WO2013003405A1 - Lubricating compositions containing polyalkylene glycol mono ethers - Google Patents

Abstract

Provided are lubricating compositions comprising in admixture at least 40 wt% of a base stock selected from the group consisting of Group I, Group II, Group III, Group IV" and Group V base stocks, or any combination thereof, one or more polyalkylene glycol mono ethers, and at least one additive. Also provided are methods of improving the friction and wear properties of a base stock selected from the group consisting of Group I, Group II, Group III, Group IV and Group V base stocks, or any combination thereof, comprising blending the base stock with one or more polyalkylene glycol mono ethers and at least one additive, to form a lubricating composition.

Description

LUBRICATING COMPOSITIONS CONTAINING

POLYALKYLENE GLYCOL MONO ETHERS

FIELD

[0001] The present disclosure relates to lubricating compositions containing one or more polyalkylene glycol mono ethers and one or more additives, and methods for improving the performance properties of lubricating compositions with polyalkylene glycol mono ethers.

BACKGROUND

[0002] Lubricant fuel/energy efficiency will be an important feature for future automotive engine lubricants and commercial vehicle engine lubricants. For automotive engine lubricant formulations, it is generally preferred to have lower viscosity fluids, e.g., belo about 15 cSt at 100°C. Lower viscosity is known to impart lower viscous drag thus offering better energy efficiency or fuel economy. It is also important to have a lubricant formulation with a low friction coefficient. Fluids with low friction coefficients exhibit low frictional loss during lubrication. Low frictional loss is important for improved fuel or energy efficiency of formulated lubricants. Moreover, improved antiwear properties and film thickness are beneficial for increasing the lifetime of engine components.

[0003] Polyalkylene glycol (PAG) fluids have been employed as lubricant base stocks. PAG fluids possess performance advantages thai provide good efficiency, including very low friction/traction for energy efficiency and good lubricity (in hydrodynamic, mix, and boundary lubrication conditions). PAG fluids also have other desirable properties, including high viscosity index (VI), low pour point, and excellent cleanliness. PAG fluids, however, have numerous drawbacks, including lack of miscibility and compatibility with mineral and synthetic hydrocarbon-based lubricants. This has limited their use in conjunction with such base stocks. PAG fluids are also polar and highly soluble in water, which can result in severe corrosion problems. Moreover, the formulation or additive response of PAG fluids can be unpredictable, rendering them difficult to formulate with.,

[0004] Polyethylene glycol, polypropylene glycol and polybutylene glycol, for example, are PAG fluids that are soluble in water, but very slightly soluble (e.g., Jess than about 0, 1 wt% at 23°C) in mineral and synthetic hydrocarbon-based base stocks. Each of these PAG fluids contains two OH groups which may contribute to their reduced solubility in non-polar solvents such as hydrocarbon-based base stocks.

[0005] As an example of a PAG, the struc ture of polyethylene glycol is shown by the following formula;

[0006] L. Rudnick and R. Shubkin, in Synthetic Lubricants and High-Perfonnance Functional Fluids (2d Ed. 1999), Chapter 6, Polyalkylene Glycols, pp. 159- 193 ("Rudnick"), describe polyalkylene glycols and their use as lubricants. Rudnick describes types of polyalkylene glycols used commercially as lubricants including, among others, "[hjomopolymers of propylene oxide (polypropylene glycols), which are the water-insoluble type" and "show limited solubility in oil", such as "monobutyl ethers" (p. 163). Rudnick also describes "[copolymers of ethylene oxide and propylene oxide, which are the water-soluble type" and "are typically diols or monobutyl ethers" (p. 163). Rudnick also describes "[pjoiymers of butyiene oxide [which] show greater oil solubility than the homopolvmers of propylene oxide," "[pjoiymers of propylene oxide and higher epoxides designed to give greater oil solubility" and "[pjoiymers of propylene oxide that are dimethyl ethers" (p. 164). Other references which discuss polyalkylene glycols and related compounds are: U.S. 4,973,414, U.S. 5,024,678, U.S. 5,599,100,

U.S. 5,746,933, U.S. 6,087,307, U.S. 200.3/0104951, U.S. 2009/0107035, U.S. 2010/0004151, U.S. 2010/0093572, EP 355 977, EP 524 783, EP 246 612A, WO 2000/23544, JP 54159411A, JP 61 166892, JP 6179888, JP 6128580. [0007] It would be desirable to have mineral and synthetic hydrocarbon-based lubricant compositions that take advantage of the desirable qualities of PAG fluids, including their good frictional properties, high VI and cleanliness, while overcoming their drawbacks, including the lack of miscibility of PAG fluids with mineral and synthetic hydrocarbon-based lubricants, corrosion due to water solubility, and unpredictable additive response.

SUMMARY

[0008] One aspect of this invention relates to a lubricating composition, comprising in admixture at least 40 wt.% of a base stock selected from the group consisting of Group

I, Group II, Group III, Group IV and Group V base stocks, or any combination thereof, one or more polyalkylene glycol mono ethers, and at least one additive.

[0009] Another aspect of this invention relates to a method of improving the triction and wear properties of a base s tock selected from the group consisting of Group I, Group

II, Group III, Group IV and Group V base stocks, or any combination thereof, comprising blending the base stock with one or more polyalkylene glycol mono ethers and at least one additive, to form a lubricating composition.

[0010] In one embodiment, the polyalkylene glycol mono ethers of the lubricating composition are represented by the formula:

wherein R i

a d may be linear or branched; ₂ = C i to C§ and may be linear or branched; R ₃ and R₂ optionally include -OH, -NH₂, and/or -CHO functional groups; and n is such that the molecular weight is up to about 5000.

[0011] In one embodiment, the polyalkylene glycol mono ethers each have a molecular weight of from about 300 up to about 1200. [0012] In one embodiment, the polyalkylene glycol mono ethers are present in an amoun t of from about 1 wt% up to about 20 wt% of the composition.

[0013] In one embodiment, the base stock of the lubricating composition is a Group IV base stock, or a blend of Group IV base stocks.

[0014] In one embodiment, the kinematic viscosity at 100°C of the lubricating composition is from about 4 cSt up to about 20 cSt.

[0015] In one embodiment, the additive in the lubricating composition is one or more chosen from the group consisting of friction modifiers, antiwear additives, viscosity improvers, detergents, dispersants, antioxidants, pour point depressants, anti-foam agents, demulsifiers, corrosion inhibitors, seal compatibility additives, antirust additives, and co-base stocks.

[0016] In one embodiment, the additive or additives are present in an amount of up to about 20 wi% of the composition.

[0017] In one embodiment, the additive is a friction modifier.

[0018] In one embodiment, the lubricating composition further comprises a co-base stock.

[0019] In one embodiment, the co-base stock is one or more chosen from the group consisting of esters and alkylated naphthalenes.

[0020] In one embodiment, the polyalkylene glycol ether in the lubricating composition is polyethylene glycol monomethyl ether or polypropylene glycol monobutyl ether, or a combination thereof. DETAILED DESCRIPTION

[0021] It lias been discovered that when one of the OH groups of a polyalkylene glycol is capped with, an R group, such as -CH₃, the solubility of the molecule in non- polar solvents, such as mineral and synthetic hydrocarbon-based base stocks, is significantly increased.

[0022] An example of such a single-capped polyalkylene glycol, i.e., a polyaklylene glycol mono ether, is polyethylene glycol monomethyl ether, represented by the formula:

wherein the molecular weight can be up to about 5000.

[0023] Another example of a single-capped polyalkylene glycol is polypropylene glycol monobutyl ether, represented by the formula:

wherein the molecular weight can be up to about 5000.

[0024] In accordance with the present invention, the single-capped polyalkylene glycols (i.e., polyalkylene glycol mono ethers) can be represented by the general formula:

R j -j-0(R.2 Hn-OH wherein R_\ === C _\ to C₁₂ (i.e., one carbon atom to 12 carbon atoms), and may be linear or branched; R? = Ci to Ce (i.e., one carbon atom to six carbon atoms), and may be linear or branched; and n is such that the molecular weight is up to about 5000. R] and R₂ optionally include -OH, -NH₂, and/or -CHO functional groups. Exemplary embodiments can include those in which, R. = Ci to C_]2, or R] = Ci to C_]0, or R] = C i to C₈, or R₅ = Ci to Ce, or Ri = Ci to C-4, or R i = Ci to C₂, or R-. = CI . Exemplary embodiments can also include those in which R₂ = Ci to Ce, or R₂ = Ci to C4, or R₂ = Ci to C₂, or R₂ = C] . It is contemplated that the molecular weights of the polyalkylene glycol mono ethers can be up to about 5000, for example up to about 4000, up to about 3000, up to about 2000, up to about 1200, up to about 900, up to about 600, or up to about 400. Additionally or alternately, the molecular weight can be from at least about 40, at least about 100, at least about 200, or at least about 300.

[0025] In exemplary embodiments, preferably Rj and R₂ are different, e.g., Rj C 3 and R₂ = Cz, Ri = C and R₂ = C3 , and so on.

[0026] In other exemplar)' embodiments, i and R₂ are the same, e.g., R i = Ci and R₂ = Ci , R_{ = C₂ and R₂ = C₂, R] = C3 and R₂ = C3 , and so on.

[0027] Surprisingly, when both protons on the two OH groups are capped, the solubility of the product in hydrocarbons was diminished. An example of such a molecule is polyethylene glycol dimethyl ether which was insoluble in Group I, II, 111 and PAO base stocks under the same conditions as the mono ethers. Polyethylene glycol dimethyl ether is represented by the formula:

[0028] It has also been discovered that lubricating compositions comprising mineral and/or synthetic hydrocarbon-based base stocks and polyalkylene glycol mono ethers provide solvency for additive packages, and unexpected improvements in average coefficient of friction, average wear scar, average film thickness, cam and lifter wear, and phosphorus retention,

[0029] A lubricating composition made comprising polyaikylene glycol mono ethers is prepared by blending or admixing with a base stock, one or more polyaikylene glycol mono ethers and an additive package comprising an effective amount of at least one additional performance enhancing additive, such as for example but not limited to at least one of a friction modifier, and/or a lubricity agent, and/or an antiwear agent, and/or extreme pressure additives, and/or a viscosity index (VI) improver, and/or a detergent, and/or a dispersani, and/or an antioxidant, and/or a pour point depressant, and/or an antifoamant, and/or a demulsifier, and/or a corrosion inhibitor, and/or a seal swell control additive, and/or antiseizure agent, and/or dye, and/or metal deactivators, and/or antistaining agent, and/or a co-basestock. Of these, those additives common to most formulated lubricating oils include one or more friction modifiers, antiwear additives, detergents, dispersants, and antioxidants, with other additives being optional depending on the intended use of the oil. 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 engines, as is known. For a review of many commonly used additives see: Klamann in "Lubricants and Related Products" Veriag Chemie, Deerfieid Beach, FL: ISBN 0-89573-177-0. Reference is also made to "Lubricant Additives" by M.W. Ronney, published by Noyes Data Corporation, Parkridge, NJ (1973). Various ma ufacturers sell such additive packages for adding to a base stock or to a blend of base stocks to form fully formulated lubricating oils for meeting performance specifications required for different applications or intended uses, and the exact identity of the various additives present in an additive package is typically maintained as a. trade secret by the manufacturer. However, the chemical nature of the various additives is known to those skilled in the art. The polyaikylene glycol mono ethers can be premixed with one or more of the additives prior to being blended or mixed with the base stock. For example, the polyaikylene glycol mono ether can be premixed with a pour point depressant. Applicants have discovered that this premixing results in improved pour point for the formulated lubricating composition. Alternatively, the polyalkylene glycol mono ether may not be premixed with any of the additives,

[0030] The lubricating compositions of the present disclosure may use Group I, Group II or Group 111 base oil stocks, Group IV polyalphaolefin (PAO) base oil stocks, Group V base oil stocks, or any combination thereof. Useful Group I-III, Group IV PAO and Group V base stocks have a Kvioo (kinetic viscosity at 100°C) of greater than about 2 cSt to about 25 cSt. Groups I, II, III, IV and λ^? are broad categories of base stocks developed and defined by the American Petroleum Institute (API Publication 1509; www iPI.org) to create guidelines for lubricant base oils. Group I base stocks generally have a viscosity index of between about 80 to 120 and contain greater than about 0,03% sulfur and less than about 90% saturates. Group II base stocks generally have a viscosity index of between about 80 to 120, and contain less than or equal to about 0.03% sulfur and greater than or equal to about 90% saturates. Group III stock generally has a viscosity index greater than about 120 and contains less than or equal to about 0.03% sulfur and greater than about 90% saturates. Group IV includes polyalphaolefins (PAO). Group V base stocks are base stocks not included in Groups I-IV. Table 1 summarizes properties of each of these five groups.

