EP3494200A1 - Huile lubrifiante pour moteur pour une protection améliorée contre l'usure et une efficacité améliorée du carburant - Google Patents

Huile lubrifiante pour moteur pour une protection améliorée contre l'usure et une efficacité améliorée du carburant

Info

Publication number
EP3494200A1
EP3494200A1 EP17754537.3A EP17754537A EP3494200A1 EP 3494200 A1 EP3494200 A1 EP 3494200A1 EP 17754537 A EP17754537 A EP 17754537A EP 3494200 A1 EP3494200 A1 EP 3494200A1
Authority
EP
European Patent Office
Prior art keywords
oil
lubricating
viscosity
dispersant
engine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17754537.3A
Other languages
German (de)
English (en)
Inventor
Michael L. Alessi
Steven M. Jetter
Steven Kennedy
Sarah E. Parker
Van An DU
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Technology and Engineering Co
Original Assignee
ExxonMobil Research and Engineering Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ExxonMobil Research and Engineering Co filed Critical ExxonMobil Research and Engineering Co
Publication of EP3494200A1 publication Critical patent/EP3494200A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C10M133/56—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/003—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/043—Mannich bases
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54—Fuel economy
    • 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
    • C10N2030/68—Shear stability
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01M—LUBRICATING OF MACHINES OR ENGINES IN GENERAL; LUBRICATING INTERNAL COMBUSTION ENGINES; CRANKCASE VENTILATING
    • F01M9/00—Lubrication means having pertinent characteristics not provided for in, or of interest apart from, groups F01M1/00 - F01M7/00
    • F01M9/02—Lubrication means having pertinent characteristics not provided for in, or of interest apart from, groups F01M1/00 - F01M7/00 having means for introducing additives to lubricant

Definitions

  • This disclosure relates to improving wear protection, while maintaining or improving fuel economy, in an engine lubricated with a lubricating oil by including a low viscosity carboxylic functionalized polymer dispersant in the lubricating oil.
  • This disclosure also relates to improving fuel efficiency, while maintaining or improving wear protection, in an engine lubricated with a lubricating oil by including a low viscosity carboxylic functionalized polymer dispersant in the lubricating oil.
  • Lubricating oil formulations typically strike a balance between the need for wear protection and the desire for fuel efficiency because the viscosity of the final fluid has a strong impact on both characteristics, but in opposite directions.
  • a higher viscosity lubricating oil will possess more internal fluid traction, which reduces fuel efficiency.
  • High molecular weight additives used in lubricating oils can greatly increase the kinematic viscosity and high-temperature high-shear viscosity of a lubricating oil formulation.
  • Dispersants are necessary components that allow engine lubricants to achieve required dispersancy performance of soot, water, and other contaminants at treat levels up to 10 wt% of the formulation. Consequently, the addition of a dispersant typically has a significant impact on the viscosity of the lubricating oil.
  • Heavy-duty engine oils such as 5W-30 SAE grade lubricating oils, utilize "standard" PIBSA-PAM (polyisobutylene succinic anhydride-polyamine) dispersants and lower base oil viscosity than the disclosed invention.
  • PIBSA-PAM polyisobutylene succinic anhydride-polyamine
  • This disclosure relates in part to a method for improving engine wear protection, while maintaining or improving fuel efficiency, in an engine lubricated with a lubricating oil by providing to the engine a lubricating oil including a lubricating oil base stock as a major component, and a carboxylic functionalized polymer dispersant with aromatic amine functionality, as a minor component in the lubricating oil, wherein the lubricating oil has a base oil viscosity at 100 deg. C ranging from 4.5 to 7.5 cSt, and wherein the lubricating oil has a cold crank simulator viscosity at -30 deg. C of less than 8500 mPa.s.
  • the lubricating oils of this disclosure are useful in internal combustion engines including direct injection, gasoline and diesel engines.
  • This disclosure also relates in part to a method for improving fuel efficiency, while maintaining or improving engine wear protection, in an engine lubricated with a lubricating oil by providing to the engine a lubricating oil including a lubricating oil base stock as a major component, and a carboxylic functionalized polymer dispersant with aromatic amine functionality, as a minor component in the lubricating oil, wherein the lubricating oil has a base oil viscosity at 100 deg. C ranging from 4.5 to 7.5 cSt, and wherein the lubricating oil has a cold crank simulator viscosity at -30 deg. C of less than 8500 mPa.s.
  • This disclosure further relates in part to a multi-grade lubricating engine oil having a composition comprising a lubricating oil base stock as a major component, and a carboxylic functionalized polymer dispersant with aromatic amine functionality, as a minor component, wherein the multi -grade lubricating engine oil has a base oil viscosity at 100 deg. C ranging from 4.5 to 7.5 cSt, and wherein the multi -grade lubricating engine oil has a cold crank simulator viscosity at -30 deg. C of less than 8500 mPa.s.
  • the carboxylic functionalized polymer dispersant with aromatic amine functionality includes a polymer backbone comprising grafted ethylene- propylene (EP) copolymers, or grafted terpolymers of ethylene, propylene and non-conjugated diene, or a combination of grafted EP copolymers and grafted EP non-conjugated diene terpolymers.
  • the carboxylic acid functionality is grafted either onto the polymer backbone, within the polymer backbone or as a terminal group on the polymer backbone.
  • the amine group has at least 3 aromatic groups and may be selected from the group consisting of bis[p-(p- aminoanilino)phenyl] -methane, 2-(7-amino-acridin-2-ylmethyl)-N-4- ⁇ 4-[4-(4-amino- pheny lamino)-benzy 1] -phenyl ⁇ -benzene- 1 ,4-diamine, N 4 - ⁇ 4-[4-(4-amino-pheny lamino)-benzyl] - phenyl ⁇ -2-[4-(4-amino-phenylamino)-cyclohexa-l,5-dienylmethyl]-benzene-l ,4-diamine, N-[4- (7-amino-acridin-2-ylmethyl)-phenyl] -benzene- 1,4-diamine, and combinations thereof. Fuel efficiency and wear protection are improved or maintained as compared to fuel efficiency
  • This disclosure further relates to a method of method of making a lubricating engine oil including the steps of: providing a lubricating oil base stock having a base oil viscosity at 100 deg. C ranging from 4.5 to 7.5 cSt, and a carboxylic functionalized polymer dispersant with aromatic amine functionality, and blending from 50 to 99 wt.%, based on the total weight of the oil, of the lubricating oil base stock with from 1 to 15 wt.%, based on the total weight of the oil, of the carboxylic functionalized polymer dispersant with aromatic amine functionality to form the lubricating engine oil, wherein the lubricating engine oil has a cold crank simulator viscosity at - 30 deg. C of less than 8500 mPa.s.
