Patent Application
20200199480
This disclosure relates to engine lubricating oils with antioxidant formation and dissipation control. In particular, this disclosure relates to lubricating oils, and methods for to controlling formation and dissipation of antioxidants in a lubricating oil in an engine or other mechanical component lubricated with the lubricating oil. The lubricating oils of this disclosure are useful as passenger vehicle engine oil (PVEO) products, commercial vehicle engine oil (CVEO) products, or other applications where lubricating oils are subjected to heat and oxidative conditions.
Lubricant viscosity control is one of the key parameters affecting oil life, which translates in oil drain interval in practical terms. Additionally, deposit formation is an issue associated with the decomposition of the base stock molecules mostly propagated by oxidative chain reactions. There are several conventional approaches to improve viscosity control of a finished lubricant product, including lubricating oil additive packages.
Improved viscosity control is necessary to increase oil life and oil drain intervals, thus reducing the amount of used oil generated as a consequence of more frequent oil changes. Longer oil life and oil drain intervals are key benefits that are desirable to end customers. Traditional additive packages provide standard protection and control leaving the main differentiation hinging on the quality of the base stock in the formulation.
What is needed is newly designed lubricants capable of controlling oil thickening for longer periods of time as compared to conventional lubricants. Further, what is needed is newly designed lubricants that enable extended oil life in combination with desired deposit control and cleanliness performance.
This disclosure relates to engine lubricating oils with antioxidant formation and dissipation control. In particular, this disclosure relates to lubricating oils, and methods for controlling formation and dissipation of antioxidants in a lubricating oil in an engine or other mechanical component lubricated with the lubricating oil. The lubricating oils of this disclosure are useful as passenger vehicle engine oil (PVEO) products, commercial vehicle engine oil (CVEO) products, or other applications where lubricating oils are subjected to heat and oxidative conditions.
This disclosure also relates in part to a method for controlling formation and dissipation of at least one oligomeric or polymeric aminic antioxidant in a lubricating oil, during operation of an engine or other mechanical component lubricated with the lubricating oil by using as the lubricating oil a formulated oil. The formulated oil has a composition comprising a lubricating oil base stock as a major component, and at least one oligomeric or polymeric aminic antioxidant, as a minor component. The at least one oligomeric or polymeric aminic antioxidant is formed over time in situ from at least one monomeric aminic antioxidant during operation of the engine or other mechanical component. The at least one oligomeric or polymeric aminic antioxidant is dissipated over time in the lubricating oil during operation of the engine or other mechanical component. The lubricating oil base stock is present in an amount from about 1 to about 95 weight percent, based on the total weight of the lubricating oil, or more preferably from about 1 to about 85 weight percent, based on the total weight of the lubricating oil, or most preferably from 70 to 95 weight percent, based on the total weight of the lubricating oil. The at least one monomeric aminic antioxidant is present in an amount from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil.
This disclosure further relates in part to a method for controlling formation and dissipation of at least one oligomeric or polymeric aminic antioxidant in a lubricating oil, during operation of an engine or other mechanical component lubricated with the lubricating oil by using as the lubricating oil a formulated oil. The formulated oil has a composition comprising a lubricating oil base stock as a major component, and at least one monomeric aminic antioxidant, as a minor component. At least one oligomeric or polymeric aminic antioxidant is formed over time in situ from the at least one monomeric aminic antioxidant during operation of the engine or other mechanical component. The at least one oligomeric or polymeric aminic antioxidant is dissipated over time in the lubricating oil during operation of the engine or other mechanical component. The lubricating oil base stock is present in an amount from about 1 to about 95 weight percent, based on the total weight of the lubricating oil, or more preferably from about 1 to about 85 weight percent, based on the total weight of the lubricating oil, or most preferably from 70 to 95 weight percent, based on the total weight of the lubricating oil. The at least one monomeric aminic antioxidant is present in an amount from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil.
This disclosure yet further relates in part to a method for controlling formation and dissipation of at least one oligomeric or polymeric aminic antioxidant in a lubricating oil, during operation of an engine or other mechanical component lubricated with the lubricating oil by using as the lubricating oil a formulated oil. The formulated oil has a composition comprising a lubricating oil base stock as a major component, and at least one oligomeric or polymeric aminic antioxidant and at least one monomeric aminic antioxidant, as minor components. The at least one oligomeric or polymeric aminic antioxidant and the at least one monomeric aminic antioxidant react to form over time in situ at least one oligomeric or polymeric aminic antioxidant reaction product during operation of the engine or other mechanical component. The at least one oligomeric or polymeric aminic antioxidant reaction product is dissipated over time in the lubricating oil during operation of the engine or other mechanical component. The lubricating oil base stock is present in an amount from about 1 to about 95 weight percent, based on the total weight of the lubricating oil, or more preferably from about 1 to about 85 weight percent, based on the total weight of the lubricating oil, or most preferably from 70 to 95 weight percent, based on the total weight of the lubricating oil. The at least one oligomeric or polymeric aminic antioxidant is present in an amount from greater than about 0.1 to about 10 weight percent, based on the total weight of the lubricating oil. The at least one monomeric aminic antioxidant is present in an amount from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil.
This disclosure also relates in part to a method for regenerating at least one oligomeric or polymeric aminic antioxidant in a lubricating oil, during operation of an engine or other mechanical component lubricated with the lubricating oil by using as the lubricating oil a formulated oil. The formulated oil has a composition comprising a lubricating oil base stock as a major component, and at least one oligomeric or polymeric aminic antioxidant and at least one monomeric aminic antioxidant, as minor components. The at least one oligomeric or polymeric aminic antioxidant dissipates over time in the lubricating oil during operation of the engine or other mechanical component. The at least one oligomeric or polymeric aminic antioxidant and the at least one monomeric aminic antioxidant react to form over time in situ at least one regenerated oligomeric or polymeric aminic antioxidant during operation of the engine or other mechanical component. The lubricating oil base stock is present in an amount from about 1 to about 95 weight percent, based on the total weight of the lubricating oil, or more preferably from about 1 to about 85 weight percent, based on the total weight of the lubricating oil, or most preferably from 70 to 95 weight percent, based on the total weight of the lubricating oil. The at least one oligomeric or polymeric aminic antioxidant is present in an amount from greater than about 0.1 to about 10 weight percent, based on the total weight of the lubricating oil. The at least one monomeric aminic antioxidant is present in an amount from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil.
This disclosure further relates in part to a lubricating oil having a composition comprising a lubricating oil base stock as a major component, and at least one oligomeric or polymeric aminic antioxidant, as a minor component. In an engine or other mechanical component lubricated with the lubricating oil, the at least one oligomeric or polymeric aminic antioxidant is formed over time in situ from at least one monomeric aminic antioxidant during operation of the engine or other mechanical component. The at least one oligomeric or polymeric aminic antioxidant is dissipated over time in the lubricating oil during operation of the to engine or other mechanical component. The lubricating oil base stock is present in an amount from about 1 to about 95 weight percent, based on the total weight of the lubricating oil, or more preferably from about 1 to about 85 weight percent, based on the total weight of the lubricating oil, or most preferably from 70 to 95 weight percent, based on the total weight of the lubricating oil. The at least one monomeric aminic antioxidant is present in an amount from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil.
This disclosure yet further relates in part to a lubricating oil having a composition comprising a lubricating oil base stock as a major component, and at least one monomeric aminic antioxidant, as a minor component. In an engine or other mechanical component lubricated with the lubricating oil, at least one oligomeric or polymeric aminic antioxidant is formed over time in situ from the at least one monomeric aminic antioxidant during operation of the engine or other mechanical component. The at least one oligomeric or polymeric aminic antioxidant is dissipated over time in the lubricating oil during operation of the engine or other mechanical component. The lubricating oil base stock is present in an amount from about 1 to about 95 weight percent, based on the total weight of the lubricating oil, or more preferably from about 1 to about 85 weight percent, based on the total weight of the lubricating oil, or most preferably from 70 to 95 weight percent, based on the total weight of the lubricating oil. The at least one monomeric aminic antioxidant is present in an amount from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil.
This disclosure also relates in part to a lubricating oil having a composition comprising a lubricating oil base stock as a major component, and at least one oligomeric or polymeric aminic antioxidant and at least one monomeric aminic antioxidant, as minor components. In an engine or other mechanical component lubricated with the lubricating oil, the at least one oligomeric or polymeric aminic antioxidant and the at least one monomeric aminic antioxidant react to form over time in situ at least one oligomeric or polymeric aminic antioxidant reaction product during operation of the engine or other mechanical component. The at least one oligomeric or polymeric aminic antioxidant reaction product is dissipated over time in the lubricating oil during operation of the engine or other mechanical component. The lubricating oil base stock is present in an amount from about 1 to about 95 weight percent, based on the total weight of the lubricating oil, or more preferably from about 1 to about 85 weight percent, based on the total weight of the lubricating oil, or most preferably from 70 to 95 weight percent, based on the total weight of the lubricating oil. The at least one oligomeric or polymeric aminic antioxidant is present in an amount from greater than about 0.1 to about 10 weight percent, based on the total weight of the lubricating oil. The at least one monomeric aminic antioxidant is present in an amount from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil.
This disclosure further relates in part to a lubricating oil having a composition comprising a lubricating oil base stock as a major component, and at least one oligomeric or polymeric aminic antioxidant and at least one monomeric aminic antioxidant, as minor components. In an engine or other mechanical component lubricated with the lubricating oil, the at least one oligomeric or polymeric aminic antioxidant dissipates over time in the lubricating oil during operation of the engine or other mechanical component. the at least one oligomeric or polymeric aminic antioxidant and the at least one monomeric aminic antioxidant react to form over time in situ at least one regenerated oligomeric or polymeric aminic antioxidant during operation of the engine or other mechanical component. The lubricating oil base stock is present in an amount from about 1 to about 95 weight percent, based on the total weight of the lubricating oil, or more preferably from about 1 to about 85 weight percent, based on the total weight of the lubricating oil, or most preferably from 70 to 95 weight percent, based on the total weight of the lubricating oil. The at least one oligomeric or polymeric aminic antioxidant is present in an amount from greater than about 0.1 to about 10 weight percent, based on the total weight of the lubricating oil. The at least one monomeric aminic antioxidant is present in an amount from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil.
It has been surprisingly found that, in accordance with this disclosure, oligomeric or polymeric aminic antioxidant formation and dissipation control in lubricating oils is improved using high treat rates of monomeric aminic antioxidants in lubricating oils, as compared to oligomeric or polymeric aminic antioxidant formation and dissipation control in lubricating oils achieved using low treat rates of monomeric aminic antioxidants in lubricating oils.
In particular, it has been surprisingly found that, in measurements of the lubricating oil by a Sequence IIIH engine test in accordance with ASTM D8111-17, oligomeric or polymeric aminic antioxidant formation and dissipation control are improved using a concentration of monomeric aminic antioxidant from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil, as compared to oligomeric or polymeric aminic antioxidant formation and dissipation control achieved using a lower concentration of the monomeric aminic antioxidant. The controlled release/in situ generation of oligomeric and polymeric antioxidants in the lubricating oils, which result from a concentration of monomeric aminic antioxidant from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil, leads to surprisingly exceptional performance in the Sequence IIIH engine test.
Other objects and advantages of the present disclosure will become apparent from the detailed description that follows.
“About” or “approximately.” All numerical values within the detailed description and the claims herein are modified by “about” or “approximately” the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.
“Major amount” as it relates to components included within the lubricating oils of the specification and the claims means greater than or equal to 50 wt. %, or greater than or equal to 60 wt. %, or greater than or equal to 70 wt. %, or greater than or equal to 80 wt. %, or greater than or equal to 90 wt. % based on the total weight of the lubricating oil.
“Minor amount” as it relates to components included within the lubricating oils of the specification and the claims means less than 50 wt. %, or less than or equal to 40 wt. %, or less than or equal to 30 wt. %, or greater than or equal to 20 wt. %, or less than or equal to 10 wt. %, or less than or equal to 5 wt. %, or less than or equal to 2 wt. %, or less than or equal to 1 wt. %, based on the total weight of the lubricating oil.
“Essentially free” as it relates to components included within the lubricating oils of the specification and the claims means that the particular component is at 0 weight % within the lubricating oil, or alternatively is at impurity type levels within the lubricating oil (less than 100 ppm, or less than 20 ppm, or less than 10 ppm, or less than 1 ppm).
“Other lubricating oil additives” as used in the specification and the claims means other lubricating oil additives that are not specifically recited in the particular section of the specification or the claims. For example, other lubricating oil additives may include, but are not limited to, antioxidants, detergents, dispersants, antiwear additives, corrosion inhibitors, viscosity modifiers, metal passivators, pour point depressants, seal compatibility agents, antifoam agents, extreme pressure agents, friction modifiers and combinations thereof.
“Other mechanical component” as used in the specification and the claims means an electric vehicle component, a hybrid vehicle component, a power train, a driveline, a transmission, a gear, a gear train, a gear set, a compressor, a pump, a hydraulic system, a bearing, a bushing, a turbine, a piston, a piston ring, a cylinder liner, a cylinder, a cam, a tappet, a lifter, a gear, a valve, or a bearing including a journal, a roller, a tapered, a needle, and a ball bearing.
“Hydrocarbon” refers to a compound consisting of carbon atoms and hydrogen atoms.
“Alkane” refers to a hydrocarbon that is completely saturated. An alkane can be linear, branched, cyclic, or substituted cyclic.
“Olefin” refers to a non-aromatic hydrocarbon comprising one or more carbon-carbon double bond in the molecular structure thereof.
“Mono-olefin” refers to an olefin comprising a single carbon-carbon double bond.
“Cn” group or compound refers to a group or a compound comprising carbon atoms at total number thereof of n. Thus, “Cm-Cn” group or compound refers to a group or compound comprising carbon atoms at a total number thereof in the range from m to n. Thus, a C1-C50 alkyl group refers to an alkyl group comprising carbon atoms at a total number thereof in the range from 1 to 50.
“Carbon backbone” refers to the longest straight carbon chain in the molecule of the compound or the group in question. “Branch” refer to any substituted or unsubstituted hydrocarbyl group connected to the carbon backbone. A carbon atom on the carbon backbone connected to a branch is called a “branched carbon.”
“Epsilon-carbon” in a branched alkane refers to a carbon atom in its carbon backbone that is (i) connected to two hydrogen atoms and two carbon atoms and (ii) connected to a branched carbon via at least four (4) methylene (CH2) groups. Quantity of epsilon carbon atoms in terms of mole percentage thereof in a alkane material based on the total moles of carbon atoms can be determined by using, e.g., 13C NMR.
“Alpha-carbon” in a branched alkane refers to a carbon atom in its carbon backbone that is with a methyl end with no branch on the first 4 carbons. It is also measured in mole percentage using 13C NMR.
“T/P methyl” in a branched alkane refers to a methyl end and a methyl in the 2 position. It is also measured in mole percentage using 13C NMR.