TABLE 1 : Base Stock Properties

[003ί ] Manufacturing plants that make Group I base stocks typically use solvents to extract the lower viscosity index (VI) components and increase the VI of the crude to the desired specifications. These solvents are typically phenol or furfural. Solvent extraction gives a product with less than 90% saturates and more than 300 ppm sulfur. The majority of lube production in the world is in the Group I category. [0032] Manufacturing plants that make Group II base stocks typically employ hydroprocessing such as hydrocracking or severe hydrotreating to increase the VI of the crude oil to the specifications value. The use of hydroprocessing typically increases the saturate content above 90% and reduces the sulfur below 300 ppm. Approximately 10% of the lube base oil production in the world is in the Group Π category, and about 30% of U.S. production is Group II.

[0033] Group III base stocks are usually produced using a three-stage process involving hydrocracking an oil feed stock, such as vacuum gas oil, to remove impurities and to saturate all aromatics which might be present to produce highly paraffinic lube oil stock of very high viscosity index, subjecting the hydrocracked stock to selective catalytic hydrodewaxing which converts normal paraffins into branched paraffins by isomerization followed by hydrofinishing to remove any residual aromatics, sulfur, nitrogen or oxygenates.

[0034] The term Group III stocks as used in the present specification and appended claims also embrace non-conventional or unconventional base stocks and/or base oils which include one or a mixture of base stoek(s) and/or base oil(s) derived from: (! ) one or more Gas-to-Liquids (GTL) materials; as well as (2) hydrodewaxed, or hydroisomerized/cat (and/or solvent) dewaxed base stock(s) and/or base oil(s) derived from synthetic wax, natural wax or waxy feeds, waxy feeds including feeds such as mineral and/or non-mineral oil waxy feed stocks, for example gas oils, slack waxes (derived from the solvent de-waxing of natural oils, mineral oils or synthetic; e.g., Fischer-Tropsch feed stocks) and waxy stocks such as waxy fuels hydrocracker bottoms, waxy raffinate, hydrocrackate, thermal crackates, foots oil or other natural, mineral oil, or even non-petroleum oil derived waxy materials such as waxy materials recovered from coal liquefaction or shale oil, linear or branched hydrocarbyl compounds with carbon number of about 20 or greater, preferably about 30 or greater, and mixtures of such base stocks and/or base oils.

[0035] GTL materials are materials thai are derived via one or more synthesis, combination, transformation, rearrangement, and/or degradation/deconsiruetive processes from gaseous carbon-containing compounds, hydrogen-containing compounds, and/or elements as feedstocks such as hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butylenes, and butynes. GTL base stocks are GTL materials of lubricating viscosity that are generally derived from hydrocarbons, for example waxy synthesized hydrocarbons, that are themselves derived from simpler gaseous carbon-containing compounds, hydrogen-containing compounds and/or elements as feedstocks. GTL base stoek(s) include oils boiling in the lube oil boiling range separated/fractionated from GTL materials such as by, for example, distillation or thermal diffusion, and subsequently subjected to well-known catalytic or solvent dewaxing processes to produce lube oils of reduced/low pour point; wax isomerates, comprising, for example, hydroisomerized or isodewaxed synthesized hydrocarbons; hydroisomerized or isodewaxed Fischer-Tropsch ("F-T") material (i.e., hydrocarbons, waxy hydrocarbons, waxes and possible analogous oxygenates); preferably hydroisomerized or isodewaxed F-T hydrocarbons or hydroisomerized or isodewaxed F-T waxes, hydroisomerized or isodewaxed synthesized waxes, or mixtures thereof.

[0036] GTL base stock(s) derived from GTL materials, especially, hydroisomerized/isodewaxed F-T material derived base stock(s), and other hydroisomerized/isodewaxed wax derived base stock(s) are characterized typically as having kinematic viscosities at 100°C of from about 2 mm²/s to about 50 mm²/s, preferably from about 3 rnnr/s to about 50 mm7s, more preferably from about 3.5 rnnr/s to about 30 mrrrVs, as exemplified by a GTL base stock derived by the isodewaxing of F-T wax, which has a kinematic viscosity of about 4 mm²/s at 100°C and a viscosity- index of about 130 or greater. The term GTL base oil/base stock and/or wax isomerate base oil/base stock as used herein and in the claims is to be understood as embracing individual fractions of GTL base stock/base oil or wax isomerate base stock/base oil as recovered in the production process, mixtures of two or more GTL base stocks/base oil fractions and/or wax isomerate base stocks/base oil fractions, as well as mixtures of one or two or more low viscosity GTL base stock(s)/base oil fraction(s) and/or wax isomerate base stock(s)/base oil fractions) with one, two or more high viscosity GTL base stock(s)/base oil fraction(s) and/or wax isomerate base stock(s)/base oil fraction(s) to - i l - produce a bi-modal blend wherein the blend exhibits a viscosity within the aforesaid recited range. Reference herein to Kinematic Viscosity refers to a measurement made by A STM method D445.

[0037] GTL base stocks derived from GTL materials, especially hydroisomerized/isodewaxed F-T material derived base stock(s), and other hydroisomerized/isodewaxed wax-derived base stock(s), such as wax hydroisomerat.es/isodewaxates, which can be used as base stock components of this invention are further characterized typically as having pour points of about -5°C or lower, preferably about -10°C or lower, more preferably about -15°C or lower, still more preferably about -20°C or lower, and under some conditions may have advantageous pour points of about -25°C or lower, with useful pour points of about -30°C to about -40°C or lower. If necessary, a separate dewaxing step may be practiced to achieve the desired pour point. References herein to pour point refer to measurement made by ASTM D97 and similar automated versions.

[0038] The GTL base stock(s) derived from GTL materials, especially hydroisomerized/isodewaxed F-T material derived base stock(s), and other hydroisomerized/isodewaxed wax-derived base stock(s) which are base stock components which can be used in this invention are also characterized typically as having viscosity indices of 80 or greater, preferably 100 or greater, and more preferably 120 or greater. Additionally, in certain particular instances, viscosity index of these base stocks may be preferably 130 or greater, more preferably 135 or greater, and even more preferably 140 or greater. For example, GTL base stock(s) that derive from GTL materials preferably F-T materials especially F-T wax generally have a viscosity index of 130 or greater. References herein to viscosity index refer to ASTM method D2270.

[0039] In addition, the GTL base stock(s) are typically highly paraffinic of greater than 90 percent saturates) and may contain mixtures of monoeycloparaffins and multicycloparaffins in combination with non-cyclic isoparaffins. The ratio of the naphfhenic (i.e., cycloparaffm) content in such combinations varies with the catalyst and temperature used. Further, GTL base stocks typically have very low sulfur and nitrogen content, generally containing less than about 10 ppm, and more typically less than about 5 ppm of each of these elements. The sulfur and nitrogen content of GTL base stock and base oil obtained by the hydroisomerization/isodewaxing of F-T material, especially F-T wax is essentially nil.

[0040] In a preferred embodiment, the GTL base stock(s) comprises paraffinic materials thai consist predominantly of non-cyclic isoparaffins and only minor amounts of cycloparaffins. These GTL base stock(s) typically comprise paraffinic materials that consist of greater than 60 wt.% non-cyclic isoparaffins, preferably greater than 80 wt% non-cyclic isoparaffins, more preferably greater than 85 wt% non-cyclic isoparaffins, and most preferably greater than 90 wt% non-cyclic isoparaffins.

[004ί ] Useful compositions of GTL base stock(s), hydroisomerized or isodewaxed F-T material derived base stock(s), and wax-derived hydroisomerized/isodewaxed base stock(s), such as wax isomerates/isodewaxates, are recited in U.S. 6,080,301: U.S. 6,090,989, and U.S. 6,165,949, for example.

[0042] Base stock(s) derived from waxy feeds, which are also suitable for use as the Group III stocks in this invention, are paraffinic fluids of lubricating viscosity derived from hydrodewaxed, or hydroisomerized/cat (and/or solvent) dewaxed waxy feed stocks of mineral oil, non-mineral oil, non-petroleum, or natural source origin, e.g. feed stocks such as one or more of gas oils, slack wax, waxy fuels hydrocracker bottoms, hydrocarbon raffinates, natural waxes, hydrocrackat.es, thermal crackates, foots oil, wax from coal liquefaction or from shale oil, or other suitable mineral oil, non-mineral oil, non-petroleum, or natural source derived waxy materials, linear or branched hydrocarbyl compounds with carbon number of about 20 or greater, preferably about 30 or greater, and mixtures of such isomerate/isodewaxate base stock(s).

[0043] Slack wax is the wax recovered from any waxy hydrocarbon oil including synthetic oil such as F-T waxy oil or petroleum oils by solvent or auto-refrigerative dewaxing. Solvent dewaxing employs chilled solvent such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), mixtures of MEK/MIBK, mixtures of MEK and toluene, while auto-refiigerative dewaxing employs pressurized, liquefied low boiling hydrocarbons such as propane or butane.

[0044] Slack waxes secured from synthetic waxy oils such as F-T waxy oil will usually have zero or nil sulfur and/or nitrogen containing compound content. Slack wax(es) secured from petroleum oils, may contain sulfur and nitrogen-containing compounds. Such heteroatom compounds must be removed by hydrotreating (and not hydrocracking), as for example by hydrodesulfurization (HDS) and hydrodenitrogenation (HD ) so as to avoid subsequent poisoning,⁷ deactivation of the bydroisomerization catalyst.

[0045] The process of making the lubricant oil base stocks from wax or waxy stocks, e.g. slack wax, F-T wax or waxy feed, may be characterized as an isomerization process. As previously indicated, if slack waxes are used as the feed, they may need to be subjected to a preliminary hydrotreating step under conditions already well known to those skilled in the art to reduce (to levels that would effectively avoid poisoning or deactivating the isomerization catalyst) or to remove sulfur- and nitrogen-containing compounds which would otherwise deactivate the hydroisomerization or hydrodewaxing catalyst used in subsequent steps. If F-T waxes are used, such preliminary treatment is not required because such waxes have only trace amounts (less than about 10 ppm, or more typically less than about 5 ppm to nil each) of sulfur and/or nitrogen compound content. However, some hydrodewaxing catalyst feed F-T waxes may benefit from prehydrotreatment for the removal of oxygenates while others may benefit from oxygenates treatment. The hydroisomerization or hydrodewaxing process may be conducted over a combination of catalysts, or over a single catalyst.