  • Figure 1 shows an inventive formulation embodiment of this disclosure, in particular, individual contributions of components and viscometric properties to three baseline formulations (comparative examples) used in the Examples. Formulation details are shown in weight percent based on the total weight percent of the formulation, of various formulations.
  • Figure 2 shows another inventive formulation embodiment of this disclosure, in particular, individual contributions of components and viscometric properties to another baseline formulation (comparative example) used in the Examples. Formulation details are shown in weight percent based on the total weight percent of the formulation, of various formulations.
  • Figure 3 graphically depicts ultrashear viscosities of inventive lubricating oil formulation E and comparative lubricating oil formulation F.
  • Figure 4 shows two inventive formulations of this disclosure, and in particular, individual contributions of components and viscometric properties to one comparative formulation used in the Examples for a 2.6 cSt HTHS viscosity formulation with a Group III basestock.
  • Figure 5 shows two more inventive formulations of this disclosure, and in particular, individual contributions of components and viscometric properties to another comparative formulation used in the Examples for a 2.9 cSt HTHS viscosity formulation with a Group III basestock.
  • Figure 6 shows two more inventive formulations of this disclosure, and in particular, individual contributions of components and viscometric properties to another comparative formulation used in the Examples for a 3.2 cSt HTHS viscosity formulation with a Group III basestock.
  • Figure 7 shows two inventive formulations of this disclosure, and in particular, individual contributions of components and viscometric properties to one comparative formulation used in the Examples for a 2.6 cSt HTHS viscosity formulation with a Group II basestock.
  • Figure 8 shows two more inventive formulations of this disclosure, and in particular, individual contributions of components and viscometric properties to another comparative formulation used in the Examples for a 2.9 cSt HTHS viscosity formulation with a Group II basestock.
  • Figure 9 shows two more inventive formulations of this disclosure, and in particular, individual contributions of components and viscometric properties to another comparative formulation used in the Examples for a 3.2 cSt HTHS viscosity formulation with a Group II basestock.
  • the high shear viscosity of a lubricating oil including as a minor component a carboxylic functionalized polymer dispersant with aromatic amine functionality is increased by at least 2 %, or at least 4%, or at least 6%, or at least 8% or at least 10% compared to a comparable lubricating oil including a conventional dispersant as opposed to the carboxylic functionalized polymer dispersant.
  • the HFRR wear scar depth in microns of inventive lubricating oils including the carboxylic functionalized polymer dispersant with aromatic amine functionality may be less than or equal to 205, or less than or equal to 202, or less than or equal to 200, or less than or equal to 195, or less than or equal to 190, or less than or equal to 185, or less than or equal to 180, or less than or equal to 175, or less than or equal to 170. or less than or equal to 165, or less than or equal to 160, or less than or equal to 155.
  • the high shear viscosity of a lubricating oil including as a minor component a carboxylic functionalized polymer dispersant with aromatic amine functionality is increased by at least 2 %, or at least 4%, or at least 6%, or at least 8% or at least 10% compared to a comparable lubricating oil including a conventional dispersant as opposed to the carboxylic functionalized polymer dispersant.
  • a lubricating oil as a minor component a carboxylic functionalized polymer dispersant with aromatic amine functionality while maintaining wear protection compared to a lubricating oil including a conventional dispersant.
  • the HTHS viscosity of the lubricating oil is decreased by at least 2 %, or at least 4%, or at least 6%, or at least 8% or at least 10% compared to a comparable lubricating oil including a conventional dispersant as opposed to the carboxylic functionalized polymer dispersant.
  • These decreases in HTHS viscosity translate directly and equivalently into increases in fuel efficiency of at least 2 %, or at least 4%, or at least 6%, or at least 8% or at least 10%.
  • the formulated oil preferably comprises a lubricating oil base stock as a maj or component, and a carboxylic functionalized polymer dispersant with aromatic amine functionality, as a minor component.
  • the lubricating oils of this disclosure are particularly advantageous as heavy duty diesel engine oil (HDEO) products.
  • the formulated oils of the instant disclosure are particularly suited for API multi-grade lubricating oils, and in particular heavy-duty engine oils, such as SAE 5W-30 grade oil.
  • the low viscosity carboxylic functionalized polymer dispersant allows for a higher base oil viscosity than in conventional multi-grade lubricating oils, which provides for improved wear protection of the engine.
  • the base oil viscosity (as defined in the Examples section) at 100 deg.
  • C of the multi-grade lubricating oils of the instant disclosure may range from 4.5 to 7.5 cSt, or from 5.0 to 7.0 cSt, or from 5.5 to 6.5 cSt, or from 5.8 to 6.2 cSt.
  • the multi-grade formulated oils including the low viscosity carboxylic functionalized polymer dispersant of the instant disclosure may have a cold crank simulator viscosity at -30 deg. C (ASTM D5293) of less than 8500 mPa.s, or less than 8000 mPa.s, or less than 7500 mPa.s, or less than 7000 mPa.s, or less than 6600 mPa.s.
  • conventional lubricating oils of the same viscosity grade which include PIBSA-PAM (polyisobutylene succinic anhydride- poly amine) dispersants, have a lower base oil viscosity at 100 deg. C and more particularly a base oil viscosity of less than 5.5 cSt, or even more particularly a base oil viscosity of less than 5.0 cSt, which yields significantly worse wear protection of the engine.
  • PIBSA-PAM polyisobutylene succinic anhydride- poly amine
  • the lubricating oils of this disclosure provide excellent engine protection including friction reduction and anti-wear performance.
  • the lubricating oils of this disclosure provide improved fuel efficiency.
  • a lower HTHS viscosity engine oil generally provides superior fuel economy to a higher HTHS viscosity product. This benefit may be demonstrated for the lubricating oils of this disclosure in track testing, such as SAE J1321 fuel consumption testing.
  • the lubricating engine oils of this disclosure have a composition sufficient to pass wear protection requirements of one or more engine tests selected from Cummins ISM, Cummins ISB, and others.
  • Lubricating base oils that are useful in the present disclosure are both natural oils, and synthetic oils, and unconventional oils (or mixtures thereof) can be used unrefined, refined, or rerefined (the latter is also known as reclaimed or reprocessed oil).
  • Unrefined oils are those obtained directly from a natural or synthetic source and used without added purification. These include shale oil obtained directly from retorting operations, petroleum oil obtained directly from primary distillation, and ester oil obtained directly from an esterification process. Refined oils are similar to the oils discussed for unrefined oils except refined oils are subjected to one or more purification steps to improve at least one lubricating oil property.