“P-methyl” in a branched alkane refers to a methyl branch anywhere on the chain, except in the 2 position. It is also measured in mole percentage using 13C NMR.
“SAE” refers to SAE International, formerly known as Society of Automotive Engineers, which is a professional organization that sets standards for internal combustion engine lubricating oils.
“SAE J300” refers to the viscosity grade classification system of engine lubricating oils established by SAE, which defines the limits of the classifications in rheological terms only.
“Base stock” or “base oil” interchangeably refers to an oil that can be used as a component of lubricating oils, heat transfer oils, hydraulic oils, grease products, and the like.
“Lubricating oil” or “lubricant” interchangeably refers to a substance that can be introduced between two or more surfaces to reduce the level of friction between two adjacent surfaces moving relative to each other. A lubricant base stock is a material, typically a fluid at various levels of viscosity at the operating temperature of the lubricant, used to formulate a lubricant by admixing with other components. Non-limiting examples of base stocks suitable in lubricants include API Group I, Group II, Group III, Group IV, and Group V base stocks. PAOs, particularly hydrogenated PAOs, have recently found wide use in lubricants as a Group IV base stock, and are particularly preferred. If one base stock is designated as a primary base stock in the lubricant, additional base stocks may be called a co-base stock.
All kinematic viscosity values in this disclosure are as determined pursuant to ASTM D445. Kinematic viscosity at 100° C. is reported herein as KV100, and kinematic viscosity at 40° C. is reported herein as KV40. Unit of all KV100 and KV40 values herein is cSt unless otherwise specified. When describing the kinematic viscosity at 100° C. is “essentially” maintained, the kinematic viscosity at 100° C. is expected to vary less than 0.2 cSt as measured by ASTM D445.
All viscosity index (“VI”) values in this disclosure are as determined pursuant to ASTM D2270.
All Noack volatility (“NV”) values in this disclosure are as determined pursuant to ASTM D5800 unless specified otherwise. Unit of all NV values is wt %, unless otherwise specified.
All pour point values in this disclosure are as determined pursuant to ASTM D5950 or D97.
All CCS viscosity (“CCSV”) values in this disclosure are as determined pursuant to ASTM 5293. Unit of all CCSV values herein is millipascal second (mPa·s), which is equivalent to centipoise), unless specified otherwise. All CCSV values are measured at a temperature of interest to the lubricating oil formulation or oil composition in question. Thus, for the purpose of designing and fabricating engine oil formulations, the temperature of interest is the temperature at which the SAE J300 imposes a minimal CCSV.
All percentages in describing chemical compositions herein are by weight unless specified otherwise. “Wt.%” means percent by weight.
This disclosure describes the controlled in situ generation of powerful oligomeric or polymeric antioxidants in the engine of a passenger vehicle, commercial vehicle, a fired engine, or other mechanical component.
Antioxidants are critical to delivering viscosity control over the entire oil drain interval. This disclosure describes the in situ generation of oligomeric and polymeric antioxidants from conventional monomeric aminic antioxidants during normal engine use. This disclosure also describes the controlled in situ regeneration of commercial oligomeric and polymeric antioxidants during engine use, by co-formulating them in situ with conventional aminic antioxidants.
Further, in accordance with this disclosure, finished lubricants can be designed with in situ generated oligomeric and polymeric antioxidants that are capable of controlling oil thickening for long durations as compared to conventional lubricants. This disclosure also enables extended oil life in combination with superior deposit control and cleanliness performance through the in situ generation of oligomeric and polymeric antioxidants.
This disclosure describes the superior performance of conventional monomeric aminic antioxidants in lubricating oils. It also allows for the in situ production of oligomeric and polymeric antioxidants from the monomeric aminic antioxidants during engine use. It further allows for a reduction of the treat rate of the oligomeric and polymeric antioxidants, replacing the balance with traditional monomeric aminic antioxidants which can react in situ to form oligomeric and polymeric antioxidants and which come at a lower cost and result in a more acceptable formulation appearance/color.
In general, formulators use low treat rates of aminic antioxidants (<2 wt %, and often less than 1 wt %) such as Irganox L57 or Irganox L67 in passenger vehicle formulations. In accordance with this disclosure, it has been found that at a high enough treat rate (5 wt % for example), monomeric aminic antioxidants can form analogous oligomers and polymers during the course of a Sequence IIIH engine test resulting in superior performance in respect to viscosity control (see
In measurements of the lubricating oil by a Sequence IIIH engine test in accordance with ASTM D8111-17, oligomeric or polymeric aminic antioxidant formation and dissipation control are improved using high treat rates (e.g., 5 wt %) of monomeric aminic antioxidants as compared to oligomeric or polymeric aminic antioxidant formation and dissipation control achieved using low treat rates (e.g., 2 wt %) of monomeric aminic antioxidants. The controlled release/in situ generation of oligomeric and polymeric antioxidants in the lubricating oils, which result from the high treat rates (e.g., 5 wt %) of monomeric aminic antioxidants, leads to exceptional performance in the Sequence IIIH engine test.
A wide range of lubricating base oils is known in the art. Lubricating base oils that are useful in the present disclosure are both natural oils, and synthetic oils, and unconventional oils (or mixtures thereof) can be used unrefined, refined, or rerefined (the latter is also known as reclaimed or reprocessed oil). Unrefined oils are those obtained directly from a natural or synthetic source and used without added purification. These include shale oil obtained directly from retorting operations, petroleum oil obtained directly from primary distillation, and ester oil obtained directly from an esterification process. Refined oils are similar to the oils discussed for unrefined oils except refined oils are subjected to one or more purification steps to improve at least one lubricating oil property. One skilled in the art is familiar with many purification processes. These processes include solvent extraction, secondary distillation, acid extraction, base extraction, filtration, and percolation. Rerefined oils are obtained by processes analogous to refined oils but using an oil that has been previously used as a feed stock.
Groups I, II, III, IV and V are broad base oil stock categories developed and defined by the American Petroleum Institute (API Publication 1509; www.API.org) to create guidelines for lubricant base oils. Group I base stocks have a viscosity index of between about 80 to 120 and contain greater than about 0.03% sulfur and/or less than about 90% saturates. Group II base stocks 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 stocks have a viscosity index greater than about 120 and contain less than or equal to about 0.03% sulfur and greater than about 90% saturates. Group IV includes polyalphaolefins (PAO). Group V base stock includes base stocks not included in Groups I-IV. The table below summarizes properties of each of these five groups.
Natural oils include animal oils, vegetable oils (castor oil and lard oil, for example), and mineral oils. Animal and vegetable oils possessing favorable thermal oxidative stability can be used. Of the natural oils, mineral oils are preferred. Mineral oils vary widely as to their crude source, for example, as to whether they are paraffinic, naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal or shale are also useful. Natural oils vary also as to the method used for their production and purification, for example, their distillation range and whether they are straight run or cracked, hydrorefined, or solvent extracted.
Group II and/or Group III hydroprocessed or hydrocracked base stocks, including synthetic oils such as polyalphaolefins, alkyl aromatics and synthetic esters are also well known base stock oils.
Synthetic oils include hydrocarbon oil. Hydrocarbon oils include oils such as polymerized and interpolymerized olefins (polybutylenes, polypropylenes, propylene isobutylene copolymers, ethylene-olefin copolymers, and ethylene-alphaolefin copolymers, for example). Polyalphaolefin (PAO) oil base stocks are commonly used synthetic hydrocarbon oil. By way of example, PAOs derived from C8, C10, C12, C14 olefins or mixtures thereof may be utilized. See U.S. Pat. Nos. 4,956,122; 4,827,064; and 4,827,073.
The number average molecular weights of the PAOs, which are known materials and generally available on a major commercial scale from suppliers such as ExxonMobil Chemical Company, Chevron Phillips Chemical Company, BP, and others, typically vary from about 250 to about 3,000, although PAO's may be made in viscosities up to about 150 cSt (100° C.). The PAOs are typically comprised of relatively low molecular weight hydrogenated polymers or oligomers of alphaolefins which include, but are not limited to, C2 to about C32 alphaolefins with the C8 to about C16 alphaolefins, such as 1-hexene, 1-octene, 1-decene, 1-dodecene and the like, being preferred. The preferred polyalphaolefins are poly-1-hexene, poly-1-octene, poly-1-decene and poly-1-dodecene and mixtures thereof and mixed olefin-derived polyolefins. However, the dimers of higher olefins in the range of C14 to C18 may be used to provide low viscosity base stocks of acceptably low volatility. Depending on the viscosity grade and the starting oligomer, the PAOs may be predominantly trimers and tetramers of the starting olefins, with minor amounts of the higher oligomers, having a viscosity range of 1.5 to 12 cSt. PAO fluids of particular use may include 3.0 cSt, 3.4 cSt, and/or 3.6 cSt and combinations thereof. Bi-modal mixtures of PAO fluids having a viscosity range of 1.5 to 150 cSt may be used if desired.
The PAO fluids may be conveniently made by the polymerization of an alphaolefin in the presence of a polymerization catalyst such as the Friedel-Crafts catalysts including, for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate. For example the methods disclosed by U.S. Pat. No. 4,149,178 or 3,382,291 to may be conveniently used herein. Other descriptions of PAO synthesis are found in the following U.S. Pat. Nos. 3,742,082; 3,769,363; 3,876,720; 4,239,930; 4,367,352; 4,413,156; 4,434,408; 4,910,355; 4,956,122; and 5,068,487. The dimers of the C14 to C18 olefins are described in U.S. Pat. No. 4,218,330.
The alkylated naphthalene can be used as base oil or base oil component and can be any hydrocarbyl molecule that contains at least about 5% of its weight derived from a naphthenoid moiety, or its derivatives. These alkylated naphthalenes include alkyl naphthalenes, alkyl naphthols, and the like. The naphthenoid group can be mono-alkylated, dialkylated, polyalkylated, and the like. The naphthenoid group can be mono- or poly-functionalized. The naphthenoid group can also be derived from natural (petroleum) sources, provided at least about 5% of the molecule is comprised of the naphthenoid moiety. Viscosities at 100° C. of approximately 3 cSt to about 50 cSt are preferred, with viscosities of approximately 3.4 cSt to about 20 cSt often being more preferred for the naphthylene component. In one embodiment, an alkyl naphthalene where the alkyl group is primarily comprised of 1-hexadecene is used. Other alkylates of naphthalene can be advantageously used. Naphthalene or methyl naphthalene, for example, can be alkylated with olefins such as octene, decene, dodecene, tetradecene or higher, mixtures of similar olefins, and the like.
Alkylated naphthalenes of the present disclosure may be produced by well-known Friedel-Crafts alkylation of aromatic compounds. See Friedel-Crafts and Related Reactions, Olah, G. A. (ed.), Inter-science Publishers, New York, 1963. For example, an aromatic compound, such as naphthalene, is alkylated by an olefin, alkyl halide or alcohol in the presence of a Friedel-Crafts catalyst. See Friedel-Crafts and Related Reactions, Vol. 2, part 1, chapters 14, 17, and 18, See Olah, G. A. (ed.), Inter-science Publishers, New York, 1964. Many homogeneous or heterogeneous, solid catalysts are known to one skilled in the art. The choice of catalyst depends on the reactivity of the starting materials and product quality requirements. For example, strong acids such as AlCl3, BF3, or HF may be used. In some cases, milder catalysts such as FeCl3 or SnCl4 are preferred. Newer alkylation technology uses zeolites or solid super acids.
Mixtures of alkylated naphthalene base stocks with other lubricating oil base stocks (e.g., Groups I, II, III, IV and V base stocks) may be useful in the lubricating oil formulations of this disclosure.
The alkylated naphthalene can be present in an amount of from about 30 to about 99.8 weight percent, or from about 35 to about 95 weight percent, or from about 40 to about 90 weight percent, or from about 45 to about 85 weight percent, or from about 50 to about 80 weight percent, or from about 55 to about 75 weight percent, or from about 60 to about 70 weight percent, based on the total weight of the formulated oil.
Other useful lubricant oil base stocks include wax isomerate base stocks and base oils, comprising hydroisomerized waxy stocks (e.g. waxy stocks such as gas oils, slack waxes, fuels hydrocracker bottoms, etc.), hydroisomerized Fischer-Tropsch waxes, Gas-to-Liquids (GTL) base stocks and base oils, and other wax isomerate hydroisomerized base stocks and base oils, or mixtures thereof Fischer-Tropsch waxes, the high boiling point residues of Fischer-Tropsch synthesis, are highly paraffinic hydrocarbons with very low sulfur content. The hydroprocessing used for the production of such base stocks may use an amorphous hydrocracking/hydroisomerization catalyst, such as one of the specialized lube hydrocracking (LHDC) catalysts or a crystalline hydrocracking/hydroisomerization catalyst, preferably a zeolitic catalyst. For example, one useful catalyst is ZSM-48 as described in U.S. Pat. No. 5,075,269, the disclosure of which is incorporated herein by reference in its entirety. Processes for making hydrocracked/hydroisomerized distillates and hydrocracked/hydroisomerized waxes are described, for example, in U.S. Pat. Nos. 2,817,693; 4,975,177; 4,921,594 and 4,897,178 as well as in British Patent Nos. 1,429,494; 1,350,257; 1,440,230 and 1,390,359. Each of the aforementioned patents is incorporated herein in their entirety. Particularly favorable processes are described in European Patent Application Nos. 464546 and 464547, also incorporated herein by reference. Processes using Fischer-Tropsch wax feeds are described in U.S. Pat. Nos. 4,594,172 and 4,943,672, the disclosures of which are incorporated herein by reference in their entirety.
Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils, and other wax-derived hydroisomerized (wax isomerate) base oils be advantageously used in the instant disclosure, and may have useful kinematic viscosities at 100° C. of about 3 cSt to about 50 cSt, preferably about 3 cSt to about 30 cSt, more preferably about 3.5 cSt to about 25 cSt, as exemplified by GTL 4 with kinematic viscosity of about 4.0 cSt at 100° C. and a viscosity index of about 141. These Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils, and other wax-derived hydroisomerized base oils may have useful pour points of 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. Useful compositions of Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils, and wax-derived hydroisomerized base oils are recited in U.S. Pat. Nos. 6,080,301; 6,090,989, and 6,165,949 for example, and are incorporated herein in their entirety by reference.
