WO2020131515A2 - Compositions lubrifiantes à contrôle d'usure amélioré - Google Patents

Compositions lubrifiantes à contrôle d'usure amélioré Download PDF

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Publication number
WO2020131515A2
WO2020131515A2 PCT/US2019/065651 US2019065651W WO2020131515A2 WO 2020131515 A2 WO2020131515 A2 WO 2020131515A2 US 2019065651 W US2019065651 W US 2019065651W WO 2020131515 A2 WO2020131515 A2 WO 2020131515A2
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Prior art keywords
base stock
cst
viscosity
base
blend
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PCT/US2019/065651
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English (en)
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WO2020131515A3 (fr
Inventor
Samuel FLORES-TORRES
Michael L. Alessi
Gary Christensen
David G.L. Holt
Kathleen K. Cooper
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Exxonmobil Research And Engineering Company
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Publication of WO2020131515A2 publication Critical patent/WO2020131515A2/fr
Publication of WO2020131515A3 publication Critical patent/WO2020131515A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/10—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/003—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/58—Elastohydrodynamic lubrication, e.g. for high compressibility layers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • This disclosure relates to lubricating fluids and oil formulations which provide improved wear control.
  • this disclosure relates to lubricant compositions, methods for improving wear control, while maintaining or improving energy efficiency, in a mechanical component having sliding or rolling between contacting surfaces, methods for controlling traction coefficient (Tc) of lubricant compositions, and methods for controlling film thickness of lubricant compositions.
  • Tc traction coefficient
  • the lubricant compositions of this disclosure are useful as finished gear, transmission, engine or industrial lubricants.
  • EHL elastohydrodynamic lubrication
  • EHL is the mode of lubrication that exists in non-conforming concentrated contacts. Examples include the contact between meshing gear teeth used in hypoid axles, worm gears, etc. and between the components in a rolling element bearing. In these contacts the load is supported over a very small contact area which results in very high contact pressures. As lubricants are drawn into the contact zone by the movement of the component surfaces, the lubricant experiences an increase in pressure. Pressures on the order of 1 GPa and above are common in EHL contacts. Most lubricating oils exhibit a large increase in viscosity in response to higher pressures. It is this characteristic that results in the separation of the two surfaces in the contact zone.
  • the lubricant is sheared under these high-pressure conditions.
  • the shearing losses depend on how the oil behaves under these extreme conditions.
  • the properties of the oil under high pressure in turn, depend on the type of base stocks used in the manufacture of the finished lubricant.
  • the generation of the EHL film is governed by what happens in the inlet region of the contact; however, the energy losses are governed by what happens when the lubricant is sheared in the high-pressure central contact region.
  • the resistance of the lubricant to the shearing effects within an EHL contact is referred to as traction.
  • the traction response is dominated by the behavior of the lubricant under shear in the central high contact pressure region of an EHL contact.
  • the traction properties generally depend on the base stock type.
  • Traction coefficients can be defined as the traction force divided by the normal force.
  • the traction force is the force transmitted across a sheared EHL film.
  • the normal force or contact load is the force of one element (such as a roller) pushing down on a second element. Therefore, the traction coefficient is a non-dimensional measure of the shear resistance imparted by a lubricant under EHL conditions.
  • Lower traction coefficients result in lower shearing forces and hence less energy loss if the two surfaces are in relative motion. Low traction is believed to be related to improved fuel economy, increased energy efficiency, reduced operating temperatures, and improved durability. In certain applications where energy loss is dominated by shearing of a lubricant (such as worm gearbox), energy efficiency directly correlates with the traction coefficient.
  • Traction coefficient of a blend can be lower than traction predicted as a linear combination of traction coefficient of straight base stocks with corresponding viscosity. It is however, higher than the traction coefficients of its components. When taken to its extreme this approach uses base stocks with highest and lowest practical viscosities and is called extreme modal blending.
  • This disclosure relates to lubricating fluids and oil formulations which provide improved wear control.
  • this disclosure relates to lubricant compositions, methods for improving wear control, while maintaining or improving energy efficiency, in a mechanical component having sliding or rolling between contacting surfaces, methods for controlling traction coefficient (Tc) of lubricant compositions, and methods for controlling film thickness of lubricant compositions.
  • Tc traction coefficient
  • the lubricant compositions of this disclosure are useful as finished gear, transmission, engine or industrial lubricants.
  • This disclosure also relates in part to a method for improving wear control, while maintaining or improving energy efficiency, in a mechanical component having sliding or rolling between contacting surfaces.
  • the method involves using a lubricant composition in the mechanical component having sliding or rolling between contacting surfaces.
  • the lubricant composition has a base stock blend as a major component, and at least one lubricant additive, as a minor component.
  • the base stock blend has at least one first base stock having a viscosity from about 1 cSt to about 50 cSt at 40°C as determined by ASTM D-445, and at least one second base stock having viscosity from about 100 cSt to about 2000 cSt at 40°C as determined by ASTM D-445.
  • the first base stock is present in an amount greater than about 50 to about 95 weight percent of the base stock blend
  • the second base stock is present in an amount from about 5 to less than about 50 weight percent of the base stock blend.
  • the second base stock is miscible with the first base stock.
  • This disclosure further relates in part to a lubricant composition having a base stock blend as a major component, and at least one lubricant additive, as a minor component.
  • the base stock blend has at least one first base stock having a viscosity from about 1 cSt to about 50 cSt at 40°C as determined by ASTM D-445, and at least one second base stock having viscosity from about 100 cSt to about 2000 cSt at 40°C as determined by ASTM D-445.
  • the first base stock is present in an amount greater than about 50 to about 95 weight percent of the base stock blend, and the second base stock is present in an amount from about 5 to less than about 50 weight percent of the base stock blend.
  • the second base stock is miscible with the first base stock.
  • This disclosure yet further relates in part to a method for controlling traction coefficient (Tc) of a lubricant composition.
  • the method involves blending at least one first base stock with at least one second base stock to give a base stock blend.
  • the first base stock has a viscosity from about 1 cSt to about 50 cSt at 40°C as determined by ASTM D-445
  • the second base stock has a viscosity from about 100 cSt to about 2000 cSt at 40°C as determined by ASTM D-445.
  • the first base stock is miscible with the second base stock.
  • the first base stock is present in the base stock blend in an amount sufficient to control traction coefficient (Tc) of the lubricant composition.
  • This disclosure also relates in part to a method for controlling film thickness of a lubricant composition.
  • the method involves blending at least one first base stock with at least one second base stock to give a base stock blend.
  • the first base stock has a viscosity from about 1 cSt to about 50 cSt at 40°C as determined by ASTM D-445
  • the second base stock has a viscosity from about 100 cSt to about 2000 cSt at 40°C as determined by ASTM D-445.
  • the second base stock is miscible with the first base stock.
  • the second base stock is present in the base stock blend in an amount sufficient to control film thickness of the lubricant composition.
  • This disclosure further relates in part to a method for improving wear control, while maintaining or improving energy efficiency, in a mechanical component having sliding or rolling between contacting surfaces.
  • the method comprises using a lubricant composition in the mechanical component having sliding or rolling between contacting surfaces.
  • the lubricant composition comprises a base stock blend as a major component, and at least one lubricant additive, as a minor component.
  • the base stock blend comprises at least one first base stock having a viscosity from about 1 cSt to about 50 cSt at 40°C as determined by ASTM D-445, and at least one second base stock having viscosity from about 1 cSt to about 50 cSt at 40°C as determined by ASTM D-445.
  • the first base stock is different from the second base stock.
  • the first base stock is present in an amount greater than about 50 to about 95 weight percent of the base stock blend, and the second base stock is present in an amount from about 5 to less than about 50 weight percent of the base stock blend.
  • the second base stock is miscible with the first base stock.
  • This disclosure yet further relates in part to a lubricant composition
  • a lubricant composition comprising a base stock blend as a major component, and at least one lubricant additive, as a minor component.
  • the base stock blend comprises at least one first base stock having a viscosity from about 1 cSt to about 50 cSt at 40°C as determined by ASTM D-445, and at least one second base stock having viscosity from about 1 cSt to about 50 cSt at 40°C as determined by ASTM D-445.
  • the first base stock is different from the second base stock.
  • the first base stock is present in an amount greater than about 50 to about 95 weight percent of the base stock blend, and the second base stock is present in an amount from about 5 to less than about 50 weight percent of the base stock blend.
  • the second base stock is miscible with the first base stock.
  • the unique base stock blend has at least one first base stock having a viscosity from about 1 cSt to about 50 cSt at 40°C as determined by ASTM D-445, and at least one second base stock having viscosity from about 100 cSt to about 2000 cSt at 40°C as determined by ASTM D-445.
  • the first base stock and second base stock are miscible with each other.
  • the first base stock is present in an amount greater than about 50 to about 95 weight percent of the base stock blend, and the second base stock is present in an amount from about 5 to less than about 50 weight percent of the base stock blend.