  • 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 80 to 120 and contain greater than 0.03% sulfur and/or less than 90% saturates.
  • Group II base stocks have a viscosity index of between 80 to 120, and contain less than or equal to 0.03% sulfur and greater than or equal to 90% saturates.
  • Group III stocks have a viscosity index greater than 120 and contain less than or equal to 0.03 % sulfur and greater than 90% saturates.
  • Group IV includes polyalphaolefins (PAO).
  • Group V base stock includes base stocks not included in Groups I-IV. The table below summarizes properties of each of these five groups.
  • Natural oils include animal oils, vegetable oils (castor oil and lard oil, for example), and mineral oils. Animal and vegetable oils possessing favorable thermal oxidative stability can be used. Of the natural oils, mineral oils are preferred. Mineral oils vary widely as to their crude source, for example, as to whether they are paraffinic, naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal or shale are also useful. Natural oils vary also as to the method used for their production and purification, for example, their distillation range and whether they are straight run or cracked, hydrorefined, or solvent extracted.
  • Group II and/or Group III hydroprocessed or hydrocracked basestocks including synthetic oils such as polyalphaolefins, alkyl aromatics and synthetic esters are also well known basestock oils.
  • Synthetic oils include hydrocarbon oil.
  • Hydrocarbon oils include oils such as polymerized and interpolymerized olefins (polybutylenes, polypropylenes, propylene isobutylene copolymers, ethylene-olefin copolymers, and ethylene-alphaolefin copolymers, for example).
  • Polyalphaolefin (PAO) oil base stocks are commonly used synthetic hydrocarbon oil.
  • PAOs derived from Ce, 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 250 to 3,000, although PAO's may be made in viscosities up to 100 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 C32 alphaolefins with the Cs to C1 ⁇ 2 alphaolefins, such as 1-octene, 1-decene, 1-dodecene and the like, being preferred.
  • the preferred polyalphaolefins are poly- 1-octene, poly- 1-decene and poly- 1-dodecene and mixtures thereof and mixed olefin- derived polyolefins.
  • the dimers of higher olefins in the range of C14 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 combinations thereof. Mixtures of PAO fluids having a viscosity range of 1.5 to approximately 100 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 Fischer-Tropsch waxes, the high boiling point residues of Fischer-Tropsch synthesis, are highly paraffinic hydrocarbons with very low sulfur content.
  • 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.
  • GTL Gas-to-Liquids
  • 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 3 cSt to 50 cSt, preferably 3 cSt to 30 cSt, more preferably 3.5 cSt to 25 cSt, as exemplified by GTL 4 with kinematic viscosity of 4.0 cSt at 100°C and a viscosity index of 141.
  • Gas-to-Liquids (GTL) base oils may have useful pour points of -20°C or lower, and under some conditions may have advantageous pour points of -25°C or lower, with useful pour points of -30°C to -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 base oil or base oil component and can be any hydrocarbyl molecule that contains at least 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 Ce up to Ceo with a range of Cs to C20 often being preferred. A mixture of hydrocarbyl groups is often preferred, and up to 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 5% of the molecule is comprised of an above-type aromatic moiety.
  • Viscosities at 100°C of approximately 3 cSt to 50 cSt are preferred, with viscosities of approximately 3.4 cSt to 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 2% to 25%, preferably 4% to 20%, and more preferably 4% to 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, is alkylated by an olefin, alkyl halide or alcohol in the presence of a Friedel-Crafts catalyst.
  • 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 4 carbon atoms, preferably C5 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 polyols
  • 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 5 to 10 carbon atoms. These esters are widely available commercially, for example, the Mobil P-41 and P-51 esters of ExxonMobil Chemical Company. [0046] Also useful are esters derived from renewable material such as coconut, palm, rapeseed, soy, sunflower and the like. These esters may be monoesters, di-esters, polyol esters, complex esters, or mixtures thereof. These esters are widely available commercially, for example, the Mobil P-51 ester of ExxonMobil Chemical Company.
  • Engine oil formulations containing renewable esters are included in this disclosure.
  • the renewable content of the ester is typically greater than 70 weight percent, preferably more than 80 weight percent and most preferably more than 90 weight percent.
  • 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 2 mm 2 /s to 50 mm 2 /s (ASTM D445). They are further characterized typically as having pour points of -5°C to -40°C or lower (ASTM D97). They are also characterized typically as having viscosity indices of 80 to 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 10 ppm, and more typically less than 5 ppm of each of these elements.
  • the sulfur and nitrogen content of GTL base stock(s) and/or base oil(s) obtained from F-T material, especially F-T wax, is essentially nil.
  • the absence of phosphorous and aromatics make this materially especially suitable for the formulation of low SAP products.
  • GTL base stock and/or base oil and/or wax isomerate base stock and/or base oil is to be understood as embracing individual fractions of such materials of wide viscosity range as recovered in the production process, mixtures of two or more of such fractions, as well as mixtures of one or two or more low viscosity fractions with one, two or more higher viscosity fractions to produce a blend wherein the blend exhibits a target kinematic viscosity.
  • the GTL material, from which the GTL base stock(s) and/or base oil(s) is/are derived is preferably a F-T material (i.e., hydrocarbons, waxy hydrocarbons, wax).
  • 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) and hydrodewaxed, or hydroisomerized/cat (and/or solvent) dewaxed base stock(s) and/or base oil(s) typically have very low sulfur and nitrogen content, generally containing less than 10 ppm, and more typically less than 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 material especially suitable for the formulation of low sulfur, sulfated ash, and phosphorus (low SAP) products.
  • Base oils for use in the formulated lubricating oils useful in the present disclosure are any of the variety of oils corresponding to API Group I, Group II, Group III, Group IV, and Group V oils and mixtures thereof, preferably API Group II, Group III, Group IV, and Group V oils and mixtures thereof, more preferably the Group III to Group V base oils due to their exceptional volatility, stability, viscometric and cleanliness features.
  • Minor quantities of Group I stock such as the amount used to dilute additives for blending into formulated lube oil products, can be tolerated but should be kept to a minimum, i.e. amounts only associated with their use as diluent/carrier oil for additives used on an "as-received" basis.
  • 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 50 to 99 weight percent, preferably from 70 to 95 weight percent, and more preferably from 85 to 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 2.5 cSt to 12 cSt (or mm 2 Is) at 100°C and preferably of 2.5 cSt to 9 cSt (or mm 2 /s) at 100°C. Mixtures of synthetic and natural base oils may be used if desired. Bi-modal mixtures of Group I, II, III, IV, and/or V base stocks may be used if desired.
  • the carboxylic functionalized polymer dispersant which is functionalized with an aromatic amine may be a carboxylic functionalized polymer.
