LOW VISCOSITY/LOW VOLATILITY LUBRICANT OIL COMPOSITIONS

COMPRISING ALKYLATED NAPHTHALENES

[0001] This application claims the benefit of U.S. provisional application no. 61/886,410, filed October 3, 2013, which is herewith incorporated by reference in its entirety.

1 FIELD

[0002] Provided herein are low viscosity, low volatility lubricant oil compositions comprising a first base oil component comprising, for example, alkylated naphthalenes, and a second base oil component wherein the composition has a kinematic viscosity at 100°C of about 7.6 cSt or less, a Noack volatility at 250°C of less than about 10%, and a viscosity index of at least about 90 for use as internal combustion engine oils, such as compression- or spark-ignition engine oils.

2 BACKGROUND

[0003] Lubricating oils are critical to the operation of the machinery of the world today.

Synthetic lubricants in the engine crankcase, rear axle, and transmission can improve fuel economy by about 3 percent, saving nearly 485 gallons of fuel and eliminating 5 metric tons of greenhouse gas emissions for a typical combination truck each year. Lubricants reduce friction and wear of critical vehicle systems including the engine, transmission and drive train. Without lubricants, the moving parts inside these systems would grind together, causing heat, stress and wear. Recent changes in legislation and new emission standards, for example PC-11 for heavy- duty diesel engines and GF-6 for passenger automobiles, have increased pressure on vehicle manufacturers to improve fuel efficiency and reduce emissions.

[0004] Within an engine there are two types of friction that impact fuel economy. One that is related to the thickness of the oil classified as viscous friction which leads to energy losses due to the pumping of the viscous oil through the engine, especially during cold engine start up and stop and go driving. The other, contact friction resulting from contact between moving metal surfaces leads to engine wear and reduced fuel economy. [0005] Conventional mineral oil lubricants due to their higher viscosity are unable to effectively slip between and lubricate the moving parts of these systems, particularly in newer truck components that are designed with close tolerances and tight fits. Conventional higher viscosity lubricants may also be making it harder for pumps, gears and shafts to move. These effects create energy losses and friction losses, and waste fuel.

[0006] Low-viscosity lubricants are less resistant to flow than lubricants presently known, a property that helps reduce friction and lowering the energy wasted pumping the oil through the engine.

[0007] Attempts have been made to use conventional low viscosity polyalphaolefin

("PAO") base stocks to achieve low viscosity engine oil formulations. The volatility

requirements for engine oils, however, limit the amount of low viscosity conventional PAO that can be used and the extent to which the viscosity of the engine oil formulation can be reduced.

[0008] Therefore, new low viscosity/low volatility lubricant oil compositions to further improve fuel efficiency are desirable.

3 SUMMARY

[0009] Provided herein is a lubricant oil composition comprising

(a) a first base oil component in the amount of about 1 weight % to about 50 weight % based on the total weight of the oil composition, wherein the first base oil component comprises a compound of Formula I

(I)

wherein R is (Cig-C4o)alkyl, (C5-C4o)cycloalkyl, (C ₅ -C ₄₀ )aryl, (C ₇ -C9)aralkyl; wherein the aralkyl is optionally substituted with (Ci-C3 ₆ )alkyl, or (C ₆ - C4o)alkenyl; and

(b) a second base oil component in the amount of about 0.1 weight % to about 80 weight % based on the total weight of the oil composition, wherein the second base oil component comprises one or more of a polyalphaolefm(PAO) base stock, Group II base stock, Group III base stock, Group V base stock, GTL base stock, alkylated benzene base stock, and ester base stock;

wherein the composition has a kinematic viscosity at 100°C of about 7.6 cSt or less, a Noack volatility at 250°C of less than about 10%, and a viscosity index of at least about 90.

[0010] Provided herein is an internal combustion engine oil, such as a compression- ignition engine oil or a spark-ignition engine oil, comprising a lubricant oil composition provided herein.

4 DETAILED DESCRIPTION 4.1 Definitions

[0011] An "alkyl" is a saturated straight chain or branched non-cyclic hydrocarbon having, for example, from 18 to 40 carbon atoms, 18 to 32 carbon atoms, 20 to 24 carbon atoms, 18 carbon atoms, 20 carbon atoms, or 32 carbon atoms. Representative alkyls include, for example, -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl and, -n-hexyl; while branched alkyls include, for example, -isopropyl, -sec-butyl, -z ^' so-butyl, -tert-butyl, -z ^' so-pentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2,3-dimethylbutyl, Guerbet alkyl and the like.

[0012] A "Guerbet alkyl" is a beta-branched alkyl of the general formula: (C _n -C _m )alkyl-

CH[(C( _n _2 ₎ -C _(m _ ₂₎ )alkyl]-CH ₂ -, wherein n < m, and wherein n and m are independently integers equal or greater than 6, but equal or less than 18, resulting in a (C ₂ n-C _2m ) Guerbet alkyl. For example, in a (C 18-C32) Guerbet alkyl, n is 9 and m is 18. In certain embodiments, the (C _n - C _m )alkyl and (C _(n _ ₂₎ -C _(m _ ₂₎ )alkyl groups of the Guerbet alkyl may be branched. Representative Guerbet alkyls include, for example, 2-butyl-octanyl, 2-hexyl-decanyl, 2-octyl-dodecanyl, 2- decyl-tetradecanyl, and 2-dodecyl-hexadecanyl.

[0013] A "cycloalkyl" is a saturated cyclic alkyl having, for example, from 3 to 12 carbon atoms or 5 to 40 carbon atoms, having a single cyclic ring or multiple condensed or bridged rings. Representative alkyls include, for example, single ring structures such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like, or multiple or bridged ring structures such as adamantyl and the like. [0014] An "aryl" is an aromatic carbocyclic group having, for example, from 6 to 40 carbon atoms having a single ring (e.g., phenyl) or multiple condensed rings (e.g., naphthyl or anthryl). Representative aryls include, for example, phenyl, naphthyl, and the like.

[0015] An "aralkyl" is an aryl-substituted alkyl group having, for example, an aryl substituted (C ₇ -Cc>)alkyl. Representative aralkyls include, for example, benzyl, diphenylmethyl, triphenylmethyl, phenylethyl, phenylbutyl, and diphenylethyl.

[0016] A "base oil" and "base stock" as referred to herein is to be considered consistent with the definitions as stated in API BASE OIL INTERCHANGEABILITY GUIDELINES FOR PASSENGER CAR MOTOR OILS AND DIESEL ENGINE OILS, July 2009 Version—

APPENDIX E. According to Appendix E, base oil is the base stock or blend of base stocks used in an API-licensed oil. Base stock is a lubricant component that is produced by a single manufacturer to the same specifications (independent of feed source or manufacturer's location) that meets the same manufacturer's specification and that is identified by a unique formula, product identification number, or both.

4.2 Lubricant Oil Compositions

[0017] Provided herein is a lubricant oil composition comprising

(a) a first base oil component in the amount of about 1 weight % to about 50 weight % based on the total weight of the oil composition, wherein the first base oil component comprises a compound of Formula I

(I)

wherein R is (Ci ₈ -C ₄ o)alkyl, (C ₅ -C ₄₀ )cycloalkyl, (C ₅ -C ₄₀ )aryl, (C ₇ -C ₉ )aralkyl; wherein the aralkyl is optionally substituted with (Ci-C36)alkyl, or (C ₆ - C ₄ o)alkenyl; and

(b) a second base oil component in the amount of about 0.1 weight % to about 80 weight % based on the total weight of the oil composition, wherein the second base oil component comprises one or more of a polyalphaolefm(PAO) base stock, Group II base stock, Group III base stock, Group V base stock, GTL base stock, alkylated benzene base stock, and ester base stock;

wherein the composition has a kinematic viscosity at 100°C of about 7.6 cSt or less, a Noack volatility at 250°C of less than about 10%, and a viscosity index of at least about 90.

[0018] In one embodiment, the lubricant oil composition has a kinematic viscosity at

100°C of about 7.6 cSt or less, about 7.0 cSt or less, about 6.5 cSt or less, about 6.0 cSt, about 5.5 cSt or less, or about 5.0 cSt or less, a Noack volatility at 250°C of less than about 10%, less than about 9%, less than about 8%, less than about 7%, or less than about 6%, and a viscosity index of at least about 90, at least about 95, at least about 100, at least about 105, at least about 110, at least about 115, or at least about 120.

[0019] Provided herein is an internal combustion engine oil, such as an compression- ignition engine oil and a spark-ignition engine oil, comprising a lubricant oil composition provided herein.

[0020] In one embodiment, the lubricant oil composition provided herein has one or more of the following properties selected from the group consisting of oxidation resistance, swell characteristics, deposit performance, reserve alkalinity, rust preventing quality, and levels of ash- forming compound, improved as compared to an oil composition comprising a second base oil component as provided herein, but not comprising the first base oil component as provided herein.

[0021] The kinematic viscosity of the lubricant oil compositions provided herein may be determined by any suitable method known to the person of ordinary skill in the art. In one embodiment, the kinematic viscosity is determined using a standardized method, such as ASTM D445, 2012, "Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (and Calculation of Dynamic Viscosity)," ASTM International, West Conshohocken, PA, 2012, DOI: 10.1520/D0445-12, www.astm.org.

[0022] The Noack volatility of the lubricant oil compositions provided herein may be determined by any suitable method known to the person of ordinary skill in the art. In one embodiment, the kinematic viscosity is determined using a standardized method, such as ASTM D5800, 2010, "Standard Test Method for Evaporation Loss of Lubricating Oils by the Noack Method," ASTM International, West Conshohocken, PA, 2010, DOI: 10.1520/D5800-10, www.astm.org.

[0023] The viscosity index of the lubricant oil compositions provided herein may be determined by any suitable method known to the person of ordinary skill in the art. In one embodiment, the viscosity index is determined using a standardized method, such as ASTM D2270, 2010el , "Standard Practice for Calculating Viscosity Index From Kinematic Viscosity at 40 and 100°C," ASTM International, West Conshohocken, PA, 2010, DOI: 10.1520/D2270- 10E01 , www.astm.org.

[0024] In one embodiment, the lubricant oil composition provided herein has a CCS viscosity of less than 3500cP at -35°C as determined by ASTM D5293, and an HTHS viscosity of less than 2.6 mPa-s at 150° C as determined by ASTM D4683. In a further embodiment, the lubricant oil composition provided herein has a kinematic viscosity of from about 20 to about 80 cSt, or from about 30 to about 40 cSt as measured at 40° C in accordance with the ASTM D445, for example, ASTM D445, 2012, "Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (and Calculation of Dynamic Viscosity)," ASTM International, West Conshohocken, PA, 2012, DOI: 10.1520/D0445-12, www.astm.org. In another embodiment, the lubricant oil composition provided herein shows a kinematic viscosity range from at 100°C from about 4 to about 6 cSt.

4.2.1 First Base Oil Component

[0025] Provided herein is a lubricant oil composition comprising a first base oil component in the amount of about 1 weight % to about 50 weight % based on the total weight of the oil composition, wherein the first base oil component comprises a compound of Formula I

Formula I

wherein R is (Ci ₈ -C ₄ o)alkyl, (C ₅ -C ₄₀ )cycloalkyl, (C ₅ -C ₄₀ )aryl, (C ₇ -C ₉ )aralkyl; and wherein the aralkyl is optionally substituted with (Ci-C3 ₆ )alkyl or (C6-C ₄ o)alkenyl. [0026] In one embodiment, the first base oil component has a kinematic viscosity at

100°C of equal or less than about 7.0 cSt, a Noack volatility at 250°C of less than about 8%, and a viscosity index equal or higher than about 80. In another embodiment, the first base oil component has a kinematic viscosity at 100°C of about 6.0 cSt or less. In one embodiment, the first base oil component has a pour point of about 0°C or less.