The hydrocarbyl aromatics can be used as base oil or base oil component and can be to any hydrocarbyl molecule that contains at least about 5% of its weight derived from an aromatic moiety such as a benzenoid moiety or naphthenoid moiety, or their derivatives. These hydrocarbyl aromatics include alkyl benzenes, alkyl naphthalenes, alkyl diphenyl oxides, alkyl naphthols, alkyl diphenyl sulfides, alkylated bis-phenol A, alkylated thiodiphenol, and the like. The aromatic can be mono-alkylated, dialkylated, polyalkylated, and the like. The aromatic can be mono- or poly-functionalized. The hydrocarbyl groups can also be comprised of mixtures of alkyl groups, alkenyl groups, alkynyl, cycloalkyl groups, cycloalkenyl groups and other related hydrocarbyl groups. The hydrocarbyl groups can range from about C6 up to about C60 with a range of about C8 to about C20 often being preferred. A mixture of hydrocarbyl groups is often preferred, and up to about three such substituents may be present. The hydrocarbyl group can optionally contain sulfur, oxygen, and/or nitrogen containing substituents. The aromatic group can also be derived from natural (petroleum) sources, provided at least about 5% of the molecule is comprised of an above-type aromatic moiety. Viscosities at 100° C. of approximately 3 cSt to about 50 cSt are preferred, with viscosities of approximately 3.4 cSt to about 20 cSt often being more preferred for the hydrocarbyl aromatic component. In one embodiment, an alkyl naphthalene where the alkyl group is primarily comprised of 1-hexadecene is used. Other alkylates of aromatics can be advantageously used. Naphthalene or methyl naphthalene, for example, can be alkylated with olefins such as octene, decene, dodecene, tetradecene or higher, mixtures of similar olefins, and the like. Useful concentrations of hydrocarbyl aromatic in a lubricant oil composition can be about 2% to about 25%, preferably about 4% to about 20%, and more preferably about 4% to about 15%, depending on the application.
Alkylated aromatics such as the hydrocarbyl aromatics of the present disclosure may be produced by well-known Friedel-Crafts alkylation of aromatic compounds. See Friedel-Crafts and Related Reactions, Olah, G. A. (ed.), Inter-science Publishers, New York, 1963. For example, an aromatic compound, such as benzene or naphthalene, is alkylated by an olefin, alkyl halide or alcohol in the presence of a Friedel-Crafts catalyst. See Friedel-Crafts and Related Reactions, Vol. 2, part 1, chapters 14, 17, and 18, See Olah, G. A. (ed.), Inter-science Publishers, New York, 1964. Many homogeneous or heterogeneous, solid catalysts are known to one skilled in the art. The choice of catalyst depends on the reactivity of the starting materials and product quality requirements. For example, strong acids such as AlCl3, BF3, or HF may be used. In some cases, milder catalysts such as FeCl3 or SnCl4 are preferred. Newer alkylation technology uses zeolites or solid super acids.
Other useful fluids of lubricating viscosity include non-conventional or unconventional base stocks that have been processed, preferably catalytically, or synthesized to provide high performance lubrication characteristics.
Non-conventional or unconventional base stocks/base oils include one or more of a mixture of base stock(s) derived from one or more Gas-to-Liquids (GTL) materials, as well as isomerate/isodewaxate base stock(s) derived from natural wax or waxy feeds, mineral and or non-mineral oil waxy feed stocks such as slack waxes, natural waxes, and waxy stocks such as gas oils, waxy fuels hydrocracker bottoms, waxy raffinate, hydrocrackate, thermal crackates, or other mineral, mineral oil, or even non-petroleum oil derived waxy materials such as waxy materials received from coal liquefaction or shale oil, and mixtures of such base stocks.
GTL materials are materials that are derived via one or more synthesis, combination, transformation, rearrangement, and/or degradation/deconstructive processes from gaseous carbon-containing compounds, hydrogen-containing compounds and/or elements as feed stocks such as hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butylenes, and butynes. GTL base stocks and/or base oils are GTL materials of lubricating viscosity that are generally derived from hydrocarbons; for example, waxy synthesized hydrocarbons, that are themselves derived from simpler gaseous carbon-containing compounds, hydrogen-containing compounds and/or elements as feed stocks.
GTL base stock(s) and/or base oil(s) include oils boiling in the lube oil boiling range (1) separated/fractionated from synthesized GTL materials such as, for example, by distillation and subsequently subjected to a final wax processing step which involves either or both of a catalytic dewaxing process, or a solvent dewaxing process, to produce lube oils of reduced/low pour point; (2) synthesized wax isomerates, comprising, for example, hydrodewaxed or hydroisomerized cat and/or solvent dewaxed synthesized wax or waxy hydrocarbons; (3) hydrodewaxed or hydroisomerized cat and/or solvent dewaxed Fischer-Tropsch (F-T) material (i.e., hydrocarbons, waxy hydrocarbons, waxes and possible analogous oxygenates); preferably hydrodewaxed or hydroisomerized/followed by cat and/or solvent dewaxing dewaxed F-T waxy hydrocarbons, or hydrodewaxed or hydroisomerized/followed by cat (or solvent) dewaxing dewaxed, F-T waxes, or mixtures thereof.
GTL base stock(s) and/or base oil(s) derived from GTL materials, especially, hydrodewaxed or hydroisomerized/followed by cat and/or solvent dewaxed wax or waxy feed, preferably F-T material derived base stock(s) and/or base oil(s), are characterized typically as having kinematic viscosities at 100° C. of from about 2 mm2/s to about 50 mm2/s (ASTM D445). They are further characterized typically as having pour points of −5° C. to about −40° C. or lower (ASTM D97). They are also characterized typically as having viscosity indices of about 80 to about 140 or greater (ASTM D2270).
In addition, the GTL base stock(s) and/or base oil(s) are typically highly paraffinic (>90% saturates), and may contain mixtures of monocycloparaffins and multicycloparaffins in combination with non-cyclic isoparaffins. The ratio of the naphthenic (i.e., cycloparaffin) content in such combinations varies with the catalyst and temperature used. Further, GTL base stock(s) and/or base oil(s) typically have very low sulfur and nitrogen content, generally containing less than 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(s) and/or base oil(s) obtained from F-T material, especially F-T wax, is essentially nil. In addition, the absence of phosphorous and aromatics make this materially especially suitable for the formulation of low SAP products.
The term GTL base stock and/or base oil and/or wax isomerate base stock and/or base oil is to be understood as embracing individual fractions of such materials of wide viscosity range as recovered in the production process, mixtures of two or more of such fractions, as well as mixtures of one or two or more low viscosity fractions with one, two or more higher viscosity fractions to produce a blend wherein the blend exhibits a target kinematic viscosity.
The GTL material, from which the GTL base stock(s) and/or base oil(s) is/are derived is preferably an F-T material (i.e., hydrocarbons, waxy hydrocarbons, wax).
Base oils for use in the formulated lubricating oils useful in the present disclosure are any of the variety of oils corresponding to API Group I, Group II, Group III, Group IV, and Group V oils and mixtures thereof, preferably API Group II, Group III, Group IV, and Group V oils and mixtures thereof, more preferably the Group III to Group V base oils due to their exceptional volatility, stability, viscometric and cleanliness features.
This other base oil typically is present in an amount ranging from about 0.1 to about 90 weight percent, or from about 1 to about 80 weight percent, or from about 1 to about 70 weight percent, or from about 1 to about 60 weight percent, or from about 1 to about 50 weight percent, based on the total weight of the composition. The base oil may be selected from any of the synthetic or natural oils typically used as crankcase lubricating oils for spark ignition and compression-ignited engines. The base oil conveniently has a kinematic viscosity, according to ASTM standards, of about 2.5 cSt to about 12 cSt (or mm2/s) at 100° C. and preferably of about 2.5 cSt to about 9 cSt (or mm2/s) at 100° C. Mixtures of synthetic and natural base oils may be used if desired. Mixtures of Group III, IV, and V may be preferable.
Illustrative oligomeric and polymeric aminic antioxidants include oligomerization and polymerization reaction products of one or more unsubstituted or hydrocarbyl-substituted diphenyl amines, one or more unsubstituted or hydrocarbyl-substituted phenyl naphthyl amines or both one or more of unsubstituted or hydrocarbyl-substituted diphenylamine with one or more unsubstituted or hydrocarbyl-substituted phenyl naphthylamine. A representative schematic is presented below:
wherein (A) and (B) each range from zero to 10, preferably zero to 5, more preferably zero to 3, most preferably 1 to 3, provided (A)+(B) is at least 2; R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached; for example:
wherein R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, R4 is a styrene or C1 to C30 alkyl, preferably R2 is a C1 to C30 alkyl, R3 is a C1 to C30 alkyl, R4 is a C1 to C30 alkyl, more preferably R2 is a C4 to C10 alkyl, R3 is a C4 to C10 alkyl and R4 is a C4 to C10 alkyl, p, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached, preferably at least one of p, q and y range from 1 to up to the valence of the aryl group to which the respective R group(s) are attached, more preferably p, q and y each individually range from at least 1 to up to the valence of the aryl group to which the respective R groups are attached.
In a preferred embodiment, the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product formed by any combination of (A) and (B) above including, but not limited to, (A)(A), (A)(B), (B)(B), (A)(A)(B), (A)(A)(A), (A)(B)(A), (B)(B)(B), (B)(B)(A), (A)(A)(A)(A), (A)(A)(B)(B), (A)(A)(A)(B), (B)(B)(B)(B), (B)(B)(B)(A), (A)(A)(A)(A)(A), (A)(B)(A)(B)(A) (A)(B)(B)(B)(A), and the like.
In another preferred embodiment, the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product formed by any combination of:
wherein R is H, C4H9, C8H17, or C4H9; and/or
In a further preferred embodiment, the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product formed by any combination of:
In yet a further preferred embodiment, the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product formed by any combination of:
Other more extensive oligomers and polymers are within the scope of this disclosure, but materials of formulae (a), (b), (c) and (d) are preferred.
The oligomeric or polymeric aminic antioxidant may contain nonpolymerized aryl amine antioxidant starting materials as a result of the preparation procedure. Additional monomeric amine antioxidants may be added to the lubricant to impart desired properties. Examples of monomeric amine antioxidants include but are not limited to diphenyl amine, alkylated diphenyl amines, styrenated diphenyl amines, phenyl-N-naphthyl amine, alkylated phenyl-N-naphthyl amines, styrenated phenyl-N-naphthyl amines, phenothiazine, alkylated phenothiazine, and styrenated phenothiazine. Other antioxidants such as hindered phenols and zinc dithiophosphates can also be added to the lubricant in addition to the polymerized amine antioxidant.
The oligomeric and polymeric aminic antioxidants useful in this disclosure can be prepared by conventional polymerization reactions. See, for example, U.S. Pat. Nos. 6,426,324 and 8,623,795. An illustrative polymerization reaction for preparing preferred oligomeric and polymeric aminic antioxidants useful in this disclosure is set forth below. The product of the reaction can yield more than the two oligomers shown below, for example, any combination of (A) and (B) below including, but not limited to, (A)(A), (A)(B), (B)(B), (A)(A)(B), (A)(A)(A), (A)(B)(A), (B)(B)(B), (B)(B)(A), (A)(A)(A)(A), (A)(A)(B)(B), (A)(A)(A)(B), (B)(B)(B)(B), (B)(B)(B)(A), (A)(A)(A)(A)(A), (A)(B)(A)(B)(A), (A)(B)(B)(B)(A), and the like.
The oligomeric or polymeric aminic antioxidant is present in an amount in the range 0.1 to 10 wt % (active ingredient), preferably 0.1 to 5 wt % (active ingredient), or 0.1 to 4 wt % (active ingredient), or 0.1 to 2.5 wt % (active ingredient) or 0.1 to 1.5 wt % (active ingredient), or to 1.5 to 4 wt % (active ingredient), of oligomerized or polymerized aminic antioxidant exclusive of any added antioxidants.
Illustrative monomeric aminic antioxidants useful in this disclosure include one or more unsubstituted or hydrocarbyl-substituted diphenyl amines, one or more unsubstituted or hydrocarbyl-substituted phenyl naphthyl amines or both one or more of unsubstituted or hydrocarbyl-substituted diphenylamine and one or more unsubstituted or hydrocarbyl-substituted phenyl naphthylamine.
Preferred monomeric aminic antioxidants useful in this disclosure include:
wherein R is H, C4H9, C8H17, or C9H19; and/or
In a further preferred embodiment, the at least one monomeric aminic antioxidant can include:
In yet a further preferred embodiment, the at least one monomeric aminic antioxidant can include:
Additional monomeric amine antioxidants may be added to the lubricant to impart desired properties. Examples of monomeric amine antioxidants include but are not limited to diphenyl amine, alkylated diphenyl amines, styrenated diphenyl amines, phenyl-N-naphthyl amine, alkylated phenyl-N-naphthyl amines, styrenated phenyl-N-naphthyl amines, phenothiazine, alkylated phenothiazine, and styrenated phenothiazine.
Monomeric amine antioxidants include unsubstituted or hydrocarbon-substituted diphenyl amines, unsubstituted or hydrocarbyl-substituted phenyl naphthyl amines and unsubstituted or hydrocarbyl-substituted phenothiazines wherein the hydrocarbyl-substituted to group is styrene or a C1 to C30 alkyl group, preferably a C1 to C10 alkyl group, more preferably a C4 to C10 alkyl group. Other monomeric aryl amines have been described in the patent literature.
The monomeric aminic antioxidants useful in this disclosure can be prepared by conventional polymerization reactions. See, for example, U.S. Pat. Nos. 6,426,324 and 8,623,795.
The monomeric aminic antioxidant is present in an amount in the range 0.1 to 10 wt % (active ingredient), preferably 0.1 to 8 wt % (active ingredient), or 0.1 to 7.5 wt % (active ingredient), or 0.1 to 5 wt % (active ingredient) or 0.1 to 2.5 wt % (active ingredient), or 1.5 to 5 wt % (active ingredient), of monomeric aminic antioxidant exclusive of any added antioxidants.
Preferably, the monomeric aminic antioxidant is present in an amount in the range greater than about 2 to 10 wt % (active ingredient), preferably 2.5 to 9.5 wt % (active ingredient), or 3 to 9 wt % (active ingredient), or 3.5 to 8.5 wt % (active ingredient), or 4 to 8 wt % (active ingredient), or 4.5 to 7.5 wt % (active ingredient), or 5 to 7 wt % (active ingredient), or 5 to 6 wt % (active ingredient), of monomeric aminic antioxidant exclusive of any added antioxidants.
The formulated lubricating oil useful in the present disclosure may additionally contain one or more of the other commonly used lubricating oil performance additives including but not limited to dispersants, detergents, other antioxidants, antiwear additives, corrosion inhibitors, rust inhibitors, metal deactivators, extreme pressure additives, anti-seizure agents, wax modifiers, viscosity index improvers, viscosity modifiers, fluid-loss additives, seal compatibility agents, friction modifiers, lubricity agents, anti-staining agents, chromophoric agents, defoamants, demulsifiers, emulsifiers, densifiers, wetting agents, gelling agents, tackiness agents, colorants, and others. For a review of many commonly used additives, see Klamann in Lubricants and Related Products, Verlag Chemie, Deerfield Beach, Fla.; ISBN 0-89573-177-0. Reference is also made to “Lubricant Additives” by M. W. Ranney, published by Noyes Data Corporation of Parkridge, N J (1973); see also U.S. Pat. No. 7,704,930, the disclosure of which is incorporated herein in its entirety. These additives are commonly delivered with varying amounts of diluent oil, that may range from 5 weight percent to 50 weight percent.