  • the carboxylic functionalized polymer backbone may be a copolymer or a terpolymer, provided that it contains at least one carboxylic acid functionality or a reactive equivalent of carboxylic acid functionality (e.g., anhydride or ester).
  • the carboxylic functionalized polymer has a carboxylic acid functionality (or a reactive equivalent of carboxylic acid functionality) grafted onto the backbone, or alternatively within the polymer backbone, or alternatively as a terminal group on the polymer backbone.
  • the carboxylic functionalized polymer described herein may be grafted with grafted ethylene-propylene (EP) copolymers, terpolymers of ethylene, propylene and non-conjugated diene (such as dicyclopentadiene or butadiene), or combinations of EP copolymers and EP non- conjugated diene terpolymers.
  • EP ethylene-propylene
  • EP copolymers such as dicyclopentadiene or butadiene
  • EP non-conjugated diene such as dicyclopentadiene or butadiene
  • the polymer backbone (other than a polyisobutylene) of the present disclosure may have a number average molecular weight (by gel permeation chromatography, polystyrene standard), which may be up to 150,000 or higher, e.g., 1 ,000 or 5,000 to 150,000 or to 120,000 or to 100,000.
  • An example of a suitable number average molecular weight range includes 10,000 to 50,000, or 6,000 to 15,000, or 30,000 to 50,000.
  • the polymer backbone has a number average molecular weight of greater than 5,000, for instance, greater than 5000 to 150,000. Other combinations of the above-identified molecular weight limitations are also contemplated.
  • the carboxylic functionalized polymer dispersant which is functionalized with an aromatic amine has a backbone which is functionalized with an amine group having at least 3 aromatic groups, or alternatively at least 4 aromatic groups.
  • an aromatic group is used in the ordinary sense of the term and is known to be defined by Huckel theory of 4 ⁇ +2 ⁇ electrons per ring system. Accordingly, one aromatic group of the invention may have 6, or 10, or 14 ⁇ electrons. Hence a benzene ring has 6 ⁇ electrons, a naphthylene ring has 10 ⁇ electrons and an acridine group has 14 ⁇ electrons.
  • the amine having at least 3 aromatic groups, or at least may be reacted with the carboxylic functionalized polymer under known reaction conditions.
  • the reaction conditions are known to a person skilled in the art for forming imides and/or amides of carboxylic functionalized polymers.
  • Non-limiting examples of suitable amines having at least 3 aromatic groups may be bis [p-(p-aminoanilino)phenyl] -methane, 2-(7-amino-acridin-2-ylmethyl)-N-4- ⁇ 4-[4-(4-amino- pheny lamino)-benzy 1] -phenyl ⁇ -benzene- 1 ,4-diamine, N 4 - ⁇ 4-[4-(4-amino-pheny lamino)-benzyl] - phenyl ⁇ -2-[4-(4-amino-phenylamino)-cyclohexa-l,5-dienylmethyl]-benzene-l ,4-diamine, N-[4- (7-amino-acridin-2-ylmethyl)-phenyl] -benzene- 1,4-diamine, or mixtures thereof.
  • the amine having at least 3 aromatic groups may be bis[p-(p- aminoanilino)phenyl] -methane, 2-(7-amino-acridin-2-ylmethyl)-N-4- ⁇ 4-[4-(4-amino- phenylamino)-benzyl] -phenyl ⁇ -benzene- 1,4-diamine or mixtures thereof.
  • the amine having at least 3 aromatic groups may be prepared by a process comprising reacting an aldehyde with an amine (typically 4-aminodiphenylamine).
  • the resultant amine may be described as an alkylene coupled amine having at least 3 aromatic groups, at least one -NH2 functional group, and at least 2 secondary or tertiary amino groups.
  • the aldehyde may be aliphatic, alicyclic or aromatic.
  • the aliphatic aldehyde may be linear or branched. Examples of a suitable aromatic aldehyde include benzaldehyde or o-vanillin.
  • Examples of an aliphatic aldehyde include formaldehyde (or a reactive equivalent thereof such as formalin or paraformaldehyde), ethanal or propanal.
  • the aldehyde may be formaldehyde or benzaldehyde.
  • the process may be carried out at a reaction temperature in the range of 40 degree C to 180 degree C, or 50 degree C to 170 degree C.
  • the reaction may or may not be carried out in the presence of a solvent.
  • suitable solvents include diluent oil, benzene, t-butyl benzene, toluene, xylene, chlorobenzene, hexane, tetrahydrofuran, or mixtures thereof.
  • the reaction may be performed in either air or an inert atmosphere. Examples of suitable inert atmosphere include nitrogen or argon, typically nitrogen.
  • the amine having at least 3 aromatic groups may also be prepared by the methodology described in Berichte der Deutschen Chemischenmaschine (1910), 43, 728-39.
  • the carboxylic functionalized polymer dispersant with aromatic amine functionality may be incorporated into the lubricating oil at from 0.1 to 20 wt.%, or from 1 to 15 wt.%, or from
  • the carboxylic functionalized polymer dispersant may also be combined with other dispersants (described below and referred to as non-low viscosity dispersants) to provide a lubricating oil with a combination of a carboxylic functionalized polymer dispersant and another non-low viscosity dispersant.
  • the other dispersants non-low viscosity dispersants
  • Dispersants help keep these byproducts in solution, thus diminishing their deposition on metal surfaces.
  • Dispersants used in the formulation of the lubricating oil may be ashless or ash-forming in nature.
  • the dispersant is ashless.
  • So-called ashless dispersants are organic materials that form substantially no ash upon combustion.
  • non-metal-containing or borated metal-free dispersants are considered ashless.
  • metal-containing detergents discussed above form ash upon combustion.
  • Suitable dispersants typically contain a polar group attached to a relatively high molecular weight hydrocarbon chain.
  • the polar group typically contains at least one element of nitrogen, oxygen, or phosphorus.
  • Typical hydrocarbon chains contain 50 to 400 carbon atoms.
  • a particularly useful class of dispersants are the alkenylsuccinic derivatives, typically produced by the reaction of a long chain hydrocarbyl substituted succinic compound, usually a hydrocarbyl substituted succinic anhydride, with a polyhydroxy or polyamino compound.
  • the long chain hydrocarbyl group constituting the oleophilic portion of the molecule which confers solubility in the oil, is normally a polyisobutylene group.
  • Many examples of this type of dispersant are well known commercially and in the literature. Exemplary U. S. patents describing such dispersants are U. S. 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 1 : 1 to 5 : 1. Representative examples are shown in U. S. Patent Nos. 3,087,936; 3, 172,892; 3,219,666; 3,272,746; 3,322,670; and 3,652,616, 3,948,800; and Canada Patent No. 1 ,094,044.