[0046] Following any needed hydrodenitrogenation or hydrosulfurization, the hydroprocessing used for the production of base stocks from such waxy feeds may use an amorphous hydrocracking/liydfoisomerization catalyst, such as a lube hydrocracking (LHDC) catalysts, for example catalysts containing Co, Mo, i, W, Mo, etc., on oxide supports, e.g., alumina, silica, silica/alumina, or a crystalline hydrocracking/hydroisomerization catalyst, preferably a zeoiitic catalyst. [0047] Hydrocarbon conversion catalysts useful in the conversion of the n-paraffm waxy feedstocks disclosed herein to form the isoparaffmic hydrocarbon base oil are zeolite catalysts, such as ZSM-5, ZSM-11, ZSM-23, ZSM-35, ZSM-12, ZSM-38, ZSM-48, offretite, ferrierite, zeolite beta, zeolite t eta, and zeolite alpha, as disclosed in U.S. 4,906,350. These catalysis are used in combination with Group VIII metals, in particular palladium or platinum. The Group VIII metals may be incorporated into the zeolite catalysts by conventional techniques, such as ion exchange,

[0048] Conversion of the waxy feed stock may be conducted over a combination of Pt/zeolite beta and Pi/ZSM-23 catalysts or over such catalysts used in series in the presence of hydrogen. In another embodiment, the process of producing the lubricant oil base stocks comprises hydroisomerization and dewaxing over a single catalyst, such as Pt/ZSM-35, In yet another embodiment, the waxy feed can be fed over a catalyst comprising Group VIII metal loaded ZSM-48, preferably Group VIII noble metal loaded ZSM-48, more preferably Pi/ZSM-48 in either one stage or two stages. In any case, useful hydrocarbon base oil products may be obtained. Catalyst ZSM-48 is described in U.S. 5,075,269.

[0049] A dewaxing step, when needed, may be accomplished using one or more of solvent dewaxing, catalytic dewaxing or hydrodewaxing processes or combinations of such processes in any sequence.

[0050] In solvent dewaxing, the hydroisomerate may be contacted with chilled solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), mixtures of ME/MIBK, or mixtures of ME /toluene and the like, and further chilled to precipitate out the higher pour point material as a waxy solid which is then separated from the solvent-containing lube oil fraction which is the raffinate. The raffinate is typically further chilled in scraped surface chillers to remove more wax solids. Auio-refrigerative dewaxing using low molecular weight hydrocarbons, such as propane, can also be used in which the hydroisomerate is mixed with, e.g., liquid propane, at least a portion of which is flashed off to chili down the hydroisomerate to precipitate out the wax. The wax is separated from the raffinate by filtration, membrane separation or cen rifugation. Tlie solvent is then stripped out of the raffinate, which is then fractionated to produce the preferred base stocks useful in the present invention.

[005i ] In catalytic dewaxing the hydroisomerate is reacted with hydrogen in the presence of a suitable dewaxing catalyst at conditions effective to lower the pour point of the hydroisomerate. Catalytic dewaxing also converts a portion of the hydroisomerate to lower boiling materials which are separated from the heavier base stock fraction. This base stock fraction can then be fractionated into two or more base stocks. Separation of the lower boiling material may be accomplished either prior to or during fractionation of the heavy base stock fraction material into the desired base stocks.

[0052] Any dewaxing catalyst which will reduce the pour point of the hydroisomerate and preferably those which provide a large yield of lube oil base stock from the hydroisomerate may be used. These include shape selective molecular sieves which, when combined with at least one catalytic metal component, have been demonstrated as useful for dewaxing petroleum oil tractions and include, for example, ferrierite, mordenite, ZSM-5, ZSM-1 1 , ZSM-23, ZSM-35, ZSM-22 also known as theta one or TON, and the silicoaluminophosphates known as SAPOs. A dewaxing catalyst which has been found to be unexpectedly particularly effective comprises a noble metal, preferably Pt, composited with H-mordenite. The dewaxing may be accomplished with the catalyst in a fixed, fluid or slurry bed. Typical dewaxing conditions include a temperature in the range of from about 400 to 600°F, a pressure of 500 to 900 psig, H₂ treat rate of 1500 to 3500 SCF/B for flow-through reactors and LHSV of 0.1 to 10, preferably 0.2 to 2.0. The dewaxing is typically conducted to convert no more than 40 wt.% and preferably no more than 30 wt% of the hydroisomerate having an initial boiling point in the range of 650 to 750°F to material boiling below its initial boiling point.

[0053] Polyalpha olefin (PAO) base stocks may also be used in the present invention. PAOs in general are typically comprised of relatively low molecular weight hydrogenated polymers or oligomers of polyalphaolefins which include, but are not limited to, C? to about C ? alphaoiefms, with the Cg to about C j 6 alphaoiefms, such as 1-octene, 1 -decene, 1-dodecene and the like, being preferred. The preferred polyaiphaoiefins are poly-l-octene, poly-l-decene and poly- 1 -dodecene and mixtures thereof and mixed olefm-derived polyolefins.

[0054] The PAO fluids may be conveniently made by the polymerization of one or a mixture of alphaolefins in the presence of a polymerization catalyst such as the Friedel-Crafts catalyst including, for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanoi, carboxylic acids or esters such as ethyl acetate or ethyl proprionate. For example, the methods disclosed by U.S. 4,149, 178 or U.S. 3,382,291 may be conveniently used herein. Other descriptions of PAO synthesis are found in the following U.S. Patents: 3,742,082; 3,769,363; 3,876,720; 4,239,930; 4,367,352; 4,413, 156; 4,434,408; 4,910,355; 4,956, 122; and 5,068,487. The dimers of the C_i4 to C_i8 olefins are described in U.S. 4,218,330. PAOs useful in the present invention may have a kinematic viscosity at 100°C from about 1.5 to about 5,000 cSt (mm²/s). For the purposes of this invention the PAO preferably has a kinematic viscosity at 100°C from about 2 to about 25 cSt (mm7s), from about 2 to about 20 cSt, or from about 2 to about 15 cSt. PAOs are often identified by reference to their approximate kinematic viscosity at 100°C. For example, PAO 6 refers to a PAO with a kinematic viscosity of approximately 6 cSt at 100°C,

[0055] The PAOs useful in the present invention can also be made by metallocene catalysis. The metallocene-catalyzed PAO (mPAO) can be a copolymer made from at least two or more different alphaolefins, or a homo-polymer made from a single alphaolefin feed employing a metallocene catalyst system.

[0056] The metallocene catalyst can be simple metallocenes, substituted metallocenes or bridged metallocene catalysts activated or promoted by, for instance, methylaluminoxane (MAO) or a non-coordinating anion, such as Ν,Ν-dimethyianiliniurn tetrakis(perfluorophenyl)borate or other equivalent non-coordinating anion. mPAO and methods for producing mPAO employing metallocene catalysis are described in WO 2007/0 1832 and U.S. published application 2009/0036725. [0057] The copolymer mPAO composition is made from at least two alphaolefins of C₃ to C₃₀ range and having monomers randomly distributed in the polymers. It is preferred that the average carbon number is at least 4.1. Advantageously, ethylene and propylene, if present in the feed, are present in the amount of less than 50 wt% individually or preferably less than 50 wt% combined. The copolymers can be isotactic, atactic, syndiotactic polymers or any other form of appropriate taciticity.

[0058] mPAO can also be made from mixed feed Linear Alpha Olefins (LAOs) comprising at least two and up to 26 different linear alphaolefins selected from C3 to C3 linear alphaolefins. The mixed feed LAO can be obtained, for example, from an ethylene growth processing using an aluminum catalyst or a metailocene catalyst. The growth olefins comprise mostly Ce to C i* LAO. LAOs from other processes can also be used.

[0059] The homo-polymer mPAO composition can be made from single alphaolefin chosen from alphaolefins in the C₃ to C₃₀ range, preferably C₃ to C-.e, most preferably €^"3 to C i4 or C₃ to Ci2. The homo-polymers can be isotactic, atactic, syndiotactic polymers or any other form of appropriate taciticity. The taciticity can be carefully tailored by the polymerization catalyst and polymerization reaction condition chosen or by the hydrogenation condition chosen.

[0060] The alphaoiefin(s) can be chosen also from any component from a conventional LAO production facility or from a refinery. It can be used alone to make homo -polymer or together with another LAO available from a refinery or chemical plant, including propylene, 1 -butene, 1-pentene, and the like, or with 1-hexene or 1 -octene made from a dedicated production facility. The alphaolefins also can be chosen from the alphaolefins produced from Fischer-Tropsch synthesis (as reported in U.S. 5,382,739). For example, C₃ to Cje alphaolefins, more preferably linear alphaolefins, are suitable to make homo-polymers. Other combinations, such as C₄- and C 14 -LAO, Ce- and C16-LAO, C₈-, Cio-, C 12-LAO, or Cs- and C _i4-LAO, C₆-, C10-, C _i4-LAO, C₄- and C i2 -LAO, etc., are suitable to make copolymers. [0061] A feed comprising a mixture of LAOs selected from C 3 to C30 LAOs or a single LAO selected from C₃ to Cie LAO, is contacted with an activated metallocene catalyst under oligomerization conditions to provide a liquid product suitable for use in lubricant components or as functional fluids. Also embraced are copolymer compositions made from at least two alphaolefins of C₃ to C ₀ range and having monomers randomly distributed in the polymers. The phrase "at least two alphaolefins" will be understood to mean "at least two different alphaolefins" (and similarly "at least three alphaolefins" means "at least three different alphaolefins", and so forth).

[0062] The product obtained is an essentially random liquid copolymer comprising the at least two alphaolefins. By "essentially random" is meant that one of ordinary skill in the art would consider the products to be random copolymer. Likewise the term "liquid" will be understood by one of ordinary skill in the art as meaning liquid under ordinary conditions of temperature and pressure, such as ambient temperature and pressure.

[0063] The process for producing mPAO employs a catalyst system comprising a metallocene compound (Formula 1 , below) together with an activator such as a non- coordinating anion ( CA) (Formula 2, below) or mefhylaluminoxane (MAO) 1 11 1 (Formula 3, below):

Formula 1

Formula 2

Formula 3

CH,

The term "catalyst system" is defined herein to mean a catalyst precursor/activator pair, such as a metallocene/activator pair. When "catalyst system" is used to describe such a pair before activation, it means the un activated catalyst (precatalvst) together with an activator and, optionally, a co-activator (such as a trialkyl aluminum compound). When it is used to describe such a pair after activation, it means the activated catalyst and the activator or other charge-balancing moiety. Furthermore, this activated "catalyst system" may optionally comprise the co-activator and/or other charge -balancing moiety. Optionally and often, the co-activator, such as trialkyl aluminum compound, is also used as an impurity scavenger.