[0027] In another embodiment, the first base oil component has a kinematic viscosity at

100°C of equal or less than about 7.0 cSt, equal or less than about 6.5 cSt, equal or less than about 6.0 cSt, equal or less than about 5.5 cSt, equal or less than about 5.0 cSt, or from about 5.0 cSt to about 7.0 cSt, a Noack volatility at 250°C of less than about 8%, less than about 12%, less than about 11%, less than about 10%, less than about 9%, less than about 7%, less than about 6%), less than about 5%, or less than about 4%, and a viscosity index equal or higher than about 80, or higher than about 85, or higher than about 90, or higher than about 95, or higher than about 100.

[0028] The kinematic viscosity, Noack volatility or viscosity index of the first base oil component of the lubricant oil composition provided herein may be determined by any suitable method known to the person of ordinary skill in the art. In one embodiment, the kinematic viscosity, Noack volatility and viscosity index is determined using the standardized methods referenced in Section 4.2 hereinabove.

[0029] Further provided herein is a lubricant oil composition comprising a first base oil component in the amount of about 1 wt % to about 40 wt %, about 1 wt % to about 30 wt %, about 1 wt % to about 20 wt %, about 1 wt % to about 10 wt %, about 5 wt % to about 50 wt %, about 10 wt % to about 50 wt %, about 20 wt % to about 50 wt %, about 30 wt % to about 50 wt %, about 40 wt % to about 50 wt %, about 10 wt % to about 20 wt %, about 20 wt % to about 30 wt %, or about 10 wt % to about 40 wt %, based on the total weight of the oil composition. In one embodiment, the lubricant oil composition comprises a first base oil component in the amount of about 20 wt % to about 30 wt % based on the total weight of the oil composition.

[0030] In one embodiment, the first base oil component comprises a compound of

Formula I, wherein R is In one embodiment, the first base oil component comprises a compound of Formula I, wherein R is (C ₂₀ -C ₂₄ )alkyl. In one embodiment, the first base oil component comprises a compound of Formula I, wherein R is C ₁₈ alkyl. In one embodiment, the first base oil component comprises a compound of Formula I, wherein R is C ₂ o alkyl. In one embodiment, the first base oil component comprises a compound of Formula I, wherein R is C ₃₂ alkyl.

[0031] In one embodiment, the first base oil component comprises a mixture of two or more compounds of Formula I. For example, the first base oil component comprises a mixture of 2, 3, 4, 5, 6, 7, 8, 9, or 10 or more compounds of Formula I. In one embodiment, the first base oil component comprises a mixture of two or more compounds of Formula I, wherein at least one compound is a compound of Formula I, wherein R is a C ₂ o alkyl and at least one compound is a compound of Formula I, wherein R is a C ₂₄ alkyl. In another embodiment, the first base oil component comprises a mixture of two or more compounds of Formula I, wherein at least one compound is a compound of Formula I, wherein R is a C ₁₈ alkyl and at least one compound is a compound of Formula I, wherein R is a (C ₂ o-C ₂₄ )alkyl.

[0032] In one embodiment, the first base oil component comprises a compound of

Formula I, wherein R is (Ci ₈ -C ₃₂ ) Guerbet alkyl. In one embodiment, the first base oil component comprises a compound of Formula I, wherein R is C ₁₈ Guerbet alkyl. In one embodiment, the first base oil component comprises a compound of Formula I, wherein R is C ₂ o Guerbet alkyl. In one embodiment, the first base oil component comprises a compound of Formula I, wherein R is C ₂₄ Guerbet alkyl. In one embodiment, the first base oil component comprises a compound of Formula I, wherein R is C ₂ 8 Guerbet alkyl. In one embodiment, the first base oil component comprises a compound of Formula I, wherein R is C ₃₂ Guerbet alkyl.

[0033] In one embodiment, the first base oil component comprises a mixture of two or more compounds of Formula I, wherein R for each of the two or more compounds is

independently selected from (Ci ₈ -C ₄ o)alkyl, (Cs-C ₄ o)cycloalkyl, (C ₅ -C ₄ o)aryl, (C ₇ -C9)aralkyl, (Ci ₈ -C ₃₂ )alkyl, (C ₂₀ -C ₂₄ )alkyl, Ci ₈ alkyl, C ₂₀ alkyl, C ₃₂ alkyl, (Ci ₈ -C ₃₂ ) Guerbet alkyl, Ci ₈

Guerbet alkyl, C ₂ o Guerbet alkyl, C ₂₄ Guerbet alkyl, C ₂₈ Guerbet alkyl, or C ₃₂ Guerbet alkyl.

[0034] In one embodiment, the compound of Formula I is a compound, wherein R is Ci-

C ₃ oo linear alkyl, or a Ci ₂ -C ₃₂ linear alkyl or a Ci ₈ -C ₃₂ branched alkyl. In one embodiment, the compound of Formula I is a compound, wherein R is a C ₃ alkyl, a C ₄ alkyl, a C ₅ alkyl, a C ₆ alkyl, a C8 alkyl, a C ₁₀ alkyl, a C ₁₂ alkyl, a C ₁₄ alkyl, a C ₁₆ alkyl, or a C ₁₈ alkyl. In another embodiment, the first base oil component is a mixture of C ₁₀ -C ₁₄ alkyl naphthalenes, or a mixture of C ₆ - Ci8 alkyl naphthalenes, or the mono C ₃ , C ₄ , C ₅ , C ₆ , C ₈ , C ₁₀ , C ₁₂ , C ₁₄ , C ₁₆ , C ₁₈ alkyl naphthalene and mixtures thereof, or the alkyl-derivatives of monomethyl, dimethyl, ethyl, diethyl, or methylethyl naphthalenes, or mixtures thereof.

[0035] In a further embodiment, the compound of Formula I is a compound, wherein R is a C10-C300 branched alkyl, or C24-C56 branched alkyl.

[0036] The compounds Formula I can be prepared by methods known to the person of ordinary skill in the art. In particular, suitable methods involve the alkylation of naphthalene with an olefin, alcohol, alkyl halide, or other alkylating agents known to those of ordinary skill in the art in the presence of a catalyst. The catalyst is a suitable Lewis acid or super acid. Suitable Lewis acids are, for example, boron trifluoride, iron trichloride, tin tetrachloride, zinc dichloride, and antimony pentafluoride. Furthermore, acidic clays, silica, or alumina are suitable. See for example U.S. Pat. Nos. 4,604,491 and 4,764,794, all of which are incorporated herein by reference in their entireties. Suitable super acid catalysts include trifluoromethane sulfonic acid, hydrofluoric acid or trifluoromethylbenzene sulfonic acid. Other suitable catalysts include acidic zeolite catalysts, such as Zeolite Beta, Zeolite Y, ZSM-5, ZSM-35, and USY. In one

embodiment, alkylated naphthalenes may be obtained by alkylating naphthalene with an olefin using aluminum chloride as a catalyst. The use of a co-catalyst such as nitromethane or nitrobenzene to promote the reaction is also suitable. See, for example, U.S. Pat. No. 2,754,548, which is incorporated herein by reference in its entirety. In another embodiment, alkylated naphthalenes may be obtained by alkylating naphthalene with an olefin using trifluoromethane sulfonic acid as a catalyst.

[0037] In one embodiment, compounds other than naphthalene may be alkylated to provide suitable alkylated naphthalenes. In a particular embodiment, the addition of longer chain alkyl groups, e.g., about C ₆ to C30, to short chain alkylated naphthalenes, e.g., methyl

naphthalene, ethyl naphthalene, propyl naphthalene, butyl naphthalene, isopropyl naphthalene, and diisopropyl naphthalene, is suitable. [0038] Suitable poly-alphaolefms may be derived from alphaolefins, i.e., alk-l-enyls, which include but are not limited to C ₂ to C ₃₂ alphaolefins, C ₁₂ to C ₁₈ alphaolefins, C ₁₀ to C ₃₂ alphaolefins, such as 1-decene, 1-dodecene, and 1-octadecene. In one embodiment, useful polyalphaolefms are poly- 1-decene or poly- 1-dodecene, poly-l-hexadecene or poly-1- hexadecenedecene, poly- 1-octadecene or poly- 1-octadecene.

[0039] Suitable alpha-olefms useful in this process for introducing linear alkyl groups are, for example, 1-dodecene, 1-tridecene, 1 -tetradecene, 1-hexadecene, 1-octadecene, 1- eicosene, 1-docosene, 1-tetracosene or 1-triacontene, a-methyl styrene or mixtures thereof.

Mixtures of the alpha-olefms, e.g., mixtures of Ci ₂ -C ₂ o, or C ₁₄ -C ₁₈ olefins or C ₁₆ -C ₁₈ olefins, are also useful. These alpha-olefins are largely items of commerce or are made by the

telomerization of ethylene by known methods. Straight chain alkenes containing an internal double bond may be for example 5-dodecene or 9-tricosene. These alkenes are also largely items of commerce.

[0040] Branched alkyl groups can be prepared from oligomerization of small olefins, such as C ₅ -C ₂ 4 alpha- or internal-olefins. When the branched alkyl group is very large (that is 8 to 300 carbons), usually only one or two of such alkyl groups are attached to the naphthalene core. The alkyl groups on the naphthalene ring can also be mixtures of the above alkyl groups. In one embodiment, mixed alkyl groups are advantageous, because they provide improvement of pour points and low temperature fluid properties, such as low temperature fluidity, stability and solvency.

[0041] Other useful alkylating agents, which may be used, include alcohols (inclusive of monoalcohols, dialcohols, trialcohols, etc.) such as hexanols, heptanols, octanols, nonanols, decanols, undecanols, dodecanols and octadecanols; and alkyl halides such as hexyl chlorides, octyl chlorides, dodecyl chlorides; and higher homologs. Also useful for preparing compounds of Formula I are various branched Guerbet alcohols containing up to 32 carbon atoms and sold under the trade name ISOFOL ^® by Sasol. Examples of useful alcohols include ISOFOL ^® 18 T, 18E, 20, 24, 28, and 32.

[0042] Other non-limiting examples of alkylating agents are those derived from uncrosslinked polyisoprenes or polybutadienes, e.g., KRASOL ^® LB 3000 having a molecular weight M _n of 2300-3000, polyisobutylenes e.g., TPC 535(MW 350), TPC 595(MW 950), TPC 5230(MW 2300), TPC 150(MW 500), TPC 137(MW 350), TPC 160(MW 600), TPC 168(MW 680), TPC 175(MW 750), TPC 181(MW 810), TPC 1105(MW 1000), TPC 1160(MW 1600), and TPC 1285(MW 3000) from Texas Petrochemicals, polybutenes. Other examples include L- 14(Mn 370), L-50(Mn 455), L-65(Mn 435),L-100(Mn 510), H-15(Mn 600), H-25(Mn 670), H- 35(Mn 725), H-40(Mn 750),H-50(Mn 815), H-100(Mn 940), H-300(Mn 1330), H-1500(Mn 2145), and H-1900(Mn 2270) from AMOCO , polybutenes PB 24 (Mn 950), PB 32(Mn 1200- 1375), PB 122(Mn 2225), PB 124(Mn 2400), and PB 128(Mn 2600) from Soltex. Still other examples include copolymers of mono- and diolefins, for example propylene/butadiene copolymers, styrene/butadiene copolymers or acrylonitrile/butadiene copolymers, terpolymers such as styrene/butadiene/alkylacrylate, terpolymers or styrene/butadiene/methacrylate terpolymers or acrylonitrile/alkylmethacrylate/butadiene terpolymers, terpolymers with ethylene, propylene and a diene, typically hexadiene, dicyclopentadiene, norbornadiene or

ethylidenenorbornene, block copolymers of styrene, such as styrene/butadiene/styrene or styrene/isoprene/styrene, graft copolymers of styrene or a-methylstyrene on polybutadiene, polybutadiene containing terminal hydroxyl groups, e.g., KRASOL ^® LBH 3000, linear polycyclopentadienes or cyclic olefins polymerized by ring-opening metathesis, e.g.,

polyoctenamers, for example VESTENAMER ^® L 3000 (Huls) having a molecular weight M _n of about 2300-3000, or polynorbornenes, e.g., of the NORSOREX ^® type (Nippon Zeon), as well as all polyunsaturated polymeric basic compounds grafted with cyclopentadiene by the Diels-Alder method of the above-mentioned type. It is particularly advantageous to use homo- and copolymers of diolefins, for example butadiene, isoprene or pentadiene, and also of cyclic, optionally polynuclear, diolefins, typically dicyclopentadiene or norbornene as well as ring- opening polymerized cyclic olefins, e.g., polyoctenamers or polynorbornenes.