  • Succinate esters are formed by the condensation reaction between hydrocarbyl substituted succinic anhydrides and alcohols or polyols. Molar ratios can vary depending on the alcohol or polyol used. For example, the condensation product of a hydrocarbyl substituted succinic anhydride and pentaerythritol is a useful dispersant.
  • Succinate ester amides are formed by condensation reaction between hydrocarbyl substituted succinic anhydrides and alkanol amines.
  • suitable alkanol amines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines and polyalkenylpolyamines such as polyethylene polyamines.
  • propoxylated hexamethylenediamine Representative examples are shown in U. S. Patent No. 4,426,305.
  • the molecular weight of the hydrocarbyl substituted succinic anhydrides used in the preceding paragraphs will typically range between 800 and 2,500 or more.
  • the above products can be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid.
  • the above products can also be post reacted with boron compounds such as boric acid, borate esters or highly borated dispersants, to form borated dispersants generally having from 0.1 to 5 moles of boron per mole of dispersant reaction product.
  • Mannich base dispersants are made from the reaction of alkylphenols, formaldehyde, and amines. See U. S. Patent No. 4,767,551 , which is incorporated herein by reference. Process aids and catalysts, such as oleic acid and sulfonic acids, can also be part of the reaction mixture. Molecular weights of the alkylphenols range from 800 to 2,500. Representative examples are shown in U.S. Patent Nos. 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,798, 165; and 3,803,039.
  • Typical high molecular weight aliphatic acid modified Mannich condensation products useful in this disclosure can be prepared from high molecular weight alkyl-substituted hydroxyaromatics or HNR2 group-containing reactants.
  • Hydrocarbyl substituted amine ashless dispersant additives are well known to one skilled in the art; see, for example, U. S. Patent Nos. 3,275,554; 3,438,757; 3,565,804; 3,755,433, 3,822,209, and 5,084, 197.
  • Preferred dispersants include borated and non-borated succinimides, including those derivatives from mono-succinimides, bis-succinimides, and/or mixtures of mono- and bis- succinimides, wherein the hydrocarbyl succinimide is derived from a hydrocarbylene group such as polyisobutylene having a Mn of from 500 to 5000, or from 1000 to 3000, or 1000 to 2000, or a mixture of such hydrocarbylene groups, often with high terminal vinylic groups.
  • Other preferred dispersants include succinic acid-esters and amides, alkylphenol-polyamine-coupled Mannich adducts, their capped derivatives, and other related components.
  • Such non-low viscosity dispersants may be used in an amount of 0.1 to 20 weight percent, preferably 0.5 to 8 weight percent, or more preferably 0.5 to 4 weight percent. On an active ingredient basis, such additives may be used in an amount of 0.06 to 14 weight percent, preferably 0.3 to 6 weight percent.
  • the hydrocarbon portion of the dispersant atoms can range from C60 to C400, 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.
  • 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 20 weight percent to 80 weight percent, or from 40 weight percent to 60 weight percent, of active dispersant in the "as delivered" dispersant product.
  • 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 friction modifiers, antiwear agents, other detergents, corrosion inhibitors, rust inhibitors, metal deactivators, extreme pressure additives, anti-seizure agents, wax modifiers, viscosity index improvers, viscosity modifiers, fluid-loss additives, seal compatibility agents, lubricity agents, anti-staining agents, chromophoric agents, defoamants, demulsifiers, emulsifiers, densifiers, wetting agents, gelling agents, tackiness agents, colorants, and others.
  • the other commonly used lubricating oil performance additives including but not limited to friction modifiers, antiwear agents, other detergents, corrosion inhibitors, rust inhibitors, metal deactivators, extreme pressure additives, anti-seizure agents, wax modifiers, viscosity index improvers, viscosity modifiers, fluid
  • Friction modifiers useful in this disclosure are any materials that can alter the coefficient of friction of a surface lubricated by any lubricant or fluid containing such material(s).
  • Organic 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 can be effectively used in combination with the base oils or lubricant compositions of the present disclosure.
  • Organic friction modifiers that lower the coefficient of friction are particularly advantageous in combination with the base oils and lube compositions of this disclosure.
  • the organic friction modifiers can be sub-grouped into metal-containing organic complex friction modifiers and other organic friction modifiers, which are discussed below.
  • Metal-containing organic complex friction modifiers useful in this disclosure are any materials that can alter the coefficient of friction of a surface lubricated by any lubricant or fluid containing such material(s).
  • Metal-containing organic complex 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 can be effectively used in combination with the base oils or lubricant compositions of the present disclosure.
  • Metal -containing organic complex friction modifiers that lower the coefficient of friction are particularly advantageous in combination with the base oils and lube compositions of this disclosure.
  • Preferred metal-containing organic complex friction modifiers useful in the lubricating engine oil formulations of this disclosure include tungsten organic complex compounds or molybdenum organic complex compounds .
  • Illustrative tungsten or molybdenum organic complex compounds include, for example, tungsten dithiophosphates or molybdenum dithiophosphates represented by the formula
  • M is tungsten or molybdenum
  • Other illustrative tungsten or molybdenum organic complex compounds include, for example, tungsten or molybdenum dithiocarbamates represented by the formula
  • M is tungsten or molybdenum
  • a tungsten or molybdenum dithiocarbamate may be in the form of a dimer or trimer, being fully sulfurized or containing residual oxygen.
  • illustrative examples may include tungsten or molybdenum organic complexes of which amine-based salts of tungsten or molybdenum oxides and tungsten or molybdenum amine complexes are more preferred.
  • Illustrative tungsten organic complex compounds useful in the lubricating engine oil formulations of this disclosure are described, for example, in U. S. Patent Nos. 4,529,526 and 4,266,945, the disclosures of which are incorporated herein by reference.
  • Other illustrative tungsten organic complex compounds useful in the lubricating engine oil formulations of this disclosure are described, for example, in U. S. Patent Application Publication Nos. 2004/0214731 and 2007/0042917, the disclosures of which are incorporated herein by reference.
  • the metal-containing organic complex friction modifier constitutes the minor component of the engine oil lubricant composition of the present disclosure and typically is present in an amount ranging from 0.01 weight percent to 5 weight percent, preferably from 0.01 weight percent to 3.5 weight percent, and more preferably from 0.01 weight percent to 2.5 weight percent, based on the total weight of the composition.
  • the concentration of the metal-containing organic complex friction modifier should be sufficient to provide from 20 parts per million (ppm) to 500 ppm of metal (e.g., tungsten or molybdenum), preferably from 40 ppm to 400 ppm of metal (e.g., tungsten or molybdenum), and more preferably from 50 ppm to 250 ppm of metal (e.g., tungsten or molybdenum), to the composition.
