WO2018067906A1 - Huiles lubrifiantes à haute conductivité pour véhicules électriques et hybrides - Google Patents
Huiles lubrifiantes à haute conductivité pour véhicules électriques et hybrides Download PDFInfo
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- WO2018067906A1 WO2018067906A1 PCT/US2017/055496 US2017055496W WO2018067906A1 WO 2018067906 A1 WO2018067906 A1 WO 2018067906A1 US 2017055496 W US2017055496 W US 2017055496W WO 2018067906 A1 WO2018067906 A1 WO 2018067906A1
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- WIPO (PCT)
- Prior art keywords
- weight percent
- lubricating oil
- group
- lubricating
- weight
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- QFCRAAWGUFQEDF-UHFFFAOYSA-N CCCC(C)(N)OC(C)=O Chemical compound CCCC(C)(N)OC(C)=O QFCRAAWGUFQEDF-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N c1ccccc1 Chemical compound c1ccccc1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
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- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
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- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/24—Compounds containing phosphorus, arsenic or antimony
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- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
- C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
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- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
- C10M135/10—Sulfonic acids or derivatives thereof
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- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
- C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
- C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
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- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
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- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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- C10M169/04—Mixtures of base-materials and additives
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- C10M171/02—Specified values of viscosity or viscosity index
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/06—Well-defined aromatic compounds
- C10M2203/065—Well-defined aromatic compounds used as base material
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- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
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- 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
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- 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
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- 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
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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- 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
- C10N2030/40—Low content or no content compositions
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- 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
- C10N2030/40—Low content or no content compositions
- C10N2030/43—Sulfur free or low sulfur content compositions
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- 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
- C10N2030/52—Base number [TBN]
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- 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
- C10N2040/02—Bearings
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- 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
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- 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
- C10N2040/14—Electric or magnetic purposes
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- 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
- C10N2040/14—Electric or magnetic purposes
- C10N2040/16—Dielectric; Insulating oil or insulators
Definitions
- This disclosure provides lubricating oils for electric and hybrid vehicles as well as mechanical and electrical systems, subsystems, and components for such vehicles.
- This disclosure also provides methods for producing a lubricating oil for electric and hybrid vehicles, as well as mechanical and electrical systems, subsystems, and components for such vehicles.
- Such a lubricating oil may serve as a cooling fluid for electric and hybrid vehicles as well as mechanical and electrical systems, subsystems, and components for such vehicles.
- a major challenge in lubricating or cooling electric and hybrid vehicles as well as mechanical and electrical systems, subsystems, and components for electric and hybrid vehicles is controlling lubricant electrical conductivity over the lifetime of the lubricant while meeting wear protection, oxidation stability, deposit control, and corrosion inhibition requirements.
- the lubricant or cooling fluid composition needs to be compatible with the materials used over a broad temperature range.
- Lubricant electrical conductivity needs to be at the right level and maintained over the service lifetime of the lubricating fluid.
- Lubricants with higher electrical conductivity are advantageous in minimizing electrical charge buildup and sparking, and protect against spark-related wear in high voltage components.
- oil-derived lubricating properties must be maintained despite exposure to high surface temperatures of electrical components in electric and hybrid vehicles.
- this lubricant stability must be balanced with other lubricant properties such as low viscosity and achieving good gear protection.
- Lubricants and working fluids that are used in electric vehicles require a combination of electrical and lubricating properties in order to perform adequately, typically deriving such performance from the components (additives and base stocks) of the fluid compositions.
- Lubricants and working fluid that are useful in such applications are often described as EV lubes (i.e. electrical vehicle lubes).
- EV lubes i.e. electrical vehicle lubes.
- Common understanding of the performance of metal-containing lubricating oil additives is that increasing concentration of such additives generally increases the electrical conductivity of a fluid composition. So controlling the concentrations of metal- containing additives is typically required to achieve desired electrical conductivity targets of finished, fully formulated EV lubes.
- electrical conductivity targets for EV lubes can limit the flexibility of formulating such lubes when using metal-containing lubricating oil additives that simultaneously impact conductivity and deliver performances such as wear protection, cleanliness, deposit protection, and oxidation protection. So achieving a balance between electrical conductivity properties and overall lube performances for EV lubes remains a challange.
- This disclosure describes the surprising finding that metal-containing lubricating oil additives are found to function as either conductivity promoters (increase electrical conductivity) or as conductivity inhibitors (decrease electrical conductivity) when used in a lubricant composition. Finding that certain metal-containing additives functioned as conductivity inhibitors was both surprising and unexpected.
- This disclosure relates to finished lubricant oil compositions having controlled, higher electrical conductivity, at 3,000 pS/m or greater, while maintaining other performance properties of the fluid, by balancing the concentrations of conductivity promotors and conductivity inhibitors in the composition.
- This disclosure relates to EV lube compositions that comprise combinations of conductivity promoters and conductivity inhibitors, with such compositions having both desirable, controlled fluid electrical conductivity, and additional performances such as wear protection, cleanliness, deposit protection, and oxidation protection.
- the lubricating oil has a composition comprising at least about 80 weight percent of a lubricating oil base stock, from about 0.8 to about 5 weight percent of one or more metal detergents, from about 0. to about 5 weight percent of one or more dispersants, from about 0 to about 1.5 weight percent of zinc dialkyldithiophosphate (ZDDP) antiwear agent, from about 0 to about 0.2 weight percent of a molybdenum dialkyldithiocarbamate (MoDTC), from about 0 to about 2 weight percent of a viscosity modifier based on active ingredient, and from about 0.01 to about 5 weight percent of other lubricating oil additives.
- ZDDP zinc dialkyldithiophosphate
- MoDTC molybdenum dialkyldithiocarbamate
- the lubricating oil has an electrical conductivity from about 3,000 pS/m to about 20,000 pS/m and a kinematic viscosity from about 2 cSt to about 20 cSt at 100°C
- This disclosure also relates in part to a lubricating oil for an electric vehicle.
- the lubricating oil has a composition comprising at least about 80 weight percent of a lubricating oil base stock, from about 0.8 to about 1.25 weight percent of one or more metal detergents, from about 0.5 to about 5 weight percent of one or more dispersants, from about 0.6 to 1.5 weight percent of zinc dialkyldithiophosphate (ZDDP) antiwear agent, about 0.15 weight percent of a molybdenum dialkyldithiocarbamate (MoDTC), from about 0 to about 2 weight percent of a viscosity modifier based on active ingredient, and from about 0 to about 5 weight percent of other lubricating oil additives.
- ZDDP zinc dialkyldithiophosphate
- MoDTC molybdenum dialkyldithiocarbamate
- the lubricating oil has an electrical conductivity from about 3,000 pS/m to about 8,000 pS/m and a kinematic viscosity from about 2 cSt to about 20 cSt at 100°C.
- Fig. 1 depicts in tabular form compositions of comparative lubricating oils and inventive lubricating oils having a conductivity from 3,000 to 8,000 pS/m.
- Fig. 2 depicts in tabular form compositions of comparative lubricating oils and inventive lubricating oils having a conductivity from 8,000 to 16,000 pS/m.
- Fig. 3 depicts in tabular form compositions of comparative lubricating oils and inventive lubricating oils having a conductivity from 16,000 to 20,000 pS/m.
- Fig. 4 depicts in tabular form compositions of inventive lubricating oils having a conductivity from 3,000 to 20,000 pS/m.
- Fig. 5 depicts in tabular form compositions of inventive lubricating oils and the effect of conductivity inhibitors.
- Fig. 6 depicts in tabular form compositions of inventive lubricating oils and the effect of conductivity promoters.
- Fig. 7 depicts in tabular form compositions of inventive lubricating oils and the effects of uncapped PIB succinimide dispersant.
- other lubricating oil additives 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.
- the term electric vehicle encompasses all-electric and fully electric vehicles, and hybrid and hybrid electric vehicles, and includes the mechanical and electrical systems, subsystems, and components used in said vehicles. These mechanical and electrical systems, subsystems and components can include, for example, electrical vehicle powertrains, powertrain components, drivetrain components, kinetic energy recovery systems (KERS), energy regenerative systems, and the like.
- KERS kinetic energy recovery systems
- the terms electric vehicle and hybrid vehicle may be used interchangeably.
- the term lubricating oil encompasses lubricating fluids, lubricants, lubricant oils, working fluids, greases, cooling fluids, cooling oils, and coolants; such terms may be used interchangeably.
- the term electric vehicle includes hybrid and hybrid electric vehicles, which may have any of a variety of parallel or series drivetrain configurations, alone or in combination.
- lubricating oil that has one or more lubricating oil additives (e.g., antioxidant, detergent, dispersant, antiwear additive, corrosion inhibitor, viscosity modifier, and metal passivator) in the lubricating oil.
- the formulated oil has a composition comprising a lubricating oil base stock as a major component, and the one or more lubricating oil additives, as a minor component.
- the lubricating oils of this disclosure are particularly advantageous as passenger electric vehicle powertrain oil products.
- the lubricating oils that contain one or more lubricating oil additives are particularly useful in controlling electrical conductivity in low viscosity electric vehicle powertrain oils, the lubricating oils of this disclosure that contain one or more lubricating oil additives are particularly useful in controlling lubricant electrical conductivity to minimize electrical charge buildup and sparking and protect spark-related wear in high votage components, where the lubricating oil has an electrical conductivity from about 3,000 pS/m to about 20,000 pS/m ambient temperature and a kinematic viscosity from about 2 cSt to about 20 cSt at 100°C.
- lubricant electrical conductivity control in electric vehicles is improved and at least one of oxidation stability, deposit control, corrosion inhibition, and lubricant compatability with electric vehicle components and materials over a broad temperature range, are maintained or improved as compared to lubricant electrical conductivity control, oxidation stability, deposit control, corrosion inhibition, and lubricant compatability with electric vehicle components and materials over a broad temperature range, achieved using a lubricating oil containing a minor component other than the one or more lubricating oil additives.
- conductivity promoters include for example one or more of components that increase the conductivity of a lubricating or working fluid.
- conductivity promoters include for example one or more of metal detergents, dispersants, and mixtures thereof.
- metal detergents include, for example, one or more of metal alkyl sulfonates, metal alkyl phenates, metal alkyl salicylates, and mixtures thereof, wherein metals are calcium, magnesium, alkali, or alkaline earth, and wherein such detergents are neutral or overbased, which is typically defined as: neutral (less than 100 TBN), moderately overbased (from about 100 TBN to about 200 TBN), highly overbased (greater than about 200 TBN).
- metal detergents are useful at concentrations of from about 0 weight % to about 6 weight %, about 0 weight % to about 4 weight %, about 0.1 weight % to about 4 weight %, about 0.1 weight % to about 3 weight %, about 0.1 weight % to about 2 weight %, about 0.1 weight % to about 1 weight %.
- neutral metal detergents are useful at concentrations of from about 0 weight % to about 6 weight %, about 0 weight % to about 4 weight %, about 0.1 weight % to about 4 weight %, about 0.1 weight % to about 3 weight %, about 0.1 weight % to about 2 weight %, about 0.1 weight % to about 1 weight %.
- calcium alkyl salicylates are useful at concentrations of from about 0 weight % to about 6 weight %, about 0 weight % to about 4 weight %, about 0.1 weight % to about 3 weight %, about 0.1 weight % to about 2 weight %, about 0.1 weight % to about 1 weight %. More preferably, calcium alkyl salicylates are useful at less than about 0.8 weight %, at less than about 0.5 weight %, at less than about 0.2 weight %, at less than about 0.1 weight %.
- dispersants include, for example, one or more of ashless dispersants, amine-type dispersants, uncapped amine-type dispersants, capped or modified amine-type dispersants, boron-modified amine-type dispersants, zinc-modified amine-type dispersants, amine alkylsuccimmides, polyamine alkylsuccimmides, boron-modified amine alkylsuccimmides, boron-modified polyamine alkylsuccimmides, and metals-modified amine alkylsuccimmides, metals-modified polyamine alkylsuccimmides, amine PIB succinimides, polyamine PIB succinimides, boron-modified amine PIB succinimides, boron-modified polyamine PIB succinimides, and metals-modified amine PIB succinimides, metals-modified polyamine PIB succinimides, metals-modified polyamine
- dispersants are useful at concentrations of from about 0 weight % to about 8 weight %, about 0 weight % to about 6 weight %, about 0.1 weight % to about 6 weight %, about 0.1 weight % to about 5 weight %, about 0.1 weight % to about 4 weight %, about 0.1 weight % to about 3 weight %, about 0.1 weight % to about 2 weight %.