During engine operation, oil-insoluble oxidation byproducts are produced. Dispersants help keep these byproducts in solution, thus diminishing their deposition on metal surfaces. Dispersants used in the formulation of the lubricating oil may be ashless or ash-forming in nature. Preferably, the dispersant is ashless. So called ashless dispersants are organic materials that form substantially no ash upon combustion. For example, non-metal-containing or borated metal-free dispersants are considered ashless. In contrast, metal-containing detergents discussed above form ash upon combustion.
Suitable dispersants typically contain a polar group attached to a relatively high molecular weight hydrocarbon chain. The polar group typically contains at least one element of nitrogen, oxygen, or phosphorus. Typical hydrocarbon chains contain 50 to 400 carbon atoms.
A particularly useful class of dispersants are the (poly)alkenylsuccinic derivatives, typically produced by the reaction of a long chain hydrocarbyl substituted succinic compound, usually a hydrocarbyl substituted succinic anhydride, with a polyhydroxy or polyamino compound. The long chain hydrocarbyl group constituting the oleophilic portion of the molecule which confers solubility in the oil, is normally a polyisobutylene group. Many examples of this type of dispersant are well known commercially and in the literature. Exemplary U.S. patents describing such dispersants are U.S. Pat. Nos. 3,172,892; 3,215,707; 3,219,666; 3,316,177; 3,341,542; 3,444,170; 3,454,607; 3,541,012; 3,630,904; 3,632,511; 3,787,374 and 4,234,435. Other types of dispersant are described in U.S. Pat. Nos. 3,036,003; 3,200,107; 3,254,025; 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,413,347; 3,697,574; 3,725,277; 3,725,480; 3,726,882; 4,454,059; 3,329,658; 3,449,250; 3,519,565; 3,666,730; 3,687,849; 3,702,300; 4,100,082; 5,705,458. A further description of dispersants may be found, for example, in European Patent Application No. 471 071, to which reference is made for this purpose.
Hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride derivatives are useful dispersants. In particular, succinimide, succinate esters, or succinate ester amides prepared by the reaction of a hydrocarbon-substituted succinic acid compound preferably having at least 50 carbon atoms in the hydrocarbon substituent, with at least one equivalent of an alkylene amine are particularly useful.
Succinimides are formed by the condensation reaction between hydrocarbyl substituted succinic anhydrides and amines. Molar ratios can vary depending on the polyamine. For example, the molar ratio of hydrocarbyl substituted succinic anhydride to TEPA can vary from about 1:1 to about 5:1. Representative examples are shown in U.S. Pat. Nos. 3,087,936; 3,172,892; 3,219,666; 3,272,746; 3,322,670; and 3,652,616, 3,948,800; and Canada Patent No. 1,094,044.
Succinate esters are formed by the condensation reaction between hydrocarbyl substituted succinic anhydrides and alcohols or polyols. Molar ratios can vary depending on the alcohol or polyol used. For example, the condensation product of a hydrocarbyl substituted succinic anhydride and pentaerythritol is a useful dispersant.
Succinate ester amides are formed by condensation reaction between hydrocarbyl substituted succinic anhydrides and alkanol amines. For example, suitable alkanol amines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines and polyalkenylpolyamines such as polyethylene polyamines. One example is propoxylated hexamethylenediamine. Representative examples are shown in U.S. Pat. No. 4,426,305.
The molecular weight of the hydrocarbyl substituted succinic anhydrides used in the preceding paragraphs will typically range between 800 and 2,500 or more. The above products can be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid. The above products can also be post reacted with boron compounds such as boric acid, borate esters or highly borated dispersants, to form borated dispersants generally having from about 0.1 to about 5 moles of boron per mole of dispersant reaction product.
Mannich base dispersants are made from the reaction of alkylphenols, formaldehyde, and amines. See U.S. Pat. No. 4,767,551, which is incorporated herein by reference. Process aids and catalysts, such as oleic acid and sulfonic acids, can also be part of the reaction mixture. Molecular weights of the alkylphenols range from 800 to 2,500. Representative examples are shown in U.S. Pat. Nos. 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,798,165; and 3,803,039.
Typical high molecular weight aliphatic acid modified Mannich condensation products useful in this disclosure can be prepared from high molecular weight alkyl-substituted hydroxyaromatics or HNR2 group-containing reactants.
Hydrocarbyl substituted amine ashless dispersant additives are well known to one skilled in the art; see, for example, U.S. Pat. Nos. 3,275,554; 3,438,757; 3,565,804; 3,755,433, 3,822,209, and 5,084,197.
Preferred dispersants include borated and non-borated succinimides, including those derivatives from mono-succinimides, bis-succinimides, and/or mixtures of mono- and bis-succinimides, wherein the hydrocarbyl succinimide is derived from a hydrocarbylene group such as polyisobutylene having a Mn of from about 500 to about 5000, or from about 1000 to about 3000, or about 1000 to about 2000, or a mixture of such hydrocarbylene groups, often with high terminal vinylic groups. Other preferred dispersants include succinic acid-esters and amides, alkylphenol-polyamine-coupled Mannich adducts, their capped derivatives, and other related components.
Polymethacrylate or polyacrylate derivatives are another class of dispersants. These dispersants are typically prepared by reacting a nitrogen containing monomer and a methacrylic or acrylic acid esters containing 5-25 carbon atoms in the ester group. Representative examples are shown in U.S. Pat. Nos. 2,100,993, and 6,323,164. Polymethacrylate and polyacrylate dispersants are normally used as multifunctional viscosity modifiers. The lower molecular weight versions can be used as lubricant dispersants or fuel detergents.
Illustrative preferred dispersants useful in this disclosure include those derived from polyalkenyl-substituted mono- or dicarboxylic acid, anhydride or ester, which dispersant has a polyalkenyl moiety with a number average molecular weight of at least 900 and from greater than 1.3 to 1.7, preferably from greater than 1.3 to 1.6, most preferably from greater than 1.3 to 1.5, functional groups (mono- or dicarboxylic acid producing moieties) per polyalkenyl moiety (a medium functionality dispersant). Functionality (F) can be determined according to the following formula:
F=(SAP×Mn)/((112,200×A.I.)−(SAP×98))
wherein SAP is the saponification number (i.e., the number of milligrams of KOH consumed in the complete neutralization of the acid groups in one gram of the succinic-containing reaction product, as determined according to ASTM D94); Mn is the number average molecular weight of the starting olefin polymer; and A.I. is the percent active ingredient of the succinic-containing reaction product (the remainder being unreacted olefin polymer, succinic anhydride and diluent).
The polyalkenyl moiety of the dispersant may have a number average molecular weight of at least 900, suitably at least 1500, preferably between 1800 and 3000, such as between 2000 and 2800, more preferably from about 2100 to 2500, and most preferably from about 2200 to about 2400. The molecular weight of a dispersant is generally expressed in terms of the molecular weight of the polyalkenyl moiety. This is because the precise molecular weight range of the dispersant depends on numerous parameters including the type of polymer used to derive the dispersant, the number of functional groups, and the type of nucleophilic group employed.
Polymer molecular weight, specifically Mn, can be determined by various known techniques. One convenient method is gel permeation chromatography (GPC), which additionally provides molecular weight distribution information (see W. W. Yau, J. J. Kirkland and D. D. Bly, “Modern Size Exclusion Liquid Chromatography”, John Wiley and Sons, New York, 1979). Another useful method for determining molecular weight, particularly for lower molecular weight polymers, is vapor pressure osmometry (e.g., ASTM D3592).
The polyalkenyl moiety in a dispersant preferably has a narrow molecular weight distribution (MWD), also referred to as polydispersity, as determined by the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn). Polymers having a Mw/Mn of less than 2.2, preferably less than 2.0, are most desirable. Suitable polymers have a polydispersity of from about 1.5 to 2.1, preferably from about 1.6 to about 1.8.
Suitable polyalkenes employed in the formation of the dispersants include homopolymers, interpolymers or lower molecular weight hydrocarbons. One family of such polymers comprise polymers of ethylene and/or at least one C3 to C2 alpha-olefin having the formula H2C═CHR1 wherein R1 is a straight or branched chain alkyl radical comprising 1 to 26 carbon atoms and wherein the polymer contains carbon-to-carbon unsaturation, and a high degree of terminal ethenylidene unsaturation. Preferably, such polymers comprise interpolymers of ethylene and at least one alpha-olefin of the above formula, wherein R1 is alkyl of from 1 to 18 carbon atoms, and more preferably is alkyl of from 1 to 8 carbon atoms, and more preferably still of from 1 to 2 carbon atoms.
Another useful class of polymers is polymers prepared by cationic polymerization of monomers such as isobutene and styrene. Common polymers from this class include polyisobutenes obtained by polymerization of a C4 refinery stream having a butene content of 35 to 75% by wt., and an isobutene content of 30 to 60% by wt. A preferred source of monomer for making poly-n-butenes is petroleum feed streams such as Raffinate II. These feed stocks are disclosed in the art such as in U.S. Pat. No. 4,952,739. A preferred embodiment utilizes polyisobutylene prepared from a pure isobutylene stream or a Raffinate I stream to prepare reactive isobutylene polymers with terminal vinylidene olefins. Polyisobutene polymers that may be employed are generally based on a polymer chain of from 1500 to 3000.
The dispersant(s) are preferably non-polymeric (e.g., mono- or bis-succinimides). Such dispersants can be prepared by conventional processes such as disclosed in U.S. Patent Application Publication No. 2008/0020950, the disclosure of which is incorporated herein by reference.
The dispersant(s) can be borated by conventional means, as generally disclosed in U.S. Pat. Nos. 3,087,936, 3,254,025 and 5,430,105.
Such dispersants may be used in an amount of about 0.01 to 20 weight percent or 0.01 to 10 weight percent, preferably about 0.5 to 8 weight percent, or more preferably 0.5 to 4 weight percent. Or such dispersants may be used in an amount of about 2 to 12 weight percent, preferably about 4 to 10 weight percent, or more preferably 6 to 9 weight percent. On an active ingredient basis, such additives may be used in an amount of about 0.06 to 14 weight percent, preferably about 0.3 to 6 weight percent. The hydrocarbon portion of the dispersant atoms can range from C60 to C1000, or from C70 to C300, or from C70 to C200. These dispersants may contain both neutral and basic nitrogen, and mixtures of both. Dispersants can be end-capped by borates and/or cyclic carbonates. Nitrogen content in the finished oil can vary from about 200 ppm by weight to about 2000 ppm by weight, preferably from about 200 ppm by weight to about 1200 ppm by weight. Basic nitrogen can vary from about 100 ppm by weight to about 1000 ppm by weight, preferably from about 100 ppm by weight to about 600 ppm by weight.
Dispersants as described herein are beneficially useful with the compositions of this disclosure and substitute for some or all of the surfactants of this disclosure. Further, in one embodiment, preparation of the compositions of this disclosure using one or more dispersants is achieved by combining ingredients of this disclosure, plus optional base stocks and lubricant additives, in a mixture at a temperature above the melting point of such ingredients, particularly that of the one or more M-carboxylates (M=H, metal, two or more metals, mixtures thereof).
As used herein, the dispersant concentrations are given on an “as delivered” basis. Typically, the active dispersant is delivered with a process oil. The “as delivered” dispersant typically contains from about 20 weight percent to about 80 weight percent, or from about 40 weight percent to about 60 weight percent, of active dispersant in the “as delivered” dispersant product.
Illustrative detergents useful in this disclosure include, for example, alkali metal detergents, alkaline earth metal detergents, or mixtures of one or more alkali metal detergents and one or more alkaline earth metal detergents. A typical detergent is an anionic material that contains a long chain hydrophobic portion of the molecule and a smaller anionic or oleophobic hydrophilic portion of the molecule. The anionic portion of the detergent is typically derived from an organic acid such as a sulfur-containing acid, carboxylic acid (e.g., salicylic acid), phosphorus-containing acid, phenol, or mixtures thereof. The counterion is typically an alkaline earth or alkali metal. The detergent can be overbased as described herein.
The detergent is preferably a metal salt of an organic or inorganic acid, a metal salt of a phenol, or mixtures thereof. The metal is preferably selected from an alkali metal, an alkaline earth metal, and mixtures thereof. The organic or inorganic acid is selected from an aliphatic organic or inorganic acid, a cycloaliphatic organic or inorganic acid, an aromatic organic or inorganic acid, and mixtures thereof.
The metal is preferably selected from an alkali metal, an alkaline earth metal, and mixtures thereof. More preferably, the metal is selected from calcium (Ca), magnesium (Mg), and mixtures thereof.
The organic acid or inorganic acid is preferably selected from a sulfur-containing acid, a carboxylic acid, a phosphorus-containing acid, and mixtures thereof.
Preferably, the metal salt of an organic or inorganic acid or the metal salt of a phenol comprises calcium phenate, calcium sulfonate, calcium salicylate, magnesium phenate, magnesium sulfonate, magnesium salicylate, an overbased detergent, and mixtures thereof.
Salts that contain a substantially stochiometric amount of the metal are described as neutral salts and have a total base number (TBN, as measured by ASTM D2896) of from 0 to 80. Many compositions are overbased, containing large amounts of a metal base that is achieved by reacting an excess of a metal compound (a metal hydroxide or oxide, for example) with an acidic gas (such as carbon dioxide). Useful detergents can be neutral, mildly overbased, or highly overbased. These detergents can be used in mixtures of neutral, overbased, highly overbased calcium salicylate, sulfonates, phenates and/or magnesium salicylate, sulfonates, phenates. The TBN ranges can vary from low, medium to high TBN products, including as low as 0 to as high as 600. Preferably the TBN delivered by the detergent is between 1 and 20. More preferably between 1 and 12. Mixtures of low, medium, high TBN can be used, along with mixtures of calcium and magnesium metal based detergents, and including sulfonates, phenates, salicylates, and carboxylates. A detergent mixture with a metal ratio of 1, in conjunction of a detergent with a metal ratio of 2, and as high as a detergent with a metal ratio of 5, can be used. Borated detergents can also be used.
Alkaline earth phenates are another useful class of detergent. These detergents can be made by reacting alkaline earth metal hydroxide or oxide (CaO, Ca(OH)2, BaO, Ba(OH)2, MgO, Mg(OH)2, for example) with an alkyl phenol or sulfurized alkylphenol. Useful alkyl groups include straight chain or branched C1-C30 alkyl groups, preferably, C4-C20 or mixtures thereof. Examples of suitable phenols include isobutylphenol, 2-ethylhexylphenol, nonylphenol, dodecyl phenol, and the like. It should be noted that starting alkylphenols may contain more than one alkyl substituent that are each independently straight chain or branched and can be used from 0.5 to 6 weight percent. When a non-sulfurized alkylphenol is used, the sulfurized product may be obtained by methods well known in the art. These methods include heating a mixture of alkylphenol and sulfurizing agent (including elemental sulfur, sulfur halides such as sulfur dichloride, and the like) and then reacting the sulfurized phenol with an alkaline earth metal base.