  • metal e.g., tungsten or molybdenum
  • metal e.g., tungsten or molybdenum
  • Illustrative other organic friction modifiers useful in the lubricating engine oil formulations of this disclosure include, for example, an alkoxylated fatty acid ester, alkanolamide, glycerol fatty acid ester, borated glycerol fatty acid ester, and fatty alcohol ether. Mixtures of the organic friction modifiers are also useful in the lubricating engine oil formulations of this disclosure.
  • 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.
  • 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.
  • Illustrative glycerol fatty acid esters include, for example, glycerol mono-oleate, glycerol mono-stearate, and the like. These can include polyol esters and hydroxyl-containing polyol esters.
  • these can include trimethylolpropane, pentaerythritol, sorbitan, and the like.
  • These esters can be polyol monocarboxylate esters, polyol dicarboxylate esters, and on occasion polyoltricarboxylate esters.
  • Preferred can be the glycerol mono-oleates, glycerol dioleates, glycerol trioleates, glycerol monostearates, glycerol distearates, and glycerol tristearates and the corresponding glycerol monopalmitates, glycerol dipalmitates, and glycerol tripalmitates, and the respective isostearates, linoleates, and the like.
  • 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 borated glycerol fatty acid esters include, for example, borated glycerol mono-oleate, borated glycerol mono-sterate, and the like.
  • the underlying alcohol portion can preferably be stearyl, myristyl, Cn - C 13 hydrocarbon, oleyl, isosteryl, and the like.
  • Preferred organic friction modifiers of this disclosure include an ethoxylated fatty acid ester and stearyl ether, isostearyl ether, or palmitic ether, and mixtures thereof.
  • a preferred organic friction modifier mixture of this disclosure comprises an ethoxylated fatty acid ester and a stearyl ether.
  • a preferred formulation of this disclosure comprises a lubricating oil base stock that includes a Group I, Group II, Group III, Group IV and/or Group V base oil, a tungsten or molybdenum organic complex friction modifier, and an organic friction modifier comprising an ethoxylated fatty acid ester or a stearyl ether.
  • Another preferred formulation of this disclosure comprises a lubricating oil base stock that includes a Group I, Group II, Group III, Group IV and/or Group V base oil, a tungsten or molybdenum organic complex friction modifier, and an organic friction modifier mixture that includes an ethoxylated fatty acid ester and a stearyl ether.
  • Useful concentrations of organic friction modifiers may range from 0.01 weight percent to 10-15 weight percent or more, often with a preferred range of 0.1 weight percent to 5 weight percent, or 0.1 weight percent to 2.5 weight percent.
  • the weight ratio of the first friction modifier to the other friction modifier can range from 0.1 : 1 to 1 :0.1.
  • a metal alkylthiophosphate and more particularly a metal dialkyl dithio phosphate in which the metal constituent is zinc, or zinc dialkyl dithio phosphate is a useful component of the lubricating oils of this disclosure.
  • ZDDP can be derived from primary alcohols, secondary alcohols or mixtures thereof.
  • ZDDP compounds generally are of the formula Zn[SP(S)(OR 1 )(OR 2 )] 2 where R 1 and R 2 are Ci-Cie 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 0.4 weight percent to 1.2 weight percent, preferably from 0.5 weight percent to 1.0 weight percent, and more preferably from 0.6 weight percent to 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 0.6 to 1.0 weight percent of the total weight of the lubricating oil.
  • Low phosphorus engine oil formulations are included in this disclosure.
  • the phosphorus content is typically less than 0.12 weight percent preferably less than 0.10 weight percent and most preferably less than 0.085 weight percent.
  • Viscosity index improvers also known as VI improvers, viscosity modifiers, and viscosity improvers
  • VI improvers also known as VI improvers, viscosity modifiers, and viscosity improvers
  • Viscosity index improvers provide lubricants with high and low temperature operability. These additives impart shear stability at elevated temperatures and acceptable viscosity at low temperatures.
  • Suitable viscosity index improvers include high molecular weight hydrocarbons, polyesters and viscosity index improver dispersants that function as both a viscosity index improver and a dispersant. Typical molecular weights of these polymers are between 10,000 to 1,500,000, more typically 20,000 to 1,200,000, and even more typically between 50,000 and 1,000,000.
  • suitable viscosity index improvers are linear or star-shaped polymers and copolymers of methacrylate, butadiene, olefins, or alkylated styrenes.
  • Polyisobutylene is a commonly used viscosity index improver.
  • Another suitable viscosity index improver is polymethacrylate (copolymers of various chain length alkyl methacrylates, for example), some formulations of which also serve as pour point depressants.
  • Other suitable viscosity index improvers 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”.
  • PARATONE® such as “PARATONE® 8921” and “PARATONE® 8941”
  • HiTEC® such as “HiTEC® 5850B”
  • Lubrizol® 7067C trade designation
  • Polyisoprene polymers are commercially available from Infineum International Limited, e.g. under the trade designation "SV200”
  • diene-styrene copolymers are commercially available from Infineum International Limited, e.g. under the trade designation "SV 260”.
  • the viscosity index improvers may be used in an amount of less than 2.0 weight percent, preferably less than 1.0 weight percent, and more preferably less than 0.5 weight percent, based on the total weight of the formulated oil or lubricating engine oil. Viscosity improvers are typically added as concentrates, in large amounts of diluent oil.
  • the viscosity index improvers may be used in an amount of from 0.25 to 2.0 weight percent, preferably 0.15 to 1.0 weight percent, and more preferably 0.05 to 0.5 weight percent, based on the total weight of the formulated oil or lubricating engine oil.
  • 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, phosphorous acid, phenol, or mixtures thereof.
  • the counterion is typically an alkaline earth or alkali metal.
  • 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.
  • 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 also useful as detergents. These carboxylic acid detergents may be prepared by reacting a basic metal compound with at least one carboxylic acid and removing free water from the reaction product. These compounds may be overbased to produce the desired TBN level.
  • Detergents made from salicylic acid are one preferred class of detergents derived from carboxylic acids.
  • Useful salicylates include long chain alkyl salicylates.
  • One useful family of compositions is of the formula
  • R is an alkyl group having 1 to 30 carbon atoms
  • n is an integer from 1 to 4
  • M is an alkaline earth metal.
  • Preferred R groups are alkyl chains of at least Cn, preferably C13 or greater. R may be optionally substituted with substituents that do not interfere with the detergent's function.
  • M is preferably, calcium, magnesium, 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.