- amine-type dispersants are useful at concentrations of from about 0 weight % to about 8 weight %, about 0 weight % to about 6 weight %, about 0.1 weight % to about 5 weight %, about 0.1 weight % to about 4 weight %, about 0.1 weight % to about 3 weight %, about 0.1 weight % to about 2 weight %.
- polyamine PIB succinimide dispersants which include for example one or more of uncapped polyamine PIB succinimides, capped polyamine PIB succinimides, boron-modified polyamine PIB succinimides, zinc-modified polyamine PIB succinimides, and mixtures thereof, are useful at concentrations of from about 0 weight % to about 8 weight %, about 0 weight % to about 6 weight %, about 0.1 weight % to about 5 weight %, about 0.1 weight % to about 4 weight %, about 0.1 weight % to about 3 weight %, about 0.1 weight % to about 2 weight %.
- conductivity inhibitors include for example one or more of components that decrease the conductivity of a lubricating or working fluid.
- conductivity inhibitors include for example one or more of zinc dialkyldithiophophates (ZDDP), molybdenum organometallic complexes, and mixtures thereof.
- ZDDP zinc dialkyldithiophophates
- magnesium alkylsulfonate detergents can function as conductivity inhibitors.
- conductivity inhibitors are useful at concentrations of from about 0 weight % to about 8 weight %, about 0 weight % to about 6 weight %, about 0.1 weight % to about 6 weight %, about 0.1 weight % to about 5 weight %, about 0.1 weight % to about 4 weight %, about 0.1 weight % to about 3 weight %, about 0.1 weight % to about 2 weight %.
- zinc dialkyldithiophosphate (ZDDP) additives are useful at concentrations of from about 0 weight % to about 6 weight %, about 0.05 weight % to about 6 weight %, about 0.05 weight % to about 5 weight %, about 0.1 weight % to about 4 weight %, about 0.1 weight % to about 3 weight %, about 0.1 weight % to about 2 weight %, about 0.1 weight % to about 1 weight %.
- molybdenum organometallic additives are useful at concentrations of from about 0 weight % to about 3 weight %, about 0.01 weight % to about 3 weight %, about 0.05 weight % to about 2 weight %, about 0.1 weight % to about 1 weight %.
- magnesium alkylsulfonate additives are useful at concentrations of from about 0 weight % to about 5 weight %, 0.05 weight % to about 5 weight %, about 0.05 weight % to about 4 weight %, about 0.05 weight % to about 3 weight %, about 0.05 weight % to about 2 weight %.
- effective weight ratios of conductivity inhibitor- to-promoter are from about 0 to about 10, preferably about 0 to about 5, more preferably 0 to about 3, even more preferably about 0 to about 2, and in certain instances are from about 0.05 to about 10, preferably about 0.05 to about 5, more preferably about 0.05 to about 3, even more preferably about 0.05 to about 2.
- the lubricant compositions of this disclosure provide advantaged lubricant electrical conductivity control, including advantaged oxidation stability, deposit control and corrosion inhibition, performance in the lubrication of electric vehicles, which may consist of, for example, one or more of powertrains, drivelines, transmissions, differentials, gears, gear trains, gear sets, gear boxes, bearings, bushings, axles, turbines, compressors, pumps, hydraulic systems, batteries, capacitors, electric motors, drive motors, generators, AC/DC converters, alternators, transformers, kinetic energy converters, kinetic energy recovery systems, and the like.
- a single lubricant composition is used in the electric vehicle.
- more than one lubricant composition is used in the electric vehicle, for example, one lubricant composition for the transmission and another lubricant composition for another component of the vehicle system.
- the lubricant compositions of this disclosure provide advantaged lubricant electrical conductivity control, including advantaged oxidation stability, deposit control and corrosion inhibition, performance under diverse lubrication regimes of electric vehicle systems and subsystems, that include, for example, hydrodynamic, elastohydrodynamic, boundary, mixed lubrication, extreme pressure regimes, and the like.
- the lubricant compositions of this disclosure provide advantaged lubricant electrical conductivity control, including advantaged oxidation stability, deposit control and corrosion inhibition, performance in electric vehicles under a range of lubrication contact pressures, from 1 MP as to greater than 10 GPas, preferably greater than 10 MP as, more preferably greater than 100 MPas, even more preferably greater than 300 MPas.
- the lubricant compositions of this disclosure provide advantaged lubricant electrical conductivity control, including advantaged oxidation stability, deposit control and corrosion inhibition, performance in electric vehicles at greater than 0.5 GPas, often at greater than 1 GPas, sometimes greater than 2 GPas, under selected circumstances greater than 5 GPas.
- the lubricant compositions of this disclosure provide advantaged lubricant electrical conductivity control, including advantaged oxidation stability, deposit control and corrosion inhibition, performance on lubricated surfaces of electric vehicles, that include, for example, the following: metals, metal alloys, non-metals, non-metal alloys, mixed carbon-metal composites and alloys, mixed carbon-nonmetal composites and alloys, ferrous metals, ferrous composites and alloys, non-ferrous metals, non-ferrous composites and alloys, titanium, titanium composites and alloys, aluminum, aluminum composites and alloys, magnesium, magnesium composites and alloys, ion-implanted metals and alloys, plasma modified surfaces; surface modified materials; coatings; mono-layer, multi-layer, and gradient layered coatings; honed surfaces; polished surfaces; etched surfaces; textured surfaces; micro and nano structures on textured surfaces; super-finished surfaces; diamond-like carbon (DLC), DLC with high-hydrogen content, DLC with moderate hydrogen content
- the lubricant compositions of this disclosure provide advantaged lubricant electrical conductivity control, including advantaged oxidation stability, deposit control and corrosion inhibition, performance in electric vehicles with the one or more lubricating oil additives at effective concentration ranges and at effective ratios in accordance with this disclosure.
- electrical conductivity is determined in accordance with ASTM 2624 (modified), kinematic viscosity is determined by ASTM D445, total acid number (TAN) is determined by ASTM D974, metals content is determined by ASTM 6376, active sulfur content is determined by ASTM D129, viscosity index (VI) is determined by ASTM D2270, density is determined by ASTM D4052, and specific heat capacity is determined by ASTM D1269.
- the lubricating oils of this disclosure have an electrical conductivity from about 3,000 pS/m to about 60,000 pS/m, or from about 3,000 pS/m to about 40,000 pS/m, or from about 3,000 pS/m to about 20,000 pS/m, or from about 3,000 pS/m to about 10,000 pS/m, or from about 3,000 pS/m to about 8,000 pS/m
- the lubricating oils of this disclosure have a kinematic viscosity at 100°C from about 2 cSt to about 20 cSt, or from about 3 cSt to about 18 cSt, or from about 4 cSt to about 16 cSt, or from about 5 cSt to about 14 cSt, or from about 6 cSt to about 12 cSt, or from about 8 cSt to about 12 cSt.
- the lubricating oils of this disclosure have a total acid number (TAN) less than about 3, or less than about 2.8, or less than about 2.6, or less than about 2.4, or less than about 2.2, or less than about 2, or less than about 1.8, or less than about 1.6, or less than about 1.4, or less than about 1.2, or less than about 1, or less than about 0.8, or less than about 0.6, or less than about 0.4, or less than about 0.2.
- TAN total acid number
- the lubricating oils of this disclosure have less than about 200 ppm active sulfur, or less than about 100 ppm active sulfur, or less than about 75 ppm active sulfur, or less than about 50 ppm active sulfur, or less than about 25 ppm active sulfur, or less than about 10 ppm active sulfur, or no sulfur.
- active sulfur is the type of sulfur that reacts with surfaces at low temperatures and is corrosive to such surfaces, especially yellow metals (e.g., brass, bronze, copper, and the like). Active sulfur is chemically aggressive, and with yellow metals being softer than steel, they can begin to pit and form spalls due to this chemical attack. Active sulfur, when in contact with copper along with the presence of heat, forms copper sulfide. This simple chemical reaction can have devastating repercussions on the reliability of electric vehicles. In extreme pressure situations, copper disulfide can be formed. Both of these crystalline forms of copper are very hard and can cause abrasive damage to powertrain surfaces. In contrast, inactive sulfur only reacts with surfaces at high temperatures.
- yellow metals e.g., brass, bronze, copper, and the like.
- Active sulfur is chemically aggressive, and with yellow metals being softer than steel, they can begin to pit and form spalls due to this chemical attack. Active sulfur, when in contact with copper along with the presence of heat, forms copper sulfide.
- the lubricating oils of this disclosure have a viscosity index (VI) greater than about 50, or greater than about 60, or greater than about 70, or greater than about 80, or greater than about 90, or greater than about 100, or greater than about 1 10, or greater than about 120.
- VI viscosity index
- the lubricating oils of this disclosure have a finished lubricant density of greater than about 0.8 g/mL, or greater than about 0.82 g/mL, or greater than about 0.84 g/mL, or greater than about 0.86 g/mL, or greater than about 0.88 g/mL, or greater than about 0.9 g/mL, or greater than about 0.92 g/mL, or greater than about 0.94 g/mL, or greater than about 0.96 g/mL, or greater than about 0.98 g/mL, or greater than about 1.0 g/mL.
- the lubricating oils of this disclosure have a finished lubricant density of from about 0.8 g/mL to about 1.2 g/mL, or from about 0.81 g/mL to about 1.0 g/mL, or from about 0.82 g/mL to about 0.96 g/mL, or from about 0.83 g/mL to about 0.92 g/mL, or from about 0.84 g/mL to about 0.9 g/mL.
- the lubricating oils of this disclosure have a finished lube specific heat capacity of greater than about 1.9 kJ/kg K, 2.0 kJ/kg K, or greater than about 2.1 kJ/kg K, or greater than about 2.2 kJ/kg K, or greater than about 2.3 kJ/kg K, or greater than about 2.4 kJ/kg K, or greater than about 2.5 kJ/kg K, or greater than about 2.7 kJ/kg K, or greater than about 2.9 kJ/kg K, or greater than about 3.1 kJ/kg K, or greater than about 3.3 kJ/kg K, or greater than about 3.5 kJ/kg K.
- the lubricating oils of this disclosure may encompass solid or semisolid lubricants, such as e.g. greases.
- Dielectric breakdown is another important property of the lubricating oils of this disclosure. Dielectric breakdown is the electrical stress that a lubricating oil can withstand without breakdown. Dielectric breakdown is determined by ASTM D877. The voltage at which breakdown occurs (i.e., a spark passing between electrodes) is the test result. The lubricating oils of this disclosure have dielectric breakdown properties sufficient to be safely and efficiently used in electric vehicles.
- Lubricating base oils that are useful in the present disclosure are natural oils, mineral oils and synthetic oils, and unconventional oils (or mixtures thereof) can be used unrefined, refined, or rerefined (the latter is also known as reclaimed or reprocessed oil).
- Unrefined oils are those obtained directly from a natural or synthetic source and used without added purification. These include shale oil obtained directly from retorting operations, petroleum oil obtained directly from primary distillation, and ester oil obtained directly from an esterification process. Refined oils are similar to the oils discussed for unrefined oils except refined oils are subjected to one or more purification steps to improve at least one lubricating oil property.
- Groups I, II, III, IV and V are broad base oil stock categories developed and defined by the American Petroleum Institute (API Publication 1509; www.API.org) to create guidelines for lubricant base oils.
- Group I base stocks have a viscosity index of between about 80 to 120 and contain greater than about 0.03% sulfur and/or less than about 90% saturates.
- Group II base stocks have a viscosity index of between about 80 to 120, and contain less than or equal to about 0.03% sulfur and greater than or equal to about 90% saturates.
- Group III stocks have a viscosity index greater than about 120 and contain less than or equal to about 0.03 % sulfur and greater than about 90% saturates.
- Group IV includes polyalphaolefins (PAO).
- Group V base stock includes base stocks not included in Groups I-IV.
- the table below summarizes properties of each of these five groups.
- a base stock is typically recognized as one specifically characterized fluid of lubricating viscosity.
- a base oil is typically recognized as one or more base stocks used in combination as a fluid of lubricating viscosity.
- Natural oils include animal oils, vegetable oils (castor oil and lard oil, for example), and mineral oils. Animal and vegetable oils possessing favorable thermal oxidative stability can be used. Of the natural oils, mineral oils are preferred. Mineral oils vary widely as to their crude source, for example, as to whether they are paraffinic, naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal or shale are also useful. Natural oils vary also as to the method used for their production and purification, for example, their distillation range and whether they are straight run or cracked, hydrorefined, or solvent extracted.