[0065] The metallocene is selected from one or more compounds according to Formula 1 above. In Formula 1 , M is selected from Group 4 transition metals, preferably zirconium (Zr), hafnium (Hi) and titanium (Ti), LI and L2 are independently selected from cyciopentadienyl ("Cp"), indenyl, and fluorenyl, which may be substituted or unsubstituted, and which may be partially hydrogenated. A is an optional bridging group which, if present, can he selected from diaikvlsilyl, dialk imeihyl, diphenyisilyi or diphenylm ethyl, ethyl enyl (— CH₂-CH₂), alkylethylenyl (— CR₂-CR₂), where alkyl can be independently C j to C ie alkyl radical or phenyl, tolyf, xylyl radical and the like, and wherein each of the two X groups, Xa and Xb, are independently selected from halides OR (R is an alkyl group, preferably selected from Q to C 5 straight or branched chain alkyl groups), hydrogen, Ci to Cie alkyl or aryl groups, haloalkyl, and the like. Usually relatively more highly substituted metallocenes give higher catalyst productivity and wider product viscosity ranges.

[0066] The polyalphaolefins preferably have a Bromine number of 1.8 or less as measured by ASTM D 1 159, preferably 1.7 or less, preferably 1.6 or less, preferably 1.5 or less, preferably 1 .4 or less, preferably 1.3 or less, preferably 1.2 or less, preferably 1.1 or less, preferably 1.0 or less, preferably 0.5 or less, preferably 0.1 or less. If necessary the polyalphaolefins can be hydrogenated to achieve a low bromine number.

[0067] The mpolyaiphaoiefins (mPAO) described herein may have monomer units represented by Formula 4 in addition to the all regular 1,2-connection:

Formula 4

where j, k and m are each, independently, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22, n is an integer from 1 to 350 (preferably 1 to 300, preferably 5 to 50) as measured by proton MR.

[0068] Any of the mpolyaiphaoiefins (mPAO) described herein may have an Mw (weight average molecular weight) of 100,000 or less, preferably between 100 and 80,000, preferably between 250 and 60,000, preferably between 280 and 50,000, preferably between 336 and 40,000 g mol.

[0069] Any of the mpolyalphaolefins (mPAO) described herein may have a M (number average molecular weight) of 50,000 or less, preferably between 200 and 40,000, preferably between 250 and 30,000, preferably between 500 and 20,000 g/mol,

[0070] Any of the mpolyalphaolefins (mPAO) described herein may have a molecular weight distribution (MWD-Mw/Mn) of greater than 1 and less than 5, preferably less than 4, preferably less than 3, preferably less than 2.5, The MWD of mPAO is always a function of fluid viscosity. Alternately, any of the polyalphaolefms described herein may have an Mw/Mn of between 1 and 2.5, alternately between 1 and 3.5, depending on fluid viscosity.

[0071] Molecular weight distribution (MWD), defined as the ratio of weight-averaged MW to number-averaged MW (= Mw/Mn), can be determined by gel permeation chromatography (GPC) using polystyrene standards, as described in p. 1 15 to 144 , Chapter 6, The Molecular Weight of Polymers in "Principles of Polymer Systems" (by Ferdinand Rodrigues, McGraw-Hill Book, 1970). The GPC solvent was HPLC Grade tetrahydrofuran, uninhibited, with a column temperature of 30°C, a flow rate of 1 mi/min, and a. sample concentration of 1 wt%, and the Column Set is a Phenogel 500 A, Linear, 10E6A.

[0072] Any of the m-polyalphaolefins (mPAO) described herein may have a substantially minor portion of a high end tail of the molecular weight distribution. Preferably, the mPAO has not more than 5.0 wt% of polymer having a molecular weight of greater than 45,000 Daltons. Additionally or alternately, the amount of the mPAO that has a molecular weight greater than 45,000 Daltons is not more than 1.5 wt%, or not more than 0.10 wt.%. Additionally or alternately, the amount of the mPAO that has a molecular weight greater than 60,000 Daltons is not more than 0,5 wt%, or not more than 0.20 wt%, or not more than 0.1 wt%. The mass fractions at molecular weights of 45,000 and 60,000 can be determined by GPC, as described above. [0073] Any mPAO described herein may have a pour point of less than ()°C (as measured by ASTM D97), preferably less than ~10°C, preferably less than -20°C, preferably less than -25°C, preferably Jess than -30°C, preferably less than -35°C, preferably less than -50°C, preferably from -10°C to -80°C, preferably from ~15°C to -70°C.

[0074] mPolyalphaolefins (mPAO) made using metallocene catalysis may have a kinematic viscosity at 100°C from about 1.5 to about 5,000 cSt (mm²/s). For the purposes of this invention the mPAO preferably has a kinematic viscosity ax 100°C from about 2 to about 25 cSt (mm^?7s), from about 2 to about 20 cSt, or from about 2 to about 15 cSt.

[0075] The lubricating compositions of the present disclosure also contain at least one additive, as described below. The use of polyalkylene glycol mono ethers greatly improves the solubility of additives in lubricating compositions when compared to the solubility of additives when using polyalkylene glycols which are not single-capped. The lubricant compositions, however, are not limited by the examples shown herein as illustrations.

Friction Modifiers

[0076] 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, lubricant compositions, or functional fluids, to modify the coefficient of friction of a lubricated surface may be effectively used in combination with the base oils or lubricant compositions of the present invention if desired. Friction modifiers that lower the coefficient of friction are particularly advantageous in combination with the base oils and lube compositions of this invention. 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, 8b, So, Fc, Cu, Zn, and others. Ligands may include hydrocarby! derivative of alcohols, poiyols, glycerols, partial ester glycerols, thiols, carboxylates, carbamates, thiocarbamates, dithiocarbamates, phosphates, thiophosphates, dithiophosphates, amides, imides, amines, thiazoies, thiadiazoies, dithiazoles, diazoles, triazoles, and other polar molecular functional groups containing effective amounts of O, , S, or P, individually or in combination. In particular, Mo-containing compounds can be particularly effective such as for example Mo-dithiocarbamat.es, Mo(DTC), Mo-dithiophosphates, Mo(DTP), Mo-amines, Mo (Am), Mo-alcoholates, Mo-alcohol-amides, etc. See U.S. 5,824,627; U.S. 6,232,276: U.S. 6, 153,564; U.S. 6, 143,701 : U.S. 6, 110,878: U.S. 5,837,657: U.S. 6,010,987; U.S. 5,906,968; U.S. 6,734, 150; U.S. 6,730,638; U.S. 6,689,725; U.S. 6,569,820; WO 99/66013 ; WO 99/47629; WO 98/26030.

[0077] Ashless friction modifiers may include lubricant materials that contain effective amounts of polar groups, for example, hydroxyl-containing hydrocarby! 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 hydrocarby! acids, a!coho!s, amides, esters, hydroxy carboxylates, and the like. In some instances fatty organic acids, fatty amines, and su!furized fatty acids may be used as suitable friction modifiers.

[0078] Useful concentrations of friction modifiers may range from about 0.01 wt% to 10-15 wt% or more, often with a preferred range of about 0.1 wt% to 5 wt%. 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 3000 ppm or more, and often with a preferred range of about 20-2000 ppm, and in some instances a more preferred range of about 30-1000 ppm. Friction modifiers of all types may be used alone or in mixtures with the materials of this invention. Often mixtures of two or more friction modifiers, or mixtures of friction modifier(s) with alternate surface active material(s), are also desirable.

Antiwear and EP Additives

[0079] Many lubricating oils require the presence of antiwear and/or extreme pressure (EP) additives in order to provide adequate antiwear protection for the engine. Increasingly specifications for engine oil performance have exhibited a trend for improved antiwear properties of the oil Antiwear and extreme EP additives perform this role by reducing friction and wear of metal parts.

[0080] While there are many different types of antiwear additives, for several decades the principal antiwear additive for interna! combustion engine crankcase oils is a metal aikyithiophosphate and more particularly a metal dialkyldithiopliospliate in which the primary metal constituent is zinc, or zinc dialkyldithiophosphate (ZDDP). ZDDP compounds generally are of the formula ZniSP(S)(OR^])(OR^z)]₂ where R¹ and R^z are Ci-Cj8 alkyl groups, preferably C₂-Ci₂ alkyl groups. These alkyl groups may be straight chain or branched. The ZDDP is typically used in amounts of from about 0.4 to 1.4 wt% of the total lube oil composition, although more or less can often be used advantageously.

[0081] However, it is found that the phosphorus from these additives has a deleterious effect on the catalyst in catalytic converters and also on oxygen sensors in automobiles. According to one aspect of this invention, as discussed below in connection with the Examples, the use of polyalkylene glycol mono ethers results in unexpected improvements in phosphorus retention.

[0082] Another way to minimize this effect is to replace some or all of the ZDDP with phosphorus-free antiwear additives.

[0083] A variety of non-phosphorous additives are also used as antiwear additives. Sulfurized olefins are useful as antiwear and EP additives. Sulfur-containing olefins can be prepared by sulfurization or various organic materials including aliphatic. arylaliphatic or alicyclic olefinic hydrocarbons containing from about 3 to 30 carbon atoms, preferably 3-20 carbon atoms. The olefinic compounds contain at least one non-aromatic double bond. Such compounds are defined by the formula

R³R⁴C=CR⁵R⁶ where each of R³-R" are independently hydrogen or a hydrocarbon radical. Preferred hydrocarbon radicals are aikyi or alkenyl radicals. Any two of R'-R° may be connected so as to form a cyclic ring. Additional information concerning siilfurized olefins and their preparation can be found in U.S. 4,941,984,

[0084] The use of polysulfides of thiophosphorus acids and thiophosphorus acid esters as lubricant additives is disclosed in U.S. Patents 2,443,264; 2,471, 1 15; 2,526,497; and 2,591,577. Addition of phosphorothionyl disulfides as an antiwear, antioxidant, and EP additive is disclosed in U.S. 3,770,854. Use of alkylthiocarbamoyl compounds (bis(dibutyl)thiocarbamoyl, for example) in combination with a molybdenum compound (oxymolybdenum diisopropylphosphorodithioate sulfide, for example) and a phosphorous ester (dibutyl hydrogen phosphite, for example) as antiwear additives in lubricants is disclosed in U.S. 4,501,678, U.S. 4,758,362 discloses use of a carbamate additive to provide improved antiwear and extreme pressure properties. The use of thiocarbamate as an antiwear additive is disclosed in U.S. 5,693,598. Thiocarbamate/molybdenum complexes such as moly-sulfur alkyl dithiocarbamate trimer complex

is alkyl) are also useful antiwear agents. The use or addition of such materials should be kept to a minimum if the object is to produce low SAP formulations.

|0085j Esters of glycerol may be used as antiwear agents. For example, mono-, dk and tri-oleates, mono-palmitates and mono-myristates may be used.

[0086] ZDDP is combined with other compositions that provide antiwear properties. U.S. 5,034, 141 discloses that a combination of a thiodixanthogen compound (octyithiodixanfhogen, for example) and a metal thiophosphate (ZDDP, for example) can improve antiwear properties. U.S. 5,034,142 discloses that use of a metal alkyoxyalkylxanthate (nickel ethoxyethylxant ate, for example) and a dixanthogen (diethoxyethyl dixanthogen, for example) in combination with ZDDP improves antiwear properties.

[0087] Preferred antiwear additives include phosphorus and sulfur compounds such as zinc dithiophosphates and/or sulfur, nitrogen, boron, molybdenum phosphorodithioat.es, molybdenum dithioearbamates and various organo-molybdenum derivatives including heterocyclics, for example dimereaptothiadiazoles, mercaptobenzothiadiazoles, triazines, and the like, alicyclics, amines, alcohols, esters, diols, triols, fatty amides and the like can also be used. Such additives may be used in an amount of about 0.01 to 6 wt%, preferably about 0.01 to 4 wt%. ZDDP-Iike compounds provide limited hydroperoxide decomposition capability, significantly below that exhibited by compounds disclosed and claimed in this patent and can therefore be eliminated from the formulation or, if retained, kept at a minimal concentration to facilitate production of low SAP formulations.