  • traction coefficient is controlled by concentration of the first base stock
  • film thickness is controlled by the concentration of the second base stock.
  • the unique base stock blend has at least one first base stock having a viscosity from about 1 cSt to about 50 cSt at 40°C as determined by ASTM D- 445, and at least one second base stock having viscosity from about 100 cSt to about 2000 cSt at 40°C as determined by ASTM D-445.
  • the first base stock and second base stock are miscible with each other.
  • the first base stock is present in an amount greater than about 50 to about 95 weight percent of the base stock blend, and the second base stock is present in an amount from about 5 to less than about 50 weight percent of the base stock blend.
  • Fig. 1 graphically shows traction performance for neat base oils, PAO 4, PAO 8, PAO 40, PAO 100, mPAO 150, mPAO 300, and mPAO 600, in accordance with the Examples.
  • Fig. 2 graphically shows traction performance for blends made with constant high viscosity base oil (mPAO 150) and varied low viscosity base oil (i.e., PAO 2, PAO 4, PAO 6 or PAO 8) under conditions lGPa, 25% SRR at 100°C, in accordance with the Examples.
  • Fig. 3 graphically shows traction performance for blends of multiple high molecular weight PAO polymers (PAO 100, mPAO 150, mPAO 300, mPAO 600, mPAO 1000) with PAO 4, in accordance with the Examples.
  • Fig. 4 graphically shows traction performance for PAO bimodal blends made by mixing high viscosity base oil (i.e., PAO 40, PAO 100, mPAO 150, mPAO 300, mPAO 600 or mPAO 1000) with a low viscosity base oil PAO 4 under conditions lGPa, 25% SRR at 100°C, in accordance with the Examples.
  • high viscosity base oil i.e., PAO 40, PAO 100, mPAO 150, mPAO 300, mPAO 600 or mPAO 1000
  • Fig. 5 graphically shows that traction coefficient is controlled by the low viscosity component of bimodal blends and is independent of finish oil viscosity, in accordance with the Examples.
  • Fig. 6 graphically shows that, at a low concentration of high viscosity base oils, the traction increased unexpectedly as the concentration of PAO 4 increased (viscosity decreasing), in accordance with the Examples.
  • Fig. 7 shows an illustrative mechanical contact zone.
  • Fig. 8 shows gears, bearings and other high load/high pressure applications that rely on elastohydrodynamic (EHD) lubrication (EHL) to maintain effective separation between moving parts in equipment leading to reduced friction and enhanced durability.
  • EHD elastohydrodynamic
  • “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).
  • Oil 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.
  • 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” or“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.
  • “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.
  • 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., 13 C 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 13 C 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 13 C 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 13 C 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.
  • 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.
  • kinematic viscosity values in this disclosure are as determined pursuant to ASTM D445.
  • KV100 Kinematic viscosity at 100°C
  • KV40 kinematic viscosity at 40°C
  • Unit of all KV100 and KV40 values herein is cSt unless otherwise specified.
  • the kinematic viscosity at 100°C is expected to vary less than 0.2 cSt as measured by ASTM D445.
  • NV Noack volatility
  • CCS viscosity CCSV
  • ASTM 5293 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.
  • This disclosure relates to a new approach for selecting and blending base oils and co base oils that can reduce the probability of metal to metal contact under mid to extreme lubrication conditions, thereby increasing durability of equipment and efficiency.
  • wear protection is improved by inducing a phase transition/separation (e.g. liquid to liquid, or solid to liquid) in the mechanical contact.
  • phase transition/separation e.g. liquid to liquid, or solid to liquid
  • this transition allows the formulator to use very low concentrations of a heavy base oil with unexpected film benefits while maintaining a lower bulk viscosity for better efficiency.
  • the function of a lubricant is to generate a thin film that separates a surface from its moving counterpart with the goal of reducing friction and wear at operating conditions.
  • This disclosure will mitigate wear and frictional losses through the use of carefully selected base oils that will generate a very high viscosity film or solid film via phase separation in the contact zone, thereby improving durability and energy efficiency.
  • This disclosure provides a solution to this problem by providing a sacrificial solid film in the contact maintaining or increasing equipment protection while the bulk viscosity of the lubricant is lower.
  • characteristics that predominantly control the properties of the fluids in the contact zone have been identified, particularly for a selected group of PAO single-component base fluids and PAO bimodal blends.
  • An illustrative mechanical contact zone is shown in Fig. 7.
  • EHD elastohydrodynamic
  • EHL elastohydrodynamic lubrication
  • the EHD film thickness depends on the oil volume entrained in the inlet, and this is determined by the velocity and rheology of the lubricant.
  • the rheology of the lubricant is controlled by the physical properties (e.g., temperature, pressure, molecular structure or composition of the fluid) and the mechanics of the system (e.g., geometry, bodies within contact).
  • the EHD contact can be, for example, a piezoviscous elastic contact. This contact is defined as a system where there is an elastic deformation effect excerpted by the pressure on the lubricant (e.g., viscosity increase) and the solid bodies making the contact (e.g., metal-metal contact), and this effect cannot be neglected.
  • the pressurized fluid within a contact is described by the Reynolds equation, and the pressure profile in the metal surface is described by Hertz equations.
  • the non-conforming contact zones, composed of metal-lubricant-metal are under extreme high pressure, up to 4 GPa. See Fig. 8. Under these high pressure conditions, the lubricant significantly increases in viscosity and the slope or profile of viscosity change versus pressure is called the pressure viscosity coefficient, alpha a.
  • the pressure viscosity coefficient, alpha a, value depends on the chemistry of the fluids as well as the composition of the blend and is one of the most important parameters that control film thickness (h) in the contact zone. Furthermore, conventional understanding is that film thickness is controlled by viscosity (which varies with temperature and pressure) as well as operation values such as speed, load, surface geometry, roughness, and material properties. Surprisingly, in accordance with this disclosure, film thickness was shown to be dependent upon the high viscosity fluid concentration, particularly within the same bimodal blend family (i.e., PAO).
  • Friction is present in all moving systems. Friction is generated due to the resistance of two sliding surfaces. In accordance with this disclosure, the work in part is with two surfaces separated by a lubricant in the EHD region, therefore, the friction observed is coming from the resistance to flow of the lubricant in the contact area. This friction is often called traction. The term traction is often used to define fluid intermolecular friction within the EHD contacts.
  • Traction is the friction caused by the molecules moving in adjacent shear planes to each other and traction is defined as the total shear stress over the entire contact area.
  • the traction coefficient is defined as shear stress divided by the pressure over the whole contact.
  • the fluid In the EHD contact (high pressure), the fluid has a viscosity that is so high that it behaves more like a solid than a liquid. Consequently, the traction observed is consistent with the measure of the shearing force of a semi-solidified fluid.
  • These forces are controlled by the high pressure rheology of the fluid which are controlled by the intermolecular friction (i.e., the resistance to flow), which results in generation of heat and loss of efficiency in the system.
  • lubricants having base oil blends are provided that are suitable for use in machines with various degrees of sliding, i.e., non-conforming
  • the disclosure is directed in general to lubricant compositions having a base stock blend.
  • film thickness is controlled by the concentration of one base stock
  • traction coefficient (Tc) is controlled by concentration of another base stock, in the base stock blend.
  • the lubricant compositions are useful as finished gear, transmission, engine, and industrial lubricants and in a preferred embodiment are used as lubricants for non-conforming concentrated contacts with high sliding such as spur gears, helical gears, hypoid gears, bevel gears, worm gears and the like.
  • the lubricant compositions have a base stock blend as a major component, and at least one lubricant additive, as a minor component.
  • the base stock blend comprises at least one first base stock having a viscosity from about 1 cSt to about 50 cSt at 40°C as determined by ASTM D-445, and at least one second base stock having viscosity from about 100 cSt to about 2000 cSt at 40°C as determined by ASTM D-445.
  • the first base stock is present in an amount greater than about 50 to about 95 weight percent of the base stock blend, and the second base stock is present in an amount from about 5 to less than about 50 weight percent of the base stock blend.
  • the second base stock is miscible with the first base stock.
  • the first base stock has a viscosity from about 1 cSt to about 50 cSt at 40°C, preferably about 1 cSt to about 40 cSt at 40°C, more preferably about 1.25 cSt to about 30 cSt at 40°C, and even more preferably about 1.5 cSt to about 20 cSt at 40°C, as determined by ASTM D-445.
  • the second base stock has viscosity from about 100 cSt to about 2000 cSt at 40°C, preferably about 100 cSt to about 1800 cSt at 40°C, more preferably about 125 cSt to about 1600 cSt at 40°C, and even more preferably about 150 cSt to about 1500 cSt at 40°C, as determined by ASTM D-445.
  • the first base stock is present in an amount greater than about 50 to about 95 weight percent, preferably from about 60 to about 95 weight percent, more preferably from about 70 to about 95 weight percent, even more preferably from about 80 to about 95 weight percent, of the base stock blend.