- Group II and/or Group III hydroprocessed or hydrocracked base stocks including synthetic oils such as alkyl aromatics and synthetic esters are also well known base stock oils.
- High-quality Group II and Group III hydroprocessed or hydrocracked hydrocarbon base stocks (which may be known respectively as Group 11+ and Group III+) are also well known as useful base stock oils.
- ExxonMobil EHCTM base stocks are Group II base stocks useful in the instant invention.
- Synthetic oils include hydrocarbon oil.
- Hydrocarbon oils include oils such as polymerized and interpolymerized olefins (polybutylenes, polypropylenes, propylene isobutylene copolymers, ethylene-olefin copolymers, and ethylene-alphaolefin copolymers, for example).
- Polyalphaolefin (PAO) oil base stocks are commonly used synthetic hydrocarbon oil.
- 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 alphaolefins which include, but are not limited to, C2 to about C32 alphaolefins with the Cs to about Ci6 alphaolefins, such as 1-octene, 1-decene, 1-dodecene and the like, being preferred.
- the preferred polyalphaolefins are poly- 1-octene, poly-l-decene and poly-l-dodecene and mixtures thereof and mixed olefin-derived poly olefins.
- the dimers of higher olefins in the range of Ci4 to Ci8 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 mixtures thereof. Mixtures of PAO fluids having a viscosity range of 1.5 to approximately 150 cSt or more may be used if desired.
- the PAO fluids may be conveniently made by the polymerization of an alphaolefin in the presence of a polymerization catalyst such as the Friedel-Crafts catalysts including, for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate.
- 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
- 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.
- hydroisomerized waxy stocks e.g. waxy stocks such as gas oils, slack waxes, fuels hydrocracker bottoms, etc.
- hydroisomerized Fischer-Tropsch waxes e.g. waxy stocks such as gas oils, slack waxes, fuels hydrocracker bottoms, etc.
- 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.
- 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
- a zeolitic catalyst preferably 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.
- 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.
- Useful compositions of Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils, and wax-derived hydroisomerized base oils are recited in U.S. 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 a 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 Ce up to about Ceo 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 AlCh, BF3, or HF may be used.
- milder catalysts such as FeCh or SnC 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 polyol
- 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 compositions 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.
- Useful base stock fluids also include polyethers, polyglycols, polyalkylene glycols (PAG), polypropanols, polyalkylene propanols, polypropylene oxides, polybutylene oxides, polytetrahydrofurans, polyalkylene tetrahydrofurans, and analogues of polyether-type fluids, where such polyethers may be uncapped, mono-capped, di-capped, or multi-capped, with functional groups which may include for example ethers, esters, ketones, urethanes, aromatics, heteroaromatics, hydrocarbyl moieties, etc.
- useful polyether-type base stock fluids include oil-soluble or hydrocarbon-soluble versions of poly ethers or PAGs or polyalkylene ethers or polyalkylene oxides.
- Other useful fluids of lubricating viscosity include non-conventional or unconventional base stocks that have been processed, preferably catalytically, or synthesized to provide high performance lubrication characteristics.
- Non-conventional or unconventional base stocks/base oils include one or more of a mixture of base stock(s) derived from one or more Gas-to-Liquids (GTL) materials, as well as isomerate/isodewaxate base stock(s) derived from natural wax or waxy feeds, mineral and or non- mineral oil waxy feed stocks such as slack waxes, natural waxes, and waxy stocks such as gas oils, waxy fuels hydrocracker bottoms, waxy raffinate, hydrocrackate, thermal crackates, or other mineral, mineral oil, or even non-petroleum oil derived waxy materials such as waxy materials received from coal liquefaction or shale oil, and mixtures of such base stocks.
- GTL Gas-to-Liquids
- 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).
- the GTL base stock(s) and/or base oil(s) are typically highly paraffinic (>90% saturates), and may contain mixtures of monocycloparaffins and multicycloparaffins in combination with non-cyclic isoparaffins.
- the ratio of the naphthenic (i.e., cycloparaffin) content in such combinations varies with the catalyst and temperature used.
- 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 formulating 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 formulated lubricating oils useful in the present disclosure are any of the variety of oils corresponding to API Group I, Group II, Group III, Group IV, and Group V oils, and mixtures thereof, preferably API Group II, Group III, Group IV, and Group V oils, and mixtures thereof, more preferably Group III, Group IV, and Group V base oils, and mixtures thereof.
- Highly paraffinic base oils can be used to advantage in the formulated lubricating oils useful in the present disclosure.
- Minor quantities of Group I stock such as the amount used to dilute additives for blending into formulated lube oil products, can also be used. Even in regard to the Group II stocks, it is preferred that the Group II stock be in the higher quality range associated with that stock, i.e. a Group II stock having a viscosity index in the range 100 ⁇ VI ⁇ 120.
- the 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 Is) at 100°C and preferably of about 2.5 cSt to about 9 cSt (or mm 2 Is) at 100° C.
- a kinematic viscosity according to ASTM standards, of about 2.5 cSt to about 12 cSt (or mm 2 Is) at 100°C and preferably of about 2.5 cSt to about 9 cSt (or mm 2 Is) 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 lubricating oil compositions include at least one antioxidant.
- Antioxidants retard the oxidative degradation of base oils during service. Such degradation may result in deposits on metal surfaces, the presence of sludge, or a viscosity increase in the lubricant.
- One skilled in the art knows a wide variety of oxidation inhibitors that are useful in lubricating oil compositions. See, Klamann in Lubricants and Related Products, op cite, and U.S. Patent Nos. 4,798,684 and 5,084,197, for example.
- Illustrative antioxidants include sterically hindered alkyl phenols such as 2,6-di-tert- butylphenol, 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-4-(2-octyl-3-propanoic) phenol; N,N- di(alkylphenyl) amines; and alkylated phenylenediamines.
- the antioxidant may be a hindered phenolic antioxidant such as butylated hydroxy toluene, suitably present in an amount of 0.01 to 5%, preferably 0.4 to 0.8%, by weight of the lubricant composition.
- the antioxidant may comprise an aromatic amine antioxidant such as mono-octylphenylalphanapthyl amine or p,p-dioctyldiphenylamine, used singly or in admixture.
- the amine antioxidant component is suitably present in a range of from 0.01 to 5% by weight of the lubricant composition, more preferably 0.5 to 1.5%.
- 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).
- phenolic antioxidants include sulfurized and non-sulfurized phenolic antioxidants.
- phenolic type or “phenolic antioxidant” used herein includes compounds having one or more than one hydroxyl group bound to an aromatic ring which may itself be mononuclear, e.g., benzyl, or poly-nuclear, e.g., naphthyl and Spiro aromatic compounds.
- phenol type includes phenol per se, catechol, resorcinol, hydroquinone, naphthol, etc., as well as alkyl or alkenyl and sulfurized alkyl or alkenyl derivatives thereof, and bisphenol type compounds including such bi-phenol compounds linked by alkylene bridges sulfuric bridges or oxygen bridges.
- Alkyl phenols include mono- and poly-alkyl or alkenyl phenols, the alkyl or alkenyl group containing from 3-100 carbons, preferably 4 to 50 carbons and sulfurized derivatives thereof, the number of alkyl or alkenyl groups present in the aromatic ring ranging from 1 to up to the available unsatisfied valences of the aromatic ring remaining after counting the number of hydroxyl groups bound to the aromatic ring.
- the phenolic antioxidant may be represented by the general formula:
- Ar is selected from the group consisting of:
- R is a C3-C100 alkyl or alkenyl group, a sulfur substituted alkyl or alkenyl group, preferably a C4-C50 alkyl or alkenyl group or sulfur substituted alkyl or alkenyl group, more preferably C3- C100 alkyl or sulfur substituted alkyl group, most preferably a C4-C50 alkyl group
- R is a C1-C100 alkylene or sulfur substituted alkylene group, preferably a C2-C50 alkylene or sulfur substituted alkylene group, more preferably a C2-C20 alkylene or sulfur substituted alkylene group
- y is at least 1 to up to the available valences of Ar
- x ranges from 0 to up to the available valances of Ar-y
- z ranges from 1 to 10
- n ranges from 0 to 20
- m is 0 to 4
- p is 0 or 1 preferably y ranges from 1 to 3
- Preferred phenolic antioxidant compounds are the hindered phenolics and phenolic esters which contain a sterically hindered hydroxyl group, and these include those derivatives of dihydroxy aryl compounds in which the hydroxyl groups are in the 0- or p-position to each other.
- Typical phenolic antioxidants include the hindered phenols substituted with C.sub. l+ 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; 2- methyl-6-t-butyl-4-dodecyl phenol; 2,6-di-t-butyl-4 methyl phenol; 2,6-di-t-butyl-4-ethyl phenol; and 2,6-di-t-butyl 4 alkoxy phenol; and
- Phenolic type antioxidants are well known in the lubricating industry and commercial examples such as EthanoxTM 1710, IrganoxTM 1076, IrganoxTM L1035, IrganoxTM 1010, IrganoxTM L109, IrganoxTM LI 18, IrganoxTM L135 and the like are familiar to those skilled in the art. The above is presented only by way of exemplification, not limitation on the type of phenolic antioxidants which can be used.
- phenol-based antioxidants include 2-t-butylphenol, 2-t-butyl-4- methylphenol, 2-t-butyl-5-methylphenol, 2,4-di-t-butylphenol, 2,4-dimethyl-6-t-butylphenol, 2-t- butyl-4-methoxyphenol, 3 -t-butyl-4-methoxy phenol, 2,5-di-t-butylhydroquinone (manufactured by the Kawaguchi Kagaku Co.
- Yonox SS n-dodecyl- 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate and 2'-ethylhexyl-3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate; 2,6-di-t-butyl-alpha-dimethylamino-p-cresol, 2,2'-methylenebis(4- alkyl-6-t-butylphenol) compounds such as 2,2'-methylenebis(4-methyl-6-t-butylphenol) (manufactured by the Kawaguchi Kagaku Co.
- Antage W-400 and 2,2'-methylenebis(4-ethyl-6-t-butylphenol) (manufactured by the Kawaguchi Kagaku Co. under the trade designation "Antage W-500”); bisphenols such as 4,4'-butylidenebis(3-methyl-6-t-butyl- phenol) (manufactured by the Kawaguchi Kagaku Co.
- catalytic antioxidants comprise an effective amount of a) one or more oil soluble polymetal organic compounds; and, effective amounts of b) one or more substituted N,N'-diaryl-o-phenylenediamine compounds or c) one or more hindered phenol compounds; or a combination of both b) and c).
- Catalytic antioxidants are more fully described in U.S. Patent No. 8, 048,833, herein incorporated by reference in its entirety.
- Illustrative aromatic amine antioxidants include phenyl-alpha-naphthyl amine which is described by the following molecular structure:
- R z is hydrogen or a Ci to C14 linear or C3 to C14 branched alkyl group, preferably Ci to Cio linear or C3 to C10 branched alkyl group, more preferably linear or branched Ce to Cs and n is an integer ranging from 1 to 5 preferably 1.
- a particular example is Irganox L06.
- aromatic amine antioxidants include other alkylated and non-alkylated aromatic amines such as aromatic monoamines.
- Typical aromatic amines antioxidants have alkyl substituent groups of at least 6 carbon atoms.
- Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally, the aliphatic groups will not contain more than 14 carbon atoms.
- the general types of such other additional amine antioxidants which may be present include diphenylamines, phenothiazines, imidodibenzyls and di phenyl phenylene diamines. Mixtures of two or more of such other additional aromatic amines may also be present. Polymeric amine antioxidants can also be used.
- the antioxidants or oxidation inhibitors that are useful in lubricant oil compositions of the disclosure are the hindered phenols (e.g., 2,6-di-(t-butyl)phenol); aromatic amines (e.g., alkylated diphenyl amines); alkyl polysulfides; selenides; borates (e.g., epoxide/boric acid reaction products); phosphorodithioic acids, esters and/or salts; and the dithiocarbamate (e.g., zinc dithiocarbamates).
- these antioxidants or oxidation inhibitors can be employed at ratios of amine/phenolic from 1 : 10 to 10: 1 of the mixtures preferred.
- the antioxidants or oxidation inhibitors that are also useful in lubricant oil compositions of the disclosure are chlorinated aliphatic hydrocarbons such as chlorinated wax; organic sulfides and polysulfides such as benzyl disulfide, bis(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, and sulfurized terpene; phosphosulfiirized hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or methyl oleate, phosphorus esters including principally dihydrocarbon and trihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite, dipentylphenyl
- Oxidation inhibitors including organic compounds containing sulfur, nitrogen, phosphorus and some alkylphenols are useful additives in the lubricating oil compositions of this disclosure.