[0043] Typically the compounds of Formula I, such as alkyl naphthalenes may be prepared by alkylation of naphthalene or short chain alkyl naphthalene, such as methyl or dimethyl naphthalene, with olefins, alcohols or alkylchlorides of 6 to 24 carbons over acidic catalyst inducing typical Friedel Crafts catalysts. Typical Friedel-Crafts catalysts are A1C1 ₃ , BF ₃ , HT, zeolites, amorphous alumnio silicates, acid clays, acidic metal oxides or metal salts, or USY. See U.S. 5,034,563, U.S. 5,516,954, and U.S. 6,436,882, all of which are incorporated herein by reference in their entireties. [0044] An α-olefm or internal olefin can be oligomerized in the presence of promoted catalyst to give predominantly olefin dimer and higher oligomers. Once the reaction has gone to completion, an aromatic composition containing one or more naphthalene compound is reacted with the oligomers, in the presence of the same catalyst, to give alkylated aromatic base oil components in high yield.

[0045] The naphthalene or mono substituted short chain alkyl naphthalenes can be derived from any conventional naphthalene -producing process from petroleum, petrochemical process or coal process or source stream. Naphthalene-containing feeds can be made from aromatization of suitable streams available from the F-T process. For example, aromatization of olefins or paraffins can produce naphthalene or naphthalene-containing component (DE84- 3414705, US20060138024 Al, both of which are incorporated herein in their entireties). Many medium or light cycle oils from petroleum refining processes contain significant amounts of naphthalene, substituted naphthalenes or naphthalene derivatives. Indeed, substituted naphthalenes recovered from whatever source, if possessing up to about three alkyl carbons can be used as raw material to produce alkylnaphthalene for lubricant oil compositions provided herein. Furthermore, alkylated naphtahlenes of Formula I recovered from whatever source or processing can be used the lubricant oil compositions provided herein, provided they possess kinematic viscosities, viscosity index and Noack volatility as previously recited.

4.2.2 Second Base Oil Component

[0046] Provided herein is lubricant oil composition comprising a second base oil component in the amount of about 0.1 weight % to about 80 weight % based on the total weight of the oil composition, wherein the second base oil component comprises one or more of a polyalphaolefm(PAO) base stock, Group II base stock, Group III base stock, Group V base stock, GTL base stock, alkylated benzene base stock, and ester base stock.

[0047] In one embodiment, the second base oil component comprises a polyalphaolefm

(PAO) base stock. In one embodiment, the second base oil component comprises a Group II base stock. In one embodiment, the second base oil component comprises a Group III base stock. In one embodiment, the second base oil component comprises a Group V base stock. In one embodiment, the second base oil component comprises a GTL base stock. In one embodiment, the second base oil component comprises an alkylated benzene base stock. In one embodiment, the second base oil component comprises an ester base stock.

[0048] Further provided herein is a lubricant oil composition comprising a second base oil component in the amount of about 0.1 wt % to about 70 wt %, about 0.1 wt % to about 60 wt %, about 0.1 wt % to about 50 wt %, about 0.1 wt % to about 40 wt %, about 0.1 wt % to about 30 wt %, about 5 wt % to about 80 wt %, about 10 wt % to about 80 wt %, about 20 wt % to about 80 wt %, about 30 wt % to about 80 wt %, about 40 wt % to about 80 wt %, about 50 wt % to about 80 wt %, about 60 wt % to about 80 wt %, about 70 wt % to about 80 wt %, about 10 wt % to about 20 wt %, about 20 wt % to about 30 wt %, or about 10 wt % to about 40 wt %, based on the total weight of the oil composition. In one embodiment, the lubricant oil composition comprises a first base oil component in the amount of about of 70 wt % to about 80 wt % based on the total weight of the oil composition.

[0049] Further provided herein is a lubricant oil composition comprising a first base oil component in the amount of about 1 wt % to about 40 wt %, about 1 wt % to about 30 wt %, about 1 wt % to about 20 wt %, about 1 wt % to about 10 wt %, about 5 wt % to about 50 wt %, about 10 wt % to about 50 wt %, about 20 wt % to about 50 wt %, about 30 wt % to about 50 wt %, about 40 wt % to about 50 wt %, about 10 wt % to about 20 wt %, about 20 wt % to about 30 wt %, or about 10 wt % to about 40 wt %, based on the total weight of the oil composition, and a second base oil component in the amount of about 0.1 wt % to about 70 wt %, about 0.1 wt % to about 60 wt %, about 0.1 wt % to about 50 wt %, about 0.1 wt % to about 40 wt %, about 0.1 wt % to about 30 wt %, about 5 wt % to about 80 wt %, about 10 wt % to about 80 wt %, about 20 wt % to about 80 wt %, about 30 wt % to about 80 wt %, about 40 wt % to about 80 wt %, about 50 wt % to about 80 wt %, about 60 wt % to about 80 wt %, about 70 wt % to about 80 wt %, about 10 wt % to about 20 wt %, about 20 wt % to about 30 wt %, or about 10 wt % to about 40 wt %, based on the total weight of the oil composition.

[0050] As set forth in API BASE OIL INTERCHANGEABILITY GUIDELINES FOR

PASSENGER CAR MOTOR OILS AND DIESEL ENGINE OILS, July 2009 Version—

APPENDIX E, Group I base stocks contain less than about 90 percent saturates, tested according to ASTM D2007 and/or greater than about 0.03 percent sulfur, tested according to ASTM D1552, D2622, D3120, D4294, or D4927; and a viscosity index of greater than or equal to about 80 and less than about 120, tested according to ASTM D2270. Group II base stocks contain greater than or equal to about 90 percent saturates; less than or equal to about 0.03 percent sulfur; and a viscosity index greater than or equal to about 80 and less than about 210. Group III base stocks contain greater than or equal to 90 percent saturates; less than or equal to about 0.03 percent sulfur; and a viscosity index greater than or equal to about 120. Group IV base stocks are polyalphaolefms (PAOs). Group V base stocks include all other base stocks not included in Group I, II, III, or IV, such as naphthenics, esters, GTL and polyglycols.

[0051] The polyalphaolefm ("PAO") is a polymer made by polymerizing alphaolefm.

Base stock may be conveniently made by the polymerization of an alphaolefm 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.

[0052] The PAO base stock may be made by any method known in the art. See, for example, U.S. 3,149,178; U.S. 3,382,291; U.S. 3,742,082; U.S. 3,769,363; U.S. 3,876,720; U.S. 4,149,178; U.S. 4,218,330; U.S. 4,239,930; U.S. 4,367,352; U.S. 4,413,156; U.S. 4,434,408; U.S. 4,910,355; U.S. 4,967,032; U.S. 4,926,004; U.S. 4,956,122; U.S. 4,914,254; U.S.

4,827,073; U.S. 4,827,064; U.S. 5,068,487; all of which are incorporated herein by reference in their entireties. PAO fluids may be optionally substituted by, e.g., carboxylic acid esters.

[0053] The average molecular weight of the PAO base stock to be used in the lubricate oil composition provided herein varies from about 250 Da to about 10,000 Da, or from about 300 Da to about 3,000 Da, with a kinematic viscosity varying from about 3 cSt to about 10 cSt at 100° C.

[0054] In one embodiment, the concentrations of a compound of Formula I, in particular, an alkylated naphthalene (AN), in the PAO base stock can vary from about 1 wt % to less than about 50 wt %, or from about 5 wt % to about 45 wt %, or from about 5 wt % to about 25 wt % of the total weight of the lubricant oil composition. [0055] In one embodiment, the PAO base stock comprises a carboxylic acid ester in the amount of less than about 10 wt % of the total weight of the lubricant oil composition. In a certain embodiment, the ester is an ester of monohydric alcohols, having about 9 to 20 carbon atoms, and of dibasic carboxylic acids, having from about 6 to 12 carbon atoms, such as adipic or azelaic acid.

[0056] In one embodiment, the second base oil component is a PAO obtained by the process disclosed in US 2013/0090273, which is incorporated herein by reference in its entirety.

[0057] Group II and/or Group III base oils are complex mixtures of hundreds of isomers of different carbon number (generally n-paraffins, cycloparaffins, and naphthenics) and contain some small amount of unsaturation (generally less than 10%) as well as other trace impurities such a sulfur and nitrogen. Group II and/or Group III base oils may be prepared, for example, in accordance with U.S. 5,935,417 and U.S. 5,993,644; both of which are incorporated herein by reference in their entireties. Typically, processes commonly used to produce conventional mineral base oil stocks known in the art are first applied to the crude oil. For example, the crude oil may be subjected to distillation, solvent dewaxing, and solvent extraction of aromatic compounds. To produce Group II and Group III base oils, the oil is then subjected to further apart processing referred to in the art as hydrotreating, hydrocracking, hydroisomerization and hydrofining. In such a process, the oil is mixed with hydrogen in a reactor in the presence of a catalyst to hydrogenate most of the double bonds or unsaturated hydrocarbons. Depending on the severity of the hydrotreatment, aromatic molecules still remaining after conventional solvent extraction are also hydrogenated to saturated ring structures. In addition, the saturated ring structures can also be ring opened to linear molecules. Most of the sulfur and nitrogen impurities are converted to hydrogen sulfide and ammonia which are removed. In some instances, the feed for this hydrotreating process is not a conventional base oil at all, but the waste products isolated during solvent dewaxing. The result is a base oil which has more n-paraffins and isoparaffms than traditional base oils, low unsaturation (generally less than 2%), very low levels of sulfur and nitrogen impurities, and a high viscosity index. Group III base oils are subjected to a more severe hydrotreating process than Group II base oils. [0058] Gas to Liquids ("GTL") base stock can be obtained by a process that converts natural gas into synthetic oil, which can then be further processed into fuels and other hydrocarbon based products. This process results in extremely pure synthetic crude oil that is virtually free of contaminants such as sulfur, aromatics and metals, which in turn can be refined into products, such as diesel fuel, and other petroleum or specialty products. Typical GTL base stock properties are listed in TABLE 1 below in comparison with typical Group III and PAO base stocks.

TABLE 1

[0059] An alkylated benzene base stock comprises alkylated benzene of Formula II with kinematic viscosity at 100°C of 1.5 to 6.0 cSt, a viscosity index of 0 to 200 and pour point of 0°C or less, or -15° C or less, or -25° C or less, or -35° C or less, or -60° C or less.