  • the second base stock is present in an amount from about 5 to less than about 50 weight percent, preferably from about 5 to about 40 weight percent, more preferably from about 5 to about 30 weight percent, even more preferably from about 5 to about 20 weight percent, of the base stock blend.
  • the first and second base stocks are miscible with each other.
  • the base stock blend is present in an amount from about 70 to about 95 weight percent, preferably from about 75 to about 95 weight percent, more preferably from about 80 to about 95 weight percent, even more preferably from about 85 to about 95 weight percent, of the lubricant composition.
  • the first base stock has a traction coefficient (Tc) from about 0.008 to about 0.015, preferably from about 0.008 to about 0.011, more preferably from about 0.008 to about 0.01, as determined by MTM TC Method.
  • the second base stock has a traction coefficient (Tc) from about 0.008 to about 0.025, preferably from about 0.09 to about 0.02, more preferably from about 0.01 to about 0.02, as determined by MTM TC Method.
  • the lubricant compositions of this disclosure have a traction coefficient (Tc) of less than 0.15, preferably from about 0.15 to about 0.0001, preferably from about 0.015 to about 0.001, as determined by MTM TC Method.
  • Tc traction coefficient
  • traction coefficient (Tc) is independent of viscosity of the lubricant composition.
  • the base stock blend is a bimodal blend.
  • miscible takes its ordinary meaning of the ability to mix in all proportions. For purposes of this disclosure, miscibility is determined at 25°C and 1 atm.
  • Fluids e.g., base stocks
  • API American Petroleum Institute
  • the lubricant compositions of this disclosure may contain other fluids in addition to the first and second base stocks.
  • the lubricant compositions may have a third fluid that can be a high viscosity or low viscosity fluid, or other combinations of fluids.
  • the first base stock can be selected from a Group I, Group II, Group III, Group IV or Group V base oil
  • the second base stock can be selected from a Group I, Group II, Group III, Group IV or Group V base oil.
  • the first base stock can be a polyalphaolefm (PAO) base oil
  • the second base stock can be a polyalphaolefin (PAO) base oil or a metallocene catalyzed polyalphaolefm (PAO) base oil.
  • the lubricant compositions of this disclosure may contain one or more first base stocks, and/or one or more second base stocks.
  • the lubricant compositions can further include one or more of a viscosity modifier, dispersant, detergent, antioxidant, pour point depressant, corrosion inhibitor, metal deactivator, seal compatibility additive, anti-foam agent, inhibitor, and anti-rust additive.
  • a viscosity modifier dispersant, detergent, antioxidant, pour point depressant, corrosion inhibitor, metal deactivator, seal compatibility additive, anti-foam agent, inhibitor, and anti-rust additive.
  • 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 rerefmed (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.
  • 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 polyalphaolefms (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, hydrorefmed, or solvent extracted.
  • Group II and/or Group III hydroprocessed or hydrocracked base stocks including synthetic oils such as polyalphaolefms, 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-alphaolefm copolymers, for example).
  • Polyalphaolefm (PAO) oil base stocks are commonly used synthetic hydrocarbon oil.
  • PAOs derived from Cs, Cio, C12, C14 olefins or mixtures thereof may be utilized. See U.S. Patent Nos. 4,956,122; 4,827,064; and 4,827,073.
  • the number average molecular weights of the PAOs 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 alphaolefms which include, but are not limited to, C2 to about C32 alphaolefms with the C8 to about Ci 6 alphaolefms, such as 1 -hexene, 1-octene, 1-decene, 1-dodecene and the like, being preferred.
  • the preferred polyalphaolefms are poly- 1 -hexene, poly- 1-octene, poly- 1-decene and poly- 1-dodecene and mixtures thereof and mixed olefin-derived polyolefins.
  • the dimers of higher olefins in the range of Cu to Cis may be used to provide low viscosity base stocks of acceptably low volatility.
  • 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 alphaolefm in the presence of a polymerization catalyst such as the Friedel-Crafts catalysts including, for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate.
  • 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.
  • a polymerization catalyst such as the Friedel-Crafts catalysts including, for example, aluminum trichloride, boro
  • 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,
  • 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
  • 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,
  • an aromatic compound such as naphthalene
  • 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.
  • 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.
  • 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.
  • strong acids such as AlCb, BF3, or HF may be used.
  • milder catalysts such as FeCb or SnCb are preferred.
  • Newer alkylation technology uses zeolites or solid super acids.
  • 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.
  • LHDC specialized lube hydrocracking
  • crystalline hydrocracking/hydroisomerization catalyst preferably a zeolitic catalyst.
  • ZSM-48 as described in U.S. Patent 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. Patent Nos. 2,817,693; 4,975,177; 4,921,594 and 4,897,178 as well as in British Patent Nos.
  • 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.
  • Gas-to-Liquids (GTL) 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.
  • hydroisomerized base oils are recited in U.S. Patent Nos. 6,080,301; 6,090,989, and 6,165,949 for example, and are incorporated herein in their entirety by reference.
  • the hydrocarbyl aromatics can be used as base oil or base oil component and can be any hydrocarbyl molecule that contains at least 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 Cr > up to about C6o with a range of about Cs 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.
  • 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.
  • an aromatic compound such as benzene or naphthalene
  • 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.
  • 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.
  • strong acids such as AlCb, BF3, or HF may be used.
  • milder catalysts such as FeCb or SnCU are preferred.
  • Newer alkylation technology uses zeolites or solid super acids.
  • Esters comprise a useful base stock. Additive solvency and seal compatibility characteristics may be secured by the use of esters such as the esters of dibasic acids with monoalkanols and the polyol esters of monocarboxylic acids.
  • Esters of the former type include, for example, the esters of dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc., with a variety of alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, etc.
  • dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n- hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, etc.
  • Particularly useful synthetic esters are those which are obtained by reacting one or more polyhydric alcohols, preferably the hindered polyols (such as the neopentyl polyols, e.g., neopentyl glycol, trimethylol ethane, 2-methyl-2-propyl-l, 3 -propanediol, trimethylol propane, pentaerythritol and dipentaerythritol) with alkanoic acids containing at least about 4 carbon atoms, preferably Cs to C30 acids such as saturated straight chain fatty acids including caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, and behenic acid, or the corresponding branched chain fatty acids or unsaturated fatty acids such as oleic acid, or mixtures of any of these materials.
  • the hindered polyols such as the neopentyl polyo
  • Suitable synthetic ester components include the esters of trimethylol propane, trimethylol butane, trimethylol ethane, pentaerythritol and/or dipentaerythritol with one or more monocarboxylic acids containing from about 5 to about 10 carbon atoms. These esters are widely available commercially, for example, the Mobil P-41 and P-51 esters of ExxonMobil Chemical Company.
  • esters derived from renewable material such as coconut, palm, rapeseed, soy, sunflower and the like. These esters may be monoesters, di-esters, polyol esters, complex esters, or mixtures thereof. These esters are widely available commercially, for example, the Mobil P-51 ester of ExxonMobil Chemical Company.
  • Engine oil formulations containing renewable esters are included in this disclosure.
  • the renewable content of the ester is typically greater than about 70 weight percent, preferably more than about 80 weight percent and most preferably more than about 90 weight percent.
  • 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-Li quids (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 Gas-to-Li quids
  • 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
  • GTL base stock(s) and/or base oil(s) derived from GTL materials are characterized typically as having kinematic viscosities at 100°C of from about 2 mm 2 /s to about 50 mm 2 /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).
  • GTL base stock(s) and/or base oil(s) are typically highly paraffinic (>90% saturates), and may contain mixtures of monocycloparaffms and multicycloparaffms in combination with non-cyclic isoparaffins.
  • the ratio of the naphthenic (i.e., cycloparaffm) content in such combinations varies with the catalyst and temperature used.
  • 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.
  • the absence of phosphorous and aromatics make this materially especially suitable for the formulation of low SAP products.
  • 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 lubricant compositions 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.
  • the base oil constitutes the major component of the engine oil lubricant composition of the present disclosure and typically is present in an amount ranging from about 50 to about 99 weight percent, preferably from about 70 to about 95 weight percent, and more preferably from about 85 to about 95 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-ignited 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 mm 2 /s) at 100°C and preferably of about 2.5 cSt to about 9 cSt (or mm 2 /s) at 100° C.
  • a kinematic viscosity according to ASTM standards, of about 2.5 cSt to about 12 cSt (or mm 2 /s) at 100°C and preferably of about 2.5 cSt to about 9 cSt (or mm 2 /s) at 100° C.
  • Mixtures of synthetic and natural base oils may be used if desired.
  • Bi-modal mixtures of Group I, II, III, IV, and/or V base stocks may be used if desired.
  • the lubricant compositions useful in the present disclosure may additionally contain one or more of the commonly used lubricant performance additives including but not limited to antioxidants, dispersants, detergents, 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.