- Two general types of oxidation inhibitors are those that react with the initiators, peroxy radicals, and hydroperoxides to form inactive compounds, and those that decompose these materials to form less active compounds. Examples are hindered (alkylated) phenols, e.g. 6-di(tert- butyl)-4-methyl-phenol[2,6-di(tert-butyl)-p-cresol, DBPC], and aromatic amines, e.g. N-phenyl- alpha-naphthal amine.
- Sulfurized alkyl phenols and alkali or alkaline earth metal salts thereof also are useful antioxidants.
- Another class of antioxidant used in lubricating oil compositions and which may also be present are oil-soluble copper compounds. Any oil-soluble suitable copper compound may be blended into the lubricating oil.
- suitable copper antioxidants include copper dihydrocarbyl thio- or dithio-phosphates and copper salts of carboxylic acid (naturally occurring or synthetic).
- Other suitable copper salts include copper dithiacarbamates, sulphonates, phenates, and acetylacetonates.
- Basic, neutral, or acidic copper Cu(I) and or Cu(II) salts derived from alkenyl succinic acids or anhydrides are known to be particularly useful.
- a sulfur-containing antioxidant may be any and every antioxidant containing sulfur, for example, including dialkyl thiodipropionates such as dilauryl thiodipropionate and distearyl thiodipropionate, dialkyldithiocarbamic acid derivatives (excluding metal salts), bis(3,5-di-t-butyl- 4-hydroxybenzyl)sulfide, mercaptobenzothiazole, reaction products of phosphorus pentoxide and olefins, and dicetyl sulfide.
- dialkyl thiodipropionates such as dilauryl thiodipropionate and distearyl thiodipropionate
- dialkyldithiocarbamic acid derivatives excluding metal salts
- bis(3,5-di-t-butyl- 4-hydroxybenzyl)sulfide bis(3,5-di-t-butyl- 4-hydroxybenzyl)sulf
- dialkyl thiodipropionates such as dilauryl thiodipropionate and distearyl thiodipropionate.
- the amine-type antioxidant includes, for example, monoalkyldiphenylamines such as monooctyldiphenylamine and monononyldiphenyl amine; dialkyldiphenylamines such as 4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, 4,4'-dihexyldiphenylamine, 4,4'-diheptyldiphenylamine, 4,4'-dioctyldiphenylamine and 4,4'- dinonyldiphenylamine; polyalkyldiphenylamines such as tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine and tetranon
- sulfur-based antioxidants include dialkylsulfides such as didodecylsulfide and dioctadecylsulfide; thiodipropionic acid esters such as didodecyl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate and dodecyloctadecyl thiodipropionate, and 2- mercaptobenzimidazole.
- Such antioxidants may be used individually or as mixtures of one or more types of antioxidants, the total amount employed being an amount of about 0.01 to about 5 wt %, preferably 0.1 to about 4.5 wt %, more preferably 0.25 to 3 wt % (on an as-received basis).
- the lubricating oil compositions include at least one detergent.
- Illustrative detergents useful in this disclosure include, for example, alkali metal detergents, alkaline earth metal detergents, or mixtures of one or more alkali metal detergents and one or more alkaline earth metal detergents.
- a typical detergent is an anionic material that contains a long chain hydrophobic portion of the molecule and a smaller anionic or oleophobic hydrophilic portion of the molecule.
- the anionic portion of the detergent is typically derived from an organic acid such as a sulfur acid, carboxylic acid (e.g., salicylic acid), phosphorous acid, phenol, or mixtures thereof.
- the counterion is typically an alkaline earth or alkali metal.
- 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 acid, a carboxylic acid, a phosphorus 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, 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 useful detergents. These carboxylic acid detergents may be prepared by reacting a basic metal compound with at least one carboxylic acid and removing free water from the reaction product. 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 C11, preferably C 13 or greater.
- R may be optionally substituted with substituents that do not interfere with the detergent's function.
- M is preferably, calcium, magnesium, or barium. More preferably, M is calcium.
- 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.
- Illustrative detergents include calcium alkylsalicylates, calcium alkylphenates and calcium alkarylsulfonates with alternate metal ions used such as magnesium, barium, or sodium.
- cleaning and dispersing agents which can be used include metal-based detergents such as the neutral and basic alkaline earth metal sulphonates, alkaline earth metal phenates and alkaline earth metal salicylates alkenylsuccinimide and alkenylsuccinimide esters and their borohydrides, phenates, salienius complex detergents and ashless dispersing agents which have been modified with sulfur compounds.
- These agents can be added and used individually or in the form of mixtures, conveniently in an amount within the range of from 0.01 to 1 part by weight per 100 parts by weight of base oil; these can also be high TBN, low TBN, or mixtures of high/low TBN.
- 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.
- the detergent concentration in the lubricating oils of this disclosure can range from about 0.01 to about 10 weight percent, preferably about 0.1 to 7.5 weight percent, and more preferably from about 0.5 weight percent to about 5 weight percent, based on the total weight of the lubricating oil.
- 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.
- the lubricating oil compositions include at least one dispersant.
- Dispersants help keep these byproducts in solution, thus diminishing their deposition on metal surfaces.
- Dispersants used in the formulating of the lubricating oil 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. For example, non-metal-containing or borated metal-free dispersants are considered ashless.
- Suitable dispersants typically contain a polar group attached to a relatively high molecular weight hydrocarbon chain.
- the polar group typically contains at least one element of nitrogen, oxygen, or phosphorus.
- Typical hydrocarbon chains contain 50 to 400 carbon atoms.
- a particularly useful class of dispersants are the (poly)alkenylsuccinic derivatives, typically produced by the reaction of a long chain hydrocarbyl substituted succinic compound, usually a hydrocarbyl substituted succinic anhydride, with a polyhydroxy or poly amino 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.
- 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.
- 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.
- Illustrative 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 5,000, or from about 1,000 to about 3,000, or about 1 ,000 to about 2,000, 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.
- 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 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 3,000, such as between 2,000 and 2,800, more preferably from about 2,100 to 2,500, and most preferably from about 2,200 to about 2,400.
- 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, "Modem 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 (M n ).
- MWD molecular weight distribution
- M w weight average molecular weight
- M n 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.
- One family of such polymers comprise polymers of ethylene and/or at least one C3 to C24 alpha-olefin.
- Preferably, such polymers comprise interpolymers of ethylene and at least one alpha-olefin of the above formula.
- 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 feedstreams such as Raffinate II. These feedstocks are disclosed in the art such as in U. S. Patent 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 1,500 to 3,000.
- Dispersants that contain the alkenyl or alkyl group have an Mn value of about 500 to about 5000 and an Mw/Mn ratio of about 1 to about 5. The preferred Mn intervals depend on the chemical nature of the agent improving filterability .
- Polyolefinic polymers suitable for the reaction with maleic anhydride or other acid materials or acid forming naterials include polymers containing a predominant quantity of C2 to C5 monoolefins, for example, ethylene, propylene, butylene, isobutylene and pentene.
- a highly suitable polyolefinic polymer is polyisobutene.
- the succinic anhydride preferred as a reaction substance is PIBSA, that is, polyisobutenyl succinic anhydride.
- the dispersant contains a succinimide comprising the reaction product of a succinic anhydride with a polyamine
- the alkenyl or alkyl substituent of the succinic anhydride serving as the reaction substance consists preferably of polymerised isobutene having an Mn value of about 1200 to about 2500. More advantageously, the alkenyl or alkyl substituent of the succinic anhydride serving as the reaction substance consists in a polymerised isobutene having an Mn value of about 2100 to about 2400.
- the agent improving filterability contains an ester of succinic acid comprising the reaction product of a succinic anhydride and an aliphatic polyhydric alcohol
- the alkenyl or alkyl substituent of the succinic anhydride serving as the reaction substance consists advantageously of a polymerised isobutene having an Mn value of 500 to 1500.
- a polymerised isobutene having an Mn value of 850 to 1200 is used.
- the amides may be amides of mono- or polycarboxylic acids or reactive derivatives thereof.
- the amides may be characterized by a hydrocarbyl group containing from about 6 to about 90 carbon atoms; each is independently hydrogen or a hydrocarbyl, aminohydrocarbyl, hydroxyhydrocarbyl or a heterocyclic-substituted hydrocarbyl group, provided that both are not hydrogen; each is, independently, a hydrocarbylene group containing up to about 10 carbon atoms.
- the amide can be derived from a monocarboxylic acid, a hydrocarbyl group containing from 6 to about 30 or 38 carbon atoms and more often will be a hydrocarbyl group derived from a fatty acid containing from 12 to about 24 carbon atoms.
- An illustrative amide that is derived from a di- or tricarboxylic acid will contain from 6 to about 90 or more carbon atoms depending on the type of polycarboxylic acid.
- the amide when the amide is derived from a dimer acid, will contain from about 18 to about 44 carbon atoms or more, and amides derived from trimer acids generally will contain an average of from about 44 to about 90 carbon atoms.
- Each is independently hydrogen or a hydrocarbyl, aminohydrocarbyl, hydroxyhydrocarbyl or a heterocyclic-substituted hydrocarbon group containing up to about 10 carbon atoms.
- heterocyclic substituted hydrocarbyl groups wherein the heterocyclic substituent is derived from pyrrole, pyrroline, pyrrolidine, morpholine, piperazine, piperidine, pyridine, pipecoline, etc.
- Specific examples include methyl, ethyl, n-propyl, n-butyl, n-hexyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, amino-methyl, aminoethyl, aminopropyl, 2-ethylpyridine, 1 -ethylpyrrolidine, 1 -ethylpiperidine, etc.
- Illustrative aliphatic monoamines include mono-aliphatic and di-aliphatic-substituted amines wherein the aliphatic groups may be saturated or unsaturated and straight chain or branched chain.
- Such amines include, for example, mono- and di-alkyl-substituted amines, mono- and dialkenyl-substituted amines, etc.
- Specific examples of such monoamines include ethyl amine, diethyl amine, n-butyl amine, di-n-butyl amine, isobutyl amine, coco amine, stearyl amine, oleyl amine, etc.
- a cycloaliphatic-substituted aliphatic amine is 2-(cyclohexyl)-ethyl amine.
- heterocyclic-substituted aliphatic amines include 2-(2-aminoethyl)-pyrrole, 2- (2-aminoethyl)-l-methylpyrrole, 2-(2-aminoethyl)-l-methylpyrrolidine and 4-(2- aminoethyl)morpholine, 1 -(2-aminoethyl)piperazine, 1 -(2-aminoethyl)piperidine, 2-(2- aminoethyl)pyridine, 1 -(2-aminoethyl)pyrrolidine, l-(3-aminopropyl)imidazole, 3-(2- aminopropyl)indole, 4-(3-aminopropyl)morpholine, l-(3-aminopropyl)-2-pipecoline,
- Illustrative cycloaliphatic monoamines are those monoamines wherein there is one cycloaliphatic substituent attached directly to the amino nitrogen through a carbon atom in the cyclic ring structure.
- Examples of cycloaliphatic monoamines include cyclohexylamines, cyclopentylamines, cyclohexenylamines, cyclopentenylamines, N-ethyl-cyclohexylamine, dicyclohexylamines, and the like.
- Examples of aliphatic-substituted, aromatic-substituted, and heterocyclic-substituted cycloaliphatic monoamines include propyl-substituted cyclohexylamines, phenyl-substituted cyclopentylamines, and pyranyl-substituted cyclohexylamine.
- Illustrative aromatic amines include those monoamines wherein a carbon atom of the aromatic ring structure is attached directly to the amino nitrogen.
- the aromatic ring will usually be a mononuclear aromatic ring (i.e., one derived from benzene) but can include fused aromatic rings, especially those derived from naphthalene.
- aromatic monoamines include aniline, di-(para-methylphenyl)amine, naphthylamine, N-(n-butyl)-aniline, and the like.
- Examples of aliphatic-substituted, cycloaliphatic-substituted, and heterocyclic-substituted aromatic monoamines are para-ethoxy -aniline, para-dodecylaniline, cyclohexyl-substituted naphthylamine, variously substituted phenathiazines, and thienyl-substituted aniline.
- Illustrative polyamines are aliphatic, cycloaliphatic and aromatic polyamines analogous to the above-described monoamines except for the presence within their structure of additional amino nitrogens.
- the additional amino nitrogens can be primary, secondary or tertiary amino nitrogens.
- Examples of such polyamines include N-amino-propyl-cyclohexylamines, N,N'-di-n- butyl-paraphenylene diamine, bis-(para-aminophenyl)methane, 1 ,4-diaminocyclohexane, and the like.