The alkylated benzene for use as a second base oil component is a compound of

Formula II

wherein x = 1 to 6, or 1 to 5, or 1 to 4. When the compound of Formula II is a monoalkylated benzene, R can be linear C ₁₀ to C30 alkyl group or a C10-C300 branched alkyl group, or a C10-C100 branched alkyl group, or a C15-C50 branched alkyl group. When n is 2 or greater than 2, one or two of the alkyl groups can be a Ci to C ₅ alkyl group, or Ci-C ₂ alkyl group. The other alkyl group or groups can be any combination of linear C10-C30 alkyl group, or branched C ₁₀ to C300 alkyl group, or C15-C50 branched alkyl group. These branched large alkyl radicals can be prepared from the oligomerization or polymerization of C3 to C ₂ o, internal or alpha-olefins or mixture of these olefins. The total number of carbons in the alkyl substituents ranges from C ₁₀ to C300. In one embodiment, the alkylated benzene stock may be prepared according to U.S.

6,071,864, U.S. 6,491,809, or EP 0,168,534; all of which are incorporated herein by reference in their entireties.

[0061] In one embodiment, the molar ratio of aromatic compound to α-olefm oligomers is from about 0.05: 1 to about 20: 1. In another embodiment, the ratio of aromatic compound to a- olefin oligomers is from about 0.1 : 1 to about 8: 1.

[0062] In one embodiment, the alkylaromatic fluids used in the lubricant oil composition provided herein have pour points of 0° C or less. In another embodiment, the alkyl methyl benzene fluid was prepared according to procedures described in U.S. Pat. No. 6,071,864, which is incorporated herein by reference in its entirety, starting from the oligomerization of a mixture of Cg, Cio and C ₁₂ linear alpha olefins, over a promoted BF ₃ catalyst to produce a product which is reacted with toluene over the same catalyst at same reaction temperature.

[0063] A dialkylbenzene ("DAB") as described in U.S. Pat. No. 6,491,809 can also be used in the lubricant oil composition provided herein. DAB can be prepared by repeated alkylation of benzene, e.g., alkylation of benzene to give mono-alkylbenzene, followed by further alkylation of this mono-alkylbenzene in the same reactor or in a separate reactor.

Alkylbenzenes can also be obtained from many detergent alkylbenzene processes. In these processes, linear alkylbenzene ("LAB") is produced by alkylation of benzene over alkylation catalyst. The mono-alkyl LAB is used as raw material for detergent production.

[0064] Further, it has been found that the hydrogenated analogues of the alkylated naphthalene or alkylated benzene described above are also effective base oil stocks, and hydrodewaxed or hydroisomerized/catalytic (and/or solvent) dewaxed wax derived base stocks/base oils. Further, it has been found that the alkylated naphthalene or alkylated benzene fluids can provide un-expected improvement of oxidation stability of the blends with GTL fluids. This oxidative stability improvement can be demonstrated by longer RBOT (ASTM D2272 method) or other oxidation test methods. Further, it has been found that the alkylated

naphthalene or alkylated benzene fluids can improve the polarity of the blends with GTL fluids. This higher polarity of the blend indicates a better solubility of additives and other polar components formed during oil service. Thus, the blend with these alkylated aromatic fluids can provide higher level of finished lubricant performance.

[0065] In one embodiment, the second base oil component is an ester. 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 mono-carboxylic 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; with a variety of alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2- ethylhexyl alcohol, etc. In one embodiment, the ester is dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, or dieicosyl sebacate.

[0066] In one embodiment, the synthetic esters are those full or partial esters which are obtained by reacting one or more polyhydric alcohols (e.g., 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 about 4 carbon atoms (e.g., C ₅ to C30 acids 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).

[0067] 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 about 5 to about 10 carbon atoms.

[0068] In one embodiment, the ester is an ester of a phosphorus-containing acid, such as tricresyl phosphate, trioctyl phosphate, or diethyl ester of decanephosphonic acid.

4.2.3 Additives

[0069] In one embodiment, the engine oil composition comprises a lubricant oil composition as provided herein, which further comprises one or more additives. In a particular embodiment, the lubricant oil compositions provided comprise one or more additives and are formulated as internal combustion engine oil compositions.

[0070] In one embodiment, the lubricant oil composition further comprises one or more additives in an amount up to about 20 wt %, or up to about 5%, or from about 0.001 wt % to about 10 wt %, of the total weight of the lubricant oil composition.

[0071] In some embodiments, the lubricant oil compositions provided herein further comprise one or more additives, wherein the additive is a detergent, a dispersant, an antioxidant, a pour point depressant, a viscosity index (VI) improver, an anti-wear agent, an extreme pressure additive, a friction modifier, a demulsifier, an antifoamant, a corrosion inhibitor, a seal swell control additive, or a metal deactivator. In a certain embodiment, the lubricant oil compositions provided herein further comprise one or more additives, wherein the additive is a detergent, a dispersants, a antioxidant, a anti-wear agent, or a VI improver.

[0072] An effective amount of one or more additives can be added to, blended into or admixed with the base stock to meet one or more formulated product specifications, such as those relating to a lubricating oil composition for diesel engines, internal combustion engines, automatic transmissions, turbine or jet, hydraulic oil, industrial oil, etc., as is known to the person of ordinary skill in the art. Further information on commonly used additives, such as the additives discussed in Section 4.2.3, is discussed in Klamann, "Lubricants and Related

Products," Verlag Chemie, Deerfield Beach, Fla. (ISBN 0-89573-177-0) and Ronney, M. W., "Lubricant Additives," Noyes Data Corporation, Parkridge, N.J. (1973). Additive packages comprising one or more additives are commercially available for blending with base stocks or a mixture of base stocks to formulate lubricating oil compositions for meeting performance specifications required for different applications or intended uses.

[0073] In certain embodiments, when lubricant oil composition further comprises one or more additives, for example, one or more additives discussed in Section 4.2.3, the additive(s) are blended into the lubricant oil composition in an amount sufficient for the additive(s) to perform the intended function. Exemplary amounts of additives that may be blended with lubricant oil compositions provided herein are shown in TABLE 2 below. In some embodiments, the exemplary amount is the total for all additives of one type comprised in the lubricant oil composition. For example, if the lubricant oil composition comprises two or more detergents, the total wt % of all detergents present in the lubricant oil composition amounts to the wt % given in TABLE 2.

TABLE 2

Detergent(s) about 0.01 - about 6.0 about 0.01 - about 4.0

Dispersant(s) about 0.1 - about 20 about 0.1 - about 8

Antioxidant(s) about 0.01 - about 5 about 0.01 - about 1.5

Pour Point Depressant(s) about 0.01 - about 5.0 about 0.01 - about 1.5

VI Improver(s) about 0.01 - about 0.25 about 0.01 - about 0.25

Anti-Wear and EP about 0.01 - about 6 about 0.01 - about 4

additive(s)

Friction Modifier(s) about 0.01 - about 5 about 0.01 - about 1.5

Demulsifier(s) about 0.05 - about 15 about 0.1 - about 3

Antifoamant(s) about 0.001 - about 3 about 0.001 - about 0.15

Corrosion Inhibitor(s) about 0.01 - about 5 about 0.01 - about 1.5

Seal Swell Control about 0.01 - about 3 about 0.01 - about 2

Additive(s)

Metal Deactivator(s) about 0.001 - about 0.35 about 0.1 - about 0.35 wt % of total weight of lubricant oil composition comprising one or more additives of the same category.

[0074] In one embodiment, the lubricant oil composition consists essentially of a first base oil component, a second base oil component in the amount of about 0.1 wt % to about 90 wt %, and one or more additives in the ranges listed in TABLE 2. In one embodiment, the lubricant oil composition comprises a first base oil component, a second base oil component in the amount of about 0.1 wt % to about 90 wt %, and one or more additives in the ranges listed in TABLE 2. In another embodiment, the lubricant oil composition comprises a first base oil component in the amount of about 1 wt % to about 50 wt %, a second base oil component in the amount of about 10 wt % to about 80 wt %, and one or more additives in the ranges listed in TABLE 2.

[0075] Many of the commercially available additives are shipped from the manufacturer and are provided with a certain amount of base oil solvent. The wt % amounts in TABLE 2, as well as other amounts mentioned in this disclosure, unless otherwise indicated are directed to the amount of actual additive, i.e., the non-solvent portion of the commercially available additive mixture.

[0076] Additives and the amount in which they may be used for lubricant oil

compositions provided herein are, for example, discussed in US2013/0090273, and WO

2004/031329 A2, each of which is incorporated herein by reference in its entirety.

4.2.3.1 Detergents

[0077] In one embodiment, the lubricant oil composition provided herein further comprises a detergent, or two or more detergents. Such lubricant oil compositions further comprising a detergent, or two or more detergents, can be used, for example, as internal combustion engine oils.

[0078] Detergents are used in lubricating compositions. 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.

[0079] Salts that contain a substantially stoichiometric amount of the metal are described as neutral salts and have a total base number ("TBN," as measured, for example, by ASTM D2896, 2011, "Standard Test Method for Base Number of Petroleum Products by Potentiometric Perchloric Acid Titration," ASTM International, West Conshohocken, PA, 2011, DOI:

10.1520/D2896-11, www.astm.org.) 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 {e.g., a metal hydroxide or oxide) with an acidic gas {e.g., carbon dioxide). In one embodiment, the detergent is is neutral, mildly overbased, or highly overbased.

[0080] In one embodiment, the detergent is partly overbased. Overbased detergents help neutralize acidic impurities produced by the combustion process and become entrapped in the oil. In one embodiment, the overbased detergent has a ratio of metallic ion to anionic portion of the detergent of about 1.05: 1 to about 50: 1, or from about 4: 1 to about 25: 1, on an equivalent basis. The resulting detergent is an overbased detergent that will typically have a TBN of about 150 or higher, often about 250 to 450 or more. In one embodiment, the overbasing cation is sodium, calcium, or magnesium. In one embodiment, the detergent is a mixture of detergents having different TBNs.

[0081] In one embodiment, the detergent is an alkali or alkaline earth metal salts of a sulfonates, phenate, carboxylate, phosphate, or salicylate.

[0082] Sulfonates may be prepared from sulfonic acids that are typically is obtained by sulfonation of alkyl substituted aromatic hydrocarbons. Hydrocarbon examples include those obtained, for example, by alkylating benzene, toluene, xylene, naphthalene, biphenyl and their halogenated derivatives (chlorobenzene, chlorotoluene, and chloronaphthalene, for example). The alkylating agents typically have about 3 to 70 carbon atoms. The alkaryl sulfonates typically contain about 9 to about 80 carbon or more carbon atoms, more typically from about 16 to 60 carbon atoms.

[0083] Further, see Klamann, "Lubricants and Related Products," Verlag Chemie,

Deerfield Beach, Fla. (ISBN 0-89573-177-0) and C. V. Smallheer and R. K. Smith "Lubricant Additives," Lezius-Hiles Co. of Cleveland, Ohio (1967) for a description of overbased metal salts of various sulfonic acids, which are useful as detergents in the lubricant oil composition provided herein.