In accordance with this disclosure, metal salts of carboxylic acids are preferred detergents. These carboxylic acid detergents may be prepared by reacting a basic metal compound with at least one carboxylic acid and removing free water from the reaction product. These compounds may be overbased to produce the desired TBN level. Detergents made from salicylic acid are one preferred class of detergents derived from carboxylic acids. Useful salicylates include long chain alkyl salicylates. One useful family of compositions is of the formula
where R is an alkyl group having 1 to 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 C11, preferably C13 or greater. R may be optionally substituted with substituents that do not interfere with the detergent's function. M is preferably, calcium, magnesium, barium, or mixtures thereof. More preferably, M is calcium.
Hydrocarbyl-substituted salicylic acids may be prepared from phenols by the Kolbe reaction (see U.S. Pat. No. 3,595,791). The metal salts of the hydrocarbyl-substituted salicylic acids may be prepared by double decomposition of a metal salt in a polar solvent such as water or alcohol.
Alkaline earth metal phosphates are also used as detergents and are known in the art.
Detergents may be simple detergents or what is known as hybrid or complex detergents. The latter detergents can provide the properties of two detergents without the need to blend separate materials. See U.S. Pat. No. 6,034,039.
Preferred detergents include calcium sulfonates, magnesium sulfonates, calcium salicylates, magnesium salicylates, calcium phenates, magnesium phenates, and other related components (including borated detergents), and mixtures thereof. Preferred mixtures of detergents include magnesium sulfonate and calcium salicylate, magnesium sulfonate and calcium sulfonate, magnesium sulfonate and calcium phenate, calcium phenate and calcium salicylate, calcium phenate and calcium sulfonate, calcium phenate and magnesium salicylate, calcium phenate and magnesium phenate. Overbased detergents are also preferred.
The detergent concentration in the lubricating oils of this disclosure can range from about 0.5 to about 6.0 weight percent, preferably about 0.6 to 5.0 weight percent, and more preferably from about 0.8 weight percent to about 4.0 weight percent, based on the total weight of the lubricating oil.
As used herein, the detergent concentrations are given on an “as delivered” basis. Typically, the active detergent is delivered with a process oil. The “as delivered” detergent typically contains from about 20 weight percent to about 100 weight percent, or from about 40 weight percent to about 60 weight percent, of active detergent in the “as delivered” detergent product.
Other antioxidants may be used in combination with the monomeric, oligomeric and polymeric aminic antioxidants. 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 cite, and U.S. Pat. Nos. 4,798,684 and 5,084,197, for example.
Useful antioxidants include amine antioxidants, preferably aromatic amine antioxidants. Other useful antioxidants include phenolic antioxidants (e.g., hindered phenolic antioxidants). Aromatic amine antioxidants may be used alone or in combination with phenolic antioxidants. Typical examples of amine 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 R10 is H, alkyl, aryl or R11S(O)xR12 where R11 is an alkylene, alkenylene, or aralkylene group, R12 is a higher alkyl group, or an alkenyl, aryl, or alkaryl group, and x is 0, 1 or 2. The aliphatic group R8 may contain from 1 to 20 carbon atoms, and preferably contains from 6 to 12 carbon atoms. The aliphatic group is an aliphatic group. Preferably, both R8 and R9 are aromatic or substituted aromatic groups, and the aromatic group may be a fused ring aromatic group such as naphthyl. Aromatic groups R8 and R9 may be joined together with other groups such as S.
Typical aromatic amine antioxidants have alkyl substituent groups of at least 6 carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally, the aliphatic groups will not contain more than 14 carbon atoms. The general types of amine antioxidants useful in the present compositions include diphenylamines, phenyl naphthylamines, phenothiazines, imidodibenzyls and diphenyl phenylene diamines. Mixtures of two or more aromatic amines are also useful. Particular examples of aromatic amine antioxidants useful in the present disclosure include: p,p′-dioctyldiphenylamine; t-octylphenyl-alpha-naphthylamine; phenyl-alpha-naphthylamine; and p-octylphenyl-alpha-naphthylamine.
The arylamines antioxidants may be used individually or in combination. Such additives may be used in an amount of 0.01 to 5 weight percent, preferably 0.01 to 1.5 weight percent, more preferably zero to less than 1.5 weight percent, more preferably zero to less than 1 weight percent.
The phenolic antioxidants may be used individually or in combination. The phenolic antioxidants may provide potential benefits in other performance aspects. Such additives may be used in an amount of 0.01 to 1 weight percent, preferably 0.01 to 0.75 weight percent, more preferably zero to less than 0.5 weight percent.
Viscosity modifiers (also known as viscosity index improvers (VI improvers), and viscosity improvers) can be included in the lubricant compositions of this disclosure.
Viscosity modifiers provide lubricants with high and low temperature operability. These additives impart shear stability at elevated temperatures and acceptable viscosity at low temperatures.
Suitable viscosity modifiers include high molecular weight hydrocarbons, polyesters and viscosity modifier dispersants that function as both a viscosity modifier and a dispersant. Typical molecular weights of these polymers are between about 10,000 to 1,500,000, more typically about 20,000 to 1,200,000, and even more typically between about 50,000 and 1,000,000.
Examples of suitable viscosity modifiers are linear or star-shaped polymers and copolymers of methacrylate, butadiene, olefins, or alkylated styrenes. Polyisobutylene is a commonly used viscosity modifier. Another suitable viscosity modifier is polymethacrylate (copolymers of various chain length alkyl methacrylates, for example), some formulations of which also serve as pour point depressants. Other suitable viscosity modifiers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (copolymers of various chain length acrylates, for example). Specific examples include styrene-isoprene or styrene-butadiene based polymers of 50,000 to 200,000 molecular weight.
Olefin copolymers are commercially available from Chevron Oronite Company LLC under the trade designation “PARATONE®” (such as “PARATONE® 8921” and “PARATONE® 8941”); from Afton Chemical Corporation under the trade designation “HiTEC®” (such as “HiTEC® 5850B”; and from The Lubrizol Corporation under the trade designation “Lubrizol® 7067C”. Hydrogenated polyisoprene star polymers are commercially available from Infineum International Limited, e.g., under the trade designation “SV200” and “SV600”. Hydrogenated diene-styrene block copolymers are commercially available from Infineum International Limited, e.g., under the trade designation “SV 50”.
The polymethacrylate or polyacrylate polymers can be linear polymers which are available from Evnoik Industries under the trade designation “Viscoplex®” (e.g., Viscoplex 6-954) or star polymers which are available from Lubrizol Corporation under the trade designation Asteric™ (e.g., Lubrizol 87708 and Lubrizol 87725).
Illustrative vinyl aromatic-containing polymers useful in this disclosure may be derived predominantly from vinyl aromatic hydrocarbon monomer. Illustrative vinyl aromatic-containing copolymers useful in this disclosure may be represented by the following general formula:
A-B
wherein A is a polymeric block derived predominantly from vinyl aromatic hydrocarbon monomer, and B is a polymeric block derived predominantly from conjugated diene monomer.
In an embodiment of this disclosure, the viscosity modifiers may be used in an amount of less than about 10 weight percent, preferably less than about 7 weight percent, more preferably less than about 4 weight percent, and in certain instances, may be used at less than 2 weight percent, preferably less than about 1 weight percent, and more preferably less than about 0.5 weight percent, based on the total weight of the formulated oil or lubricating engine oil. Viscosity modifiers are typically added as concentrates, in large amounts of diluent oil.
As used herein, the viscosity modifier concentrations are given on an “as delivered” basis. Typically, the active polymer is delivered with a diluent oil. The “as delivered” viscosity modifier typically contains from 20 weight percent to 75 weight percent of an active polymer for polymethacrylate or polyacrylate polymers, or from 8 weight percent to 20 weight percent of an active polymer for olefin copolymers, hydrogenated polyisoprene star polymers, or hydrogenated diene-styrene block copolymers, in the “as delivered” polymer concentrate.
Conventional pour point depressants (also known as lube oil flow improvers) may be added to the compositions of the present disclosure if desired. These pour point depressant may be added to lubricating compositions of the present disclosure to lower the minimum temperature at which the fluid will flow or can be poured. Examples of suitable pour point depressants include polymethacrylates, polyacrylates, polyarylamides, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, and terpolymers of dialkylfumarates, vinyl esters of fatty acids and allyl vinyl ethers. U.S. Pat. Nos. 1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,655, 479; 2,666,746; 2,721,877; 2,721,878; and 3,250,715 describe useful pour point depressants and/or the preparation thereof. Such additives may be used in an amount of about 0.01 to 5 weight percent, preferably about 0.01 to 1.5 weight percent.
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 phthalate, for example), and polybutenyl succinic anhydride. Such additives may be used in an amount of about 0.01 to 3 weight percent, preferably about 0.01 to 2 weight percent.
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, polysiloxanes, 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 demulsifiers; usually the amount of these additives combined is less than 1 weight percent and often less than 0.1 weight percent.
Antirust additives (or corrosion inhibitors) are additives that protect lubricated metal surfaces against chemical attack by water or other contaminants. A wide variety of these are commercially available.
One type of antirust additive is a polar compound that wets the metal surface preferentially, protecting it with a film of oil. Another type of antirust additive absorbs water by incorporating it in a water-in-oil emulsion so that only the oil touches the metal surface. Yet another type of antirust additive chemically adheres to the metal to produce a non-reactive surface. Examples of suitable additives include zinc dithiophosphates, metal phenolates, basic metal sulfonates, fatty acids and amines. Such additives may be used in an amount of about 0.01 to 5 weight percent, preferably about 0.01 to 1.5 weight percent.
A friction modifier is any material or materials that can alter the coefficient of friction of a surface lubricated by any lubricant or fluid containing such material(s). Friction modifiers, also known as friction reducers, or lubricity agents or oiliness agents, and other such agents that change the ability of base oils, formulated lubricant compositions, or functional fluids, to modify the coefficient of friction of a lubricated surface may be effectively used in combination with the base oils or lubricant compositions of the present disclosure if desired. Friction modifiers that lower the coefficient of friction are particularly advantageous in combination with the base oils and lube compositions of this disclosure.
Illustrative friction modifiers may include, for example, organometallic compounds or materials, or mixtures thereof. Illustrative organometallic friction modifiers useful in the lubricating engine oil formulations of this disclosure include, for example, molybdenum amine, molybdenum diamine, an organotungstenate, a molybdenum dithiocarbamate, molybdenum dithiophosphates, molybdenum amine complexes, molybdenum carboxylates, and the like, and mixtures thereof. Similar tungsten based compounds may be preferable.
Other illustrative friction modifiers useful in the lubricating engine oil formulations of this disclosure include, for example, alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, borated glycerol fatty acid esters, fatty alcohol ethers, and mixtures thereof.
Illustrative alkoxylated fatty acid esters include, for example, polyoxyethylene stearate, fatty acid polyglycol ester, and the like. These can include polyoxypropylene stearate, polyoxybutylene stearate, polyoxyethylene isosterate, polyoxypropylene isostearate, polyoxyethylene palmitate, and the like.
Illustrative alkanolamides include, for example, lauric acid diethylalkanolamide, palmic acid diethylalkanolamide, and the like. These can include oleic acid diethyalkanolamide, stearic acid diethylalkanolamide, oleic acid diethylalkanolamide, polyethoxylated hydrocarbylamides, polypropoxylated hydrocarbylamides, and the like.
Illustrative polyol fatty acid esters include, for example, glycerol mono-oleate, saturated mono-, di-, and tri-glyceride esters, glycerol mono-stearate, and the like. These can include polyol esters, hydroxyl-containing polyol esters, and the like.
Illustrative borated glycerol fatty acid esters include, for example, borated glycerol mono-oleate, borated saturated mono-, di-, and tri-glyceride esters, borated glycerol mono-sterate, and the like. In addition to glycerol polyols, these can include trimethylolpropane, pentaerythritol, sorbitan, and the like. These esters can be polyol monocarboxylate esters, polyol dicarboxylate esters, and on occasion polyoltricarboxylate esters. Preferred can be the glycerol mono-oleates, glycerol dioleates, glycerol trioleates, glycerol monostearates, glycerol distearates, and glycerol tristearates and the corresponding glycerol monopalmitates, glycerol dipalmitates, and glycerol tripalmitates, and the respective isostearates, linoleates, and the like. On occasion the glycerol esters can be preferred as well as mixtures containing any of these. Ethoxylated, propoxylated, butoxylated fatty acid esters of polyols, especially using glycerol as underlying polyol can be preferred.
Illustrative fatty alcohol ethers include, for example, stearyl ether, myristyl ether, and the like. Alcohols, including those that have carbon numbers from C3 to C50, can be ethoxylated, propoxylated, or butoxylated to form the corresponding fatty alkyl ethers. The underlying alcohol portion can preferably be stearyl, myristyl, C11-C13 hydrocarbon, oleyl, isosteryl, and the like.
The lubricating oils of this disclosure exhibit desired properties, e.g., wear control, in the presence or absence of a friction modifier.
Useful concentrations of friction modifiers may range from 0.01 weight percent to 5 weight percent, or about 0.1 weight percent to about 2.5 weight percent, or about 0.1 weight percent to about 1.5 weight percent, or about 0.1 weight percent to about 1 weight percent. Concentrations to of molybdenum-containing materials are often described in terms of Mo metal concentration.
Advantageous concentrations of Mo may range from 25 ppm to 700 ppm or more, and often with a preferred range of 50-200 ppm. Friction modifiers of all types may be used alone or in mixtures with the materials of this disclosure. Often mixtures of two or more friction modifiers, or mixtures of friction modifier(s) with alternate surface active material(s), are also desirable.
A metal alkylthiophosphate and more particularly a metal dialkyl dithio phosphate in which the metal constituent is zinc, or zinc dialkyl dithio phosphate (ZDDP) can be a useful component of the lubricating oils of this disclosure. ZDDP can be derived from primary alcohols, secondary alcohols or mixtures thereof. ZDDP compounds generally are of the formula
Zn[SP(S)(OR1)(OR2)]2
where R1 and R2 are C1-C18 alkyl groups, preferably C2-C12 alkyl groups. These alkyl groups may be straight chain or branched. Alcohols used in the ZDDP can be propanol, 2-propanol, butanol, secondary butanol, pentanols, hexanols such as 4-methyl-2-pentanol, n-hexanol, n-octanol, 2-ethyl hexanol, alkylated phenols, and the like. Mixtures of secondary alcohols or of primary and secondary alcohol can be preferred. Alkyl aryl groups may also be used.
Preferable zinc dithiophosphates which are commercially available include secondary zinc dithiophosphates such as those available from for example, The Lubrizol Corporation under the trade designations “LZ 677A”, “LZ 1095” and “LZ 1371”, from for example Chevron Oronite under the trade designation “OLOA 262” and from for example Afton Chemical under the trade designation “HITEC 7169”.