- Illustrative hydroxy-substituted amines are those having hydroxy substituents bonded directly to a carbon atom other than a carbonyl carbon atom; that is, they have hydroxy groups capable of functioning as alcohols.
- Examples of such hydroxy-substituted amines include ethanolamine, di-(3-hydroxypropyl)-amine, 3-hydroxybutyl-amine, 4-hydroxybutyl-amine, diethanolamine, di-(2-hydroxyamine, N-(hydroxypropyl)-propylamine, N-(2-methyl)- cyclohexylamine, 3-hydroxycyclopentyl parahydroxyaniline, N-hydroxyethal piperazine and the like.
- the amines are alkylene polyamines including hydrogen, or a hydrocarbyl, amino hydrocarbyl, hydroxyhydrocarbyl or heterocyclic-substituted hydrocarbyl group containing up to about 10 carbon atoms.
- alkylene polyamines include methylene polyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, hexylene polyamines, heptylene polyamines, etc.
- Alkylene polyamines include ethylene diamine, triethylene tetramine, propylene diamine, trimethylene diamine, hexamethylene diamine, decamethylene diamine, hexamethylene diamine, decamethylene diamine, octamethylene diamine, di(heptamethylene) triamine, tripropylene tetramine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, di(trimethylene)triamine, and the like. Higher homologs as are obtained by condensing two or more of the above-illustrated alkylene amines are useful, as are mixtures of two or more of any of the afore-described polyamines.
- Ethylene polyamines such as those mentioned above, are especially useful for reasons of cost and effectiveness.
- Such polyamines are described in detail under the heading "Diamines and Higher Amines” in The Encyclopedia of Chemical Technology, Second Edition, Kirk and Othmer, Volume 7, pages 27-39, Interscience Publishers, Division of John Wiley and Sons, 1965, which is hereby incorporated by reference for the disclosure of useful polyamines.
- Such compounds are prepared most conveniently by the reaction of an alkylene chloride with ammonia or by reaction of an ethylene imine with a ring-opening reagent such as ammonia, etc. These reactions result in the production of the somewhat complex mixtures of alkylene polyamines, including cyclic condensation products such as piperazines.
- polyamine bottoms can be characterized as having less than 2, usually less than 1% (by weight) material boiling below about 200°C.
- ethylene polyamine bottoms which are readily available and found to be quite useful, the bottoms contain less than about 2% (by weight) total diethylene triamine (DETA) or triethylene tetramine (TETA).
- DETA diethylene triamine
- TETA triethylene tetramine
- E-100 Gas chromatography analysis of such a sample showed it to contain about 0.93% "Light Ends” (most probably DETA), 0.72% TETA, 21.74% tetraethylene pentamine and 76.61% pentaethylene hexamine and higher (by weight).
- These alkylene polyamine bottoms include cyclic condensation products such as piperazine and higher analogs of diethylene triamine, triethylene tetramine and the like.
- Illustrative dispersants are selected from: Mannich bases that are condensation reaction products of a high molecular weight phenol, an alkylene polyamine and an aldehyde such as formaldehyde; succinic-based dispersants that are reaction products of a olefin polymer and succinic acylating agent (acid, anhydride, ester or halide) further reacted with an organic hydroxy compound and/or an amine; high molecular weight amides and esters such as reaction products of a hydrocarbyl acylating agent and a polyhydric aliphatic alcohol (such as glycerol, pentaerythritol or sorbitol).
- Mannich bases that are condensation reaction products of a high molecular weight phenol, an alkylene polyamine and an aldehyde such as formaldehyde
- succinic-based dispersants that are reaction products of a olefin polymer and succinic acylating agent (acid
- Ashless (metal-free) polymeric materials that usually contain an oil soluble high molecular weight backbone linked to a polar functional group that associates with particles to be dispersed are typically used as dispersants.
- hydrocarbon backbone materials are olefin polymers and copolymers, i.e., ethylene, propylene, butylene, isobutylene, styrene; there may or may not be further functional groups incorporated into the backbone of the polymer, whose molecular weight ranges from 300 tp to 5000.
- Polar materials such as amines, alcohols, amides or esters are attached to the backbone via a bridge.
- 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 2,000 ppm by weight, preferably from about 200 ppm by weight to about 1,200 ppm by weight.
- Basic nitrogen can vary from about 100 ppm by weight to about 1,000 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.
- the lubricating oil compositions include at least one antiwear agent.
- suitable antiwear agents include oil soluble amine salts of phosphorus compounds, sulfurized olefins, metal dihydrocarbyldithio-phosphates (such as zinc dialkyldithiophosphates), thiocarbamate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides.
- Antiwear agents used in the formulating of the lubricating oil may be ashless or ash- forming in nature.
- the antiwear agent is ashless.
- So called ashless antiwear agents are materials that form substantially no ash upon combustion.
- non-metal-containing antiwear agents are considered ashless.
- oil soluble phosphorus amine antiwear agents include an amine salt of a phosphorus acid ester or mixtures thereof.
- the amine salt of a phosphorus acid ester includes phosphoric acid esters and amine sails thereof; dialkyldithiophosphoric acid esters and amine salts thereof; amine salts of phosphites; and amine salts of phosphorus-containing carboxylic esters, ethers, and amides; and mixtures thereof.
- the amine salt of a phosphorus acid ester may be used alone or in combination.
- oil soluble phosphorus amine salts include partial amine salt-partial metal salt compounds or mixtures thereof.
- the phosphorus compound further includes a sulfur atom in the molecule.
- the amine salt of the phosphorus compound may be ashless, i.e., metal-free (prior to being mixed with other components).
- the amines which may be suitable for use as the amine salt include primary amines, secondary amines, tertiary amines, and mixtures thereof.
- the amines include those with at least one hydrocarbyl group, or, in certain embodiments, two or three hydrocarbyl groups.
- the hydrocarbyl groups may contain 2 to 30 carbon atoms, or in other embodiments 8 to 26, or 10 to 20, or 13 to 19 carbon atoms.
- Primary amines include ethylamine, propylamine, butylamine, 2-ethylhexylamine, octylamine, and dodecylamine, as well as such fatty amines as n-octylamine, n-decylamine, n- dodeclyamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine and oleyamine.
- fatty amines include commercially available fatty amines such as "ArmeenTM” amines (products available from Akzo Chemicals, Chicago, 111.), such as Armeen C, Armeen O, Armeen OL, Armeen T, Armeen HT, Armeen S and Armeen SD, wherein the letter designation relates to the fatty group, such as coco, oleyl, tallow, or stearyl groups.
- Examples of suitable secondary amines include dim ethylamine, diethylamine, dipropylamine, dibutylamine, diamylamine, dihexylamine, diheptylamine, methylethylamine, ethylbutylamine and ethylamylamine.
- the secondary amines may be cyclic amines such as piperidine, piperazine and morpholine.
- the amine may also be a tertiary-aliphatic primary amine.
- the aliphatic group in this case may be an alkyl group containing 2 to 30, or 6 to 26, or 8 to 24 carbon atoms.
- Tertiary alkyl amines include monoamines such as tert-butylamine, tert-hexylamine, 1 -methyl- 1-amino- cyclohexane, tert-octylamine, tert-decylamine, tertdodecyl amine, tert-tetradecylamine, tert- hexadecylamine, tert-octadecylamine, tert-tetracosanylamine, and tert-octacosanylamine.
- the phosphorus acid amine salt includes an amine with Cn to Ci4 tertiary alkyl primary groups or mixtures thereof. In one embodiment the phosphorus acid amine salt includes an amine with Ci4 to Cie tertiary alkyl primary amines or mixtures thereof. In one embodiment the phosphorus acid amine salt includes an amine with Cis to C22 tertiary alkyl primary amines or mixtures thereof.
- amines may also be used in the disclosure.
- a useful mixture of amines is "PrimeneTM 81R” and “PrimeneTM JMT.”
- PrimeneTM 81R and PrimeneTM JMT are mixtures of C 11 to C 14 tertiary alkyl primary amines and Ci8 to C22 tertiary alkyl primary amines respectively.
- oil soluble amine salts of phosphorus compounds include a sulfur- free amine salt of a phosphorus-containing compound may be obtained/obtainable by a process comprising: reacting an amine with either (i) a hydroxy-substituted di-ester of phosphoric acid, or (ii) a phosphorylated hydroxy-substituted di- or tri-ester of phosphoric acid.
- a process comprising: reacting an amine with either (i) a hydroxy-substituted di-ester of phosphoric acid, or (ii) a phosphorylated hydroxy-substituted di- or tri-ester of phosphoric acid.
- the hydrocarbyl amine salt of an alkylphosphoric acid ester is the reaction product of a C 14 to Cie alkylated phosphoric acid with Primene 81RTTM (produced and sold by Rohm & Haas) which is a mixture of C11 to C14 tertiary alkyl primary amines.
- hydrocarbyl amine salts of dialkyldithiophosphoric acid esters include the reaction product(s) of isopropyl, methyl-amyl (4-methyl-2-pentyl or mixtures thereof), 2- ethylhexyl, heptyl, octyl or nonyl dithiophosphoric acids with ethylene diamine, morpholine, or Primene 81RTM, and mixtures thereof.
- the dithiophosphoric acid may be reacted with an epoxide or a glycol. This reaction product is further reacted with a phosphorus acid, anhydride, or lower ester.
- the epoxide includes an aliphatic epoxide or a styrene oxide. Examples of useful epoxides include ethylene oxide, propylene oxide, butene oxide, octene oxide, dodecene oxide, and styrene oxide. In one embodiment, the epoxide may be propylene oxide.
- the glycols may be aliphatic glycols having from 1 to 12, or from 2 to 6, or 2 to 3 carbon atoms.
- the dithiocarbamate-containing compounds may be prepared by reacting a dithiocarbamate acid or salt with an unsaturated compound.
- the dithiocarbamate containing compounds may also be prepared by simultaneously reacting an amine, carbon disulfide and an unsaturated compound. Generally, the reaction occurs at a temperature from 25°C to 125°C.
- Suitable olefins that may be sulfurized to form the sulfurized olefin include propylene, butylene, isobutylene, pentene, hexane, heptene, octane, nonene, decene, undecene, dodecene, undecyl, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, octadecenene, nonodecene, eicosene or mixtures thereof.
- hexadecene, heptadecene, octadecene, octadecenene, nonodecene, eicosene or mixtures thereof and their dimers, trimers and tetramers are especially useful olefins.
- the olefin may be aDiels- Alder adduct of a diene such as 1,3-butadiene and an unsaturated ester, such as, butylacrylate.
- Another class of sulfurized olefin includes fatty acids and their esters.
- the fatty acids are often obtained from vegetable oil or animal oil; and typically contain 4 to 22 carbon atoms.
- suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid or mixtures thereof.
- the fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil or mixtures thereof.
- fatty acids and/or ester are mixed with olefins.
- Polyols include diols, triols, and alcohols with higher numbers of alcoholic OH groups.
- Polyhydric alcohols include ethylene glycols, including di-, tri- and tetraethylene glycols; propylene glycols, including di-, tri- and tetrapropylene glycols; glycerol; butane diol; hexane diol; sorbitol; arabitol; mannitol; sucrose; fructose; glucose; cyclohexane diol; erythritol; and penta- erythritols, including di- and tripentaerythritol.
- the polyol is diethylene glycol, triethylene glycol, glycerol, sorbitol, penta erythritol or dipentaerythritol.
- the ashless antiwear agent may be a monoester of a polyol and an aliphatic carboxylic acid, often an acid containing 12 to 24 carbon atoms.
- the monoester of a polyol and an aliphatic carboxylic acid is in the form of a mixture with a sunflower oil or the like, which may be present in the mixture from 5 to 95, in several embodiments from 10 to 90, or from 20 to 85, or 20 to 80 weight percent of said mixture.
- the aliphatic carboxylic acids (especially a monocarboxylic acid) which form the esters are those acids typically containing 12 to 24, or from 14 to 20 carbon atoms. Examples of carboxylic acids include dodecanoic acid, stearic acid, lauric acid, behenic acid, and oleic acid.
- Illustrative antiwear additives useful in this disclosure include, for example, metal salts of a carboxylic acid.
- the metal is selected from a transition metal and mixtures thereof.
- the carboxylic acid is selected from an aliphatic carboxylic acid, a cycloaliphatic carboxylic acid, an aromatic carboxylic acid, and mixtures thereof.
- the metal is preferably selected from a Group 10, 11 and 12 metal, and mixtures thereof.
