comprising incorporating a polymer composition comprising repeat units of diphenylamine monomers of formula I

wherein

the number average molecular weight (Mn) of the polymer composition is from about 350 g/mol to about 5000 g/mol;

into a base oil,

wherein the lubricating oil composition comprises from about 0.01 wt % to about 20 wt %, based on the total weight of the lubricating oil composition, of the polymer composition.

24. The lubricating oil composition of claim 1, wherein the polymer composition is an oligomer composition.

25. The lubricating oil composition of claim 18, wherein the polymer composition is an oligomer composition.