Viscosity Improvers

[0088] Viscosity improvers (also known as Viscosity Index modifiers, and VI improvers) provide lubricants with high and low temperature operabiiity. These additives increase the viscosity of the oil composition at elevated temperatures which increases film thickness, while having limited effect on viscosity at low temperatures.

[0089] Suitable viscosity improvers include high molecular weight hydrocarbons, polyesters and viscosity index improver dispersants that function as both a viscosity index improver and a dispersant. Typical molecular weights of these polymers are between about 1,000 to 1 ,000,000, more typically about 2,000 to 500,000, and even more typically between about 25,000 and 100,000.

[0090] Examples of suitable viscosity improvers are polymers and copolymers of methacrylate, butadiene, olefins, or alkylated styrenes. Polyisobutyiene is a commonly used viscosity index improver. Another suitable viscosity index improver is polvmethacrylate (copolymers of various chain length alkyl inethacryiates, for example), some formulations of which also serve as pour point depressants. Other suitable viscosity index improvers include copolymers of ethylene and propylene, liydrogenated block copolymers of styrene and isoprene, and polyacrylates (copolymers of various chairs length acrylates, for example). Specific examples include styrene-isoprene or styrene- butadiene based polymers of 50,000 to 200,000 molecular weight.

[0091] The amount of viscosity modifier may range from 0.01 to 8 wt%, preferably 0.01 to 4 wt%, more preferably 0.01 to 2 wt% based on active ingredient and depending on the specific viscosity modifier used.

Detergents

[0092] Detergents are commonly 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.

[0093] Salts that, contain a substantially stochiometric amount of the metal are described as neutral salts and have a total base number (TB , as measured by ASTM D2896) of from 0 to 80. Many compositions are overbased, containing large amounts of a metal base that is achieved by reacting an excess of a metal compound (a metal hydroxide or oxide, for example) with an acidic gas (such as carbon dioxide). Useful detergents can be neutral, mildly overbased, or highly overbased.

[0094] It is desirable for at least some detergent to be overbased. Overbased detergents help neutralize acidic impurities produced by the combustion process and become entrapped in the oil. Typically, the overbased material has a ratio of metallic ion to anionic portion of the detergent of about 1.05: 1 to 50: 1 on an equivalent basis. More preferably, the ratio is from about 4: 1 to about 25: 1. Tlie resulting detergent is an overbased detergent that will tvpicallv have a TBN of about 150 or higher, often about 250 to 450 or more. Preferably, the overbasing cation is sodium, calcium, or magnesium. A mixture of detergents of differing TBN can be used in the present invention.

[0095] Preferred detergents include the alkali or alkaline earth metal salts of sulfonates, phenates, carboxylates, phosphates, and salicylates.

[0096] Sulfonates may be prepared from sulfonic acids that are typically obtained by sulfonation of alkyl substituted aromatic hydrocarbons. Hydrocarbon examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, biphenyl and their halogenated derivatives (chlorobenzene, chlorotoluene, and cbloronapbthalene, 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.

[0097] Klamann in Lubricants and Related Products, op cit discloses a number of overbased metal salts of various sulfonic acids which are useful as detergents and dispersants in lubricants. The book entitled "Lubricant Additives", C. V. Smallheer and R, K. Smith, published by the Lezius-Hiles Co. of Cleveland, Ohio (1967), similarly discloses a number of overbased sulfonates that are useful as dispersants/detergents.

[0098] Alkaline earth phenates are another useful class of detergent. These detergents can be made by reacting alkaline earth metal hydroxide or oxide (CaO, Ca(OH)₂, BaO, Ba(OH)₂, MgO, Mg(OH)₂, for example) with an alkyl phenol or sulfurized alkylphenol. Useful alkyl groups include straight chain or branched ( ^' · ·(^' .·,, alkyl groups, preferably, C4 -C20. Examples of suitable phenols include isobutyiphenoi, 2-ethylhexylphenol, nonylphenol, dodecyl phenol, and the like. It should be noted that starting alkylphenols may contain more than one alkyl substituent that are each independently straight chain or branched. When a non-sulfurized alkylphenol is used, the sulfurized product may be obtained by methods well known in the art. These methods include heating a mixture of alkylphenol and sulfurizing agent (including elemental sulfur, sulfur halides such as sulfur dichloride, and the like) and then reacting the su!furizcd phenol with an alkaline earth metal base.

[0099] Metal salts of carboxylic acids are also useful as detergents. These carboxylic acid detergents may be prepared by reacting a basic metal compound with at least one carboxylic acid and removing free water from the reaction product. These compounds may be overbased to produce the desired TBN level. Detergents made from salicylic acid are one preferred class of detergents derived from carboxylic acids. Useful salicylates include long chain alkyl salicylates. One useful family of compositions is of the formula

where R is 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. Preferred R groups are alkyl chains of at least Cn, preferably Co or greater. R may be optionally substituted with substituents that do not interfere with the detergent's function. M is preferably, calcium, magnesium, or barium. More preferably, M is calcium.

[00100] Hydrocarbyl-substituted salicylic acids may be prepared from phenols by the Kolbe reaction. See U.S. 3,595,79! for additional information on synthesis of these compounds. The metal salts of the hydrocarbyl-substituted salicylic acids may be prepared by double decomposition of a metal salt in a polar solvent such as water or alcohol.

Alkaline earth metal phosphates are also used as detergents. [00102] Detergents may be simple detergents or what is known as hybrid or complex detergents. The latter detergents can provide the properties of two detergents without the need to blend separate materials. See U.S. 6,034,039, for example.

[00103] Preferred detergents include calcium phenates, calcium sulfonates, calcium salicylates, magnesium phenates, magnesium sulfonates, magnesium salicylates and other related components (including borated detergents). Typically, the total detergent concentration is about 0.01 to about 8.0 wt%, preferably, about 0.1 to 4.0 wt%.

Dispersants

[00104] During machinery operation, oil-insoluble oxidation byproducts are produced. Dispersants help keep these byproducts in solution, thus diminishing their deposition on metal surfaces. Dispersants may be ashless or ash-forming in nature. Preferably, the dispersani 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.

[00105] Suitable dispersants typically contain a polar group attached to a relatively high molecular weight hydrocarbon chain. The polar group typically contains at least one element of nitrogen, oxygen, or phosphorus. Typical hydrocarbon chains contain 50 to 400 carbon atoms.

[00106] Chemically, many dispersants may be characterized as phenates, sulfonates, sulfurized phenates, salicylates, naphthenates, stearates, carbamates, thiocarbamates, phosphorus derivatives, A particularly useful class of dispersants are the alkenylsuecinic derivatives, typically produced by the reaction of a long chain substituted alkenyi succinic compound, usually 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 normally a polyisobutylene group. Many examples of this type of dispersant are well known commercially and in the literature. Exemplary U.S. patents describing such dispersants are 3, 172,892; 3,215,707; 3,219,666; 3,316,177; 3,341 ,542; 3,444, 170; 3,454,607; 3,541,012; 3,630,904; 3,632,51 1 ; 3,787,374 and 4,234,435. Other types of dispersant are described in U.S. Patents 3,036,003; 3,200,107; 3,254,025; 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,413,347; 3,697,574; 3,725,277; 3,725,480; 3,726,882; 4,454,059; 3,329,658; 3,449,250; 3,519,565; .3,666,730; 3,687,849; 3,702,300; 4, 100,082; 5,705,458. A further description of dispersants may be found, for example, in European Patent Application No, 471 071, to which reference is made for this purpose.

[00107] Hydrocarbyl-substituted succinic acid compounds are popular dispersants. In particular, suecinimide, succinate esters, or succinate ester amides prepared by the reaction of a hydrocarbon-substituted succinic acid compound preferably having at least 50 carbon atoms in the hydrocarbon substituent, with at least one equivalent of an alkyiene amine are particularly useful.

|00I08] 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 TEPA can vary from about 1 : 1 to about 5: 1. Representative examples are shown in U.S. Patents 3,087,936; 3, 172,892; 3,219,666; 3,272,746; 3,322,670; and 3,652,616, 3,948,800; and Canada Patent No. 1 ,094,044,

[00109] Succinate esters are formed by the condensation reaction between alkenyl succinic anhydrides and alcohols or polyois. Molar ratios can vary depending on the alcohol or polyol used. For example, the condensation product of an alkenyl succinic anhydride and pentaerythritol is a useful dispersant.

[00110] Succinate ester amides are formed by condensation reaction between alkenyl succinic anhydrides and alkanol amines. For example, suitable alkanol amines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines and polyalkenylpolyamines such as polyethylene polyamines. One example is propoxylated hexamethylenediamine. Representative examples are shown in U.S. 4,426,305. [00111 ] The molecular weight of the alkenyl succinic anhydrides used in the preceding paragraphs will typically range between 800 and 2,500. The above products can be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid, and boron compounds such as borate esters or highly borated dispersants. The dispersants can be boraied with from about 0.1 to about 5 moles of boron per mole of dispersant reaction product.

[00112] Mannich base dispersants are made from the reaction of alkylphenols, formaldehyde, and amines. See U.S. 4,767,551. Process aids and catalysts, such as oleic acid and sulfonic acids, can also be pari of the reaction mixture. Molecular weights of the alkylphenols range from 800 to 2,500, Representative examples are shown in U.S. Patents 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953 ; 3,798,165; and 3,803,039.

[00113] Typical high molecular weight aliphatic acid modified Mannich condensation products usefui in this invention can be prepared from high molecular weight alkyl- substituted hydroxyaromatics or HN(R)₂ group-containing reactants.

[00114] Examples of high molecular weight alkyl-substituted hydroxyaromatic compounds are polypropylphenol, polybutylphenol, and other polyalkylphenols. These polyaikyiphenois can be obtained by the alkylation, in the presence of an alkylating catalyst, such as BF₃, 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.

[00115] Examples of HN(R)₂ group-containing reactants are alkylene pofyamines, 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 are well known and include the mono- and di-amino alkanes and their substituted analogs, e.g., efhyiamine and diethanol amine; aromatic diamines, e.g., phenylene diamine, diamino naphthalenes; heterocyclic amines, e.g., morpholme, pyrrole, pyrrolidine, imidazole, imidazolidine, and piperidine; melamine and their substituted analogs.

[001 ] Examples of alkylene polyamide reactants include ethylenediamine, (Methylene tri amine, 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 H₂N-Z-NH-)_nH, mentioned before, 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-, tetra-, pentapropylene tri-, tetra-, penta- and hexaamines are also suitable reactants. The alkylene polyamines are usually obtained by the reaction of ammonia and dihalo alkanes, such as diehloro alkanes. Thus the alkylene polyamines obtained from the reaction of 2 to 1 1 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,

[00117] Aldehyde reactants useful in the preparation of the high molecular products useful in this invention include the aliphatic aldehydes such as formaldehyde (also as paraformaldehyde and formalin), acetaldehyde and aldol (β-hydroxybutyraldehyde). Formaldehyde or a formaldehyde-yielding reactant is preferred.

[00118] Hydrocarbyl substituted amine ashless dispersant additives are well known to one skilled in the art; see, for example, U.S. 3,275,554; 3,438,757; 3,565,804; 3,755,433; 3,822,209 and 5,084, 197.