- the carboxylic acid is preferably an aliphatic, saturated, unbranched carboxylic acid having from about 8 to about 26 carbon atoms, and mixtures thereof.
- the metal is preferably selected from nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), and mixtures thereof.
- the carboxylic acid is preferably selected from caprylic acid (C8), pelargonic acid (C9), capric acid (CIO), undecylic acid (Cl l), lauric acid (C12), tridecylic acid (C13), myristic acid (CI 4), pentadecylic acid (CI 5), palmitic acid (CI 6), margaric acid (CI 7), stearic acid (CI 8), nonadecylic acid (C19), arachidic acid (C20), heneicosylic acid (C21), behenic acid (C22), tricosylic acid (C23), lignoceric acid (C24), pentacosylic acid (C25), cerotic acid (C26), and mixtures thereof.
- the metal salt of a carboxylic acid comprises zinc stearate, silver stearate, palladium stearate, zinc palmitate, silver palmitate, palladium palmitate, and mixtures thereof.
- the metal salt of a carboxylic acid is present in the engine oil compositions of this disclosure in an amount of from about 0.01 weight percent to about 5 weight percent, based on the total weight of the formulated oil.
- 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 lubricating oils 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 Ci-Cis alkyl groups, preferably C2-C12 alkyl groups. These alkyl groups may be straight chain or branched.
- Alcohols used in the ZDDP can be 2-propanol, butanol, secondary butanol, pentanols, hexanols such as 4-methyl-2-pentanol, n-hexanol, n-octanol, 2-ethyl hexanol, alkylated phenols, and the like. Mixtures of secondary alcohols or of primary and secondary alcohol can be preferred. Alkyl aryl groups may also be used.
- Preferable zinc dithiophosphates which are commercially available include secondary zinc dithiophosphates such as those available from for example, The Lubrizol Corporation under the trade designations "LZ 677A”, “LZ 1095” and “LZ 1371", from for example Chevron Oronite under the trade designation "OLOA 262" and from for example Afton Chemical under the trade designation "HITEC 7169".
- the ZDDP is typically used in amounts of from about 0.4 weight percent to about 1.2 weight percent, preferably from about 0.5 weight percent to about 1.0 weight percent, and more preferably from about 0.6 weight percent to about 0.8 weight percent, based on the total weight of the lubricating oil, although more or less can often be used advantageously.
- the ZDDP is a secondary ZDDP and present in an amount of from about 0.6 to 1.0 weight percent of the total weight of the lubricating oil.
- Low phosphorus engine oil compositions are included in this disclosure.
- the phosphorus content is typically less than about 0.12 weight percent, preferably less than about 0.10 weight percent, and most preferably less than about 0.085 weight percent, and in certain instances less than about 0.065 weight percent.
- antiwear agents useful in this disclosure include, for example, zinc alkyldithiophosphates, aryl phosphates and phosphites, sulfur-containing esters, phosphosulfur compounds, and metal or ash-free dithiocarbamates.
- the antiwear additive concentration in the lubricating oils of this disclosure can range from about 0.01 to about 5 weight percent, preferably about 0.1 to 4.5 weight percent, and more preferably from about 0.2 weight percent to about 4 weight percent, based on the total weight of the lubricating oil.
- the lubricating oil compositions include at least one corrosion inhibitor.
- Corrosion inhibitors are used to reduce the degradation of metallic parts that are in contact with the lubricating oil composition.
- Suitable corrosion inhibitors include aryl thiazines, alkyl substituted dimercaptothiodiazoles, alkyl substituted dimercaptothiadiazoles, and mixtures thereof.
- Corrosion inhibitors are additives that protect lubricated metal surfaces against chemical attack by water or other contaminants. A wide variety of these are commercially available. As used herein, corrosion inhibitors include antirust additives and metal deactivators.
- One type of corrosion inhibitor is a polar compound that wets the metal surface preferentially, protecting it with a film of oil.
- Another type of corrosion inhibitor absorbs water by incorporating it in a water-in-oil emulsion so that only the oil touches the metal surface.
- Yet another type of corrosion inhibitor chemically adheres to the metal to produce a non-reactive surface.
- 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.
- Illustrative corrosion inhibitors include (short-chain) alkenyl succinic acids, partial esters thereof and nitrogen-containing derivatives thereof; and synthetic alkarylsulfonates, such as metal dinonylnaphthalene sulfonates.
- Corrosion inhbiitors include, for example, monocarboxylic acids which have from 8 to 30 carbon atoms, alkyl or alkenyl succinates or partial esters thereof, hydroxy-fatty acids which have from 12 to 30 carbon atoms and derivatives thereof, sarcosines which have from 8 to 24 carbon atoms and derivatives thereof, amino acids and derivatives thereof, naphthenic acid and derivatives thereof, lanolin fatty acid, mercapto-fatty acids and paraffin oxides.
- Particularly preferred corrosion inhibitors are indicated below.
- monocarboxylic acids C8-C30
- Caprylic acid pelargonic acid
- decanoic acid undecanoic acid
- lauric acid myristic acid
- palmitic acid palmitic acid
- stearic acid arachic acid
- behenic acid cerotic acid
- montanic acid melissic acid
- oleic acid docosanic acid
- erucic acid eicosenic acid
- beef tallow fatty acid soy bean fatty acid, coconut oil fatty acid, linolic acid, linoleic acid, tall oil fatty acid, 12-hydroxystearic acid, laurylsarcosinic acid, myritsylsarcosinic acid, palmitylsarcosinic acid, stearylsarcosinic acid, oleylsarcosinic acid, alkylated (C8-C20) phenoxyacetic acids,
- polybasic carboxylic acids which function as corrosion inhibitors include alkenyl (C10-C100) succinic acids and ester derivatives thereof, dimer acid, N-acyl-N-alkyloxyalkyl aspartic acid esters (U.S. Patent No. 5,275,749).
- alkylamines which function as corrosion inhibitors or as reaction products with the above carboxylates to give amides and the like are represented by primary amines such as laurylamine, coconut-amine, n-tridecylamine, myristylamine, n-pentadecylamine, palmitylamine, n-heptadecylamine, stearylamine, n- nonadecylamine, n-eicosylamine, n-heneicosylamine, n-docosylamine, n-tricosylamine, n- pentacosylamine, oleylamine, beef tallow-amine, hydrogenated beef tallow-amine and soy bean- amine.
- primary amines such as laurylamine, coconut-amine, n-tridecylamine, myristylamine, n-pentadecylamine, palmitylamine, n-heptadecylamine, stearylamine
- secondary amines examples include dilaurylamine, di-coconut-amine, di-n-tri decyl amine, dimyristylamine, di-n-pentadecylamine, dipalmitylamine, di-n-pentadecylamine, distearylamine, di-n-nonadecylamine, di-n-eicosylamine, di-n-heneicosylamine, di-n- docosylamine, di-n-tricosylamine, di-n-pentacosyl-amine, dioleylamine, di-beef tallow-amine, di- hydrogenated beef tallow-amine and di-soy bean-amine.
- N- alkylpolyalkyenediamines examples include: ethylenediamines such as laurylethylenediamine, coconut ethylenediamine, n-tridecylethylenediamine-, myristylethylenediamine, n- pentadecylethylenediamine, palmitylethylenediamine, n-heptadecylethylenediamine, stearylethylenediamine, n-nonadecylethylenediamine, n-eicosylethylenediamine, n- heneicosylethylenediamine, n-docosylethylendiamine, n-tricosylethylenediamine, n- pentacosylethylenediamine, oleylethylenediamine, beef tallow-ethylenediamine, hydrogenated beef tallow-ethylenediamine and soy bean-ethylenediamine; propylenediamines such as laurylpropylenediamine, coconut propylenedi
- corrosion inhibitors include 2,5-dimercapto-l,3,4-thiadiazoles and derivatives thereof, mercaptobenzothiazoles, alkyltriazoles and benzotriazoles.
- dibasic acids useful as corrosion inhibitors are sebacic acid, adipic acid, azelaic acid, dodecanedioic acid, 3-methyladipic acid, 3-nitrophthalic acid, 1,10-decanedicarboxylic acid, and fumaric acid.
- the corrosion inhibitors can be a straight or branch-chained, saturated or unsaturated monocarboxylic acid or ester thereof which may optionally be sulfurized in an amount up to 35% by weight.
- the acid is a C4 to C22 straight chain unsaturated monocarboxylic acid.
- the preferred concentration of this additive is from 0.001% to 0.35% by weight of the total lubricant composition.
- the preferred monocarboxylic acid is sulfurized oleic acid.
- other suitable materials are oleic acid itself; valeric acid and erucic acid.
- An illustrative corrosion inhibitor includes a triazole as previously defined. The triazole should be used at a concentration from 0.005% to 0.25% by weight of the total composition.
- the preferred triazole is tolylotriazole which may be included in the compositions of the disclosure include triazoles, thiazoles and certain diamine compounds which are useful as metal deactivators or metal passivators.
- Examples include triazole, benzotriazole and substituted benzotriazoles such as alkyl substituted derivatives.
- the alkyl substituent generally contains up to 1.5 carbon atoms, preferably up to 8 carbon atoms.
- the triazoles may contain other substituents on the aromatic ring such as halogens, nitro, amino, mercapto, etc.
- suitable compounds are benzotriazole and the tolyltriazoles, ethylbenzotriazoles, hexylbenzotriazoles, octylbenzotriazoles, chlorobenzotriazoles and nitrobenzotriazoles. Benzotriazole and tolyltriazole are particularly preferred.
- a straight or branched chain saturated or unsaturated monocarboxylic acid which is optionally sulfurized in an amount which may be up to 35% by weight; or an ester of such an acid; and a triazole or alkyl derivatives thereof, or short chain alkyl of up to 5 carbon atoms; n is zero or an integer between 1 and 3 inclusive; and is hydrogen, morpholino, alkyl, amido, amino, hydroxy or alkyl or aryl substituted derivatives thereof; or a triazole selected from 1 ,2,4 triazole, 1 ,2,3 triazole, 5-anilo-l ,2,3,4-thiatriazole, 3-amino-l , 2,4 triazole, 1 -H-benzotriazole-l -yl- methylisocyanide, methylene-bis-benzotriazole and naphthotriazole.
- the corrosion inhibitors may be used in an amount of 0.01 to 5 wt %, preferably 0.01 to 1.5 wt %, more preferably 0.01 to 0.2 wt %, still more preferably 0.01 to 0.1 wt % (on an as- received basis) based on the total weight of the lubricating oil composition.
- 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.
- 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 between 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 compositions of which also serve as pour point depressants.
- Other suitable viscosity modifiers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (copolymers of various chain length acrylates, for example). Specific examples include styrene-isoprene or styrene-butadiene based polymers of 50,000 to 200,000 molecular weight.
- Olefin copolymers are commercially available from Chevron Oronite Company LLC under the trade designation "PARATONE®” (such as “PARATONE® 8921” and “PARATONE® 8941”); from Afton Chemical Corporation under the trade designation “HiTEC®” (such as “HiTEC® 5850B”; and from The Lubrizol Corporation under the trade designation "Lubrizol® 7067C”.
- Hydrogenated polyisoprene star polymers are commercially available from Infineum International Limited, e.g., under the trade designation "SV200” and “SV600”.
- Hydrogenated diene-styrene block copolymers are commercially available from Infineum International Limited, e.g., under the trade designation "SV 50".
- the polymethacrylate or polyacrylate polymers can be linear polymers which are available from Evnoik Industries under the trade designation "Viscoplex®” (e.g., Viscoplex 6-954) or star polymers which are available from Lubrizol Corporation under the trade designation 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 formulated oil or lubricating engine oil. Viscosity modifiers are typically added as concentrates, in large amounts of diluent oil.
- the viscosity modifiers may be used in an amount of 0.01 to 20 wt %, preferably 0.1 to 10 wt %, more preferably 0.5 to 7.5 wt %, still more preferably 1 to 5 wt % (on an as-received basis) based on the total weight of the lubricating oil composition.
- 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.
- the lubricating oil compositions include at least one metal passivator.
- the metal passivators/deactivators include, for example, benzotriazole, tolyltriazole, 2- mercaptobenzothiazole, dialkyl-2,5-dimercapto-l ,3,4-thiadiazole; ⁇ , ⁇ '- disalicylideneethylenediamine, ⁇ , ⁇ '-disalicyli-denepropylenediamine; zinc dialkyldithiophosphates and dialkyl dithiocarbamates.
- yellow metal passivator refers to a metallurgical grouping that includes brass and bronze alloys, aluminum bronze, phosphor bronze, copper, copper nickel alloys, and beryllium copper.