  • the commonly used lubricant performance additives including but not limited to antioxidants, dispersants, detergents, antiwear additives, corrosion inhibitors, rust inhibitors, metal deactivators, extreme pressure additives, anti-seizure agents, wax modifiers, viscosity index improvers, viscos
  • 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 lubricant compositions. See, Klamann in Lubricants and Related Products, op cite, and U.S. Patent Nos. 4,798,684 and 5,084,197, for example.
  • Useful antioxidants include hindered phenols. These phenolic antioxidants may be ashless (metal-free) phenolic compounds or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are the hindered phenolics which are the ones which contain a sterically hindered hydroxyl group, and these include those derivatives of dihydroxy aryl compounds in which the hydroxyl groups are in the o- or p-position to each other. Typical phenolic antioxidants include the hindered phenols substituted with C6+ alkyl groups and the alkylene coupled derivatives of these hindered phenols.
  • phenolic materials of this type 2-t-butyl-4-heptyl phenol; 2-t-butyl-4-octyl phenol; 2-t-butyl-4-dodecyl phenol; 2,6-di-t- butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol; 2-methyl-6-t-butyl-4-heptyl phenol; and 2-methyl-6-t-butyl-4-dodecyl phenol.
  • Other useful hindered mono-phenolic antioxidants may include for example hindered 2,6-di-alkyl-phenolic proprionic ester derivatives.
  • Bis-phenolic antioxidants may also be advantageously used in combination with the instant disclosure.
  • ortho-coupled phenols include: 2,2’-bis(4-heptyl-6-t-butyl-phenol); 2,2’-bis(4-octyl- 6-t-butyl-phenol); and 2,2’-bis(4-dodecyl-6-t-butyl-phenol).
  • Para-coupled bisphenols include for example 4,4’-bis(2,6-di-t-butyl phenol) and 4,4’-methylene-bis(2,6-di-t-butyl phenol).
  • catalytic antioxidants comprise an effective amount of a) one or more oil soluble polymetal organic compounds; and, effective amounts ofb) one or more substituted N,N'-diaryl-o-phenylenediamine compounds or c) one or more hindered phenol compounds; or a combination of both b) and c).
  • Catalytic antioxidants are more fully described in U.S. Patent No. 8, 048,833, herein incorporated by reference in its entirety.
  • Non-phenolic oxidation inhibitors which may be used include aromatic amine antioxidants and these may be used either as such or in combination with phenolics.
  • Typical examples of non-phenolic antioxidants include: alkylated and non-alkylated aromatic amines such as aromatic monoamines of the formula R 8 R 9 R 10 N where R 8 is an aliphatic, aromatic or substituted aromatic group, R 9 is an aromatic or a substituted aromatic group, and R 10 is H, alkyl, aryl or R u S(0)xR 12 where R 11 is an alkylene, alkenylene, or aralkylene group, R 12 is a higher alkyl group, or an alkenyl, aryl, or alkaryl group, and x is 0, 1 or 2.
  • the aliphatic group R 8 may contain from 1 to about 20 carbon atoms, and preferably contains from about 6 to 12 carbon atoms.
  • the aliphatic group is a saturated aliphatic group.
  • both R 8 and R 9 are aromatic or substituted aromatic groups, and the aromatic group may be a fused ring aromatic group such as naphthyl.
  • Aromatic groups R 8 and R 9 may be joined together with other groups such as S.
  • Typical aromatic amines antioxidants have alkyl substituent groups of at least about 6 carbon atoms.
  • Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally, the aliphatic groups will not contain more than about 14 carbon atoms.
  • the general types of amine antioxidants useful in the present compositions include diphenylamines, phenyl naphthylamines, phenothiazines, imidodibenzyls and diphenyl phenylene diamines. Mixtures of two or more aromatic amines are also useful. Polymeric amine antioxidants can also be used.
  • aromatic amine antioxidants useful in the present disclosure include: p,p’- dioctyldiphenylamine; t-octylphenyl-alpha-naphthylamine; phenyl-alphanaphthylamine; and p-octylphenyl-alpha-naphthylamine.
  • Sulfurized alkyl phenols and alkali or alkaline earth metal salts thereof also are useful antioxidants.
  • Preferred antioxidants include hindered phenols, arylamines. These antioxidants may be used individually by type or in combination with one another. Such additives may be used in an amount of about 0.01 to 5 weight percent, preferably about 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. Dispersants
  • Dispersants help keep these byproducts in solution, thus diminishing their deposition on metal surfaces.
  • Dispersants used in the formulation of the lubricant may be ashless or ash-forming in nature.
  • the dispersant is ashless.
  • So called ashless dispersants are organic materials that form substantially no ash upon combustion.
  • non-metal-containing or borated metal-free dispersants are considered ashless.
  • 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)alkenyl succinic 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. Patent Nos. 3,172,892; 3,215,707; 3,219,666; 3,316,177; 3,341,542;
  • hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride derivatives are useful dispersants.
  • 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. Patent 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.
  • suitable alkanol amines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines and polyalkenylpolyamines such as polyethylene polyamines.
  • propoxylated hexamethylenediamine Representative examples are shown in U.S. Patent 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. Patent 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. Patent 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. Patent 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. Patent 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:
  • 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); M n 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 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).
  • GPC gel permeation chromatography
  • 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 (M w ) to number average molecular weight (Mn).
  • MWD molecular weight distribution
  • M w weight average molecular weight
  • Mn number average molecular weight
  • 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.
  • such polymers comprise interpolymers of ethylene and at least one alpha-olefin of the above formula, wherein R 1 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.
  • 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. Patent 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 Cioo, 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.
  • the dispersant concentrations are given on an“as delivered” basis.
  • 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.
  • 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.
  • TBN total base number
  • 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.
  • 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.
  • alkaline earth metal hydroxide or oxide Ca(OH)2, BaO, Ba(OH)2, MgO, Mg(OH)2, for example
  • 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.
  • 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.
  • the sulfurized product may be obtained by methods well known in the art. These methods include heating a mixture of alkylphenol and sulfurizing agent (including elemental sulfur, sulfur halides such as sulfur dichloride, and the like) and then reacting the sulfurized phenol with an alkaline earth metal base.
  • metal salts of carboxylic acids are preferred detergents.
  • 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
  • R is an alkyl group having 1 to about 30 carbon atoms
  • n is an integer from 1 to 4
  • M is an alkaline earth metal.
  • Preferred R groups are alkyl chains of at least Cn, 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. Patent 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. Patent 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 lubricant compositions 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 lubricant composition.
  • the detergent concentrations are given on an“as delivered” basis.
  • 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.
  • Viscosity modifiers also known as viscosity index improvers (VI improvers), and viscosity improvers
  • VI improvers viscosity index improvers
  • Viscosity modifiers 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.
  • 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“Hi TEC®” (such as “HiTEC® 5850B”; and from The Lubrizol Corporation under the trade designation“Lubrizol® 7067C”.
  • Hydrogenated polyisoprene star polymers are commercially available from Infmeum International Limited, e.g., under the trade designation“SV200” and“SV600”.
  • Hydrogenated diene-styrene block copolymers are commercially available from Infmeum 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 AstericTM (e.g., Lubrizol 87708 and Lubrizol 87725).
  • Viscoplex® e.g., Viscoplex 6-954
  • AstericTM 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 is a polymeric block derived predominantly from vinyl aromatic hydrocarbon monomer
  • B is a polymeric block derived predominantly from conjugated diene monomer
  • 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 lubricant composition. Viscosity modifiers are typically added as concentrates, in large amounts of diluent oil.
  • the viscosity modifier concentrations are given on an“as delivered” basis.
  • 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.
  • pour point depressants also known as lube oil flow improvers
  • pour point depressants may be added to lubricant compositions of the present disclosure to lower the minimum temperature at which the fluid will flow or can be poured.
  • suitable pour point depressants include polymethacrylates, polyacrylates, polyarylamides, condensation products of haloparaffm waxes and aromatic compounds, vinyl carboxylate polymers, and terpolymers of dialkylfumarates, vinyl esters of fatty acids and allyl vinyl ethers.
  • 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 lubricants 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 are additives that protect lubricated metal surfaces against chemical attack by water or other contaminants. A wide variety of these are commercially available.
  • 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.
  • 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 lubricant compositions 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.
  • illustrative friction modifiers useful in the lubricant compositions 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.
  • glycerol polyols these can include trimethylolpropane, pentaerythritol, sorbitan, and the like.
  • 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.
  • 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 lubricant compositions 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 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 can be a useful component of the lubricant compositions of this disclosure.
  • ZDDP can be derived from primary alcohols, secondary alcohols or mixtures thereof.
  • ZDDP compounds generally are of the formula
  • R 1 and R 2 are C I -C I X 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 lubricant, although more or less can often be used advantageously.
  • 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 lubricant composition.
  • lubricant 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.