[0084] In another embodiment, the detergent is an alkaline earth phenates. Alkaline earth phenates can be obtained by reacting alkaline earth metal hydroxide or oxide (e.g., CaO, Ca(OH) ₂ , BaO, Ba(OH) ₂ , MgO, Mg(OH) ₂ ) with an alkyl phenol or sulfurized alkylphenol. Such alkyl group includes straight chain or branched (C1-C30) or (C ₄ -C ₂ o) alkyl groups. The phenol is, for example, isobutylphenol, 2-ethylhexylphenol, nonylphenol, and dodecyl phenol. 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 (starting alkylphenols may contain more than one alkyl substituent that are each independently straight chain or branched ) and sulfurizing agent (including elemental sulfur, sulfur halides, such as sulfur dichloride) and then reacting the sulfurized phenol with an alkaline earth metal base. [0085] In another embodiment, the detergent is a metal salt of a carboxylic acid. These carboxylic acid detergents may be prepared by the reaction of 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. In a particular embodiment, the detergent is a metal salt of salicylic acid. In a certain embodiment, the salicylic acid is a long chain alkyl salicylates. In a particular embodiment, the metal salt of the salicylic acid is a compound of the following formula:

wherein R is a hydrogen atom or an alkyl group having 1 to about 30 carbon atoms, n is an integer from 1 to 4, and M is an alkaline earth metal. In a certain embodiment, R is at least a Cn, or at least C ₁₃ alkyl chain. In a particular embodiment, R may be optionally substituted with substituents that do not interfere with the detergent's function. In one embodiment, M is calcium, magnesium, or barium. In a particular embodiment, M is calcium. See also

US2013/0090273, which is incorporated herein by reference in its entirety.

[0086] Hydrocarbyl-substituted salicylic acids may be prepared from phenols by the

Kolbe reaction. See U.S. 3,595,791 for additional information on synthesis of these compounds, which is incorporated herein by reference in its entirety. 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.

[0087] In one embodiment, the detergent is an alkaline earth metal phosphates.

[0088] In one embodiment, the detergent is a simple detergent or a hybrid or complex detergent. The hybrid or complex detergents can provide the properties of two detergents without the need to blend separate materials. See hereto U.S. 6,034,039, which is incorporated herein by reference in its entirety.

[0089] In a particular embodiment, the detergent is a calcium phenate, a calcium sulfonates, a calcium salicylates, a magnesium phenates, a magnesium sulfonates, a magnesium salicylates, or related components (such as borated detergents).

[0090] In one embodiment, the lubricant oil composition comprises a detergent, two one or more detergents, in the amount of about 0.01 wt % to about 6.0 wt %, or about 0.1 wt % to about 4.0 wt % of the total weight of the lubricant oil composition.

4.2.3.2 Dispersants

[0091] In one embodiment, the lubricant oil composition provided herein further comprises a dispersant, or two or more dispersants. Such lubricant oil compositions further comprising a dispersant, or two or more dispersants, can be used, for example, as internal combustion engine oils.

[0092] During engine operation, oil-insoluble oxidation byproducts are produced.

Dispersants help keep these byproducts in solution, thus diminishing their deposition on metal surfaces. In one embodiment, the dispersant is ashless or ash-forming. In one embodiment, 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.

[0093] In one embodiment, the dispersant is a high molecular weight hydrocarbon chain, such as a hydrocarbon chain with 50 to 400 carbon atoms, with a polar group attached. In certain embodiments, the polar group comprises at least one element of nitrogen, oxygen, or

phosphorus.

[0094] In certain embodiment, the dispersant is a phenate, sulfonate, sulfurized phenate, salicylate, naphthenate, stearate, carbamate, thiocarbamate, or phosphorus derivative. In a particular embodiment, the dispersant is a alkenylsuccinic acid derivative, produced by, for example, the reaction of a long chain substituted alkenyl succinic compound, for example, a substituted succinic anhydride, with a polyhydroxy or polyamino compound. The long chain group constituting the oleophilic portion of the molecule, which confers solubility in the oil, is, for example, a polyisobutylene group. Exemplary U.S. patents describing dispersants are U.S. Pat. Nos. 3,172,892; 3,2145,707; 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, all of which are incorporated herein by reference in their entireties. Other dispersants 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; all of which are incorporated herein by reference in their entireties. A further description of dispersants may be found, for example, in European Patent Application No. 471 071, which is incorporated herein by reference in its entirety.

[0095] In one embodiment, the dispersant is a hydrocarbyl-substituted succinic acid. In a particular embodiment, the dispersant is a succinimide, succinate ester, or succinate ester amide prepared by the reaction of a hydrocarbon-substituted succinic acid compound having, for example, at least 50 carbon atoms in the hydrocarbon substituent, with at least one equivalent of an alkylene amine.

[0096] Succinimides are formed by the condensation reaction between alkenyl succinic anhydrides and amines. Molar ratios can vary depending on the polyamine. For example, the molar ratio of alkenyl succinic anhydride to tetraethylenepentamine ("TEPA") can vary from about 1 : 1 to about 5: 1. Representative examples are disclosed in U.S. Pat. Nos. 3,087,936; 3,172,892; 3,219,666; 3,272,746; 3,322,670; and 3,652,616, 3,948,800; and Canada Pat. No. 1,094,044; all of which are herein incorporated by reference in their entireties.

[0097] Succinate esters are formed by the condensation reaction between alkenyl succinic anhydrides and alcohols or polyols. Molar ratios can vary depending on the alcohol or polyol used. In one embodiment, the dispersant is obtained by the condensation of an alkenyl succinic anhydride and pentaerythritol.

[0098] Succinate ester amides are formed by condensation reaction between alkenyl succinic anhydrides and alkanol amines. In one embodiment, the alkanol amines is ethoxylated polyalkylpolyamine, propoxylated polyalkylpolyamine or a polyalkenylpolyamine, such as polyethylene polyamine. In a particular embodiment, the alkanol amine is propoxylated hexamethylenediamine. Representative examples are shown in U.S. 4,426,305, which is herein incorporated by reference in its entirety.

[0099] The molecular weight of the alkenyl succinic anhydrides used in the preceding paragraphs is, for example, from about 800 to about 2,500. The above products can be post- reacted with various reagents, such as sulfur, oxygen, formaldehyde, carboxylic acids (e.g., oleic acid), and boron compounds (e.g., borate esters or highly borated dispersants). The dispersants can be borated with from about 0.1 to about 5 moles of boron per mole of dispersant reaction product.

[00100] Mannich base dispersants are made from the reaction of alkylphenols, formaldehyde, and amines. See, for example, U.S. Pat. No. 4,767,551 , which is herein incorporated by reference in its entirety. 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 about 800 to about 2,500. Representative examples are disclosed 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; all of which are herein incorporated by reference in their entirety.

[00101] Typical high molecular weight aliphatic acid modified Mannich condensation products useful as dispersants for the lubricant oil compositions provided herein can be prepared from high molecular weight alkyl-substituted hydro xyaromatics or HN(R) ₂ group-containing reactants.

[00102] Examples of high molecular weight alkyl-substituted hydroxyaromatic compounds can include polypropylphenol, polybutylphenol, and other polyalkylphenols. These polyalkylphenols can be obtained by the alkylation, in the presence of an alkylating catalyst, such as BF ₃ , of phenol with high molecular weight polypropylene, polybutylene, and other polyalkylene compounds to give alkyl substituents on the benzene ring of phenol having an average 600-100,000 molecular weight. [00103] Examples of HN(R) ₂ group-containing reactants can include alkylene polyamines, principally polyethylene polyamines. Other representative organic compounds containing at least one HN(R) ₂ group suitable for use in the preparation of Mannich condensation products include the mono- and di-amino alkanes and their substituted analogs, e.g. , ethylamine and diethanol amine; aromatic diamines, e.g., phenylene diamine, diamino naphthalenes; heterocyclic amines, e.g. , morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine, and piperidine;

melamine and their substituted analogs.

[00104] Examples of alkylene polyamide reactants include ethylenediamine, diethylene triamine, triethylene tetraamine, tetraethylene pentaamine, pentaethylene hexamine,

hexaethylene heptaamine, heptaethylene octaamine, octaethylene nonaamine, nonaethylene decamine, and decaethylene undecamine and mixture of such amines having nitrogen contents corresponding to the alkylene polyamines, in the formula H ₂ N-(Z-NH— ) _n H, Z is a divalent ethylene and n is 1 to 10 of the foregoing formula. Corresponding propylene polyamines such as propylene diamine and di-, tri-, terra-, penta-propylene tri-, terra-, penta- and hexaamines are also suitable reactants. The alkylene polyamines are usually obtained by the reaction of ammonia and dihalo alkanes, such as dichloro alkanes. Thus the alkylene polyamines obtained from the reaction of 2 to 11 moles of ammonia with 1 to 10 moles of dichloroalkanes having 2 to 6 carbon atoms and the chlorines on different carbons are suitable alkylene polyamine reactants.

[00105] Aldehyde reactants useful in the preparation of the high molecular products useful in the preparation of the lubricant oil compositions provided herein include the aliphatic aldehydes, such as formaldehyde (also as paraformaldehyde and formalin), acetaldehyde, and aldol (β-hydroxybutyraldehyde). In certain embodiments, formaldehyde or a formaldehyde- yielding reactant is used.

[00106] Hydrocarbyl substituted amine ashless dispersant additives are disclosed in, 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; all of which are incorporated herein by reference in their entireties.

[00107] In certain embodiments, the dispersant can be a borated or non-borated succinimide, for example, a derivatives from a mono-succinimide, bis-succinimide, and/or mixture of mono- and bis-succinimides, wherein the hydrocarbyl succinimide is derived from a hydrocarbylene group such as polyisobutylene having a Mn from about 500 to about 5000 or a mixture of such hydrocarbylene groups. In another embodiment, the dispersant is a succinic acid-ester or amide, alkylphenolpolyamine-coupled Mannich adduct, its capped derivative (i.e., a blocked phenol), and other related components.

[00108] Further, see Klamann, "Lubricants and Related Products," Verlag Chemie,

Deerfield Beach, Fla. (ISBN 0-89573-177-0) and C. V. Smallheer and R. K. Smith "Lubricant Additives," Lezius-Hiles Co. of Cleveland, Ohio (1967) for a description of overbased metal salts of various sulfonic acids, which are useful as dispersants in the lubricant oil composition provided herein.

[00109] In one embodiment, the lubricant oil composition comprises a dispersant, or two or more dispersants in the amount of about 0.1 wt % to about 20 wt %, or about 0.1 wt % to about 8 wt % of the total weight of the lubricant oil composition.

4.2.3.3 Antioxidants

[00110] In one embodiment, the lubricant oil composition provided herein further comprises an antioxidant, or two or more antioxidants. Such lubricant oil compositions further comprising an antioxidant, or two or more antioxidants, can be used, for example, as internal combustion engine oils.

[00111] Antioxidants retard the oxidative degradation of base oils during service. Such degradation may result in deposits on metal surfaces, the presence of sludge, or a viscosity increase in the lubricant oil composition. A wide variety of antioxidants may be used as additives for the lubricant oil compositions provided herein. See, Klamann, "Lubricants and Related Products," Verlag Chemie, Deerfield Beach, Fla. (ISBN 0-89573-177-0), U.S.

4,798,684, and U.S. 5,084,197, for example, each of which is incorporated herein by reference in its entirety.

[00112] In one embodiment, the antioxidant can be a phenol. In certain embodiments, these phenolic anti-oxidants may be ashless (metal-free) phenolic compounds or neutral or basic metal salts of said phenol. Phenolic antioxidants for use in the lubricant oil compositions provided herein are, for example, sterically hindered phenols, which are phenols with a sterically hindered hydroxyl group. A sterically hindered phenol, for example, includes those derivatives of dihydroxy aryl compounds in which the hydroxyl groups are in the o- or p-position to each other. In certain embodiments, phenolic antioxidants include those sterically hindered phenols substituted with alkyl groups of 6 or more carbon atoms and the alkylene coupled derivatives of these hindered phenols In a certain embodiment, the antioxidant is phenolic antioxidant, such as 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. In another embodiment, the antioxidant are 2,6-di-alkyl- phenolic proprionic ester derivatives. In a certain embodiment, the antioxidant is a bis-phenolic antioxidant, such as and ortho-coupled phenols, for example, 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), or such as para- coupled bisphenols, for example, 4,4'-bis(2,6-di-t-butyl phenol) and 4,4'-methylene-bis(2,6-di-t- butyl phenol).