- Typical yellow metal passivators include, for example, benzotriazole, totutriazole, tolyltriazole, mixtures of sodium tolutriazole and tolyltriazole, and combinations thereof. In one particular and non-limiting embodiment, a compound containing tolyltriazole is selected.
- Typical commercial yellow metal passivators include IRGAMETTM-30, and IRGAMETTM-42, available from Ciba Specialty Chemicals, now part of BASE, and VANLUBETM 601 and 704, and CUV ANTM 303 and 484, available from R.T. Vanderbilt Company, Inc.
- the metal passivator concentration in the lubricating oils of this disclosure can range from about 0.01 to about 5.0 weight percent, preferably about 0.01 to 3.0 weight percent, and more preferably from about 0.01 weight percent to about 1.5 weight percent, based on the total weight of the lubricating oil.
- the formulated lubricating oil useful in the present disclosure may additionally contain one or more of the other commonly used lubricating oil performance additives including but not limited to polar agents, non-polar agents, ionic liquids, conductivity agents, extreme pressure additives, anti-seizure agents, wax modifiers, fluid-loss additives, seal compatibility agents, lubricity agents, anti-staining agents, chromophoric agents, defoamants, demulsifiers, emulsifiers, densifiers, wetting agents, gelling agents, tackiness agents, colorants, lipids (hydrophilic, lipophilic, amphiphilic), phospholipids, glycolipids, glycerophospholipids, lecithin, and others.
- polar agents including but not limited to polar agents, non-polar agents, ionic liquids, conductivity agents, extreme pressure additives, anti-seizure agents, wax modifiers, fluid-loss additives, seal compatibility agents, lubricity
- Conductivity agents useful in the present disclosure encompass materials, components, chemicals, or fluids having polar functional groups, generally comprising heteroatoms, such as e.g. O, N, P, S, B, halides, metals, and such polar functional groups generally comprising e.g. esters, ethers, ketones, alcohols, alkoxides, aldehydes, carboxylates, carboxylic acids, carboxylate salts, sulfates, sulfones, sulfonates, sulfinates, heteroatom-metal salts, amine salts, amines, amides, imides, imines, hetero-aromatics, organometallics, and the like.
- polar functional groups generally comprising heteroatoms, such as e.g. O, N, P, S, B, halides, metals, and such polar functional groups generally comprising e.g. esters, ethers, ketones, alcohols, alkoxides, aldeh
- Conductivity agents encompass both conductivity promoters and conductivity inhibitors.
- Conductivity promoters encompass materials, components, chemicals, or fluids that increase the conductivity of a composition by a tangible quantity when added to such composition in an effective amount.
- conductivity promoters increase the conductivity of a composition by an increment of about 100 pS/m or more when added to such composition in an effective amount.
- Conductivity promotors include, for example, ionic liquids, phospholipids, fatty acids, dispersants, calcium detergents, polar basestock fluids, and mixtures thereof.
- Conductivity inhibitors encompass materials, components, chemicals, or fluids that decrease the conductivity of a composition by a tangible quantity when added to such composition in an effective amount.
- conductivity inhibitors decrease the conductivity of a composition by an increment of about 100 pS/m or more when added to such composition in an effective amount.
- Conductivity inhibitors include, for example, zinc-type antiwear agents, molybdenum-type friction modifiers or antiwear agents, magnesium detergents, and mixtures thereof.
- the additives useful in this disclosure do not have to be soluble in the lubricating oils.
- Insoluble additives such as zinc stearate in oil can be dispersed in the lubricating oils of this disclosure.
- ILs Ionic Liquids
- Ionic liquids are so-called salt melts which are preferably liquid at room temperature and/or by definition have a melting point ⁇ 100°C. They have almost no vapor pressure and therefore have no cavitation properties.
- salt melts which are preferably liquid at room temperature and/or by definition have a melting point ⁇ 100°C. They have almost no vapor pressure and therefore have no cavitation properties.
- these liquids can be used in equipment in which there is an electric charge buildup, e.g., electric vehicles.
- Suitable cations for ionic liquids include a quaternary ammonium cation, a phosphonium cation, an imidazolium cation, a pyridinium cation, a pyrazolium cation, an oxazolium cation, a pyrrolidinium cation, a piperidinium cation, a thiazolium cation, a guanidinium cation, a morpholinium cation, a trialkylsulfonium cation or a triazolium cation, which may be substituted with an anion selected from the group consisting of [PFe]-, [BF4] 1 , [CF3CO2] 31 , [CF3SO3]- as well as its higher homologs, [C4F9--SO3] 31 or [CsFiv- SO3]- and higher perfluoroalkylsulfonates, [(CF 3 S0 2
- R 1 and R 2 independently of one another are selected from hydrogen; linear or branched, saturated or unsaturated, aliphatic or alicyclic alkyl groups with 1 to 20 carbon atoms; heteroaryl, heteroaryl-Ci-C6-alkyl groups with 3 to 8 carbon atoms in the heteroaryl radical and at least one heteroatom of N, O and S, which may be combined with at least one group selected from C1-C6 alkyl groups and/or halogen atoms; aryl-aryl C1-C6 alkyl groups with 5 to 12 carbon atoms in the aryl radical, which may be substituted with at least one C1-C6 alkyl group; R 3 may be a perfluoroe
- Ionic liquids with highly fluorinated anions are especially preferred because they usually have a high thermal stability.
- the water uptake ability may be reduced significantly by such anions, e.g., in the case of the bis(trifluoromethylsutfonyl)imide anion.
- Illustrative ionic liquids include, for example, butylmethylpyrrolidinium bis(trifluoromethylsulfonyl)imide (MBPimide), methylpropylpyrrolidinium bis(trifluoromethylsulfonyl)imide (MPPimide), hexylmethylimidazolium tris(perfluoroethyl)trifluorophosphate (HMIMPFET), hexylmethylimidazolium bis(trifluoromethylsulfonyl)imide (HMIMimide), hexylmethylpyrrolidinium bis(trifluoromethylsulfonyl)imide (HMP), tetrabutylphosphonium tris(perfluoroethyl)trifluorophosphate (BuPPFET), octylmethylimidazolium hexafluorophosphate (OMIM PF6), hexylpyridinium bis(trifluorophosphat
- Cation/anion combinations leading to ionic liquids include, for example, dialkylimidazolium, pyridinium, ammonium and phosphonium, etc. with organic anions such as sulfonates, imides, methides, etc., as well as inorganic anions such as halides and phosphates, etc., such that any other combination of cations and anions with which a low melting point can be achieved is also conceivable.
- Ionic liquids have an extremely low vapor pressure, depending on their chemical structure, are nonflammable and often have thermal stability up to more than 260°C and furthermore are also suitable as lubricants.
- the respective desired properties of the lubricant oil are achieved with the ionic liquids through a suitable choice of cations and anions. These desirable properties include adjusting electrical conductivity of the lubricant to spread the area of use, increasing the service life and lubricating effect of the lubricant, and adjusting the viscosity to improve the temperature suitability.
- Suitable cations for ionic liquids have proven to be a phosphonium cation, an imidazolium cation, a pyridinium cation or a pyrrolidinium cation which may be combined with an anion containing fluorine and selected from bis(trifluoromethylsulfonyl)imide, bis(perfluoroalkylsulfonyl)imide, perfluoroalkyl sulfonate, tris(perfluoroalkyl)methidenes, bis(perfluoroalkyl)imidenes, bis(perfluoroaryl)imides, perfluoroarylperfluoroalkylsulfonylimides and tris(perfluoro-alkyl) trifluorophosphate or with a halogen-free alkyl sulfate anion.
- Ionic liquids useful in the present disclosure are those that are soluble in hydrocarbon, hydrophobic-type, fluids (i.e. oil-soluble), and soluble in suitable lubricating/working fluids.
- Ionic liquids that are also useful in the present disclosure are those that are soluble in polar, hydrophilic- or amphiphilic-type, fluids (e.g. esters, ethers, etc.), and soluble in suitable lubricating/working fluids.
- ionic liquids useful in the present disclosure may also be used in solid or semisolid lubricants such as e.g. greases.
- such ionic liquid additives may be used in an amount of about 0.1 to 10 weight percent, preferably 0.5 to 7.5 weight percent, more preferably about 0.75 to 5 weight percent.
- antistatic fluids or "antistatic additives”, which also are petroleum distillates, can be added to adjust the conductivity of a lubricant oil to safe levels, e.g., at or above 100 pico-siemens per meter conductivity. Very small quantities of these antistatic fluids are required to raise the conductivity to the desired levels, namely, some 10 to 30 milliliters per 1,000 gallons of hydrocarbon.
- the antistatic additive is selected from a population of commercially available materials based on the ability of the material's chemical compatibility with the lubricating oil and the cost effectiveness of adjusting the conductivity of the lubricating oil to the desired level for the lubricating oil's anticipated application.
- Typical antistatic fluids are ExxonMobilTM Chemical's line of de-aromatized hydrocarbon fluids known as ExxsolTM fluids.
- Representative fluids and their distillation points include ExxsolTM antistatic fluids hexane (65 IBP (°C) min, 71 DP (°C) max, and additive amount 30 ml/1000 gal), D 40 (150 IBP (°C) min, 210 DP (°C) max, and additive amount 30 ml/1000 gal), D 3135 (152 IBP (°C) min, 182 DP (°C) max, and additive amount 10 ml/1000 gal), and D 60 (177 IBP (°C) min, 220 DP (°C) max, and additive amount 30 ml/1000 gal).
- the IBP is the temperature at which 1% of the material is distilled
- the DP is the temperature at which 96% of the material is distilled.
- antistatic agents are based on long-chain aliphatic amines (optionally ethoxylated) and amides, quaternary ammonium salts (e.g., behentrimonium chloride or cocamidopropyl betaine), esters of phosphoric acid, polyethylene glycol esters, or polyols.
- Additional antistatic agents include long-chain alkyl phenols, ethoxylated amines, glycerol esters, such as glycerol monostearate, amides, glycols, and fatty acids.
- the quantity of antistatic additive required to adjust the conductivity of the lubricating oil is determined by measuring the conductivity of the lubricating oil as the antistatic additive is mixed in and stopping when the desired conductivity consistent with the application to be reached.
- the amount of antistatic additive mixed in will range between 0.001% and 10% of the lubricating oil by weight, and preferentially between 1% and 7.5% by weight, though it may be mixed in at a liquid volume of between 10 and 100,000 parts per million.
- pour point depressants also known as lube oil flow improvers
- pour point depressants may be added to lubricating oil compositions of the present disclosure if desired.
- These pour point depressant may be added to lubricating compositions of the present disclosure to lower the minimum temperature at which the fluid will flow or can be poured.
- suitable pour point depressants include polymethacrylates, polyacrylates, polyarylamides, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, and terpolymers of dialkylfumarates, vinyl esters of fatty acids and allyl vinyl ethers.
- 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 0.1 to 3 weight percent, more preferably about 0.5 to 1.5 weight percent.
- the lubricating oil compositions can include at least one seal compatibility agent.
- Seal compatibility agents help to swell elastomeric seals by causing a chemical reaction in the fluid or physical change in the elastomer.
- Suitable seal compatibility agents for lubricating oils include organic phosphates, aromatic esters, aromatic hydrocarbons, esters (butylbenzyl phthalate, for example), and polybutenyl succinic anhydride.
- Such additives may be used in an amount of about 0.01 to 5 weight percent, preferably 0.1 to 3 weight percent, more preferably about 0.5 to 1.5 weight percent.
- Antifoam agents may advantageously be added to lubricant compositions. These agents retard the formation of stable foams. Silicones and organic polymers are typical antifoam agents. For example, polysiloxanes, such as silicon oil or polydimethyl siloxane, provide antifoam properties. Antifoam agents are commercially available and may be used in conventional minor amounts along with other additives such as demulsifiers; usually the amount of these additives combined is less than 1 weight percent and often less than 0.1 weight percent. In an embodiment, such additives may be used in an amount of about 0.01 to 5 weight percent, preferably 0.1 to 3 weight percent, more preferably about 0.5 to 1.5 weight percent.
- the lubricating oil compositions can include at least one friction modifier.
- a friction modifier is any material or materials that can alter the coefficient of friction of a surface lubricated by any lubricant or fluid containing such material(s). Friction modifiers, also known as friction reducers, or lubricity agents or oiliness agents, and other such agents that change the ability of base oils, formulated lubricant compositions, or functional fluids, to modify the coefficient of friction of a lubricated surface may be effectively used in combination with the base oils or lubricant compositions of the present disclosure if desired. Friction modifiers that lower the coefficient of friction are particularly advantageous in combination with the base oils and lube compositions of this disclosure.