  • 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 lubricant composition.
  • Anti-foam Agent 0.001-3 0.001-0.15
  • 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 concentrations of the low and high viscosity base stock blends described herein have the ability to control traction coefficient and film thickness in the lubricant compositions incorporating the blends.
  • the use of these fluid blends is desirable in lubricant compositions in the presence of salicylate, sulfonate and phenate detergents, along with antioxidants and ashless antioxidants, along with succinimide based dispersants, along with zinc dialkyldithiophosphates, along with organic and metallic friction modifiers, along with corrosion inhibitors, and along with defoamants.
  • the low and high viscosity base stock blends are useful in all lubricant applications.
  • the disclosure is directed to base stock blends useful in the preparation of finished gear, transmission, engine, and industrial lubricants, and in a preferred embodiment are used as lubricants for non-conforming concentrated contacts with high sliding such as spur gears, helical gears, hypoid gears, bevel gears, worm gears and the like.
  • Lubricant compositions according to the present disclosure are particularly useful in applications wherein there are EHL contacts that have a component of sliding. Examples include spherical roller bearings, deep groove ball bearings, angular contact bearings among others. Additionally, most gear systems contain multiple sliding EHL contacts between meshing gear teeth. Examples include spur gears, helical gears, hypoid gears, bevel bears, worm gears, and the like.
  • Worm gears form an extended elliptical contact against the wheel and operate under high sliding EHL conditions. Therefore, there is a significant benefit to the lubricant compositions of this disclosure in terms of energy savings.
  • Rolling element bearings have many configurations and depending on the type of configuration, there may or may not be a benefit to having a lubricant composition of this disclosure. This may also be determined by one of ordinary skill in the art in possession of the present disclosure. Where there is sliding between the ball and the raceway, the oil is being sheared such that the lubricants described in this disclosure will reduce the energy losses.
  • the present disclosure is particularly beneficial in any system that includes machine elements that contain gears of any kind and rolling element bearings.
  • Examples of such systems include electricity generating systems, industrial manufacturing equipment such as paper, steel and cement mills, hydraulic systems, automotive drive trains, aircraft propulsion systems, etc. It will be recognized by one of ordinary skill in the art in possession of the present disclosure that the various embodiments set forth herein, including preferred and more preferred embodiments, may be combined in a manner consistent with achieving desired lubricant properties.
  • the Examples focus are directed to traction and pressure viscosity coefficient behaviors of PAO lubricant base fluids and their blends.
  • the Examples are separated into two parts, selected single-component lubricant base stocks and selected two-component binary blends of these same lubricants.
  • the lubricants were tested in a Mini-Traction Machine (MTM).
  • MTM Mini-Traction Machine
  • traction coefficient was determined by a PCS Instruments MTM using standard steel specimens, a lubricant temperature of 100°C, a 1.0 GPa peak contact pressure, a lubricant entraining velocity of 2 ms, and a 25% slide-to-roll ratio (hereinafter "MTM TC
  • Suitable MTM testing properties include, for example, 0.1 to 3.5 GPa, peak contact pressure, -40°C to 200°C lubricant temperature, and a lubricant entraining velocity of from 0.25 to 10.0 m/s. Other methods can be used to determine traction coefficient provided the
  • viscosity was determined by ASTM D-445.
  • mPAO 150 is SpectraSyn Elite® 150
  • mPAO 300 is SpectraSyn Elite® 300
  • mPAO 600 is 600 cSt Alpha Olefin
  • mPAO 1000 is 1000 cSt Alpha Olefin.
  • a further listing of base oils used in the Examples is set forth in Table 3 below.
  • Bimodal blends were done in two ways as shown in Table 3. First, a series of low viscosity base oil (i.e., PAO 2, PAO 4, PAO 6 or PAO 8) were blended with the high viscosity base oil mPAO150. Second, a series of high viscosity base oil (i.e., PAO 100, mPAO 150, mPAO 300, mPAO 600 or mPAO 1000) were blended with a low viscosity base oil PAO 4.
  • Table 4 shows bimodal blend results for kinematic viscosity determined by ASTM D-445, and traction coefficient determined by MTM TC Method.
  • Fig. 1 graphically shows traction performance for neat base oils, PAO 4, PAO 8, PAO 40, PAO 100, mPAO 150, mPAO 300, and mPAO 600.
  • Fig. 1 shows the following: tractions increase as the viscosity of the base oils increase up to a KV 40; neat oil traction responses reach a plateau around PAO40 or before; variability of the test increases as traction increases (arrow lines); and after viscosity surpasses mPAO 150, shear heating effects contribution (shear heating) has a substantial effect on traction performance.
  • the base oil mPAO 150 was mixed with a variety of low viscosity (LV) base oils (i.e., PAO 2, PAO 4, PAO 6 or PAO 8) to make the fluids in Table 3.
  • LV low viscosity
  • Fig. 2 graphically shows traction performance for blends made with constant high viscosity base oil (mPAO 150) and varied low viscosity base oil (i.e., PAO 2, PAO 4, PAO 6 or PAO 8) under conditions lGPa, 25% SRR at 100°C. Traction coefficient shows a clear dependency on oil viscosity and type of low viscosity component.
  • mPAO 150 constant high viscosity base oil
  • PAO 2 varied low viscosity base oil
  • Fig. 2 shows the following: as the concentration of the low viscosity component is increased, the viscosity of the fluid decreases and traction also decreases; a significant decrease in traction also observed when the LV fluid was replaced with a lower molecular weight fluid; at the same concentration of LV component, traction trend behave as follows: PAO 8 > PA06 > PA04 > PAO 2; and in the case of PAO 2 and PAO 8, minimum traction points were observed lower than the neat LV component.
  • the PAO 2 mixtures and PAO 2 neat are situated outside of the EHL region (mix boundary region), hence having higher traction due to metal-metal contact.
  • the base oil PAO 4 was blended with a variety of high viscosity (HV) base oils at different ratios (i.e., PAO 100, mPAO 150, mPAO 300, mPAO 600 or mPAO 1000) with the traction subsequently measured.
  • HV high viscosity
  • Fig. 3 graphically shows traction performance for blends of multiple high molecular weight PAO polymers (PAO 100, mPAO 150, mPAO 300, mPAO 600, mPAO 1000) with PAO 4.
  • Fig. 3 shows traction increase as viscosity of the bimodal blends increase.
  • Fig. 3 shows the following: the expected behavior of traction being controlled by viscosity; and extreme bimodal behavior confirmed, meaning the more separation of the viscosities of the components used to make the final fluids, the lower the traction at the same viscosity.
  • Fig. 4 graphically shows traction performance for PAO bimodal blends made by mixing high viscosity base oil (i.e., PAO 40, PAO 100, mPAO 150, mPAO 300, mPAO 600 or mPAO 1000) with a low viscosity base oil PAO 4 under conditions lGPa, 25% SRR at 100°C.
  • Fig. 4 shows that traction coefficients are predominantly controlled by PA04 concentration, and are independent of the high viscosity component and finished oil KV.
  • Fig. 5 graphically shows that traction coefficient is controlled by the low viscosity component of bimodal blends and is independent of finish oil viscosity.
  • Fig. 6 graphically shows that traction coefficient is controlled by high viscosity base oil (i.e., Lucant base oil) at concentration higher than 15 percent by weight. At a low

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  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

La présente invention concerne un procédé permettant d'améliorer la régulation de l'usure, tout en maintenant ou en améliorant l'efficacité énergétique, dans une pièce mécanique ayant un glissement ou un roulement entre des surfaces de contact. Le procédé implique l'utilisation d'une composition lubrifiante dans la pièce mécanique ayant un glissement ou un roulement entre des surfaces de contact. La composition lubrifiante comprend un mélange de matières de base en tant que constituant principal, et au moins un additif lubrifiant, en tant que constituant secondaire. Le mélange de charge de base a au moins une première charge de base présentant une viscosité de 1 à 50 cSt à 40 °C et au moins une seconde charge de base ayant une viscosité de 100 à 2 000 cSt à 40 °C. La première charge de base est présente en une quantité supérieure à une valeur située dans la plage allant de 50 à 95 % en poids du mélange de la charge de base, et la seconde charge de base est présente en une quantité située entre 5 et moins de 50 % en poids du mélange de charge de base. La seconde charge de base est miscible avec la première charge de base.