  • Preferred detergents include calcium phenates, calcium sulfonates, calcium salicylates, magnesium phenates, magnesium sulfonates, magnesium salicylates 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 1.0 to 6.0 weight percent, preferably 2.0 to 5.0 weight percent, and more preferably from 2.0 weight percent to 4.0 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 20 weight percent to 80 weight percent, or from 40 weight percent to 60 weight percent, of active detergent in the "as delivered” detergent product.
  • 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.
  • 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 propionic ester derivatives.
  • Bis-phenolic antioxidants may also be advantageously used in combination with the instant disclosure.
  • ortho-coupled phenols include: 2,2'-bis(4-heptyl-6-t-butyl-phenol); 2,2'-bis(4-octyl- 6-t-butyl-phenol); and 2,2'-bis(4-dodecyl-6-t-butyl-phenol).
  • Para-coupled bisphenols include for example 4,4'-bis(2,6-di-t-butyl phenol) and 4,4'-methylene-bis(2,6-di-t-butyl phenol).
  • catalytic antioxidants comprise an effective amount of a) one or more oil soluble polymetal organic compounds; and, effective amounts 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.
  • Non-phenolic oxidation inhibitors which may be used include aromatic amine antioxidants and these may be used either as such or in combination with phenolics.
  • Typical examples of non-phenolic antioxidants include: alkylated and non-alkylated aromatic amines such as aromatic monoamines of the formula R 8 R 9 R 10 N where R 8 is an aliphatic, aromatic or substituted aromatic group, R 9 is an aromatic or a substituted aromatic group, and R 10 is H, alkyl, aryl or R n S(0)xR 12 where R 11 is an alkylene, alkenylene, or aralkylene group, R 12 is a higher alkyl group, or an alkenyl, aryl, or alkaryl group, and x is 0, 1 or 2.
  • the aliphatic group R 8 may contain from 1 to 20 carbon atoms, and preferably contains from 6 to 12 carbon atoms.
  • the aliphatic group is a saturated aliphatic group.
  • both R 8 and R 9 are aromatic or substituted aromatic groups, and the aromatic group may be a fused ring aromatic group such as naphthyl.
  • Aromatic groups R 8 and R 9 may be joined together with other groups such as S.
  • Typical aromatic amines antioxidants have alkyl substituent groups of at least 6 carbon atoms.
  • Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally, the aliphatic groups will not contain more than 14 carbon atoms.
  • the general types of amine antioxidants useful in the present compositions include diphenylamines, phenyl naphthylamines, phenothiazines, imidodibenzyls and diphenyl phenylene diamines. Mixtures of two or more aromatic amines are also useful. Polymeric amine antioxidants can also be used.
  • aromatic amine antioxidants useful in the present disclosure include: ⁇ , ⁇ '- dioctyldiphenylamine; t-octylphenyl-alpha-naphthylamine; phenyl-alphanaphthylamine; and p-octylphenyl-alpha-naphthylamine.
  • Sulfurized alkyl phenols and alkali or alkaline earth metal salts thereof also are useful antioxidants.
  • Preferred antioxidants include hindered phenols, arylamines. These antioxidants may be used individually by type or in combination with one another. Such additives may be used in an amount of 0.01 to 10 weight percent, preferably 0.01 to 5 weight percent, more preferably 1 to less than 4 weight percent, even more preferably 2 to less than 3.5 weight percent.
  • pour point depressants also known as lube oil flow improvers
  • pour point depressants 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.
  • 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 0.01 to 3 weight percent, preferably 0.01 to 2 weight percent.
  • Anti-foam agents may advantageously be added to lubricant compositions. These agents retard the formation of stable foams. Silicones and organic polymers are typical anti-foam agents. For example, polysiloxanes, such as silicon oil or poly dimethyl siloxane, provide antifoam properties. Anti-foam agents are commercially available and may be used in conventional minor amounts along with other additives such as demulsifiers; usually the amount of these additives combined is less than 1 weight percent and often less than 0.1 weight percent.
  • Antirust additives are additives that protect lubricated metal surfaces against chemical attack by water or other contaminants. A wide variety of these are commercially available.
  • antirust additive is a polar compound that wets the metal surface preferentially, protecting it with a film of oil.
  • Another type of antirust additive absorbs water by incorporating it in a water-in-oil emulsion so that only the oil touches the metal surface.
  • Yet another type of antirust additive chemically adheres to the metal to produce a non-reactive surface.
  • suitable additives include zinc dithiophosphates, metal phenolates, basic metal sulfonates, fatty acids and amines. Such additives may be used in an amount of 0.01 to 5 weight percent, preferably 0.01 to 1.5 weight percent.
  • Typical amounts of such additives useful in the present disclosure are shown in Table 1 below.
  • Anti-foam Agent 0.001-3 0.001-0.15
  • additives are all commercially available materials. These additives may be added independently but are usually precombined in packages which can be obtained from suppliers of lubricant oil additives. Additive packages with a variety of ingredients, proportions and characteristics are available and selection of the appropriate package will take the requisite use of the ultimate composition into account.
  • Base oil viscosity for the purpose of this disclosure is defined as the kinematic viscosity at 100 deg. C of the combination of base stocks used in the lubricating engine oil (no additives included).
  • Group III (A) is 4 cSt Yubase 4 supplied by SK Lubricants, which is a hydrocracked and catalyst dewaxed basestock.
  • Group III (B) is a 4 or 8 cSt base oil supplied by Shell, which is produced via Fischer Tropsch Synthesis.
  • Formulation A is the first inventive example, in which a carboxylic functionalized polymer dispersant with aromatic amine functionality (also referred to as low-viscosity dispersant) is included as part of the total dispersant content (3% low-viscosity dispersant out of 10% total dispersant).
  • the conventional dispersant used at 7 wt.% of the lubricating oil was a conventional PIBSA-PAM disperstant.
  • Formulation B is identical to Formulation A but uses only conventional dispersant (0% low- viscosity dispersant out of 10% total dispersant).
  • Formulation C represents 5W-30 grade engine oil, utilizing a commercial additive package containing conventional dispersant).
  • Formulation D represents a 5W-30 grade engine oil using a conventional PIBSA-PAM dispersant at 9.85wt.% loading).
  • Formulation E is similar to Formulation A in Figure 1 (Inventive Example 1); however, the base oil content was adjusted to achieve a HTHS viscosity of 3.4 cSt.
  • Formulation F is similar to Formulation C in Figure 1 (Comparative Example 2); however, the base oil content was adjusted to achieve a HTHS viscosity of 3.4 cSt.