[00119] Preferred dispersants include borated and non-borated succinimides, including those derivatives from mono-succinimides, bis-succinimides, and/or mixtures of mono- and bis-succinimides, wherein the hydrocarbyl succinimide is derived from a hydrocarbylene group such as polvisobutylene having a Mn of from about 500 to about 5000 or a mixture of such hydrocarbylene groups. Other preferred dispersants include succinic acid-esters and amides, alkyiphenol-polyamine-coupled Mannich adducts, their capped derivatives, and other related components. Such additives may be used in an amount of about 0.1 to 20 wt%, preferably about 0.1 to 8 wt%.

Antioxidants

[00120] 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. One skilled in the art knows a wide variety of oxidation inhibitors that are useful in lubricating oil compositions. See, Klamann in Lubricants and Related Products, op cit, and U.S. Patents 4,798,684 and 5,084,197, for example.

[00121] Useful antioxidants include hindered phenols. These phenolic antioxidants may be ashless (metal-free) phenolic compounds or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are the hindered phenolics which are the ones which contain a sterically hindered hydroxy! group, and these include those derivatives of dihydroxy aryl compounds in which the hydroxy! groups are in the o- or p-position to each other. Typical phenolic antioxidants include the hindered phenols substituted with C '- alkyl groups and the alkylene coupled derivatives of these hindered phenols. Examples of phenolic materials of this type 2-t-butyl-4-heptyi phenol; 2-t-butyl-4-octyl phenol; 2-t-butyl-4-dodeeyl phenol; 2,6-di-t-butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol; 2-meihyl-6-t-butyl- 4-heptyl phenol; and 2-methyl-6-t-butyl-4-dodecyl phenol. Other useful hindered mono- phenolic antioxidants may include for example hindered 2,6-di-alkyl-phenolic proprionic ester derivatives. Bis-phenolic antioxidants may also be advantageously used in combination with the instant invention. Examples of ortho-coupled phenols include: 2,2 '-bis(4-heptyl-6-t-butyl-phenol); 2,2 '-bis(4-octyl-6-t-butyl-phenol); and

2,2^'-bis(4-dodecyl-6-t-butyi-phenol). Para-coupled bisphenols include for example 4,4^'-bis(2,6-di-t-butyl phenol) and 4,4^'-methylene-bis(2,6-di-t-butyl phenol).

[00122] Non-phenolic oxidation inhibitors which may be used include aromatic amine antioxidants and these may be used either as such or in combination with phenolics. Typical examples of non-phenolic antioxidants include: alkylated and non-alkylated aromatic amines such as aromatic monoamines of the formula R⁸R⁹R¹⁰N where R⁸ is an aliphatic, aromatic or substituted aromatic group, R⁹ is an aromatic or a substituted aromatic group, and Rⁱ is H, alkyi, aryl or R^{i i}S(0)xR^{5 z} where R¹¹ is an alkylene, alkenylene, or aralkylene group, R¹² is a higher alkyi group, or an alkenyl, aryl, or alkaryl group, and x is 0, 1 or 2. The aliphatic group R⁸ may contain from 1 to about 20 carbon atoms, and preferably contains from about 6 to 12 carbon atoms. The aliphatic group is a saturated aliphatic group. Preferably, both R⁸ and R^y are aromatic or substituted aromatic groups, and the aromatic group may be a fused ring aromatic group such as naphthyf. Aromatic groups R⁸ and R⁹ may be joined together with other groups such as S.

|00123] Typical aromatic amines antioxidants have alkyi substiruent groups of at least about 6 carbon atoms. Examples of aliphatic groups include hexyi, heptyl, octyl, nonyl, and decyl. Generally, the aliphatic groups will not contain more than about 14 carbon atoms. The general types of amine antioxidants useful in the present compositions include diphenylamines, phenyl naphthylamines, phenothiazines, imidodibenzyis and diphenyl phenyiene diamines. Mixtures of two or more aromatic amines are also useful. Polymeric amine antioxidants can also be used. Particular examples of aromatic amine antioxidants useful in the present invention include: p,p^'-dioetyldiphenyiamine; t-octylphenyl-alpha-naphthylamine; phenyl-alphanaphthylamine; and p-octyiphenyi- alpha-naphthyf amine.

[00124] Sulfurized alkyi phenols and alkali or alkaline earth metal salts thereof also are useful antioxidants.

[00125] Another class of antioxidant used in lubricating oil compositions is oil-soluble copper compounds. Any oil-soluble suitable copper compound may be blended into the lubricating oil Examples of suitable copper antioxidants include copper dihydrocarbyl tl io- or dithio-pbospbates and copper salts of carboxylic acid (naturally occurring or synthetic). Other suitable copper salts include copper dithiacarbamates, sulphonates, phenates, and aceiyiacetonates. Basic, neutral, or acidic copper Cu(I) and or Cu(II) salts derived from alkenyl succinic acids or anhydrides are know to be particularly useful.

[ΘΘ126] Preferred antioxidants include hindered phenols, arylamines. These antioxidants may be used individually by type or in combination with one another. Such additives may be used in an amount of about 0.01 to 5 wt%, preferably about 0.01 to 1.5 wt%, more preferably zero to less than 1.5 wt%, most preferably zero.

Pour Point Depressants

[00127] Conventional pour point depressants (also known as lube oil flow improvers) may be added to the compositions of the present invention if desired. These pour point depressants may be added to lubricating compositions of the present invention to lower the minimum temperature at which the fluid will flow or can be poured. Examples of suitable pour point depressants include polymethacrylates, polyacrylates, polyarylamid.es, condensation products of haloparaffm waxes and aromatic compounds, vinyl carboxylate polymers, and terpolymers of dialkylfumarat.es, vinyl esters of fatty acids and ally! vinyl ethers. U.S. Patents 1 ,815,022; 2,015,748; 2, 191 ,498; 2,387,501 ; 2,655,479; 2,666,746; 2,721 ,877; 2,721 ,878; and 3,250,715 describe useful pour point depressants and/or the preparation thereof. Such additives may be used in an amount of about 0.01 to 5 wt%, preferably about 0.01 to 1.5 wt%.

Anti-Foam Agents

[00128] Anti-foam agents may advantageously be added to lubricant compositions. These agents retard the formation of stable foams. Silicones and organic polymers are typical anti-foam agents. For example, po!ysiloxanes, such as silicon oil or polydimethyl siloxane, provide antifoam properties. Anti-foam agents are commercially available and may be used in conventional minor amounts along with other additives such as demuisifiers; usually the amount of these additives combined is less than 1 percent and often less than 0.1 percent. Corrosion Inhibitors

[00129] 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. Patents 2,719, 125; 2,719, 126; and 3,087,932. Such additives may be used in an amount of about 0.01 to 5 wt%, preferably about 0.01 to 1.5 wt%.

Seal Compatibility Additives

[00130] Seal compatibility agents help to swell elastomeric seals by causing a chemical reaction in the fluid or physical change in the elastomer. Suitable seal compatibility agents for lubricating oils include organic phosphates, aromatic esters, aromatic hydrocarbons, esters (butylbenzyl phthaiate, for example), and poiybutenyl succinic anhydride. Such additives may be used in an amount of about 0.01 to 3 wt%, preferably about 0.01 to 2 wt%.

Inhibitors and Antirust Additives

[00131 ] Antirust additives (or corrosion inhibitors) are additives that protect lubricated metal surfaces against chemical attack by water or other contaminants. A wide variety of these are commercially available; they are referred to in Klamann in Lubricants and Related Products, op cit.

[00132] One type of antirust additive is a polar compound that wets the metal surface preferentially, protecting it with a film of oil. Another type of antirust additive absorbs water by incorporating it in a water-in-oil emulsion so that only the oil touches the metal surface. Yet another type of antirust additive chemically adheres to the metal to produce a non-reactive surface. Examples of suitable additives include zinc dithiophosphat.es, metal phenolates, basic metal sulfonates, fatty acids and amines. Such additives may be used in an amount of about 0.01 to 5 wt%, preferably about 0,01 to 1.5 wt%. Co-Basestocks

[00133] In lubricating oil compositions of the present invention in which the base stock is a Group I, Group II, Group III or Group TV base stock, or combination thereof, the lubricating oil compositions may also include one or more co-base stocks which provide further increased solubility of the polyalkylene glycol mono ethers and additives in the Group I, Group II, Group III and/or Group IV base stock.

100134] Esters comprise a useful co-basestock. Additive solvency and seal compatibility characteristics may be secured by the use of esters such as the esters of dibasic acids with monoalkanols and the polyol esters of monocarboxylic acids. Esters of the former type include, for example, the esters of dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, aikenyi succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, aikenyi malonic acid, etc., with a variety of alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, etc. Specific examples of these types of esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyf sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyi phthalate, dieicosyl sebacate, etc.

[00135] Particularly useful synthetic esters are those full or partial esters which are obtained by reacting one or more polyhydric alcohols (preferably the hindered polyols such as the neopentyl polyols e.g. neopentyl glycol, trimethylol ethane, 2-methyl- 2 -propyl- 1,3 -propanediol, trimethylol propane, pentaerythntol and dipentaeryt^'hritol) with alkanoic acids containing at least about 4 carbon atoms (preferably to C_?o acids such as saturated straight chain fatty acids including caprylic acid, capric acid, 1 auric 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).

[00136] 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. [00137] Alkylated naphthalenes are also a useful co-basestock. The alkyl groups on the alkylated naphthalene preferably have from about 6 to 30 carbon atoms, with particular preference to about 12 to 18 carbon atoms. A preferred class of alkylating agents are the olefins with the requisite number of carbon atoms, for example, the hexenes, heptenes, ocienes, nonenes, decenes, uiidecenes, dodecenes. Mixtures of the olefins, e.g. mixtures of C12-C20 or Cu-Cis olefins, are useful. Branched alkylating agents, especially oligomerized olefins such as the trimers, tetramers, pentamers, etc., of light olefins such as ethylene, propylene, the butyl enes, etc., are also useful.

Typical Additive Amounts

[00138] When lubricating oil compositions contain one or more of the additives discussed above, the additive(s) are blended into the composition in an amount sufficient for it to perform its intended function. Typical amounts of such additives useful in the present invention are shown in Table 1 below.

[00139] Note that many of the additives are shipped from the manufacturer and used with a certain amount of base oil solvent in the formulation. Accordingly, the weight amounts in the table below, as well as other amounts mentioned in this text, unless otherwise indicated are directed to the amount of active ingredient (that is the non- solvent portion of the ingredient). The wt% indicated below are based on the total weight of the lubricating oil composition.

TABLE 2

Typical Amounts of Various Lubricant Oil Components

Compound Approximate wt% Approximate wt%

(useful) (preferred)

Friction Modifiers 0.01-15 0.01-5

Antiwear Additives 0.01-6 0.01-4

Viscosity Improvers 0.01 -8 0.01-2

Detergents 0.01-8 0.01-4

Dispersants 0.1-20 0.1-8

Antioxidants 0.01-5 0.01 -1.5

Pour Point Depressants 0.01-5 0.01-1.5

Anti-foam Agents 0.001-1 0.001 -0.1

Corrosion Inhibitors 0.01-5 0.01-1.5

Co-basestocks 0-50 0-40

Base Stocks Balance Balance

[00140] Lubricating compositions are prepared by blending together or admixing one or more base stocks from the group consisting of Group I, Group Π, Group III, Group IV, and Group V base stocks, one or more polyaikylene glycol mono ethers, and one or more additives.