PCT/US2019/065651 2018-12-19 2019-12-11 Compositions lubrifiantes à contrôle d'usure amélioré WO2020131515A2 (fr)

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US11345872B2 (en) * 2020-01-30 2022-05-31 ExxonMobil Technology and Engineering Company Sulfur-free, ashless, low phosphorus lubricant compositions with improved oxidation stability

Citations (95)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US479A (en) 1837-11-23 Improvement in windmills
US2655A (en) 1842-05-30 Manner of constructing portable tents
US1815022A (en) 1930-05-03 1931-07-14 Standard Oil Dev Co Hydrocarbon oil and process for manufacturing the same
US2015748A (en) 1933-06-30 1935-10-01 Standard Oil Dev Co Method for producing pour inhibitors
US2100993A (en) 1934-12-14 1937-11-30 Rohm & Haas Process for preparing esters and products
US2191498A (en) 1935-11-27 1940-02-27 Socony Vacuum Oil Co Inc Mineral oil composition and method of making
US2387501A (en) 1944-04-04 1945-10-23 Du Pont Hydrocarbon oil
US2666746A (en) 1952-08-11 1954-01-19 Standard Oil Dev Co Lubricating oil composition
US2721877A (en) 1951-08-22 1955-10-25 Exxon Research Engineering Co Lubricating oil additives and a process for their preparation
US2721878A (en) 1951-08-18 1955-10-25 Exxon Research Engineering Co Strong acid as a polymerization modifier in the production of liquid polymers
US2817693A (en) 1954-03-29 1957-12-24 Shell Dev Production of oils from waxes
US3036003A (en) 1957-08-07 1962-05-22 Sinclair Research Inc Lubricating oil composition
US3087936A (en) 1961-08-18 1963-04-30 Lubrizol Corp Reaction product of an aliphatic olefinpolymer-succinic acid producing compound with an amine and reacting the resulting product with a boron compound
US3172892A (en) 1959-03-30 1965-03-09 Reaction product of high molecular weight succinic acids and succinic anhydrides with an ethylene poly- amine
US3200107A (en) 1961-06-12 1965-08-10 Lubrizol Corp Process for preparing acylated amine-cs2 compositions and products
US3215707A (en) 1960-06-07 1965-11-02 Lubrizol Corp Lubricant
US3250715A (en) 1964-02-04 1966-05-10 Lubrizol Corp Terpolymer product and lubricating composition containing it
US3272746A (en) 1965-11-22 1966-09-13 Lubrizol Corp Lubricating composition containing an acylated nitrogen compound
US3275554A (en) 1963-08-02 1966-09-27 Shell Oil Co Polyolefin substituted polyamines and lubricants containing them
US3316177A (en) 1964-12-07 1967-04-25 Lubrizol Corp Functional fluid containing a sludge inhibiting detergent comprising the polyamine salt of the reaction product of maleic anhydride and an oxidized interpolymer of propylene and ethylene
US3322670A (en) 1963-08-26 1967-05-30 Standard Oil Co Detergent-dispersant lubricant additive having anti-rust and anti-wear properties
US3329658A (en) 1962-05-14 1967-07-04 Monsanto Co Dispersency oil additives
US3382291A (en) 1965-04-23 1968-05-07 Mobil Oil Corp Polymerization of olefins with bf3
US3413347A (en) 1966-01-26 1968-11-26 Ethyl Corp Mannich reaction products of high molecular weight alkyl phenols, aldehydes and polyaminopolyalkyleneamines
US3438757A (en) 1965-08-23 1969-04-15 Chevron Res Hydrocarbyl amines for fuel detergents
US3444170A (en) 1959-03-30 1969-05-13 Lubrizol Corp Process which comprises reacting a carboxylic intermediate with an amine
US3449250A (en) 1962-05-14 1969-06-10 Monsanto Co Dispersency oil additives
US3454607A (en) 1969-02-10 1969-07-08 Lubrizol Corp High molecular weight carboxylic compositions
US3454555A (en) 1965-01-28 1969-07-08 Shell Oil Co Oil-soluble halogen-containing polyamines and polyethyleneimines
US3519565A (en) 1967-09-19 1970-07-07 Lubrizol Corp Oil-soluble interpolymers of n-vinylthiopyrrolidones
US3541012A (en) 1968-04-15 1970-11-17 Lubrizol Corp Lubricants and fuels containing improved acylated nitrogen additives
US3595791A (en) 1969-03-11 1971-07-27 Lubrizol Corp Basic,sulfurized salicylates and method for their preparation
US3630904A (en) 1968-07-03 1971-12-28 Lubrizol Corp Lubricating oils and fuels containing acylated nitrogen additives
US3632511A (en) 1969-11-10 1972-01-04 Lubrizol Corp Acylated nitrogen-containing compositions processes for their preparationand lubricants and fuels containing the same
US3652616A (en) 1969-08-14 1972-03-28 Standard Oil Co Additives for fuels and lubricants
US3687849A (en) 1968-06-18 1972-08-29 Lubrizol Corp Lubricants containing oil-soluble graft polymers derived from degraded ethylene-propylene interpolymers
US3697574A (en) 1965-10-22 1972-10-10 Standard Oil Co Boron derivatives of high molecular weight mannich condensation products
US3702300A (en) 1968-12-20 1972-11-07 Lubrizol Corp Lubricant containing nitrogen-containing ester
US3703536A (en) 1967-11-24 1972-11-21 Standard Oil Co Preparation of oil-soluble boron derivatives of an alkylene polyamine-substituted phenol-formaldehyde addition product
US3704308A (en) 1965-10-22 1972-11-28 Standard Oil Co Boron-containing high molecular weight mannich condensation
US3725480A (en) 1968-11-08 1973-04-03 Standard Oil Co Ashless oil additives
US3726882A (en) 1968-11-08 1973-04-10 Standard Oil Co Ashless oil additives
US3742082A (en) 1971-11-18 1973-06-26 Mobil Oil Corp Dimerization of olefins with boron trifluoride
US3751365A (en) 1965-10-22 1973-08-07 Standard Oil Co Concentrates and crankcase oils comprising oil solutions of boron containing high molecular weight mannich reaction condensation products
US3755433A (en) 1971-12-16 1973-08-28 Texaco Inc Ashless lubricating oil dispersant
US3756953A (en) 1965-10-22 1973-09-04 Standard Oil Co Vatives of high molecular weight mannich reaction condensation concentrate and crankcase oils comprising oil solutions of boron deri
US3769363A (en) 1972-03-13 1973-10-30 Mobil Oil Corp Oligomerization of olefins with boron trifluoride
US3787374A (en) 1971-09-07 1974-01-22 Lubrizol Corp Process for preparing high molecular weight carboxylic compositions
US3798165A (en) 1965-10-22 1974-03-19 Standard Oil Co Lubricating oils containing high molecular weight mannich condensation products
US3803039A (en) 1970-07-13 1974-04-09 Standard Oil Co Oil solution of aliphatic acid derivatives of high molecular weight mannich condensation product
GB1350257A (en) 1970-06-05 1974-04-18 Shell Int Research Process for the preparation of a lubricating oil
US3822209A (en) 1966-02-01 1974-07-02 Ethyl Corp Lubricant additives
US3876720A (en) 1972-07-24 1975-04-08 Gulf Research Development Co Internal olefin
GB1390359A (en) 1971-05-13 1975-04-09 Shell Int Research Process for the preparation of lubricating oil with high viscosity index
GB1429494A (en) 1972-04-06 1976-03-24 Shell Int Research Process for the preparation of a lubricating oil
US3948800A (en) 1971-07-01 1976-04-06 The Lubrizol Corporation Dispersant compositions
GB1440230A (en) 1972-08-04 1976-06-23 Shell Int Research Process for the preparation of lubricating oils
US4100082A (en) 1976-01-28 1978-07-11 The Lubrizol Corporation Lubricants containing amino phenol-detergent/dispersant combinations
US4149178A (en) 1976-10-05 1979-04-10 American Technology Corporation Pattern generating system and method
US4218330A (en) 1978-06-26 1980-08-19 Ethyl Corporation Lubricant
US4234435A (en) 1979-02-23 1980-11-18 The Lubrizol Corporation Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation
US4239930A (en) 1979-05-17 1980-12-16 Pearsall Chemical Company Continuous oligomerization process
CA1094044A (fr) 1977-02-25 1981-01-20 Norman A. Meinhardt Traduction non-disponible
US4367352A (en) 1980-12-22 1983-01-04 Texaco Inc. Oligomerized olefins for lubricant stock
US4413156A (en) 1982-04-26 1983-11-01 Texaco Inc. Manufacture of synthetic lubricant additives from low molecular weight olefins using boron trifluoride catalysts
US4426305A (en) 1981-03-23 1984-01-17 Edwin Cooper, Inc. Lubricating compositions containing boronated nitrogen-containing dispersants
US4434408A (en) 1980-03-11 1984-02-28 Sony Corporation Oscillator having capacitor charging and discharging controlled by non-saturating switches