The ZDDP is typically used in amounts of from about 0.3 weight percent to about 1.5 weight percent, preferably from about 0.4 weight percent to about 1.2 weight percent, more preferably from about 0.5 weight percent to about 1.0 weight percent, and even more preferably from about 0.6 weight percent to about 0.8 weight percent, based on the total weight of the lubricating oil, although more or less can often be used advantageously. Preferably, the ZDDP is a secondary ZDDP and present in an amount of from about 0.6 to 1.0 weight percent of the total weight of the lubricating oil.
The types and quantities of performance additives used in combination with the instant disclosure in lubricant compositions are not limited by the examples shown herein as illustrations.
When lubricating oil compositions contain one or more of the additives discussed above, the additive(s) are blended into the composition in an amount sufficient for it to perform its intended function. Typical amounts of such additives useful in the present disclosure are shown in Table 1 below.
It is noted that many of the additives are shipped from the additive manufacturer as a concentrate, containing one or more additives together, with a certain amount of base oil diluents. Accordingly, the weight amounts in the table below, as well as other amounts mentioned herein, are directed to the amount of active ingredient (that is the non-diluent portion of the ingredient). The weight percent (wt %) indicated below is based on the total weight of the lubricating oil composition.
The foregoing additives are all commercially available materials. These additives may be added independently but are usually precombined in packages which can be obtained from suppliers of lubricant oil additives. Additive packages with a variety of ingredients, proportions and characteristics are available and selection of the appropriate package will take the requisite use of the ultimate composition into account.
The following non-limiting examples are provided to illustrate the disclosure.
Engine oil candidates were formulated. All of the ingredients used in the candidate formulated oils were commercially available. The nomenclature of illustrative antioxidants used in the candidate formulated oils include octylated/butylated diphenylamine (Irganox® L57 from BASF Corporation) and bis(nonylphenyl)amine (Irganox® L67 from BASF Corporation).
Irganox® L57 is a mixture of several different substituted diphenyl amine antioxidants. The four most common molecular weights, and the relative amounts, for the Irganox® L57 constituents are as follows:
Oligomers from Irganox® L57 can be formed, for example, self-oligomers like A+A, A+A+A, or C+C+C+C or mixed oligomers like A+B, A+B+C, B+A+D+D in a myriad of combinations. When the monomers of Irganox® L57 oligomerize, they can form dimers, trimers and higher order oligomers in varying abundance which is in part governed by the relative abundance of the monomers as well as the relative reactivity of the monomer. The relative concentration of higher order oligomers will decrease as the size of the oligomer increases due to molecular diversity that is produced. As such, the oligomers expected to be formed in the highest concentration will be dimers, followed by trimers and so forth.
The candidates were fully formulated lubricants. In addition to Irganox® L57, the formulations contained typical base stocks combined with dispersants, detergents, antiwear additives, friction modifiers, and the like.
Formulated oils including an inventive example (i.e., inventive Example 2 having 5 weight percent Irganox® L57) and a comparative example (i.e., comparative Example 1 having 0.75 weight percent Irganox® L57) were tested according to a Sequence IIIH engine test until % viscosity increase exceeded 100%. The monomeric aminic antioxidants were each added to an engine oil at the indicated concentration. The Sequence IIIH Test (ASTM D8111) is a fired-engine, dynamometer lubricant test for evaluating automotive engine oils for certain high-temperature performance characteristics, including oil thickening, varnish deposition and oil consumption. The Sequence IIIH engine test results are shown below.
The inventive Example 2 provided outstanding viscosity performance while maintaining improved deposits performance. Lower % viscosity increase is better. Higher “merits” is better.
Used oil samples from the Sequence IIIH engine testing were analyzed by liquid chromatography mass spectrometry (LCMS) to quantify the relative concentration of molecular ions of interest. The data was then analyzed by the following equation:
[(oligomer ions at time point/total ions at time point)−(oligomer ions at zero hours/total ions at zero hours)]×1000=relative amount of oligomers detected by LCMS
In this way, all data was normalized prior to the start of the test. Values reported are the relative increase in the amount of that oligomer. Values less than 1 can be considered noise in the system, while values greater than 1 represent a real increase in the amount of an oligomer.
Ion counts for oligomers of Irganox® L57 in comparative Example 1 formulated oil analyzed by LCMS are shown in
Ion counts for oligomers of Irganox® L57 in inventive Example 2 formulated oil analyzed by LCMS are shown in
In an embodiment, a preformed oligomeric or polymeric aminic antioxidant can be co-formulated with a monomeric aminic antioxidant. The presence of additional monomeric aminic antioxidant starting material allows for the oligomeric or polymeric antioxidant to form even larger oligomers and polymers and regenerate itself throughout the oil drain interval.
In particular, in addition to formulated oils containing only monomeric aminic antioxidants, there can also be oils that are formulated with an oligomeric aminic antioxidant (such as MCP 2568, Nycoperf® A0337, or Vanlube® 9317) in addition to a monomeric aminic antioxidant (such as Irganox® L57, Irganox® L67, or Irganox® L06). In this embodiment, the monomeric aminic antioxidant can further react with the preexisting oligomeric aminic antioxidants to form various combinations of even higher order oligomers. This function is self-healing as the newly attached monomers replace other portions of the preexisting oligomer that have degraded during the lifetime of the formulated oil. This additional oligomerization can also improve the antioxidancy of the preexisting oligomers, as some higher order oligomers are more potent antioxidants than lower order oligomers.
In another embodiment, simplified formulations containing only monomeric aminic antioxidant and base stock, generate in situ oligomeric and polymeric aminic antioxidants in lubricating oil formulations.
In yet another embodiment, some consumers have a particular preference for oils that are not dark in color. The color of a formulated oil can be measured using various methods, including ASTM D1500. In this embodiment, it is sometimes preferable to have a formulated oil with a color less than 6 according to ASTM D1500. Current available oligomeric aminic antioxidants often suffer from the problem of being very dark in nature. When used in a formulated oil at an appropriate treat rate, these materials can result in a final formulation color that is unacceptable to the consumer. One particular advantage of this disclosure is that these formulations are not dark in nature because monomeric aminic antioxidants tend to be much lighter in color according to ASTM D1500.
The lubricating oils of this disclosure can also be test in accordance with the General Motors Oxidation and Deposit Test (GMOD) in accordance with GMW17043, 2nd Edition, May 2016. The GMOD test procedure covers engine tests for evaluating automotive engine oils for certain high temperature performance characteristics, including oil thickening, and piston deposits. Additionally, secondary requirements that can be conducted include mini rotary viscometer measurements, cold cranking simulator measurements, and phosphorus retention measurements.
It has been found that, with in situ generated oligomeric and polymeric aminic antioxidants in lubricating oil formulations, viscosity control and deposit control are improved in the finished formulations designed for engine oil applications.
A method for controlling formation and dissipation of at least one oligomeric or polymeric aminic antioxidant in a lubricating oil, during operation of an engine or other mechanical component lubricated with the lubricating oil by using as the lubricating oil a formulated oil, said formulated oil having a composition comprising a lubricating oil base stock as a major component; and at least one oligomeric or polymeric aminic antioxidant, as a minor component; wherein the at least one oligomeric or polymeric aminic antioxidant is formed over time in situ from at least one monomeric aminic antioxidant during operation of the engine or other mechanical component; wherein the at least one oligomeric or polymeric aminic antioxidant is dissipated over time in the lubricating oil during operation of the engine or other mechanical component; wherein the lubricating oil base stock is present in an amount from about 1 to about 95 weight percent, based on the total weight of the lubricating oil; and wherein the at least one monomeric aminic antioxidant is present in an amount from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil.
The method of claim 1 wherein, in measurements of the lubricating oil by a Sequence IIIH engine test in accordance with ASTM D8111-17, viscosity control and deposit control are improved using a concentration of the at least one monomeric aminic antioxidant from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil, as compared to viscosity control and deposit control achieved using a lower concentration of the at least one monomeric aminic antioxidant.
The method of claim 1 wherein the at least one monomeric aminic antioxidant comprises at least one unsubstituted or hydrocarbyl-substituted diphenyl amine, at least one unsubstituted or hydrocarbyl-substituted phenyl naphthyl amine, or mixtures thereof.
The method of claim 1 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product of at least one unsubstituted or hydrocarbyl-substituted diphenyl amine, at least one unsubstituted or hydrocarbyl-substituted phenyl naphthyl amine, or both at least one unsubstituted or hydrocarbyl-substituted diphenylamine and at least one unsubstituted or hydrocarbyl-substituted phenyl naphthylamine.
The method of claim 1 wherein the at least one oligomeric or polymeric aminic antioxidant comprises:
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is at least 2; R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The method of claim 1 wherein the at least one monomeric aminic antioxidant comprises:
wherein R is H, C4H9, C8H17, or C9H19; and/or
The method of claim 1 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product of
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is at least 2; R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The method of claim 7 wherein the at least one oligomeric or polymeric aminic antioxidant is an oligomerization or polymerization reaction product comprising: (A)(A), (A)(B), (B)(B), (A)(A)(B), (A)(A)(A), (A)(B)(A), (B)(B)(B), (B)(B)(A), (A)(A)(A)(A), (A)(A)(B)(B), (A)(A)(A)(B), (B)(B)(B)(B), (B)(B)(B)(A), (A)(A)(A)(A)(A), (A)(B)(A)(B)(A), (A)(B)(B)(B)(A), or mixtures thereof.
The method of claim 7 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product formed by any combination of:
wherein R is H, C4H9, C8H17, or C9H19; and/or
The method of claim 1 wherein the at least one oligomeric or polymeric aminic antioxidant is an oligomerization or polymerization reaction product selected from the group consisting of:
wherein R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, R4 is a styrene or C1 to C30 alkyl, p, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The method of claim 1 wherein the lubricating oil base stock is present in an amount from about 1 to about 80 weight percent, based on the total weight of the lubricating oil.
The method of claim 1 wherein the at least one monomeric aminic antioxidant is present in an amount from about 4 to about 8 weight percent, based on the total weight of the lubricating oil.
The method of claim 1 wherein the at least one oligomeric or polymeric aminic antioxidant is present in an amount from about 0.1 to about 5 weight percent, based on the total weight of the lubricating oil.
The method of claim 1 wherein the formulated oil further comprises one or more of a viscosity modifier, dispersant, detergent, other antioxidant, pour point depressant, corrosion inhibitor, metal deactivator, seal compatibility additive, anti-foam agent, inhibitor, and anti-rust additive.
The method of claim 14 wherein the other antioxidant comprises at least one aromatic amine antioxidant, at least one phenolic antioxidant, or mixtures thereof.
The method of claim 1 wherein the at least one oligomeric or polymeric aminic antioxidant is formed over time in situ during a Sequence IIIH engine test in accordance with ASTM D8111-17, or a General Motors Oxidation and Deposit Test (GMOD) in accordance with GMW17043, 2nd Edition, May 2016.
The method of claim 1 wherein the lubricating oil is a passenger vehicle engine oil (PVEO), a commercial vehicle engine oil (CVEO), or a lubricating oil that is subjected to heat and oxidative conditions.
A method for controlling formation and dissipation of at least one oligomeric or polymeric aminic antioxidant in a lubricating oil, during operation of an engine or other mechanical component lubricated with the lubricating oil by using as the lubricating oil a formulated oil, said formulated oil having a composition comprising a lubricating oil base stock as a major component; and at least one monomeric aminic antioxidant, as a minor component; wherein at least one oligomeric or polymeric aminic antioxidant is formed over time in situ from the at least one monomeric aminic antioxidant during operation of the engine or other mechanical component; wherein the at least one oligomeric or polymeric aminic antioxidant is dissipated over time in the lubricating oil during operation of the engine or other mechanical component; wherein the lubricating oil base stock is present in an amount from about 1 to about 95 weight percent, based on the total weight of the lubricating oil; and wherein the at least one monomeric aminic antioxidant is present in an amount from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil.
The method of claim 18 wherein, in measurements of the lubricating oil by a Sequence IIIH engine test in accordance with ASTM D8111-17, viscosity control and deposit control are improved using a concentration of the at least one monomeric aminic antioxidant from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil, as compared to viscosity control and deposit control achieved using a lower concentration of the at least one monomeric aminic antioxidant.
The method of claim 18 wherein the at least one monomeric aminic antioxidant comprises at least one unsubstituted or hydrocarbyl-substituted diphenyl amine, at least one unsubstituted or hydrocarbyl-substituted phenyl naphthyl amine, or mixtures thereof.
The method of claim 18 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product of at least one unsubstituted or hydrocarbyl-substituted diphenyl amine, at least one unsubstituted or hydrocarbyl-substituted phenyl naphthyl amine, or both at least one unsubstituted or hydrocarbyl-substituted diphenylamine and at least one unsubstituted or hydrocarbyl-substituted phenyl naphthylamine.
The method of claim 18 wherein the at least one oligomeric or polymeric aminic antioxidant comprises:
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is at least 2; R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The method of claim 18 wherein the at least one monomeric aminic antioxidant comprises:
wherein R is H, C4H9, C8H17, or C9H19; and/or
The method of claim 18 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product of
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is at least 2; R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The method of claim 24 wherein the at least one oligomeric or polymeric aminic antioxidant is an oligomerization or polymerization reaction product comprising: (A)(A), (A)(B), (B)(B), (A)(A)(B), (A)(A)(A), (A)(B)(A), (B)(B)(B), (B)(B)(A), (A)(A)(A)(A), (A)(A)(B)(B), (A)(A)(A)(B), (B)(B)(B)(B), (B)(B)(B)(A), (A)(A)(A)(A)(A), (A)(B)(A)(B)(A), (A)(B)(B)(B)(A), or mixtures thereof.
The method of claim 24 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product formed by any combination of:
wherein R is H, C4H9, C8H17, or C9H19; and/or
The method of claim 18 wherein the at least one oligomeric or polymeric aminic antioxidant is an oligomerization or polymerization reaction product selected from the group consisting of:
wherein R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, R4 is a styrene or C1 to C30 alkyl, p, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The method of claim 18 wherein the lubricating oil base stock is present in an amount from about 1 to about 80 weight percent, based on the total weight of the lubricating oil.
The method of claim 18 wherein the at least one monomeric aminic antioxidant is present in an amount from about 4 to about 8 weight percent, based on the total weight of the lubricating oil.
The method of claim 18 wherein the at least one oligomeric or polymeric aminic antioxidant is present in an amount from about 0.1 to about 5 weight percent, based on the total weight of the lubricating oil.
The method of claim 18 wherein the formulated oil further comprises one or more of a viscosity modifier, dispersant, detergent, other antioxidant, pour point depressant, corrosion inhibitor, metal deactivator, seal compatibility additive, anti-foam agent, inhibitor, and anti-rust additive.
The method of claim 31 wherein the other antioxidant comprises at least one aromatic amine antioxidant, at least one phenolic antioxidant, or mixtures thereof.