- Illustrative friction modifiers may include, for example, organometallic compounds or materials, or mixtures thereof.
- Illustrative organometallic friction modifiers useful in the lubricating engine oil 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 lubricating engine oil 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 lubricating oils of this disclosure exhibit desired properties, e.g., wear control, in the presence or absence of a friction modifier.
- Useful concentrations of friction modifiers may range from 0.01 weight percent to 5 weight percent, or about 0.1 weight percent to about 2.5 weight percent, or about 0.1 weight percent to about 1.5 weight percent, or about 0.1 weight percent to about 1 weight percent. Concentrations 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.
- the lubricating oil compositions can include at least one extreme pressure agent (EP).
- EP agents that are soluble in the oil include sulfur- and chlorosulfur-containing EP agents, chlorinated hydrocarbon EP agents and phosphorus EP agents.
- EP agents include chlorinated wax; sulfurized olefins (such as sulfurized isobutylene), organic sulfides and polysulfides such as dibenzyldisulfide, bis-(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, sulfurized terpene, and sulfurized Diels-Alder adducts; phosphosulfurized hydrocarbons such as the reaction product of phosphorus sulfide with turpentine or methyl oleate; phosphorus esters such as the dihydrocarbon and trihydrocarbon phosphites, e.
- the extreme pressure agents may be used in an amount of 0.01 to 5 wt %, preferably 0.01 to 1.5 wt %, more preferably 0.01 to 0.2 wt %, still more preferably 0.01 to 0.1 wt % (on an as-received basis) based on the total weight of the lubricating oil composition.
- Typical amounts of such additives useful in the present disclosure are shown in Table 1 below.
- Viscosity Modifier (solid 0-20 0.1-10
- Antifoam Agent 0-3 0.001-0.15
- 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 lubricating oil has a composition comprising at least about 80 weight percent of a lubricating base oil, from about 0.8 to about 5 weight percent of one or more metal detergents, from about 0 to about 5 weight percent of one or more dispersants, from about 0 to about 1.5 weight percent of zinc dialkyldithiophosphate (ZDDP) antiwear agent, from about 0 to about 0.2 weight percent of a molybdenum dialkyldithiocarbamate (MoDTC), from about 0 to about 2 weight percent of an active viscosity modifier, and from about 0.01 to about 5 weight percent of other lubricating oil additives.
- ZDDP zinc dialkyldithiophosphate
- MoDTC molybdenum dialkyldithiocarbamate
- the lubricating oil has an electrical conductivity from about 3,000 pS/m to about 20,000 pS/m and a kinematic viscosity from about 2 cSt to about 20 cSt at 100°C.
- the lubricating oil has a composition comprising at least about 80 weight percent of a lubricating base oil, from about 0.8 to about 1.25 weight percent of one or more metal detergents, from about 0.5 to about 5 weight percent of one or more dispersants, from about 0.6 to about 1.5 weight percent of zinc dialkyldithiophosphate (ZDDP) antiwear agent, about 0.15 weight percent of a molybdenum dialkyldithiocarbamate (MoDTC), from about 0 to about 2 weight percent of an active viscosity modifier, and from about 0.01 to about 5 weight percent of other lubricating oil additives. Each weight percent is based on the total weight of the lubricating oil.
- the lubricating oil has an electrical conductivity from about 3,000 pS/m to about 8,000 pS/m and a kinematic viscosity from about 2 cSt to about 20 cSt at 100°C.
- Lubricant compositions and the viscosity and conductivity test results for such compositions are provided below and in FIGS. 1-7.
- the components of compositions are described in weight percent, where weight percent is based on the total weight of the lubricating oil.
- FIGS. 1-4 provide examples of compositions that have suitable electrical conductivity over the range of about 3,000 pS/m to about 20,000 pS/m.
- FIG. 5 identifies conductivity inhibitors and provides the effects of reducing the conductivity of a lubricant composition.
- conductivity inhibitors identified were: zinc dithiodialkylphosphate (Ex.45), molybdenum dithiocarbamate (Ex.46), and magnesium alkylsulfonate (Ex.47). Their inhibitor effects were observed by comparison to the composition of Example 25. These inhibitor effects were demonstrated in this case in a higher conductivity range, from about 7,500 pS/m to over 100,000 pS/m, but such effects are also operative in the lower conductivity range of 3,000 pS/m to 20,000 pS/m.
- FIG. 6 demonstrates the conductivity promoter activity of a mixture of calcium salicylate detergents (having TBN ranging from ⁇ 100 to >200), at combined concentrations of up to about 1.3 weight percent. Increases in electrical conductivity were observed by comparing compositions with and without salicylate detergents, for example, compositions Ex.3 versus Ex.35, and Ex.5 versus Ex.48, and Ex.10 versus Ex.18. The conductivity promoter of activity of these calcium salicylate detergents was effective over a range of conductivity inhibitor concentrations, for example, up to about 1.4 weight percent for ZDDP.
- FIG. 7 illustrates the influence of uncapped PIB succinimide dispersant on the conductivity activity of conductivity inhibitors.
- the conductivity inhibitors for example ZDDP, MoDTC
- Lubricating oils for electric vehicles were prepared by blending at least one lubricating oil base stock selected from a Group I, Group II, Group III, Group IV, Group V base stock, and combinations thereof, with one or more lubricating oil additives selected from an antioxidant, a detergent, a dispersant, an antiwear additive, a viscosity modifier, a friction modifier, and an antifoam agent in weight percent.
- lubricating oil additives selected from an antioxidant, a detergent, a dispersant, an antiwear additive, a viscosity modifier, a friction modifier, and an antifoam agent in weight percent.
- Optional additives are one or more of a pour point depressant, metal deactivator, seal compatibility additive, extreme pressure agent, and corrosion inhibitor.
- a lubricating oil for use in an electric or hybrid vehicles comprising: at least 80 weight percent of a lubricating base oil, from 0.8 to 5 weight percent of one or more metal detergents, from O to 5 weight percent of one or more dispersants, from O to 1.5 weight percent of zinc dialkyldithiophosphate (ZDDP) antiwear agent, from 0 to 0.2 weight percent of a molybdenum dialkyldithiocarbamate (MoDTC), from 0 to 2 weight percent of a viscosity modifier based on active ingredient, and from 0.01 to 5 weight percent of other lubricating oil additives, and wherein the lubricating oil has an electrical conductivity from 3,000 pS/m to 20,000 pS/m, and kinematic viscosity from 2 cSt to 20 cSt at 100°C.
- ZDDP zinc dialkyldithiophosphate
- MoDTC molybdenum dialkyldithiocarbamate
- the lubricating base oil comprises a Group I base stock, a Group II base stock, a Group III base stock, a Group IV base stock, a Group V base stock, or mixtures thereof.
- a method for lubricating electric or hybrid vehicles comprising: providing to one or more components of the electric or hybrid vehicle powertrain a lubricating oil comprising at least 80 weight percent of a lubricating base oil, from 0.8 to 5 weight percent of one or more metal detergents, from 0 to 5 weight percent of one or more dispersants, from 0 to 1.5 weight percent of zinc dialkyldithiophosphate (ZDDP) antiwear agent, from 0 to 0.2 weight percent of a molybdenum dialkyldithiocarbamate (MoDTC), from 0 to 2 weight percent of a viscosity modifier based on active ingredient, and from 0.01 to 5 weight percent of other lubricating oil additives, and wherein the lubricating oil has an electrical conductivity from 3,000 pS/m to 20,000 pS/m, and kinematic viscosity from 2 cSt to 20 cSt at 100°C.
- ZDDP zinc dialkyldithiophosphate
- the lubricating base oil comprises a Group I base stock, a Group II base stock, a Group III base stock, a Group IV base stock, a Group V base stock, or mixtures thereof.
- the one or more components of the electric or hybrid vehicle powertrain include one or more of an electric motor, an electric drive motor, a motor, a transmission, a front axle, a rear axle, a gear box, a differential, gears, bearings, a battery, a capacitor, a generator, an alternator, a converter, a kinetic energy accumulator, or a kinetic energy recovery system.
- a method of producing a lubricating oil for use in electric or hybrid vehicles comprising: providing at least 80 weight percent of a lubricating base oil, from 0.8 to 5 weight percent of one or more metal detergents, from 0 to 5 weight percent of one or more dispersants, from O to 1.5 weight percent of zinc dialkyldithiophosphate (ZDDP), from O to 0.2 weight percent of molybdenum dialkyldithiocarbamate (MoDTC), from 0 to 2 weight percent of an active viscosity modifier, and from 0.01 to 5 weight percent of other lubricating oil additives; and blending the lubricating base oil, the one or more dispersants, the one or more metal detergents, the zinc dialkyldithiophosphate, the molybdenum dialkyldithiocarbamate, the active viscosity modifier and the one or more other lubricating oil additives to produce the lubricating oil, and wherein the lubricating oil has electrical conductivity of from 3,000
Abstract
La présente invention concerne une huile lubrifiante pour véhicules électriques et hybrides. L'huile lubrifiante a une composition comprenant au moins 80 % en poids d'une huile de base lubrifiante, de 0,8 à 5 % en poids d'un ou plusieurs détergents métalliques, de 0 à 5 % en poids d'un ou plusieurs dispersants, de 0 à 1,5 % en poids d'un agent antiusure dialkyldithiophosphate de zinc, de 0 à 0,2 % en poids d'un dialkyldithiocarbamate de molybdène, de 0 à 2 % en poids d'un modificateur de viscosité à base d'un principe actif, et de 0,01 à 5 % en poids d'autres additifs d'huile lubrifiante. L'huile lubrifiante présente une conductivité électrique de 3 000 à 20 000 pS/m et une viscosité cinématique de 2 à 20 cSt à 100 °C. La présente invention concerne également des procédés de production de l'huile lubrifiante, des procédés de lubrification de véhicules électriques et hybrides, et des procédés de régulation de la conductivité électrique d'une huile lubrifiante à l'aide de promoteurs de conductivité et d'inhibiteurs de conductivité.
Priority Applications (3)
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SG11201901539UA SG11201901539UA (en) | 2016-10-07 | 2017-10-06 | High conductivity lubricating oils for electric and hybrid vehicles |
EP17787781.8A EP3523405A1 (fr) | 2016-10-07 | 2017-10-06 | Huiles lubrifiantes à haute conductivité pour véhicules électriques et hybrides |
JP2019518507A JP2019529675A (ja) | 2016-10-07 | 2017-10-06 | 電動車両およびハイブリッド車両のための高伝導率の潤滑油 |
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US15/725,635 US20180100115A1 (en) | 2016-10-07 | 2017-10-05 | High conductivity lubricating oils for electric and hybrid vehicles |
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WO2018067906A1 true WO2018067906A1 (fr) | 2018-04-12 |
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PCT/US2017/055485 WO2018067902A1 (fr) | 2016-10-07 | 2017-10-06 | Compositions d'huile lubrifiante pour un groupe motopropulseur de véhicule électrique |
PCT/US2017/055499 WO2018067908A1 (fr) | 2016-10-07 | 2017-10-06 | Huiles lubrifiantes à faible conductivité pour véhicules électriques et hybrides |
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PCT/US2017/055485 WO2018067902A1 (fr) | 2016-10-07 | 2017-10-06 | Compositions d'huile lubrifiante pour un groupe motopropulseur de véhicule électrique |
PCT/US2017/055499 WO2018067908A1 (fr) | 2016-10-07 | 2017-10-06 | Huiles lubrifiantes à faible conductivité pour véhicules électriques et hybrides |
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EP (3) | EP3523410A1 (fr) |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2020132763A (ja) * | 2019-02-20 | 2020-08-31 | 日立建機株式会社 | 作業機械用油圧作動油及びそれを用いた作業機械 |
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JP2019532151A (ja) | 2019-11-07 |
US20180100114A1 (en) | 2018-04-12 |
US20180100115A1 (en) | 2018-04-12 |
WO2018067902A1 (fr) | 2018-04-12 |
EP3523410A1 (fr) | 2019-08-14 |
SG11201901512RA (en) | 2019-04-29 |
SG11201901704WA (en) | 2019-04-29 |
JP2019532150A (ja) | 2019-11-07 |
EP3523406A1 (fr) | 2019-08-14 |
EP3523405A1 (fr) | 2019-08-14 |
SG11201901539UA (en) | 2019-04-29 |
JP2019529675A (ja) | 2019-10-17 |
US20180100117A1 (en) | 2018-04-12 |
WO2018067908A1 (fr) | 2018-04-12 |
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