US4454059A (en) 1976-11-12 1984-06-12 The Lubrizol Corporation Nitrogenous dispersants, lubricants and concentrates containing said nitrogenous dispersants
US4594172A (en) 1984-04-18 1986-06-10 Shell Oil Company Process for the preparation of hydrocarbons
US4767551A (en) 1985-12-02 1988-08-30 Amoco Corporation Metal-containing lubricant compositions
US4798684A (en) 1987-06-09 1989-01-17 The Lubrizol Corporation Nitrogen containing anti-oxidant compositions
US4827073A (en) 1988-01-22 1989-05-02 Mobil Oil Corporation Process for manufacturing olefinic oligomers having lubricating properties
US4827064A (en) 1986-12-24 1989-05-02 Mobil Oil Corporation High viscosity index synthetic lubricant compositions
US4897178A (en) 1983-05-02 1990-01-30 Uop Hydrocracking catalyst and hydrocracking process
US4910355A (en) 1988-11-02 1990-03-20 Ethyl Corporation Olefin oligomer functional fluid using internal olefins
US4921594A (en) 1985-06-28 1990-05-01 Chevron Research Company Production of low pour point lubricating oils
US4943672A (en) 1987-12-18 1990-07-24 Exxon Research And Engineering Company Process for the hydroisomerization of Fischer-Tropsch wax to produce lubricating oil (OP-3403)
US4952739A (en) 1988-10-26 1990-08-28 Exxon Chemical Patents Inc. Organo-Al-chloride catalyzed poly-n-butenes process
US4956122A (en) 1982-03-10 1990-09-11 Uniroyal Chemical Company, Inc. Lubricating composition
US4975177A (en) 1985-11-01 1990-12-04 Mobil Oil Corporation High viscosity index lubricants
US5068487A (en) 1990-07-19 1991-11-26 Ethyl Corporation Olefin oligomerization with BF3 alcohol alkoxylate co-catalysts
US5075269A (en) 1988-12-15 1991-12-24 Mobil Oil Corp. Production of high viscosity index lubricating oil stock
EP0464547A1 (fr) 1990-07-05 1992-01-08 Mobil Oil Corporation Production de lubrifiants à haute indice de viscosité
EP0464546A1 (fr) 1990-07-05 1992-01-08 Mobil Oil Corporation Production de lubrifiants à haut indice de viscosité
US5084197A (en) 1990-09-21 1992-01-28 The Lubrizol Corporation Antiemulsion/antifoam agent for use in oils
US5430105A (en) 1992-12-17 1995-07-04 Exxon Chemical Patents Inc. Low sediment process for forming borated dispersant
US5705458A (en) 1995-09-19 1998-01-06 The Lubrizol Corporation Additive compositions for lubricants and functional fluids
US6034039A (en) 1997-11-28 2000-03-07 Exxon Chemical Patents, Inc. Lubricating oil compositions
US6080301A (en) 1998-09-04 2000-06-27 Exxonmobil Research And Engineering Company Premium synthetic lubricant base stock having at least 95% non-cyclic isoparaffins
US6090989A (en) 1997-10-20 2000-07-18 Mobil Oil Corporation Isoparaffinic lube basestock compositions
US6165949A (en) 1998-09-04 2000-12-26 Exxon Research And Engineering Company Premium wear resistant lubricant
US6323164B1 (en) 2000-11-01 2001-11-27 Ethyl Corporation Dispersant (meth) acrylate copolymers having excellent low temperature properties
US20080020950A1 (en) 2006-07-19 2008-01-24 Christopher Gray Lubricating Oil Composition
US7704930B2 (en) 2002-01-31 2010-04-27 Exxonmobil Research And Engineering Company Mixed TBN detergents and lubricating oil compositions containing such detergents
US8048833B2 (en) 2007-08-17 2011-11-01 Exxonmobil Research And Engineering Company Catalytic antioxidants

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7732389B2 (en) * 2005-02-04 2010-06-08 Exxonmobil Chemical Patents Inc. Lubricating fluids with low traction characteristics
US8834705B2 (en) * 2006-06-06 2014-09-16 Exxonmobil Research And Engineering Company Gear oil compositions
JP5398218B2 (ja) * 2008-10-06 2014-01-29 Ｊｘ日鉱日石エネルギー株式会社 潤滑油組成物
US20140113847A1 (en) * 2012-10-24 2014-04-24 Exxonmobil Research And Engineering Company High viscosity index lubricating oil base stock and viscosity modifier combinations, and lubricating oils derived therefrom
US20140274848A1 (en) * 2013-03-15 2014-09-18 Exxonmobil Research And Engineering Company Low traction energy conserving fluids containing base stock blends

Patent Citations (101)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US479A (en) 1837-11-23 Improvement in windmills
US2655A (en) 1842-05-30 Manner of constructing portable tents
US1815022A (en) 1930-05-03 1931-07-14 Standard Oil Dev Co Hydrocarbon oil and process for manufacturing the same
US2015748A (en) 1933-06-30 1935-10-01 Standard Oil Dev Co Method for producing pour inhibitors
US2100993A (en) 1934-12-14 1937-11-30 Rohm & Haas Process for preparing esters and products
US2191498A (en) 1935-11-27 1940-02-27 Socony Vacuum Oil Co Inc Mineral oil composition and method of making
US2387501A (en) 1944-04-04 1945-10-23 Du Pont Hydrocarbon oil
US2721878A (en) 1951-08-18 1955-10-25 Exxon Research Engineering Co Strong acid as a polymerization modifier in the production of liquid polymers
US2721877A (en) 1951-08-22 1955-10-25 Exxon Research Engineering Co Lubricating oil additives and a process for their preparation
US2666746A (en) 1952-08-11 1954-01-19 Standard Oil Dev Co Lubricating oil composition
US2817693A (en) 1954-03-29 1957-12-24 Shell Dev Production of oils from waxes
US3036003A (en) 1957-08-07 1962-05-22 Sinclair Research Inc Lubricating oil composition
US3444170A (en) 1959-03-30 1969-05-13 Lubrizol Corp Process which comprises reacting a carboxylic intermediate with an amine
US3172892A (en) 1959-03-30 1965-03-09 Reaction product of high molecular weight succinic acids and succinic anhydrides with an ethylene poly- amine
US3341542A (en) 1959-03-30 1967-09-12 Lubrizol Corp Oil soluble acrylated nitrogen compounds having a polar acyl, acylimidoyl or acyloxy group with a nitrogen atom attached directly thereto
US3219666A (en) 1959-03-30 1965-11-23 Derivatives of succinic acids and nitrogen compounds
US3215707A (en) 1960-06-07 1965-11-02 Lubrizol Corp Lubricant
US3200107A (en) 1961-06-12 1965-08-10 Lubrizol Corp Process for preparing acylated amine-cs2 compositions and products
US3254025A (en) 1961-08-18 1966-05-31 Lubrizol Corp Boron-containing acylated amine and lubricating compositions containing the same
US3087936A (en) 1961-08-18 1963-04-30 Lubrizol Corp Reaction product of an aliphatic olefinpolymer-succinic acid producing compound with an amine and reacting the resulting product with a boron compound
US3329658A (en) 1962-05-14 1967-07-04 Monsanto Co Dispersency oil additives
US3449250A (en) 1962-05-14 1969-06-10 Monsanto Co Dispersency oil additives
US3275554A (en) 1963-08-02 1966-09-27 Shell Oil Co Polyolefin substituted polyamines and lubricants containing them
US3322670A (en) 1963-08-26 1967-05-30 Standard Oil Co Detergent-dispersant lubricant additive having anti-rust and anti-wear properties
US3250715A (en) 1964-02-04 1966-05-10 Lubrizol Corp Terpolymer product and lubricating composition containing it
US3316177A (en) 1964-12-07 1967-04-25 Lubrizol Corp Functional fluid containing a sludge inhibiting detergent comprising the polyamine salt of the reaction product of maleic anhydride and an oxidized interpolymer of propylene and ethylene
US3454555A (en) 1965-01-28 1969-07-08 Shell Oil Co Oil-soluble halogen-containing polyamines and polyethyleneimines
US3382291A (en) 1965-04-23 1968-05-07 Mobil Oil Corp Polymerization of olefins with bf3
US3565804A (en) 1965-08-23 1971-02-23 Chevron Res Lubricating oil additives
US3438757A (en) 1965-08-23 1969-04-15 Chevron Res Hydrocarbyl amines for fuel detergents
US3756953A (en) 1965-10-22 1973-09-04 Standard Oil Co Vatives of high molecular weight mannich reaction condensation concentrate and crankcase oils comprising oil solutions of boron deri
US3798165A (en) 1965-10-22 1974-03-19 Standard Oil Co Lubricating oils containing high molecular weight mannich condensation products
US3751365A (en) 1965-10-22 1973-08-07 Standard Oil Co Concentrates and crankcase oils comprising oil solutions of boron containing high molecular weight mannich reaction condensation products
US3697574A (en) 1965-10-22 1972-10-10 Standard Oil Co Boron derivatives of high molecular weight mannich condensation products