[00141] The lubricating compositions can be used as automotive engine lubricants and commercial vehicle engine lubricants. The lubricating compositions demonstrate superior performance with regard to average friction coefficient, average wear scar, average film thickness, cam and lifter wear, and phosphorus retention when compared to similar compositions thai do not contain polyaikylene glycol mono ethers. The lubricating compositions can also be used as industrial lubricants.

[00142] In the lubricating compositions, the base stock can be Group I, Group II, Group III, Group IV, or Group V, or any combination of these base stocks. These base stocks, or combinations of these base stocks can be used in the lubricating compositions in amounts of up to about 99 wt% of the composition, up to about 95 wt% of the composition, up to about 90 wt.% of the composition, up to about 80 wt% of the composition, up to about 70 wt% of the composition, up to about 60 wt% of the composition, up to about 50 wt% of the composition, or up to about 40 wt% of the composition. Additionally or alternately, the base stocks can be used in the lubricating compositions in amounts of at least about 40 wt% of the composition, at least about 50 wt% of the composition, at least about 60 wt% of the composition, at least about 70 wt% of the composition, at least about 80 wt% of the composition, at least about 90 wt% of the composition, or at least about 95 wt% of the composition. Further additionally or alternately, the base stocks can be used in the lubricating compositions in amounts of from about 40 wt% of the composition to about 99 wt% of the composition, from about 50 wt% of the composition to about 99 wt% of the composition, from about 60 wt% of the composition to about 99 wt% of the composition, from about 70 wt% of the composition to about 99 wt% of the composition, from about 75 wt% of the composition to about 99 wt% of the composition, from about 75 wt% of the composition to about 95 wt% of the composition, or from about 75 wt% of the composition to about 85 wt% of the composition.

[00143] In the lubricating compositions, the Group I, Group Π, Group III, Group IV and Group V base stocks, or combinations of these base stocks, can have a kinematic viscosity at 100°C of up to about 25 cSt, up to about 20 cSt, up to about 15 cSt, up to about 12 cSt, up to about 10 cSt, up to about 8 cSt, or up to about 6 cSt. Additionally or alternately, the Group I, Group Π, Group III, Group IV and Group V base stocks, or combinations of these base stocks, can have a kinematic viscosity at 100°C of at least about 2 cSt, at least about 4 cSt, or at least about 6 cSt. Further additionally or alternately, the Group I, Group Π, Group III, Group IV and Group V base stocks, or combinations of these base stocks, can have a kinematic viscosity at 100°C of from about 2 cSt to about 25 cSt, from about 2. cSt to about 15 cSt, from about 2. cSt to about 12 cSt, from about 4 cSt to about 10 cSt, or from about 4 cSt to about 8 cSt.

[00144] In the lubricating compositions, the polyalkylene glycol mono ethers can be used in an amount of up to about 60 wt%, up to about 50 wt% of the composition, up to about 40 wt% of the composition, up to about 30 wt% of the composition, up to about 20 wt% of the composition, up to about 15 wt% of the composition, up to about 10 wt% of the composition, up to about 5 wt% of the composition, or up to about 3 wt% of the composition. Additionally or alternately, the polyalkylene glycol mono ethers can be used in an amount of from about 0,5 wt%, from about 1 wt% of the composition, from about 2 wt% of the composition, from about 5 wt% of the composition, or from about 10 wt% of the composition. Further additionally or alternately, the polyalkylene glycol mono ethers can be used in an amount of from about i to about 25 wt% of the composition, or from about 1 to about 15 wt% of the composition, or from about 1 to about 5 wt% of the composition, from about 5 to about 25 wt% of the composition, or from about 10 to about 20 wt% of the composition.

[00ί 45] In an embodiment of the lubricating compositions, at least one of the performance additives of the lubricating compositions is a friction modifier. Additionally or alternately, at least one of the additives is an antiwear and/or extreme pressure (EP) additive. In a further embodiment of the lubricating compositions, the additive package is present in an amount of up to about 30 wt% of the composition, up to about 25 wt% of the composition, up to about 20 wt% of the composition, up to about 15 wt% of the composition, up to about 10 wt% of the composition, or up to about 5 wt% of the composition.

[00146] The lubricating compositions have improved frictionai properties, and, thus, improved efficiency. Preferably, the average friction coefficient of the lubricating compositions is less than about 0.15, less than about 0.14, less than about 0.13, less than about 0.12, less than about 0.11, or less than about 0.10.

100147] The lubricating compositions have improved wear properties, as indicated by average wear scar. Preferably, the average wear scar of the lubricating compositions is less than about 150 microns, less than about 140 microns, or less than about 130 microns,

[00148] The lubricating compositions have improved average film thickness. Preferably, the average film thiclaiess of the lubricating compositions is greater than about 50%, greater than about 60%, greater than about 70%, or greater than about 80%. [00149] Average friction coefficients, average wear scar and average film thicknesses can be measured by a High Frequency Reciprocating Rig (HFR ) test. The FTFRR is manufactured by PCS Instruments and identified as model HFR2 (AutoHFRR). The test equipment and procedure are similar to the ASTM D6079 method except the test oil temperature is raised from 32°C to 195°C at 2°C/minute, 400 g load, 60 Hz frequency, and 0,5 mm stroke length,

[00150] The lubricating compositions have improved cam and lifter wear, as measured in accordance with the Sequence IIIG engine test, ASTM D7320. Preferably the cam and lifter wear is less than about 25 microns, or less than about 20 microns, or less than about 16 microns.

[00151 ] The lubricating compositions have improved phosphorus retention as measured in accordance with the Sequence IIIG engine test, ASTM D7320. Preferably the phosphorus retention is greater than about 80%, or greater than about 85%, or greater than about 90%>.

[00152] The pour points of the lubricating compositions were measured according to the ASTM D97 standard. Preferably, the pour point of the lubricating compositions is less than about -30°C, or less than about -40°C.

[00153] The kinematic viscosities at 40°C of the lubricating compositions were measured according to the ASTM D445 standard. Preferably, the lubricating compositions have a kinematic viscosity at 40°C of from about 30 cSt to about 50 cSt, or from about 35 cSt to about 45 cSt.

[00154] The kinematic viscosities at 100°C of the lubricating compositions were measured according to the ASTM T3445 standard. Preferably, the lubricating compositions have a kinematic viscosity at I00^cC of up to about 25 cSt, up to about 20 cSt, up to about 15 cSt, up to about 12 cSt, up to about 10 cSt, up to about 8 cSt, or up to about 6 cSt. Additionally or alternately, the lubricating compositions have a kinematic viscosity at 1G0°C of at least about 2 cSt, at least about 4 cSt, or at least about 6 cSt. Further additionally or alternately, the lubricating compositions have a kinematic viscosity at 100°C of from about 2 cSt to about 25 cSt, from about 2 cSt to about 15 cSt, from about 2 cSt to about 12 cSt, from about 4 cSt to about 10 cSt, or from about 4 cSt to about 8 cSt,

[00155] The invention will now be more particularly described with reference to the following non-limiting Examples.

EXAMPLES

Example 1

[00156] The solubility of single-capped polyaikyiene glycols (i.e., polyaikyiene glycol mono ethers) was demonstrated in a series of base stocks and compared to the solubility of uncapped polyaikyiene glycols in a series of base stocks. Each blend in Table 3 was stirred and heated up to 105^CC for one hour. After cooling for approximately one hour to room temperature (approximately 23°C), the blends were observed for two to six weeks to determine the solubility of the single-capped and uncapped polyaikyiene glycols. If the blend was clear ("C"), the polyaikyiene glycol was soluble in the base stock. If the blend was hazy ("H"), the polyaikyiene glycol was insoluble in the base stock,

[00157] Table 3 shows that polyethylene glycol monomethyl ether (550 molecular weight (MW)) was soluble in Group I, Group II, Group III and PAO base stocks, and that polypropylene glycol monobutyl ether (340 molecular weight (MW)) was soluble in Group I, Group III and PAO base stocks. Table 3 also shows that polyethylene glycol was insoluble in Group I and PAO base stocks, that polypropylene glycol was insoluble in Group I, Group II and PAO base stocks, and that polybutylene glycol was insoluble in Group I and PAO base stocks. Each of the above glycols are available from Sigma-Aldrich Corp. (St. Louis, Missouri). Table 3 further shows that SYNALOX EPB-165 and SYNALOX 50-15B were insoluble in Group III base stocks. SYNALOX EPB-165 is a water-soluble fluid that consists of random copolymers of ethyle e oxide and propylene oxide with a terminal butoxy group. SYNALOX 50-15B is an alcohol started material containing oxyethylene and oxypropylene groups with a single terminal hydroxy! group having the structure:

RO-[CH₂C(CH₃)HO]_!1[CH₂CH₂0]_m-H (MW 500).

SYNALOX EPB-165 and SYNALOX 50-15B are available from The Dow Chemical Company (Midland, Michigan). Finally, Table 3 shows that SYNALOX, EPB-165 is soluble in alkylated naphthalene.

TABLE 3

TABLE 3 (continued)

TABLE 3 (continued)

Table 3 (continued)

[00158] In addition, the following were observed. Four grams of Group III Petronas Etro 4 were mixed with one gram of SYNALOX 50-15B, stirred and heated up to 105°C for one hour. Upon cooling for approximately one hour to room temperature (approximately 23 °C), the blend was observed to be hazy. Then two grams of TMP were added and the blend was stirred and heated up to 105°C. After cooling for approximately one hour to room temperature (approximately 23°C), the blend was observed to be dear. The same results were observed with the remaining Group HI base stocks in Table 3.

Example 2

[00159] A fully formulated 5W30 engine oil composition (Inventive Oil 1) was prepared by blending PAO 6 with a single-capped polyalkyiene glycol (polypropylene glycol monobutyl ether (PPG-MBE) (molecular weight 1000), available from Sigma-Aldrich. Corp. (St. Louis, Missouri)) in the amount of 2 wt% of the composition and a commercial 5W30 additive package with a treat rate of 17 wt% of the composition. Comparative Oils 1, 2 and 3 were prepared by blending the components shown in Table 4.

[001 0] Noack volatility was measured in accordance with ASTM D5800. Average friction coefficients, average wear scar and average film thicknesses were measured by a High Frequency Reciprocating Rig (HFRR) test. The HFRR is manufactured by PCS Instruments and identified as model HFR2 (AutoHFRR). The test equipment and procedure are similar to the ASTM 136079 method except the test oil temperature is raised from 32°C to 195°C at 2°C/minute, 400 g load, 60 Hz frequency, and 0.5 mm stroke length.