[00113] In one embodiment, the antioxidant can be a non-phenolic antioxidant, for example, an aromatic amine antioxidants. In a certain embodiment, the lubricant oil composition comprises at least a first and a second additive, wherein the first additive is a non-phenolic antioxidant and the second additive is a phenolic antioxidant. In a certain embodiment, the non- phenolic antioxidant is, for example, an alkylated and non-alkylated aromatic amines, such as aromatic monoamines of Formula R ⁸ R ⁹ R ¹⁰ N, wherein R ⁸ is an aliphatic, aromatic or substituted aromatic group, R ⁹ is an aromatic or a substituted aromatic group, and R ¹⁰ is H, alkyl R ⁸ is an aliphatic, aryl, or heteroaryl, wherein the aryl groups is optionally substituted or substituted aromatic group, R ⁹ is an aromatic or a substituted aromatic group, and R ¹⁰ is H, alkyl, aryl (wherein the substituents are defined as in WO2004/031329A2, which is incorporated herein by reference in its entirety); and R ⁿ S(0)xR ¹² , wherein R ¹¹ is an alkylene, alkenylene, or aralkylene group, R ¹² is a higher alkyl group, or an alkenyl, aryl, or alkaryl group, and x is 0, 1 or 2

(wherein the substituents are defined as in WO2004/031329A2). Furthermore, the aliphatic group R ⁸ may contain from 1 to about 20 carbon atoms, or contains from about 6 to 12 carbon atoms. The aliphatic group is a saturated aliphatic group. In one embodiment, both R ⁸ and R ⁹ are aromatic or substituted aromatic groups, and the aromatic group may be a fused ring aromatic group such as naphthyl. Aromatic groups R ⁸ and R ⁹ may be joined together with other groups such as S. [00114] In a particular embodiment, the aromatic amine antioxidant has a (C ₆ -C ₁₄ ) alkyl substituent. The alkyl is, for example, hexyl, heptyl, octyl, nonyl, and decyl. In certain embodiment, the aromatic amine antioxidant is, for example, diphenylamine, phenyl

naphthylamine, phenothiazine, imidodibenzyl, and diphenyl phenylene diamine. In a particular embodiment, the aromatic amine antioxidant is, for example, ρ,ρ'-dioctyldiphenylamine; t- octylphenyl-alphanaphthylamine; phenyl-alpha naphthylamine; and p-octylphenyl- alphanaphthylamine. In some embodiments, the lubricant oil composition provided herein contains two or more aromatic amine antioxidants. In one embodiment, the antioxidant is a polymeric amine antioxidant.

[00115] In one embodiment, the antioxidant is a sulfurized alkyl phenols, or alkali or alkaline earth metal salts thereof.

[00116] In one embodiment, the antioxidant is a copper compound. In a certain embodiment, the copper compound is an oil-soluble copper compound. In a particular embodiment, the copper compound is, for example, copper dihydrocarbyl thio- or dithio- phosphates, copper salts of carboxylic acids (naturally occurring or synthetic), copper dithiacarbamates, copper sulphonates, copper phenates, and copper acetylacetonates. In a certain embodiment, the copper compound is a basic, neutral, or acidic copper Cu(I) or Cu(II) salt, derived from alkenyl succinic acids or anhydrides.

[00117] In a particular embodiment, an antioxidant is a sterically hindered phenol or an arylamine. In a certain embodiment, the antioxidant provided herein may be used individually or in combination with one another.

[00118] In one embodiment, the lubricant oil composition comprises an antioxidant, or two or more antioxidants, in the amount of about 0.01 wt %to about 5 wt %, about 0.01 wt % to about 1.5 wt %, or less than about 1.5 wt %, of the total weight of the lubricant oil composition. In a particular embodiment, the lubricant oil composition does not comprise an antioxidant.

4.2.3.4 Pour Point Depressants

[00119] In one embodiment, the lubricant oil composition provided herein further comprises a pour point depressant, or two or more pour point depressants. Such lubricant oil compositions further comprising a pour point depressant, or two or more pour point depressants, can be used, for example, as internal combustion engine oils.

[00120] Conventional pour point depressants (also known as lube oil flow improvers) may be added to the lubricant oil compositions provided herein. These pour point depressant may be added to the lubricating oil composition provided herein to, for example, lower the minimum temperature at which the fluid will flow or can be poured. In one embodiment, the pour point depressant is a polymethacrylate, a polyacrylate, a polyarylamide, a condensation product of haloparaffm waxes and aromatic compounds, a vinyl carboxylate polymer, or terpolymer of dialkylfumarates, a vinyl ester of a fatty acid and an allyl vinyl ether. For further description of pour point depressant and/or the preparation of the same, see 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; all of which are incorporated herein by reference in their entireties.

[00121] In one embodiment, the lubricant oil composition comprises a pour point depressant, or two or more pour point depressants, in the amount of about 0.01 wt % to about 5 wt %, or about 0.0 lwt % to about 1.5 wt %, of the total weight of the lubricant oil composition.

4.2.3.5 VI Improvers

[00122] In one embodiment, the lubricant oil composition provided herein further comprises a VI improver, or two or more VI improvers. Such lubricant oil compositions further comprising a VI improver, or two or more VI improvers, can be used, for example, as internal combustion engine oils.

[00123] In one embodiment, VI improvers include high molecular weight hydrocarbons, polyesters and VI improver dispersants that function as both a viscosity index improver and a dispersant. In a certain embodiment, the molecular weight of these VI improver polymers is between about 1,000 Da to about 1,000,000 Da, or about 25,000 Da to about 500,000 Da, or about 50,000 Da to about 400,000 Da. In another embodiment, the VI improvers have a shear stability index (SSI) of, for example, about 4 to about 65. Examples of VI improvers are polymers and copolymers of methacrylate, butadiene, olefins, or alkylated styrenes.

Polyisobutylene is a VI improver. In one embodiment, VI improvers are polymethacrylates (for example, copolymers of various chain length alkyl methacrylates) and polyacrylates (for example, copolymers of various chain length acrylates).

[00124] In another embodiment, VI improvers are copolymers of ethylene and propylene or copolymers of propylene and butylene. In certain embodiments, these copolymers have a molecular weight of about 100,000 Da to about 400,000 Da. In certain embodiments, hydrogenated block copolymers of styrene and isoprene can be used. In a particular

embodiment, the copolymer is a styrene-isoprene or styrene-butadiene based polymer having a molecular weight of about 50,000 Da to about 200,000 Da.

[00125] In one embodiment, the lubricant oil composition comprises a VI improver, or two or more VI improvers, in the amount of about O.Olwt % to about 0.25 wt %, of the total weight of the lubricant oil composition.

4.2.3.6 Anti-Wear Agents or Extreme Pressure Additives

[00126] In one embodiment, the lubricant oil composition provided herein further comprises an anti-wear agent, or two or more anti-wear agents. Such lubricant oil compositions further comprising an anti-wear agent, or two or more anti-wear agents, can be used, for example, as internal combustion engine oils. In one embodiment, the lubricant oil composition provided herein further comprises an extreme pressure additive, or two or more extreme pressure additives. Such lubricant oil compositions further comprising an extreme pressure additive, or two or more extreme pressure additives, can be used, for example, as internal combustion engine oils.

[00127] The anti-wear or extreme pressure ("EP") additives provide, for example, adequate anti-wear protection for the combustion engine. Anti-wear or extreme EP additives inter alia reduce friction and wear of engine metal parts.

[00128] In one embodiment, the anti-wear additive for use in, for example, internal combustion engine crankcase oils, is a metal alkylthiophosphate, in particular a metal dialkyldithiophosphate, in which the primary metal constituent is zinc, or zinc

dialkyldithiophosphate ("ZDDP"). In certain embodiments, ZDDP compounds are compounds of Formula III. Zn[SP(S)(OR ¹ )(OR ² )] ₂

Formula III

wherein R ¹ and R ² are (Ci-Cig)alkyl groups. In a particular embodiment, R ¹ and R ² are (C ₂ - Ci ₂ )alkyl groups.

[00129] In one embodiment, the anti-wear additive is a phosphorus-free anti-wear additive. In certain embodiments, the anti-wear additives in the lubricant oil composition further comprise two or more anti-wear additives, wherein a first anti-wear additive is ZDDP and a second anti-wear additive is a phosphorus-free anti-wear additive.

[00130] In certain embodiments, the anti-wear additive is a sulfurized olefin. Sulfurized olefins can be prepared, for example, by sulfurization or various organic materials, such as aliphatic, arylaliphatic, alicyclic olefmic hydrocarbons containing, for example, from 3 to 30 carbon atoms or 3 to 20 carbon atoms (see Leslie R. Rudnick Lubricant Additives: Chemistry and Applications (Second Edition) and references cited therein).

[00131] In certain embodiments, the EP additive is a sulfurized olefin.

[00132] The sulfurized olefins provided herein are olefins of Formula IV

R ³ R ⁴ C=CR ⁵ R ⁶

Formula IV

wherein each of R ³ -R ⁶ independently is hydrogen, alkenyl, or alkenyl. Any two of R ³ -R ⁶ may be connected so as to form a cyclic ring. Additional information concerning sulfurized olefins and their preparation can be found in U.S. 4,941,984, incorporated herein in its entirety.

[00133] In certain embodiments, the anti-wear agent is a thiocarbamate/molybdenum complex, such as moly-sulfur (Cg-Ci8)alkyl dithiocarbamate trimer complex.

[00134] In certain embodiments, the anti-wear agent is an ester of glycerol, such as mono-, di-, and tri-oleates, mono-palmitates and mono-myristates.

[00135] Further anti-wear agents or EP additives are disclosed in U.S. 2,443,264, U.S.

2,471,115, U.S. 2,526,497, and U.S. 2,591,577 (polysulfides of thiophosphorus acids and thiophosphorus acid esters as additives); U.S. 3,770,854 (phosphorothionyl disulfides); U.S. Pat. No. 4,501 ,678 (alkylthiocarbamoyl compounds (e.g., bis(dibutyl)thiocarbamoyl) in combination with a molybdenum compound (e.g. , oxymolybdenum diisopropyl-phosphorodithioate sulfide) and a phosphorous ester (e.g., dibutyl hydrogen phosphite)); U.S. 4,758,362 (carbamate additives); U.S. 5,693,598 (thiocarbamate); U.S. 5,034, 141 (combination of a thiodixanthogen compound (e.g., octylthiodixanthogen) and a metal thiophosphate (e.g., ZDDP)); can improve anti-wear properties, each of which is incorporated herein by reference in its entirety.

[00136] In certain embodiments, the anti-wear agent is a phosphorus and sulfur compound, such as zinc dithiophosphate and/or sulfur, nitrogen, boron, molybdenum

phosphorodithioates, molybdenum dithiocarbamates and various organo-molybdenum derivatives, such as heterocyclic compounds, for example, dimercaptothiadiazoles,

mercaptobenzothiadiazoles, and triazines. In a particular embodiment, the anti-wear agent is an alicyclic, an amine, an alcohol, an ester, a diol, a triol, a fatty amide and the like can also be used.

[00137] In one embodiment, the lubricant oil composition comprises an anti-wear agent, or two or more anti-wear agents, in the amount of about 0.0 lwt % to about 6 wt %, or about 0.01 wt %to about 4 wt %, of the total weight of the lubricant oil composition. In another

embodiment, the lubricant oil composition comprises an EP additive, or two or more EP additives, in the amount of about 0.01 wt % to about 6 wt %, or about 0.01 wt % to about 4 wt %, of the total weight of the lubricant oil composition.