US3704308A (en) 1965-10-22 1972-11-28 Standard Oil Co Boron-containing high molecular weight mannich condensation
US3272746A (en) 1965-11-22 1966-09-13 Lubrizol Corp Lubricating composition containing an acylated nitrogen compound
US3413347A (en) 1966-01-26 1968-11-26 Ethyl Corp Mannich reaction products of high molecular weight alkyl phenols, aldehydes and polyaminopolyalkyleneamines
US3725277A (en) 1966-01-26 1973-04-03 Ethyl Corp Lubricant compositions
US3822209A (en) 1966-02-01 1974-07-02 Ethyl Corp Lubricant additives
US3519565A (en) 1967-09-19 1970-07-07 Lubrizol Corp Oil-soluble interpolymers of n-vinylthiopyrrolidones
US3666730A (en) 1967-09-19 1972-05-30 Lubrizol Corp Oil-soluble interpolymers of n-vinylthiopyrrolidones
US3703536A (en) 1967-11-24 1972-11-21 Standard Oil Co Preparation of oil-soluble boron derivatives of an alkylene polyamine-substituted phenol-formaldehyde addition product
US3541012A (en) 1968-04-15 1970-11-17 Lubrizol Corp Lubricants and fuels containing improved acylated nitrogen additives
US3687849A (en) 1968-06-18 1972-08-29 Lubrizol Corp Lubricants containing oil-soluble graft polymers derived from degraded ethylene-propylene interpolymers
US3630904A (en) 1968-07-03 1971-12-28 Lubrizol Corp Lubricating oils and fuels containing acylated nitrogen additives
US3725480A (en) 1968-11-08 1973-04-03 Standard Oil Co Ashless oil additives
US3726882A (en) 1968-11-08 1973-04-10 Standard Oil Co Ashless oil additives
US3702300A (en) 1968-12-20 1972-11-07 Lubrizol Corp Lubricant containing nitrogen-containing ester
US3454607A (en) 1969-02-10 1969-07-08 Lubrizol Corp High molecular weight carboxylic compositions
US3595791A (en) 1969-03-11 1971-07-27 Lubrizol Corp Basic,sulfurized salicylates and method for their preparation
US3652616A (en) 1969-08-14 1972-03-28 Standard Oil Co Additives for fuels and lubricants
US3632511A (en) 1969-11-10 1972-01-04 Lubrizol Corp Acylated nitrogen-containing compositions processes for their preparationand lubricants and fuels containing the same
GB1350257A (en) 1970-06-05 1974-04-18 Shell Int Research Process for the preparation of a lubricating oil
US3803039A (en) 1970-07-13 1974-04-09 Standard Oil Co Oil solution of aliphatic acid derivatives of high molecular weight mannich condensation product
GB1390359A (en) 1971-05-13 1975-04-09 Shell Int Research Process for the preparation of lubricating oil with high viscosity index
US3948800A (en) 1971-07-01 1976-04-06 The Lubrizol Corporation Dispersant compositions
US3787374A (en) 1971-09-07 1974-01-22 Lubrizol Corp Process for preparing high molecular weight carboxylic compositions
US3742082A (en) 1971-11-18 1973-06-26 Mobil Oil Corp Dimerization of olefins with boron trifluoride
US3755433A (en) 1971-12-16 1973-08-28 Texaco Inc Ashless lubricating oil dispersant
US3769363A (en) 1972-03-13 1973-10-30 Mobil Oil Corp Oligomerization of olefins with boron trifluoride
GB1429494A (en) 1972-04-06 1976-03-24 Shell Int Research Process for the preparation of a lubricating oil
US3876720A (en) 1972-07-24 1975-04-08 Gulf Research Development Co Internal olefin
GB1440230A (en) 1972-08-04 1976-06-23 Shell Int Research Process for the preparation of lubricating oils
US4100082A (en) 1976-01-28 1978-07-11 The Lubrizol Corporation Lubricants containing amino phenol-detergent/dispersant combinations
US4149178A (en) 1976-10-05 1979-04-10 American Technology Corporation Pattern generating system and method
US4454059A (en) 1976-11-12 1984-06-12 The Lubrizol Corporation Nitrogenous dispersants, lubricants and concentrates containing said nitrogenous dispersants
CA1094044A (fr) 1977-02-25 1981-01-20 Norman A. Meinhardt Traduction non-disponible
US4218330A (en) 1978-06-26 1980-08-19 Ethyl Corporation Lubricant
US4234435A (en) 1979-02-23 1980-11-18 The Lubrizol Corporation Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation
US4239930A (en) 1979-05-17 1980-12-16 Pearsall Chemical Company Continuous oligomerization process
US4434408A (en) 1980-03-11 1984-02-28 Sony Corporation Oscillator having capacitor charging and discharging controlled by non-saturating switches
US4367352A (en) 1980-12-22 1983-01-04 Texaco Inc. Oligomerized olefins for lubricant stock
US4426305A (en) 1981-03-23 1984-01-17 Edwin Cooper, Inc. Lubricating compositions containing boronated nitrogen-containing dispersants
US4956122A (en) 1982-03-10 1990-09-11 Uniroyal Chemical Company, Inc. Lubricating composition
US4413156A (en) 1982-04-26 1983-11-01 Texaco Inc. Manufacture of synthetic lubricant additives from low molecular weight olefins using boron trifluoride catalysts
US4897178A (en) 1983-05-02 1990-01-30 Uop Hydrocracking catalyst and hydrocracking process
US4594172A (en) 1984-04-18 1986-06-10 Shell Oil Company Process for the preparation of hydrocarbons
US4921594A (en) 1985-06-28 1990-05-01 Chevron Research Company Production of low pour point lubricating oils
US4975177A (en) 1985-11-01 1990-12-04 Mobil Oil Corporation High viscosity index lubricants
US4767551A (en) 1985-12-02 1988-08-30 Amoco Corporation Metal-containing lubricant compositions
US4827064A (en) 1986-12-24 1989-05-02 Mobil Oil Corporation High viscosity index synthetic lubricant compositions
US4798684A (en) 1987-06-09 1989-01-17 The Lubrizol Corporation Nitrogen containing anti-oxidant compositions
US4943672A (en) 1987-12-18 1990-07-24 Exxon Research And Engineering Company Process for the hydroisomerization of Fischer-Tropsch wax to produce lubricating oil (OP-3403)
US4827073A (en) 1988-01-22 1989-05-02 Mobil Oil Corporation Process for manufacturing olefinic oligomers having lubricating properties
US4952739A (en) 1988-10-26 1990-08-28 Exxon Chemical Patents Inc. Organo-Al-chloride catalyzed poly-n-butenes process
US4910355A (en) 1988-11-02 1990-03-20 Ethyl Corporation Olefin oligomer functional fluid using internal olefins
US5075269A (en) 1988-12-15 1991-12-24 Mobil Oil Corp. Production of high viscosity index lubricating oil stock
EP0464547A1 (fr) 1990-07-05 1992-01-08 Mobil Oil Corporation Production de lubrifiants à haute indice de viscosité
EP0464546A1 (fr) 1990-07-05 1992-01-08 Mobil Oil Corporation Production de lubrifiants à haut indice de viscosité
US5068487A (en) 1990-07-19 1991-11-26 Ethyl Corporation Olefin oligomerization with BF3 alcohol alkoxylate co-catalysts
US5084197A (en) 1990-09-21 1992-01-28 The Lubrizol Corporation Antiemulsion/antifoam agent for use in oils
US5430105A (en) 1992-12-17 1995-07-04 Exxon Chemical Patents Inc. Low sediment process for forming borated dispersant
US5705458A (en) 1995-09-19 1998-01-06 The Lubrizol Corporation Additive compositions for lubricants and functional fluids
US6090989A (en) 1997-10-20 2000-07-18 Mobil Oil Corporation Isoparaffinic lube basestock compositions
US6034039A (en) 1997-11-28 2000-03-07 Exxon Chemical Patents, Inc. Lubricating oil compositions
US6080301A (en) 1998-09-04 2000-06-27 Exxonmobil Research And Engineering Company Premium synthetic lubricant base stock having at least 95% non-cyclic isoparaffins
US6165949A (en) 1998-09-04 2000-12-26 Exxon Research And Engineering Company Premium wear resistant lubricant
US6323164B1 (en) 2000-11-01 2001-11-27 Ethyl Corporation Dispersant (meth) acrylate copolymers having excellent low temperature properties
US7704930B2 (en) 2002-01-31 2010-04-27 Exxonmobil Research And Engineering Company Mixed TBN detergents and lubricating oil compositions containing such detergents
US20080020950A1 (en) 2006-07-19 2008-01-24 Christopher Gray Lubricating Oil Composition
US8048833B2 (en) 2007-08-17 2011-11-01 Exxonmobil Research And Engineering Company Catalytic antioxidants

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Friedel-Crafts and Related Reactions", vol. 2, 1964, INTER-SCIENCE PUBLISHERS
M. W. RANNEY: "Lubricants and Related Products", 1973, NOYES DATA CORPORATION
W. W. YAUJ. J. KIRKLANDD. D. BLY: "Modern Size Exclusion Liquid Chromatography", 1979, JOHN WILEY AND SONS

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