The method of claim 18 wherein the at least one oligomeric or polymeric aminic antioxidant is formed over time in situ during a Sequence IIIH engine test in accordance with ASTM D8111-17, or a General Motors Oxidation and Deposit Test (GMOD) in accordance with GMW17043, 2nd Edition, May 2016.
The method of claim 18 wherein the lubricating oil is a passenger vehicle engine oil (PVEO), a commercial vehicle engine oil (CVEO), or a lubricating oil that is subjected to heat and oxidative conditions.
A method for controlling formation and dissipation of at least one oligomeric or polymeric aminic antioxidant in a lubricating oil, during operation of an engine or other mechanical component lubricated with the lubricating oil by using as the lubricating oil a formulated oil, said formulated oil having a composition comprising a lubricating oil base stock as a major component; and at least one oligomeric or polymeric aminic antioxidant and at least one monomeric aminic antioxidant, as minor components; wherein the at least one oligomeric or polymeric aminic antioxidant and the at least one monomeric aminic antioxidant react to form over time in situ at least one oligomeric or polymeric aminic antioxidant reaction product during operation of the engine or other mechanical component; wherein the at least one oligomeric or polymeric aminic antioxidant reaction product is dissipated over time in the lubricating oil during operation of the engine or other mechanical component; wherein the lubricating oil base stock is present in an amount from about 1 to about 95 weight percent, based on the total weight of the lubricating oil; wherein the at least one oligomeric or polymeric aminic antioxidant is present in an amount from greater than about 0.1 to about 10 weight percent, based on the total weight of the lubricating oil; and wherein the at least one monomeric aminic antioxidant is present in an amount from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil.
The method of claim 35 wherein, in measurements of the lubricating oil by a Sequence IIIH engine test in accordance with ASTM D8111-17, viscosity control and deposit control are improved using a concentration of the at least one monomeric aminic antioxidant from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil, as compared to viscosity control and deposit control achieved using a lower concentration of the at least one monomeric aminic antioxidant.
The method of claim 35 wherein the at least one monomeric aminic antioxidant comprises at least one unsubstituted or hydrocarbyl-substituted diphenyl amine, at least one unsubstituted or hydrocarbyl-substituted phenyl naphthyl amine, or mixtures thereof.
The method of claim 35 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product of at least one unsubstituted or hydrocarbyl-substituted diphenyl amine, at least one unsubstituted or hydrocarbyl-substituted phenyl naphthyl amine, or both at least one unsubstituted or hydrocarbyl-substituted diphenylamine and at least one unsubstituted or hydrocarbyl-substituted phenyl naphthylamine.
The method of claim 35 wherein the at least one monomeric aminic antioxidant comprises:
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is at least 2; R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The method of claim 35 wherein the at least one monomeric aminic antioxidant comprises:
wherein R is H, C4H9, C8H17, or C9H19; and/or
The method of claim 35 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product of
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is at least 2; R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The method of claim 41 wherein the at least one oligomeric or polymeric aminic antioxidant is an oligomerization or polymerization reaction product comprising: (A)(A), (A)(B), (B)(B), (A)(A)(B), (A)(A)(A), (A)(B)(A), (B)(B)(B), (B)(B)(A), (A)(A)(A)(A), (A)(A)(B)(B), (A)(A)(A)(B), (B)(B)(B)(B), (B)(B)(B)(A), (A)(A)(A)(A)(A), (A)(B)(A)(B)(A), (A)(B)(B)(B)(A), or mixtures thereof.
The method of claim 41 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product formed by any combination of:
wherein R is H, C4H9, C8H17, or C9H19; and/or
The method of claim 35 wherein the at least one oligomeric or polymeric aminic antioxidant is an oligomerization or polymerization reaction product selected from the group consisting of:
wherein R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, R4 is a styrene or C1 to C30 alkyl, p, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The method of claim 35 wherein the at least one oligomeric or polymeric aminic antioxidant reaction product is the oligomerization or polymerization reaction product of:
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is at least 2; R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached; with at least one monomeric aminic antioxidant comprising:
wherein R is H, C4H9, C8H17, or C9H19; and/or
The method of claim 35 wherein the lubricating oil base stock is present in an amount from about 1 to about 80 weight percent, based on the total weight of the lubricating oil.
The method of claim 35 wherein the at least one monomeric aminic antioxidant is present in an amount from about 4 to about 8 weight percent, based on the total weight of the lubricating oil.
The method of claim 35 wherein the at least one oligomeric or polymeric aminic antioxidant is present in an amount from about 1 to about 8 weight percent, based on the total weight of the lubricating oil.
The method of claim 35 wherein the formulated oil further comprises one or more of a viscosity modifier, dispersant, detergent, other antioxidant, pour point depressant, corrosion inhibitor, metal deactivator, seal compatibility additive, anti-foam agent, inhibitor, and anti-rust additive.
The method of claim 49 wherein the other antioxidant comprises at least one aromatic amine antioxidant, at least one phenolic antioxidant, or mixtures thereof.
The method of claim 35 wherein the at least one oligomeric or polymeric aminic antioxidant is formed over time in situ during a Sequence IIIH engine test in accordance with ASTM D8111-17, or a General Motors Oxidation and Deposit Test (GMOD) in accordance with GMW17043, 2nd Edition, May 2016.
The method of claim 35 wherein the lubricating oil is a passenger vehicle engine oil (PVEO), a commercial vehicle engine oil (CVEO), or a lubricating oil that is subjected to heat and oxidative conditions.
A method for regenerating at least one oligomeric or polymeric aminic antioxidant in a lubricating oil, during operation of an engine or other mechanical component lubricated with the lubricating oil by using as the lubricating oil a formulated oil, said formulated oil having a composition comprising a lubricating oil base stock as a major component; and at least one oligomeric or polymeric aminic antioxidant and at least one monomeric aminic antioxidant, as minor components; wherein the at least one oligomeric or polymeric aminic antioxidant dissipates over time in the lubricating oil during operation of the engine or other mechanical component; wherein the at least one oligomeric or polymeric aminic antioxidant and the at least one monomeric aminic antioxidant react to form over time in situ at least one regenerated oligomeric or polymeric aminic antioxidant during operation of the engine or other mechanical component; wherein the lubricating oil base stock is present in an amount from about 1 to about 95 weight percent, based on the total weight of the lubricating oil; wherein the at least one oligomeric or polymeric aminic antioxidant is present in an amount from greater than about 0.1 to about 10 weight percent, based on the total weight of the lubricating oil; and wherein the at least one monomeric aminic antioxidant is present in an amount from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil.
The method of claim 53 wherein, in measurements of the lubricating oil by a Sequence IIIH engine test in accordance with ASTM D8111-17, viscosity control and deposit control are improved using a concentration of the at least one monomeric aminic antioxidant from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil, as compared to viscosity control and deposit control achieved using a lower concentration of the at least one monomeric aminic antioxidant.
The method of claim 53 wherein the at least one monomeric aminic antioxidant comprises at least one unsubstituted or hydrocarbyl-substituted diphenyl amine, at least one unsubstituted or hydrocarbyl-substituted phenyl naphthyl amine, or mixtures thereof.
The method of claim 53 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product of at least one unsubstituted or hydrocarbyl-substituted diphenyl amine, at least one unsubstituted or hydrocarbyl-substituted phenyl naphthyl amine, or both at least one unsubstituted or hydrocarbyl-substituted diphenylamine and at least one unsubstituted or hydrocarbyl-substituted phenyl naphthylamine.
The method of claim 53 wherein the at least one monomeric aminic antioxidant comprises:
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is at least 2; R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The method of claim 53 wherein the at least one monomeric aminic antioxidant comprises:
wherein R is H, C4H9, C8H17, or C9H19; and/or
The method of claim 53 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product of
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is at least 2; R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The method of claim 59 wherein the at least one oligomeric or polymeric aminic antioxidant is an oligomerization or polymerization reaction product comprising: (A)(A), (A)(B), (B)(B), (A)(A)(B), (A)(A)(A), (A)(B)(A), (B)(B)(B), (B)(B)(A), (A)(A)(A)(A), (A)(A)(B)(B), (A)(A)(A)(B), (B)(B)(B)(B), (B)(B)(B)(A), (A)(A)(A)(A)(A), (A)(B)(A)(B)(A), (A)(B)(B)(B)(A), or mixtures thereof.
The method of claim 59 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product formed by any combination of:
wherein R is H, C4H9, C8H17, or C9H19; and/or
The method of claim 53 wherein the at least one oligomeric or polymeric aminic antioxidant is an oligomerization or polymerization reaction product selected from the group consisting of:
wherein R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, R4 is a styrene or C1 to C30 alkyl, p, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The method of claim 53 wherein the at least one regenerated oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product of:
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is at least 2; R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached; with at least one monomeric aminic antioxidant comprising:
wherein R is H, C4H9, C8H17, or C9H19; and/or
The method of claim 53 wherein the lubricating oil base stock is present in an amount from about 1 to about 80 weight percent, based on the total weight of the lubricating oil.
The method of claim 53 wherein the at least one monomeric aminic antioxidant is present in an amount from about 4 to about 8 weight percent, based on the total weight of the lubricating oil.
The method of claim 53 wherein the at least one oligomeric or polymeric aminic antioxidant is present in an amount from about 1 to about 8 weight percent, based on the total weight of the lubricating oil.
The method of claim 53 wherein the formulated oil further comprises one or more of a viscosity modifier, dispersant, detergent, other antioxidant, pour point depressant, corrosion inhibitor, metal deactivator, seal compatibility additive, anti-foam agent, inhibitor, and anti-rust additive.
The method of claim 67 wherein the other antioxidant comprises at least one aromatic amine antioxidant, at least one phenolic antioxidant, or mixtures thereof.
The method of claim 53 wherein the at least one oligomeric or polymeric aminic antioxidant is formed over time in situ during a Sequence IIIH engine test in accordance with ASTM D8111-17, or a General Motors Oxidation and Deposit Test (GMOD) in accordance with GMW17043, 2nd Edition, May 2016.
The method of claim 53 wherein the lubricating oil is a passenger vehicle engine oil (PVEO), a commercial vehicle engine oil (CVEO), or a lubricating oil that is subjected to heat and oxidative conditions.
A lubricating oil having a composition comprising a lubricating oil base stock as a major component, and at least one oligomeric or polymeric aminic antioxidant, as a minor component; wherein, in an engine or other mechanical component lubricated with the lubricating oil, the at least one oligomeric or polymeric aminic antioxidant is formed over time in situ from at least one monomeric aminic antioxidant during operation of the engine or other mechanical component; wherein the at least one oligomeric or polymeric aminic antioxidant is dissipated over time in the lubricating oil during operation of the engine or other mechanical component; wherein the lubricating oil base stock is present in an amount from about 1 to about 95 weight percent, based on the total weight of the lubricating oil; and wherein the at least one monomeric aminic antioxidant is present in an amount from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil.
The lubricating oil of claim 71 wherein, in measurements of the lubricating oil by a Sequence IIIH engine test in accordance with ASTM D8111-17, viscosity control and deposit control are improved using a concentration of the at least one monomeric aminic antioxidant from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil, as compared to viscosity control and deposit control achieved using a lower concentration of the at least one monomeric aminic antioxidant.
The lubricating oil of claim 71 wherein the at least one monomeric aminic antioxidant comprises at least one unsubstituted or hydrocarbyl-substituted diphenyl amine, at least one unsubstituted or hydrocarbyl-substituted phenyl naphthyl amine, or mixtures thereof.
The lubricating oil of claim 71 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product of at least one unsubstituted or hydrocarbyl-substituted diphenyl amine, at least one unsubstituted or hydrocarbyl-substituted phenyl naphthyl amine, or both at least one unsubstituted or hydrocarbyl-substituted diphenylamine and at least one unsubstituted or hydrocarbyl-substituted phenyl naphthylamine.
The lubricating oil of claim 71 wherein the at least one monomeric aminic antioxidant comprises:
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is at least 2; R2 is a styrene or
C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The lubricating oil of claim 71 wherein the at least one monomeric aminic antioxidant comprises:
wherein R is H, C4H9, C8H17, or C9H19; and/or
The lubricating oil of claim 71 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product of
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is at least 2; R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The lubricating oil of claim 77 wherein the at least one oligomeric or polymeric aminic antioxidant is an oligomerization or polymerization reaction product comprising: (A)(A), (A)(B), (B)(B), (A)(A)(B), (A)(A)(A), (A)(B)(A), (B)(B)(B), (B)(B)(A), (A)(A)(A)(A), (A)(A)(B)(B), (A)(A)(A)(B), (B)(B)(B)(B), (B)(B)(B)(A), (A)(A)(A)(A)(A), (A)(B)(A)(B)(A), (A
The lubricating oil of claim 77 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product formed by any combination of:
wherein R is H, C4H9, C8H17, or C9H19; and/or
The lubricating oil of claim 71 wherein the at least one oligomeric or polymeric aminic antioxidant is an oligomerization or polymerization reaction product selected from the group consisting of:
wherein R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, R4 is a styrene or C1 to C30 alkyl, p, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The lubricating oil of claim 71 wherein the lubricating oil base stock is present in an amount from about 1 to about 80 weight percent, based on the total weight of the to lubricating oil.
The lubricating oil of claim 71 wherein the at least one monomeric aminic antioxidant is present in an amount from about 4 to about 8 weight percent, based on the total weight of the lubricating oil.
The lubricating oil of claim 71 wherein the at least one oligomeric or polymeric aminic antioxidant is present in an amount from about 1 to about 8 weight percent, based on the total weight of the lubricating oil.
The lubricating oil of claim 71 wherein the formulated oil further comprises one or more of a viscosity modifier, dispersant, detergent, other antioxidant, pour point depressant, corrosion inhibitor, metal deactivator, seal compatibility additive, anti-foam agent, inhibitor, and anti-rust additive.
The lubricating oil of claim 84 wherein the other antioxidant comprises at least one aromatic amine antioxidant, at least one phenolic antioxidant, or mixtures thereof.
The lubricating oil of claim 71 wherein the at least one oligomeric or polymeric aminic antioxidant is formed over time in situ during a Sequence IIIH engine test in accordance with ASTM D8111-17, or a General Motors Oxidation and Deposit Test (GMOD) in accordance with GMW17043, 2nd Edition, May 2016.
The lubricating oil of claim 71 which is a passenger vehicle engine oil (PVEO), a commercial vehicle engine oil (CVEO), or a lubricating oil that is subjected to heat and oxidative conditions.
A lubricating oil having a composition comprising a lubricating oil base stock as a major component, and at least one monomeric aminic antioxidant, as a minor component; wherein, in an engine or other mechanical component lubricated with the lubricating oil, at least one oligomeric or polymeric aminic antioxidant is formed over time in situ from the at least one monomeric aminic antioxidant during operation of the engine or other mechanical component; wherein the at least one oligomeric or polymeric aminic antioxidant is dissipated over time in the lubricating oil during operation of the engine or other mechanical component; wherein the lubricating oil base stock is present in an amount from about 1 to about 95 weight percent, based on the total weight of the lubricating oil; and wherein the at least one monomeric aminic antioxidant is present in an amount from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil.