4.2.3.7 Friction Modifiers

[00138] In one embodiment, the lubricant oil composition provided herein further comprises a friction modifier, or two or more friction modifiers. Such lubricant oil compositions further comprising a friction modifier, or two or more friction modifiers, can be used, for example, as internal combustion engine oils.

[00139] 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 oil compositions provided herein.

[00140] Friction modifiers may include metal-containing compounds or materials as well as ashless compounds or materials, or mixtures thereof. Metal-containing friction modifiers may include metal salts or metal-ligand complexes where the metals may include alkali, alkaline earth, or transition group metals. Such metal-containing friction modifiers may also have low- ash characteristics. Transition metals may include Mo,W, Sb, Sn, Fe, Cu, Zn, and others.

Ligands may include hydrocarbyl derivative of alcohols, polyols, glycerols, partial ester glycerols, thiols, carboxylates, carbamates, thiocarbamates, dithiocarbamates, phosphates, thiophosphates, dithiophosphates, amides, imides, amines, thiazoles, thiadiazoles, dithiazoles, diazoles, triazoles, and other polar molecular functional groups containing effective amounts of O, N, S, or P, individually or in combination. In particular, Mo-containing compounds can be particularly effective such as for example Mo-dithiocarbamates, Mo(DTC), Mo- dithiophosphates, Mo(DTP), Mo-amines, Mo(Am), Mo-alcoholates, Mo-alcohol-amides, and the like. See U.S. Pat. Nos. 5,824,627; 6,232,276; 6,153,564; 6,143,701; 6,110,878; 5,837,657; 6,010,987; 5,906,968; 6,734,150; 6,730,638; 6,689,725; 6,569,820; WO99/66013; W099/47629; and WO98/26030; all of which are incorporated herein by reference in their entireties. Also in particular W-containing compounds can be particularly effective, such as for example amine tungstates described in U.S. Pat. Nos. 3,290,245; 7,820,602; 8,030,256; 8,080,500; 8,080,500; 7,858,565; 7,879,777; all of which are incorporated herein by reference in their entireties.

[00141] Ashless friction modifiers may have also include lubricant materials that contain effective amounts of polar groups, for example, hydroxyl-containing hydrocarbyl base oils, glycerides, partial glycerides, glyceride derivatives, and the like. Polar groups in friction modifiers may include hydrocarbyl groups containing effective amounts of O, N, S, or P, individually or in combination. Other friction modifiers that may be particularly effective include, for example, salts (both ash-containing and ashless derivatives) of fatty acids, fatty alcohols, fatty amides, fatty esters, hydroxyl-containing carboxylates, and comparable synthetic long-chain hydrocarbyl acids, alcohols, amides, esters, hydroxyl carboxylates, and the like. In some instances fatty organic acids, fatty amines, and sulfurized fatty acids may be used as suitable friction modifiers. [00142] Concentrations of molybdenum-containing materials are often described in terms of Mo metal concentration. Advantageous concentrations of Mo may range from about 10 ppm to about 3000 ppm or more, from about 20 to about 2000 ppm, or from about 30 to about 1000 ppm. Friction modifiers of all types may be used alone or in mixtures with lubricant oil composition provided herein. In one embodiment, the lubricant oil composition comprises mixtures of two or more friction modifiers, or mixtures of friction modifier(s) with alternate surface active material(s).

[00143] In one embodiment, the lubricant oil composition comprises a friction modifier, or two or more friction modifiers, in the amount of about 0.01 wt % to about 10-15 wt %, or about 0.1 wt % to about 5 wt %, of the total weight of the lubricant oil composition. In another embodiment, the lubricant oil composition comprises a friction modifier, or two or more friction modifiers, in the amount of about 0.01 wt % to about 5 wt %, or about 0.1 wt % to about 1.5 wt %, of the total weight of the lubricant oil composition.

4.2.3.8 Demulsifiers

[00144] In one embodiment, the lubricant oil composition provided herein further comprises a demulsifier, or two or more demulsifiers. Such lubricant oil compositions further comprising a demulsifier, or two or more demulsifiers, can be used, for example, as internal combustion engine oils.

[00145] Demulsifying agents are, for example, alkoxylated phenols and phenol- formaldehyde resins and synthetic alkylaryl sulfonates, such as metallic dinonylnaphthalene sulfonates. In one embodiment, the demulsifmg agent is a polymer comprising a

polyoxyalkylene glycol having a molecular weight of about 450 Da to about 5000 Da, or more than 5000 Da. In another embodiment, a demulsifier comprises a polyoxyalkylene glycol produced from alkoxylation of n-butanol with a mixture of alkylene oxides to form a random alkoxylated product. In a particular embodiment, the demulsifier comprises a polyoxyalkylene glycol produced by alkoxylation of n-butanol with a mixture of alkylene oxides to form a random alkoxylated product. [00146] In one embodiment, the lubricant oil composition comprises a demulsifier, or two or more demulsifiers, in the amount of about 0.05 wt % to about 15 wt %, or about 0.1 wt % to about 3 wt %, of the total weight of the lubricant oil composition.

4.2.3.9 Antifoamants

[00147] In one embodiment, the lubricant oil composition provided herein further comprises an antifoamant, or two or more antifoamants. Such lubricant oil compositions further comprising an antifoamant, or two or more antifoamants, can be used, for example, as internal combustion engine oils.

[00148] Antifoamants may be added to lubricant oil compositions provided herein. These agents retard the formation of stable foams. In one embodiment, the antifoamant is a silicone or organic polymer. In a particular embodiment, the antifoamant is a polysiloxane, such as silicon oil or polydimethyl siloxane.

[00149] In one embodiment, the lubricant oil composition comprises an antifoamant, or two or more antifoamants, in the amount of about less than about 1 wt %, or less than about 0.1 wt %. In another embodiment, the lubricant oil composition comprises an antifoamant, or two or more antifoamants, in the amount of about less than about 0.001 wt %, to about 3 wt %, or about 0.001 wt % to about 0.15 wt %, of the total weight of the lubricant oil composition.

4.2.3.10 Corrosion Inhibitors

[00150] In one embodiment, the lubricant oil composition provided herein further comprises a corrosion inhibitor, or two or more corrosion inhibitors. Such lubricant oil compositions further comprising a corrosion inhibitor, or two or more corrosion inhibitors, can be used, for example, as internal combustion engine oils.

[00151] Corrosion inhibitors are used to reduce the degradation of metallic parts that are in contact with the lubricating oil composition. Suitable corrosion inhibitors include

thiadiazoles. See, for example, U.S. Pat. Nos. 2,719,125; 2,719,126; and 3,087,932, all of which are incorporated herein by reference in their entireties. [00152] Corrosion inhibitors further protect lubricated metal surfaces against chemical attack by water or other contaminants. A wide variety of corrosion inhibitors are commercially available; they are referred to in Klamann, "Lubricants and Related Products," Verlag Chemie, Deerfield Beach, Fla. (ISBN 0-89573-177-0). One type of corrosion inhibitor is a polar compound that wets the metal surface, protecting it with a film of oil. Another type of corrosion inhibitor absorbs water by incorporating it in a water-in-oil emulsion, so that only the oil touches the metal surface. Yet another type of corrosion inhibitor chemically adheres to the metal to produce a non-reactive surface. In one embodiment, the corrosion inhibitor is a zinc

dithiophosphate, a metal phenolate, a basic metal sulfonate, a fatty acids, or an amine.

[00153] In one embodiment, the lubricant oil composition comprises a corrosion inhibitor, or two or more corrosion inhibitors, in the amount of about 0.01 wt % to about 5 wt %, or about 0.01 wt % to about 1.5 wt %, of the total weight of the lubricant oil composition.

4.2.3.1 1 Seal Swell Control Additives

[00154] In one embodiment, the lubricant oil composition provided herein further comprises a seal swell control additive, or two or more seal swell control additives. Such lubricant oil compositions further comprising a seal swell control additive, or two or more seal swell control additives, can be used, for example, as internal combustion engine oils.

[00155] 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 are, for example, organic phosphates, aromatic esters, aromatic hydrocarbons, esters (e.g., butylbenzyl phthalate), and polybutenyl succinic anhydride.

[00156] In one embodiment, the lubricant oil composition comprises a seal swell control additive, or two or more seal swell control additives, in the amount of about 0.01 wt % to about 3 wt %, or about 0.01 wt % to about 2 wt %, of the total weight of the lubricant oil composition.

4.2.3.12 Metal Deactivators

[00157] In one embodiment, the lubricant oil composition provided herein further comprises a metal deactivator, or two or more metal deactivators. Such lubricant oil compositions further comprising a metal deactivator, or two or more metal deactivators, can be used, for example, as internal combustion engine oils.

[00158] In one embodiment, a metal deactivator is a 2,5-dimercapto-l,3,4-thiadiazole or a derivative thereof, a mercaptobenzothiazole, an alkyltriazole, or a benzotriazole. In one embodiment, the metal deactivator is a diacid, such as sebacic acid, adipic acid, azelaic acid, dodecanedioic acid, 3-methyladipic acid, 3-nitrophthalic acid, 1,10-decanedicarboxylic acid, and fumaric acid.

[00159] In another embodiment, the metal deactivator is a straight or branch-chained, saturated or unsaturated monocarboxylic acid or ester thereof, which may optionally be sulphurized in an amount up to 35% by weight. In one embodiment, the acid is a C ₄ to C ₂₂ straight chain unsaturated monocarboxylic acid. In a particular embodiment, the metal deactivator is a monocarboxylic acid, such as sulphurised oleic acid. In another embodiment, the metal deactivator is oleic acid, valeric acid, or erucic acid. In a certain embodiment, the metal deactivator is a triazole. In a particular embodiment, the triazole is a tolylotriazole. In another embodiment, the metal deactivator is a thiazole and certain diamine compounds known to the person of ordinary skill in the art. In one embodiment, the metal deactivator is a triazole, benzotriazole or substituted benzotriazole, such as an alkyl substituted benzotriazoles. The alkyl substituent generally contains up to up to 8 carbon atoms. The triazoles may be optionally substituted with, for example, halogen, nitro, amino, and mercapto. In certain embodiments, the metal deactivator is a triazole, wherein the triazole is benzotriazole, tolyltriazole,

ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, chlorobenzotriazole, or

nitrobenzotriazole. In a particular embodiment, the metal deactivator is benzotriazole or tolyltriazole. In one embodiment, the metal deactivator is a straight or branched chain saturated or unsaturated monocarboxylic acid which is optionally sulphurised in an amount which may be up to 35% by weight, or an ester of such an acid; a triazole or alkyl derivatives thereof, ; or a triazole selected from 1,2,4 triazole, 1,2,3 triazole, 5-anilo-l,2,3,4-thiatriazole, 3-amino-l,2,4 triazole, 1-H-benzotriazole-l-yl-methylisocyanide, methylene-bis-benzotriazole and

naphthotriazole. [00160] In one embodiment, the lubricant oil composition comprises a metal deactivator, or two or more metal deactivators, in the amount of about 0.00 lwt % to about 0.35 wt %, or about 0.1 wt % to about 0.35 wt % of the total weight of the lubricant oil composition.

4.3 Methods and Formulation

[00161] Provided herein is a method of improving oxidation resistance, swell

characteristics, deposit performance, reserve alkalinity, rust preventing quality, or levels of ash- forming compounds of a lubricating oil composition described herein by mixing a first base oil component provided herein with a second base oil component provided herein and optionally one or more additives, wherein said oxidation resistance, swell characteristics, deposit performance, reserve alkalinity, rust preventing quality, or levels of ash- forming compound of a lubricating oil composition are improved as compared to an oil composition comprising the second base oil component as provided herein, but not comprising the first base oil component as provided herein.