[00161 ] The results in Table 4 showed that when PPG-MBE and the additive package were blended in PAO 6 (Inventive Oil 1 ), the Noack volatility remained nearly the same compared to Comparative Oil 3 (despite the high volatility of PPG-MBE relative to PAO 6). The pour point and kinematic viscosities of Inventive Oil 1 and Comparative Oil 3 were also virtually the same. Unexpectedly, the friction coefficient, wear scar, and film thickness of Inventive Oil 1 improved significantly relative to Comparative Oils 1, 2 and 3. These results showed an unexpected synergistic effect in Inventive Oil 1 when PPG-MBE was included in the presence of the additive package. This can be seen by looking at the data for Comparative Oils 2 and 3 and Inventive Oil 1. Comparative Oil 2 contained 98 wt% PAO 6 and 2 wt% PPG-MBE, and had a friction coefficient of 0.151, a wear scar of 202 microns, and a film thickness of 32%. Comparative Oil 3 contained 83% PAO 6 and 17 wt.% of a commercial additive package, and had a friction coefficient of 0.152, a wear scar of 187 microns, and a film thickness of 49%. Inventive Oil 1 was the same as Comparative Oil 3, except that 2 wt% of PPG-MBE was added and PAO 6 was decreased by 2 wt% to 81 wt%. Surprisingly, Inventive Oil 1 had a friction coefficient of 0.131, a wear scar of 145.5 microns, and a film thickness of 61%. Each of these properties was significantly better than either Comparative Oil 2 (which contained 2 wt% PPG-MBE and no additive package) or Comparative Oil 3 (which contained 17 wt% additive package and no PPG-MBE). These results demonstrated an unexpected synergistic effect when PPG-MBE was included in the presence of the additive package. It was also observed that the additives in the additive package remained soluble in Inventive Oil 1 in the presence of 2 wt% of PPG-MBE.

TABLE 4

Example 3

[00162] Fully formulated 5VV30 engine oil compositions (Inventive Oils 2 and 3) were prepared by blending PAO 6 with, a single-capped polyaikylene glycol (polyethylene glycol monomethyl ether (PEG-MME) (molecular weight 550), available from Sigma-Aldrich Corp. (St, Louis, Missouri)) in the amount of 2 wt% and 4 wt% of the composition and a commercial 5W30 additive package with a treat rate of 17 wt% of the composition. Comparative Oils 4, 5, 6 and 7 were prepared by blending the components shown in Table 5.

[00163] Noack volatility was measured in accordance with ASTM D5800. Average friction coefficients, average wear scar and average film thicknesses were measured by a High Frequency Reciprocating Rig (HFRR) test. The HFRR is manufactured by PCS Instruments and identified as model HFR2 (AutoHFRR). The test equipment and procedure are similar to the ASTM D6079 method except the test oil temperature is raised from 32°C to 195°C at 2°C/mirmte, 400 g load, 60 Hz frequency, and 0.5 mm stroke length.

[001 4] The results in Table 5 showed that when PEG-MME and the additive package were blended in PAO 6 with 2 wt% PEG-MME (Inventive Oil 2) and with 4 wt% PEG-MME (Inventive Oil 3), the oack volatilities remained nearly the same (despite the high volatility of PEG-MME relative to PAO 6). The pour points and kinematic viscosities of Inventive Oils 2 and 3 and Comparative Oil 7 were also virtually the same. Unexpectedly, the friction coefficient, wear scar and film thickness improved significantly relative to Comparative Oils 5, 6 and 7. These results showed an unexpected synergistic effect in Inventive Oils 2 and 3 when PEG-MME was included in the presence of the additive package. This can be seen by looking at the data for Comparative Oils 5, 6 and 7 and Inventive Oils 2 and .3. Comparative Oil 5 contained 98 wt.% PAO 6 and 2 wt% PEG-MME, and had a friction coefficient of 0.197, a wear scar of 308 microns, and a film thickness of 4%. Comparative Oil 6 contained 96 wt% PAO 6 and 4 wt% PEG-MME, and had a friction coefficient of 0.179, a wear scar of 312.5 microns, and a film thickness of 4%. Comparative Oil 7 contained 83% PAO 6 and 17 wt% of a commercial additive package, and had a friction coefficient of 0.152, a wear scar of 187 microns, and a film thickness of 49%. Inventive Oil 2 was the same as Comparative Oil 7, except that 2 wt% of PEG-MME was added and PAO 6 was decreased by 2 wt% to 81 wt%. Inventive Oil 3 was the same as Comparative Oil 7, except that 4 wt% of PEG-MME was added and PAO 6 was decreased by 4 wt% to 79 wt%. Surprisingly, Inventive Oils 2 and 3 had friction coefficients of 0.097 and 0.122, wear scars of 139 and 12.3 microns, and film thicknesses of 84% and 87%, respectively. Each of these properties was significantly better than either Comparative Oils 5 and 6 (which contained 2 and 4 wt% PEG-MME and no additive package) or Comparative Oil 7 (which contained 17 wt% additive package and no PEG-MME). These results demonstrated an unexpected synergistic effect when PEG-MME was added in the presence of the additive package. It was also observed that the additives in the additive package remained soluble in Inventive Oils 2 and 3 in the presence of 2 and 4 wi% of PEG-MME. TABLE 5

[00165] A fully formulated 5W30 engine oil composition (Inventive Oil 4) was prepared by adding a single-capped polyalkyfene glycol (polypropylene glycol monobutyl ether (PPG-MBE) (molecular weight 340), available from Sigma- Aldrich Οθφ. (St. Louis, Missouri)) in the amount of 5 wt% to Comparative Oil 8, which was a fully formulated commercial 5W30 engine oil.

[00ί 66] Piston deposit, cam and lifter wear, viscosity increase, oil consumption and phosphoms retention were measured in accordance with the Sequence IIIG engine test, ASTM D7320. This test is designed to measure the ability of an oil to control piston deposit, wear, viscosity increase and oil consumption when an engine is operated at very high speeds and loads. This tes t also measures the amount of phosphorus that is retained in the erankcase. A higher result in this parameter indicates that phosphorus is being retained in the crankca.se and is not available to poison three-way catalysts (catalytic converters) that are used to control emissions.

|00I67] The results in Table 6 show that several properties remained virtually unchanged with the addition of the PPG-MBE, including the piston deposit weight, viscosity increase and oil consumption. Unexpectedly, the addition of the PPG-MBE resulted in a significant decrease in cam and lifter wear of 44%, and a significant increase in phosphorus retention of 5%. Accordingly, this formulation passed the Sequence IIIG engine test in accordance with ASTM D7320. These results showed an unexpected synergistic effect in the Inventive Oil 4. This can be seen by looking at the data for Comparative Oil 8 and Inventive Oil 4. Inventive Oil 4 was the same as Comparative Oil 8, except that 5 wt% of PPG-MBE was added. Comparative Oil 8 had a cam and lifter wear of 27 microns and a phosphorus retention of 85,6%. Surprisingly, Inventive Oil 4 had a cam and lifter wear of 15 microns (44% better) and a phosphorus retention of 90.4% (5% better). Each of these properties was significantly better than Comparative Oil 8, and demonstrated an unexpected synergistic effect when PPG-MBE is included in the presence of the additive package. It was also observed that the additives in the additive package remained soluble in inventive Oil 4 in the presence of 5 wt.% of PPG-MBE.

TABLE 6

Example 5

[00168] Blends of single-capped polyalkylene glycol (polypropylene glycol monobut l ether (PPG-MBE) (molecular weight 340), available from Sigma-Aldrich Cosp. (St. Louis, Missouri)) with zinc dialkyldithiophosphate (ZDDP) in a lubricating oil were prepared as shown in Table 7.

[00169] Average wear scar was measured by a High Frequency Reciprocating Rig (HFRR) test. The HFRR is manufactured by PCS Instruments and identified as model HFR2 (AutoHFRR). The test equipment and procedure are similar to the ASTM D6079 method except the test oil temperature is raised from 32°C to 195°C at 2^c'C/minute, 400 g load, 60 Hz frequency, and 0.5 mm stroke length or 400 g load, 60 Hz frequency at constant temperature, such as 100°C or 60°C. Phosphorus retention was measured in accordance with the Sequence TTIG engine test, ASTM D7320.

[00ί 70] The results in Table 7 show that the addition of PPG-MBE significantly improved average wear scar and reduced phosphorus loss.

TABLE 7

Claims

CLAIMS:

1. A lubricating composition, comprising in admixture:

at least 40 wt% of a base stock selected from the group consisting of Group I, Group XX, Group III, Group IV and Group V base stocks, or any combination thereof; one or more polyalkylene glycol mono ethers; and

at least one additive,

2. The lubricating composition of claim 1, wherein the polyalkylene glycol mono ethers are represented by the formula:

wherein R₃ = d to Ci₂ and may be linear or branched; R> = C-, to Ce and may be linear or branched; R_\ and R₂ optionally include -OH, -NH₂, and/or -CHO functional groups; and n is such that the molecular weight is up to about 5000.

3. The lubricating composition of claim 2, wherein the polyalkylene glycol mono ethers each have a molecular weight of from about 300 up to about 1200.

4. The lubricating composition of claim 2, wherein the polyalkylene glycol mono ethers are present in an amount of from about 1 wt% up to about 20 wt% of the composition.

5. The lubricating composition of claim 2, wherein the base stock is a Group IV base stock, or a blend of Group IV base stocks.

6. The lubricating composition of claim 2, wherein the kinematic viscosity at 100°C of the composition is from about 4 cSt up to about 20 cSt.

7. The lubricating composition of claim 2, wherein the additive is one or more chosen from the group consisting of friction modifiers, antiwear additives, viscosity improvers, detergents, dispersants, antioxidants, pour point depressants, anti-foam agents, dernulsifiers, corrosion inhibitors, seal compatibility additives, antimst additives, and co-base stocks.

8. The lubricating composition of claim 7, wherein the additive or additives are present in an amount of up to about 20 wt% of the composition.

9. The lubricating composition of claim 2, wherein the additive is a friction modifier.

10. The lubricating composition of claim 2, further comprising a co-base stock.

11. The lubricating composition of claim 10, wherein the co-base stock is one or more chosen from the group consisting of esters and alkylated naphthalenes.

12. The lubricating composition of claim 2, wherein the polyalkylene glycol ether is polyethylene glycol monomethyl ether or polypropylene glycol monobutyl ether, or a. combination thereof,

13. A method of improving the friction and wear properties of a base stock selected from the group consisting of Group I, Group II, Group III, Group IV and Group V base stocks, or any combination thereof, comprising blending the base stock with one or more polyalkylene glycol mono ethers and at least one additive, to form a lubricating composition.

14. The method of claim 13, wherein the polyalkylene glycol mono ethers are represented by the formula:

R₁- O(R₂H_n-OH wherein Rj = C] to Cj? and may be linear or branched; R₂ = C , to Ce and may be linear or branched; R i and R2 may contain other functional groups, including, -OH, -NH₂, and -CHO; and n is such that the molecular weight is up to about 5000.

15. The method of claim 14, wherein the polyalkylene glycol mono ethers each have a. molecular weight of from about 300 up to about 1200.

16. The method of claim 14, wherein the polyalkylene glycol mono ethers are present in an amount of from about 1 wt% up to about 20 wt% of the composition.

17. The method of claim 14, wherein the base stock is a Group IV base stock, or a blend of Group W base stocks.

18. The method of claim 14, wherein the kinematic viscosity at 100°C of the composition is from about 4 cSt up to about 20 cSt.

19. The method of claim 14, wherein the additive is one or more chosen from the group consisting of friction modifiers, antiwear additives, viscosity improvers, detergents, dispersants, antioxidants, pour point depressants, anti-foam agents, demulsifiers, corrosion inhibitors, seal compatibility additives, antirust additives, and co-base stocks.

20. The method of claim 14, wherein the additive or additives are present in an amount of up to about 20 wt% of the composition.

21. The method of claim 14, further comprising blending in a co-base stock.

22. The method of claim 21, wherein the co-base stock is one or more chosen from the group consisting of esters and alkylated naphthalenes.

23. The method of claim 14, wherein the polyalkylene glycol ether is polyethylene glycol monomethyl ether or polypropylene glycol monobutyl ether, or a combination thereof.