The lubricating oil of claim 88 wherein, in measurements of the lubricating oil by a Sequence IIIH engine test in accordance with ASTM D8111-17, viscosity control and deposit control are improved using a concentration of the at least one monomeric aminic antioxidant from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil, as compared to viscosity control and deposit control achieved using a lower concentration of the at least one monomeric aminic antioxidant.
The lubricating oil of claim 88 wherein the at least one monomeric aminic antioxidant comprises at least one unsubstituted or hydrocarbyl-substituted diphenyl amine, at least one unsubstituted or hydrocarbyl-substituted phenyl naphthyl amine, or mixtures thereof.
The lubricating oil of claim 88 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product of at least one unsubstituted or hydrocarbyl-substituted diphenyl amine, at least one unsubstituted or hydrocarbyl-substituted phenyl naphthyl amine, or both at least one unsubstituted or hydrocarbyl-substituted diphenylamine and at least one unsubstituted or hydrocarbyl-substituted phenyl naphthylamine.
The lubricating oil of claim 88 wherein the at least one monomeric to aminic antioxidant comprises:
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is at least 2; R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The lubricating oil of claim 88 wherein the at least one monomeric aminic antioxidant comprises:
wherein R is H, C4H9, C8H17, or C9H19; and/or
The lubricating oil of claim 88 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product of
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is at least 2; R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The lubricating oil of claim 94 wherein the at least one oligomeric or polymeric aminic antioxidant is an oligomerization or polymerization reaction product comprising: (A)(A), (A)(B), (B)(B), (A)(A)(B), (A)(A)(A), (A)(B)(A), (B)(B)(B), (B)(B)(A), (A)(A)(A)(A), (A)(A)(B)(B), (A)(A)(A)(B), (B)(B)(B)(B), (B)(B)(B)(A), (A)(A)(A)(A)(A), (A)(B)(A)(B)(A), (A)(B)(B)(B)(A), or mixtures thereof.
The lubricating oil of claim 94 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product formed by any combination of:
wherein R is H, C4H9, C8H17, or C9H19; and/or
The lubricating oil of claim 88 wherein the at least one oligomeric or to polymeric aminic antioxidant is an oligomerization or polymerization reaction product selected from the group consisting of:
wherein R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, R4 is a styrene or C1 to C30 alkyl, p, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The lubricating oil of claim 88 wherein the lubricating oil base stock is present in an amount from about 1 to about 80 weight percent, based on the total weight of the lubricating oil.
The lubricating oil of claim 88 wherein the at least one monomeric aminic antioxidant is present in an amount from about 4 to about 8 weight percent, based on the total weight of the lubricating oil.
The lubricating oil of claim 88 wherein the at least one oligomeric or polymeric aminic antioxidant is present in an amount from about 1 to about 8 weight percent, based on the total weight of the lubricating oil.
The lubricating oil of claim 88 wherein the formulated oil further comprises one or more of a viscosity modifier, dispersant, detergent, other antioxidant, pour point depressant, corrosion inhibitor, metal deactivator, seal compatibility additive, anti-foam agent, inhibitor, and anti-rust additive.
The lubricating oil of claim 101 wherein the other antioxidant comprises at least one aromatic amine antioxidant, at least one phenolic antioxidant, or mixtures thereof.
The lubricating oil of claim 88 wherein the at least one oligomeric or polymeric aminic antioxidant is formed over time in situ during a Sequence IIIH engine test in accordance with ASTM D8111-17, or a General Motors Oxidation and Deposit Test (GMOD) in accordance with GMW17043, 2nd Edition, May 2016.
The lubricating oil of claim 88 which is a passenger vehicle engine oil (PVEO), a commercial vehicle engine oil (CVEO), or a lubricating oil that is subjected to heat and oxidative conditions.
A lubricating oil having a composition comprising a lubricating oil base stock as a major component, and at least one oligomeric or polymeric aminic antioxidant and at least one monomeric aminic antioxidant, as minor components; wherein, in an engine or other mechanical component lubricated with the lubricating oil, the at least one oligomeric or polymeric aminic antioxidant and the at least one monomeric aminic antioxidant react to form over time in situ at least one oligomeric or polymeric aminic antioxidant reaction product during operation of the engine or other mechanical component; wherein the at least one oligomeric or polymeric aminic antioxidant reaction product is dissipated over time in the lubricating oil during operation of the engine or other mechanical component; wherein the lubricating oil base stock is present in an amount from about 1 to about 95 weight percent, based on the total weight of the lubricating oil; wherein the at least one oligomeric or polymeric aminic antioxidant is present in an amount from greater than about 0.1 to about 10 weight percent, based on the total weight of the lubricating oil; and wherein the at least one monomeric aminic antioxidant is present in an amount from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil.
The lubricating oil of claim 105 wherein, in measurements of the lubricating oil by a Sequence IIIH engine test in accordance with ASTM D8111-17, viscosity control and deposit control are improved using a concentration of the at least one monomeric aminic antioxidant from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil, as compared to viscosity control and deposit control achieved using a lower concentration of the at least one monomeric aminic antioxidant.
The lubricating oil of claim 105 wherein the at least one monomeric aminic antioxidant comprises at least one unsubstituted or hydrocarbyl-substituted diphenyl amine, at least one unsubstituted or hydrocarbyl-substituted phenyl naphthyl amine, or mixtures thereof.
The lubricating oil of claim 105 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product of at least one unsubstituted or hydrocarbyl-substituted diphenyl amine, at least one unsubstituted or hydrocarbyl-substituted phenyl naphthyl amine, or both at least one unsubstituted or hydrocarbyl-substituted diphenylamine and at least one unsubstituted or hydrocarbyl-substituted phenyl naphthylamine.
The lubricating oil of claim 105 wherein the at least one monomeric aminic antioxidant comprises:
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is at least 2; R2 is a styrene or
C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The lubricating oil of claim 105 wherein the at least one monomeric aminic antioxidant comprises:
wherein R is H, C4H9, C8H17, or C9H19; and/or
The lubricating oil of claim 105 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product of
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is at least 2; R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The lubricating oil of claim 111 wherein the at least one oligomeric or polymeric aminic antioxidant is an oligomerization or polymerization reaction product comprising: (A)(A), (A)(B), (B)(B), (A)(A)(B), (A)(A)(A), (A)(B)(A), (B)(B)(B), (B)(B)(A), (A)(A)(A)(A), (A)(A)(B)(B), (A)(A)(A)(B), (B)(B)(B)(B), (B)(B)(B)(A), (A)(A)(A)(A)(A), (A)(B)(A)(B)(A), (A)(B)(B)(B)(A), or mixtures thereof.
The lubricating oil of claim 111 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product formed by any combination of:
wherein R is H, C4H9, C8H17, or C9H19; and/or
The lubricating oil of claim 105 wherein the at least one oligomeric or polymeric aminic antioxidant is an oligomerization or polymerization reaction product selected from the group consisting of:
wherein R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, R4 is a styrene or C1 to C30 alkyl, p, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The method of claim 105 wherein the at least one oligomeric or polymeric aminic antioxidant reaction product is the oligomerization or polymerization reaction product of:
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is at least 2; R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached; with at least one monomeric aminic antioxidant comprising:
wherein R is H, C4H9, C8H17, or C9H19; and/or
The lubricating oil of claim 105 wherein the lubricating oil base stock is present in an amount from about 1 to about 80 weight percent, based on the total weight of the lubricating oil.
The lubricating oil of claim 105 wherein the at least one monomeric aminic antioxidant is present in an amount from about 4 to about 8 weight percent, based on the total weight of the lubricating oil.
The lubricating oil of claim 105 wherein the at least one oligomeric or polymeric aminic antioxidant is present in an amount from about 1 to about 8 weight percent, based on the total weight of the lubricating oil.
The lubricating oil of claim 105 wherein the formulated oil further comprises one or more of a viscosity modifier, dispersant, detergent, other antioxidant, pour point depressant, corrosion inhibitor, metal deactivator, seal compatibility additive, anti-foam agent, inhibitor, and anti-rust additive.
The lubricating oil of claim 119 wherein the other antioxidant comprises at least one aromatic amine antioxidant, at least one phenolic antioxidant, or mixtures thereof.
The lubricating oil of claim 105 wherein the at least one oligomeric or polymeric aminic antioxidant is formed over time in situ during a Sequence IIIH engine test in accordance with ASTM D8111-17, or a General Motors Oxidation and Deposit Test (GMOD) in accordance with GMW17043, 2nd Edition, May 2016.
The lubricating oil of claim 105 which is a passenger vehicle engine oil (PVEO), a commercial vehicle engine oil (CVEO), or a lubricating oil that is subjected to to heat and oxidative conditions.
A lubricating oil having a composition comprising a lubricating oil base stock as a major component, and at least one oligomeric or polymeric aminic antioxidant and at least one monomeric aminic antioxidant, as minor components; wherein, in an engine or other mechanical component lubricated with the lubricating oil, the at least one oligomeric or polymeric aminic antioxidant dissipates over time in the lubricating oil during operation of the engine or other mechanical component; wherein the at least one oligomeric or polymeric aminic antioxidant and the at least one monomeric aminic antioxidant react to form over time in situ at least one regenerated oligomeric or polymeric aminic antioxidant during operation of the engine or other mechanical component; wherein the lubricating oil base stock is present in an amount from about 1 to about 95 weight percent, based on the total weight of the lubricating oil; wherein the at least one oligomeric or polymeric aminic antioxidant is present in an amount from greater than about 0.1 to about 10 weight percent, based on the total weight of the lubricating oil; and wherein the at least one monomeric aminic antioxidant is present in an amount from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil.
The lubricating oil of claim 123 wherein, in measurements of the lubricating oil by a Sequence IIIH engine test in accordance with ASTM D8111-17, viscosity control and deposit control are improved using a concentration of the at least one monomeric aminic antioxidant from greater than about 2 to about 10 weight percent, based on the total weight of the lubricating oil, as compared to viscosity control and deposit control achieved using a lower concentration of the at least one monomeric aminic antioxidant.
The lubricating oil of claim 123 wherein the at least one monomeric aminic antioxidant comprises at least one unsubstituted or hydrocarbyl-substituted diphenyl amine, at least one unsubstituted or hydrocarbyl-substituted phenyl naphthyl amine, or mixtures thereof.
The lubricating oil of claim 123 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product of at least one unsubstituted or hydrocarbyl-substituted diphenyl amine, at least one unsubstituted or hydrocarbyl-substituted phenyl naphthyl amine, or both at least one unsubstituted or hydrocarbyl-substituted diphenylamine and at least one unsubstituted or hydrocarbyl-substituted phenyl naphthylamine.
The lubricating oil of claim 123 wherein the at least one monomeric aminic antioxidant comprises:
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is at least 2; R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The lubricating oil of claim 123 wherein the at least one monomeric aminic antioxidant comprises:
wherein R is H, C4H9, C8H17, or C9H19; and/or
The lubricating oil of claim 123 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product of
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is at least 2; R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The lubricating oil of claim 129 wherein the at least one oligomeric or polymeric aminic antioxidant is an oligomerization or polymerization reaction product comprising: (A)(A), (A)(B), (B)(B), (A)(A)(B), (A)(A)(A), (A)(B)(A), (B)(B)(B), (B)(B)(A), (A)(A)(A)(A), (A)(A)(B)(B), (A)(A)(A)(B), (B)(B)(B)(B), (B)(B)(B)(A), (A)(A)(A)(A)(A), (A)(B)(A)(B)(A), (A)(B)(B)(B)(A), or mixtures thereof.
The lubricating oil of claim 129 wherein the at least one oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product formed by any combination of:
wherein R is H, C4H9, C8H17, or C9H19; and/or
The lubricating oil of claim 123 wherein the at least one oligomeric or polymeric aminic antioxidant is an oligomerization or polymerization reaction product selected from the group consisting of:
wherein R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, R4 is a styrene or C1 to C30 alkyl, p, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached.
The method of claim 123 wherein the at least one regenerated oligomeric or polymeric aminic antioxidant is the oligomerization or polymerization reaction product of:
wherein (A) and (B) each range from zero to 10, provided (A)+(B) is at least 2; R2 is a styrene or C1 to C30 alkyl, R3 is a styrene or C1 to C30 alkyl, q and y individually range from 0 to up to the valence of the aryl group to which the respective R groups are attached; with at least one monomeric aminic antioxidant comprising:
wherein R is H, C4H9, C8H17, or C9H19; and/or
The lubricating oil of claim 123 wherein the lubricating oil base stock is present in an amount from about 1 to about 80 weight percent, based on the total weight of the lubricating oil.
The lubricating oil of claim 123 wherein the at least one monomeric aminic antioxidant is present in an amount from about 4 to about 8 weight percent, based on the total weight of the lubricating oil.
The lubricating oil of claim 123 wherein the at least one oligomeric or polymeric aminic antioxidant is present in an amount from about 1 to about 8 weight percent, based on the total weight of the lubricating oil.
The lubricating oil of claim 123 wherein the formulated oil further comprises one or more of a viscosity modifier, dispersant, detergent, other antioxidant, pour point depressant, corrosion inhibitor, metal deactivator, seal compatibility additive, anti-foam agent, inhibitor, and anti-rust additive.
The lubricating oil of claim 137 wherein the other antioxidant comprises at least one aromatic amine antioxidant, at least one phenolic antioxidant, or mixtures thereof.
The lubricating oil of claim 123 wherein the at least one regenerated oligomeric or polymeric aminic antioxidant is formed overtime in situ during a Sequence IIIH engine test in accordance with ASTM D8111-17, or a General Motors Oxidation and Deposit Test (GMOD) in accordance with GMW17043, 2nd Edition, May 2016.
The lubricating oil of claim 123 which is a passenger vehicle engine oil (PVEO), a commercial vehicle engine oil (CVEO), or a lubricating oil that is subjected to heat and oxidative conditions.
All patents and patent applications, test procedures (such as ASTM methods, UL methods, and the like), and other documents cited herein are fully incorporated by reference to the extent such disclosure is not inconsistent with this disclosure and for all jurisdictions in which such incorporation is permitted.
When numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated. While the illustrative embodiments of the disclosure have been described with particularity, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the disclosure. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and descriptions set forth herein but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present disclosure, including all features which would be treated as equivalents thereof by those skilled in the art to which the disclosure pertains.
The present disclosure has been described above with reference to numerous embodiments and specific examples. Many variations will suggest themselves to those skilled in this art in light of the above detailed description. All such obvious variations are within the full intended scope of the appended claims
This application claims the benefit of U.S. Provisional Application No. 62/781,720, filed on Dec. 19, 2018, and is also related to U.S. Provisional Application No. 62/781,751, filed on Dec. 19, 2018 the entire contents of which are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| 62781720 | Dec 2018 | US |