[00162] Further provided herein is a method of improving fuel efficiency in an internal combustion engine by lubricating said engine with a lubricant oil composition provided herein, wherein the fuel efficiency is improved as compared to fuel efficiency achieved by lubricating said engine with an oil composition comprising the second base oil component as provided herein, but not comprising the first base oil component as provided herein.

[00163] A lubricant oil composition can be made using the first base oil component by blending or admixing the second base oil component, an optional additive package comprising an effective amount of at least one additive, such as a detergent, a dispersant, an antioxidant, a pour point depressant, a VI improver, an anti-wear agent, an extreme pressure additive, a friction modifier, a demulsifier, an antifoamanta corrosion inhibitor, a seal swell control additive, or a metal deactivator. An effective amount of one or more additives, or an additive package containing one or more such additives, is added to, blended into or admixed with the base stock to meet one or more formulated product specifications, such as those relating to a lube oil for diesel engines, internal combustion engines, automatic transmissions, turbine or jet, hydraulic oil, industrial oil, etc., as is known. 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; and "Lubricant Additives" by M. W. Ronney, published by Noyes Data Corporation, Parkridge, N.J. (1973). Additive packages for adding to a base stock or to a blend of base stocks to form fully formulated lubricated oil compositions for meeting performance specifications required for different applications or intended uses are commercially available.

[00164] In particular, the lubricant oil compositions provided herein can be prepared using conventional techniques. For example, Group II and/or Group III base oils and alkylated naphthalene can be added to a reaction vessel and mixed at temperatures from about 40°C to about 60°C for a period of time ranging from about 20 minutes to about 2 hours.

[00165] The following examples are presented to illustrate the lubricant oil compositions provided herein and should not be construed to limit the claimed invention.

5 EXAMPLES

5.1 Example 1: Preparation of Monoalkyl Naphthalenes

[00166] The monoalkyl naphthalenes of the current invention can be made in any of the ways known to those skilled in the art. For example, alpha olefins and Guerbet alcohols were used as electrophiles in reactions with naphthalene in the presence of suitable catalysts to prepare the monoalkyl naphthalene used in the practice of the present invention.

[00167] Specifically, Alkylate 32 was prepared by the alkylation of naphthalene with

Guebert alcohol Isofol 18E (mixture of 3.0 wt % - 6.0 wt % of 2-hexyldecanol, 85.0 wt % to 90.0 wt % of 2-octyldecanol and 2-hexyldodecanol, and 3.0 wt % to 6.0 wt % of 2-octyldodecanol) using a rare earth triflate salt, such as Sc(OTf)3, as a catalyst by methods known to those skilled in the art.

[00168] Similarly, Alkylate 30 was prepared by the alkylation of naphthalene with a mixture of alpha olefins of chain length of 18 to 26 carbon atoms, using standard Friedel-Crafts alkylation methods known to those skilled in the art.

5.2 Example 2

[00169] This Example presents Kinematic Viscosity, Viscosity Index and Noack Volatility data for exemplary compounds of Formula (I) and for Synesstic™ 5 (ExxonMobil Chemical Company, 13501 Katy Freeway, Houston, TX 77079-1398, USA), an exemplary state of the art commercially available alkylated naphthalene.

[00170] For Alkylate 30 and Alkylate 32, prepared as described in Example 1, as well as, commercially available Synesstic™ 5 the parameters shown in TABLE 3 were determined.

TABLE 3

[00171] The data presented in TABLE 3, TABLE 5, TABLE 7, and TABLE 9 has been obtained using the following standardized methods:

• ASTM Standard ASTM D445 , 2012, "Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (and Calculation of Dynamic Viscosity)," ASTM International, West Conshohocken, PA, 2012, DOI: 10.1520/D0445-12, www.astm.org;

• ASTM D2270, 201 Oe 1 , "Standard Practice for Calculating Viscosity Index From Kinematic Viscosity at 40 and 100°C," ASTM International, West Conshohocken, PA, 2010, DOI: 10.1520/D2270-10E01, www.astm.org; and

• ASTM D5800, 2010, "Standard Test Method for Evaporation Loss of Lubricating Oils by the Noack Method," ASTM International, West Conshohocken, PA, 2010, DOI: 10.1520/D5800-10, www.astm.org.

[00172] This Example demonstrates that the exemplary compounds Formula (I) presented in this Example have a higher Viscosity Index and lower Noack Volatility compared to

Synesstic™ 5, an exemplary state of the art commercially available alkylated naphthalene. 5.3 Example 3

[00173] This Example presents Kinematic Viscosity, Viscosity Index and Noack Volatility data for exemplary lubricant oil compositions as provided herein.

[00174] Alkylate 30, prepared as described in Example 1, was blended with low viscosity

PAOs (Synfluid ^® PAOs available from Chevron Phillips Chemical (Synfluid ^® PAO 4 cSt, and Synfluid ^® PAO 5 cSt available from Chevron Phillips Chemical Company LLC, 10001 Six Pines Drive, The Woodlands, TX 77380), in the proportions described in TABLE 4.

TABLE 4

5.4 Example 4

[00176] This Example presents Kinematic Viscosity, Viscosity Index and Noack Volatility data for exemplary lubricant oil compositions provided herein.

[00177] Alkylate 32, prepared as described in Example 1, was blended with low viscosity

PAOs (Synfluid ^® PAOs available from Chevron Phillips Chemical (Synfluid ^® PAO 4 cSt, and Synfluid® PAO 5 cSt available from Chevron Phillips Chemical Company LLC, 10001 Six Pines Drive, The Woodlands, TX 77380), in the proportions described in TABLE 6

TABLE 6

[00178] TABLE 7 shows the measured properties of the Lubricant Oil Compositions E-F.

TABLE 7

5.5 Example 5

[00179] This Example presents Kinematic Viscosity, Viscosity Index and Noack Volatility data for comparative lubricant oil compositions comprising Synesstic™ 5 (ExxonMobil

Chemical Company, 13501 Katy Freeway, Houston, TX 77079-1398, USA), an exemplary state of the art commercially available alkylated naphthalene.

[00180] Synesstic™ 5 was blended with low viscosity PAOs (Synfluid® PAOs available from Chevron Phillips Chemical (Synfluid® PAO 4 cSt, and Synfluid® PAO 5 cSt available from Chevron Phillips Chemical Company LLC, 10001 Six Pines Drive, The Woodlands, TX 77380), in the proportions described in TABLE 8. TABLE 8

TABLE 9 shows the measured properties of the Comparative Lubricant Oil I-IV.

TABLE 9

[00182] The Example demonstrates that the Lubricant Oil Compositions A-H relative to the Comparative Lubricant Oil Compositions I-IV have lower Noack Volatility, while maintaining low Kinematic Viscosity.

5.6 Example 6

[00183] The methods provided in this example are used to demonstrate oxidation resistance, swell characteristics, deposit performance, reserve alkalinity, rust preventing qualities, and levels of ash-forming compounds of lubricant oil compositions provided herein. [00184] The lubricant oil compositions demonstrates CCS viscosities at -35 C, as determined by ASTM D5293, of less than 6200 mPa-s, less than 5000 mPa-s, less than 4000 mPa-s, less than 3500 mPa-s, less than 3000 mPa-s, less than 2500 mPa-s, less than 2000 mPa-s, or less than 1700 mPa-s.

[00185] The lubricant oil compositions demonstrates high-temperature, high-shear

(HTHS) viscosities at 150° C, as determined by ASTM D4683 of less than 2.6 mPa-s, less than 2.3 mPa-s, less than 2.0 mPa-s, or less than 1.85 mPa-s.

[00186] Oxidation Resistance

[00187] The oxidation resistance of lubricant oil compositions is determined using ASTM

D4310, 2010, "Standard Test Method for Determination of Sludging and Corrosion Tendencies of Inhibited Mineral Oils," ASTM International, West Conshohocken, PA, 2010, DOI:

10.1520/D4310-10, www.astm.org. Oxidation resistance is the ability of oil to resist the direct and indirect attack of oxygen during engine operation. This test method is used to evaluate the tendency of oils to corrode copper catalyst metal and to form sludge during oxidation in the presence of oxygen, water, and copper and iron metals at an elevated temperature. The way in which oil is formulated determines its ability to resist oxidation. The oxidation stability

(oxidation lifetime) is determined by following the acid number of lubricant oil composition for a certain number of test hours required for the oil to reach an acid number of 2.0 mg KOH/g.

[00188] Swell Characteristics

[00189] The swell characteristics of the lubricant oil compositions is tested using the

ASTM D4289 test procedure. Some engine oil formulations have been shown to lack compatibility with certain elastomers used for seals in automotive engines. These deleterious effects on the elastomer are greatest with new engine oils (that is, oils that have not been exposed to an engine's operating environment) and when the exposure is at elevated temperatures.

ASTM D4289 is a test method that provides quantitative procedures for the evaluation of the compatibility of automotive engine oils with several reference elastomers typical of those used in the sealing materials in contact with these oils. Compatibility is evaluated by determining the changes in volume, Durometer A hardness and tensile properties when the elastomer specimens are immersed in the oil for a specified time and temperature.

[00190] Deposit Performance

[00191] Deposit Performance of the lubricant oil compositions is measured using the

TEOST MHT-4 (ASTM D7097) Thermo-Oxidation Engine Oil Simulation Test ("TEOST") . The MHT-4 TEOST is a bench test developed to determine piston deposit performance experienced when engines are run under high power/high temperature conditions. The deposit performance is measured in weight of deposit in mg.

[00192] Reserve Alkalinity

[00193] The reserve alkalinity of lubricant oil compositions is tested using ASTM D2896, by determining the Total Base Number ("TBN"). TBN determines how effective the control of acids formed is during the combustion process. The higher the TBN, the more effective it is in suspending wear, causing contaminants and reducing the corrosive effects of acids over an extended period of time. The reserve alkalinity is measured in milligrams of potassium hydroxide per gram (mg KOH/g).

[00194] Rust Preventing Qualities

[00195] The rust preventing qualities of lubricant oil compositions is tested using the Ball

Rust Test ("BRT") of ASTM D6557. The BRT is an 18-hour bench test procedure in which a hydraulic lifter ball in test oil is subjected to acids and air. The ball is rated automatically for reflectance intensity as a measure of surface area corrosion. The BRT is designed to evaluate an oil's ability to inhibit rust of internal engine parts in cyclic cold and hot operation where significant water and acid build-up can occur. The rust preventing qualities is measured by gray value rating.

[00196] Levels of Ash-Forming Compounds

[00197] The levels of ash- forming compounds of lubricant oil compositions is tested using

ASTM D784. Sulfated ash is defined as the residue remaining after an engine oil sample has been carbonized (i.e., combusted), and the residue subsequently treated with sulphuric acid and heated to constant weight. The primary ash- forming materials in engine oils include calcium, magnesium, sodium and potassium. These materials may be present in abrasive solids, soluble metallic soaps and any remaining catalyst. Abrasive solids and catalysts can lead to wear on injectors, fuel pumps, pistons and rings, as well as engine deposits. Soluble metallic soaps can also lead to engine deposits, as well as filter plugging. The level of ash-forming compounds is determined by the weight of residue remaining after the conclusion of the test.

[00198] The embodiments, described herein are intended to be merely exemplary, and those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific procedures described herein. All such equivalents are considered to be within the scope of the present invention and are covered by the following embodiments.

[00199] All references (including patent applications, patents, and publications) cited herein are incorporated herein by reference in their entirety and for all purposes to the same extent as if each individual publication or patent or patent application was specifically and individually indicated to be incorporated by reference in its entirety for all purposes.