  • HTHS viscosity is generally accepted as a proxy for fuel economy measurement in heavy duty engines. The lower the HTHS, the more fuel economy benefit is typically observed. In the case of Formulations E and F, the HTHS viscosities were adjusted to be equivalent so that a relevant comparison of wear protection at equivalent "fuel economy" might be achieved. This comparison is addressed below by measuring viscosity under even greater shear as a proxy for film thickness (see Example 3 below).
  • HFRR High Frequency Reciprocating Rig
  • Formulations A and B both contain 10 wt% dispersants but formulation A includes 3% carboxylic functionalized polymer dispersant with aromatic amine functionality (low-viscosity dispersant) while formulation B uses only conventional dispersants.
  • the KV100, KV40, CCS at - 30C (ASTM D5293), and HTHS (ASTM D4683) of Formulation A are all lower than Formulation B (see Figure 1).
  • Lower viscosity, especially lower HTHS viscosity is understood to convey fuel economy benefits.
  • the substitution of 3% conventional dispersant in Formulation B causes Formulation B to fail the CCS requirement ( ⁇ 6600 cSt at -30C) for 5W grade oils. Without the 3% of carboxylic functionalized polymer dispersant with aromatic amine functionality, Formulation A could not be classified as a 5W-30 oil.
  • Formulation A is an SAE 5W-30 grade oil which includes carboxylic functionalized polymer dispersant with aromatic amine functionality at 3 wt%.
  • Formulations C and D are competitive SAE 5W-30 grade oils that do not contain carboxylic functionalized polymer dispersant with aromatic amine functionality.
  • the KVlOO, KV40, CCS at -30C, and HTHS of Formulation A is lower than those of Formulations C and D (see Figure 1).
  • the Base Oil Viscosity of Formulation A is 5.99 cSt at 100 deg.
  • Formulation E contains the same base oils and additives as Formulation A, including 3 wt% carboxylic functionalized polymer dispersant with aromatic amine functionality, but has been adjusted using base oil mixture to have an HTHS viscosity of 3.4 cP.
  • Formulation F contains the same base oils and additives as Formulation C, including 0 wt% carboxylic functionalized polymer dispersant with aromatic amine functionality, but has been adjusted using base oil mixture to have an HTHS viscosity of 3.4 cP. The viscosity of these two formulations was tested under very high shear conditions at 100 deg. C.
  • Figure 3 graphically depicts the ultrashear viscosities of formulations E (inventive) and F (comparative) at 100 deg.
  • the circle shaped points are for formulation E and show the unexpectedly higher shear viscosity for the lubricating engine oil including the carboxylic functionalized polymer dispersant which is functionalized with an aromatic amine.
  • the triangle shaped points are for formulation F and show the lower shear viscosity for the lubricating engine oil including the conventional dispersant. The shear experienced by the formulations in these tests exceeds the shear rate of the HTHS test. At all shear conditions, Formulation E shows a higher viscosity than Formulation F. Higher viscosity under shear indicates a thicker lubricant film under these conditions and correspondingly increased wear protection.
  • formulation E inventive
  • formulation F comparative
  • inventive formulation E with its higher shear viscosity than comparative formulation F will have improved engine wear protection.
  • Formulation GA is the comparative example, in which 10% of the dispersant used is a conventional PIBSA-PAM dispersant.
  • formulation GB is identical to Formulation GA but also uses the carboxylic functionalized polymer dispersant with aromatic functionality along with conventional dispersant (5% low-viscosity dispersant out of 10% total dispersant).
  • Inventive formulation GC also uses the carboxylic functionalized polymer dispersant with aromatic functionality along with conventional dispersant (10% low-viscosity dispersant out of 10% total dispersant).
  • Formulation GD is the comparative example, in which 10% of the dispersant used is a conventional PIBSA-PAM dispersant.
  • formulation GE is identical to Formulation GD but also uses the carboxylic functionalized polymer dispersant with aromatic functionality along with conventional dispersant (5% low-viscosity dispersant out of 10% total dispersant).
  • Inventive formulation GF also uses the carboxylic functionalized polymer dispersant with aromatic functionality along with conventional dispersant (10% low-viscosity dispersant out of 10% total dispersant).
  • the formulations were adjusted to equivalent HTHS viscosity (2.9) and tested in HFRR to indicate wear protection.
  • HTHS viscosity 2.9
  • HFRR wear scars at equivalent HTHS.
  • Formulation GG is the comparative example, in which 10% of the dispersant used is a conventional PIBSA-PAM dispersant.
  • formulation GH is identical to Formulation GG but also uses the carboxylic functionalized polymer dispersant with aromatic functionality along with conventional dispersant (5% low-viscosity dispersant out of 10% total dispersant).
  • Inventive formulation GI also uses the carboxylic functionalized polymer dispersant with aromatic functionality along with conventional dispersant (10% low-viscosity dispersant out of 10% total dispersant). The formulations were adjusted to equivalent HTHS viscosity (3.2) and tested in HFRR to indicate wear protection. As can be seen in Figure 6, increased levels of the carboxylic functionalized polymer dispersant with aromatic functionality enables higher base oil viscosity, which leads to lower HFRR wear scars at equivalent HTHS.
  • Formulation GJ is the comparative example, in which 10% of the dispersant used is a conventional PIBSA-PAM dispersant.
  • formulation GK is similar to Formulation GJ but also uses the carboxylic functionalized polymer dispersant with aromatic functionality along with conventional dispersant (5% low-viscosity dispersant out of 10% total dispersant).
  • Inventive formulation GL also uses the carboxylic functionalized polymer dispersant with aromatic functionality at 10%, but with a blend of two different viscosity Group II base stocks.
  • Formulation GM is the comparative example, in which 10% of the dispersant used is a conventional PIBSA-PAM dispersant.
  • formulation GN is identical to Formulation GM but also uses the carboxylic functionalized polymer dispersant with aromatic functionality along with conventional dispersant (5% low-viscosity dispersant out of 10% total dispersant).
  • Inventive formulation GO also uses the carboxylic functionalized polymer dispersant with aromatic functionality along with conventional dispersant (10% low-viscosity dispersant out of 10% total dispersant).
  • the formulations were adjusted to equivalent HTHS viscosity (2.9) and tested in HFRR to indicate wear protection.
  • HTHS viscosity 2.9
  • HFRR wear scars at equivalent HTHS.
  • Formulation GP is the comparative example, in which 10% of the dispersant used is a conventional PIBSA-PAM dispersant.
  • formulation GQ is identical to Formulation GP but also uses the carboxylic functionalized polymer dispersant with aromatic functionality along with conventional dispersant (5% low-viscosity dispersant out of 10% total dispersant).
  • Inventive formulation GR also uses the carboxylic functionalized polymer dispersant with aromatic functionality along with conventional dispersant (10% low-viscosity dispersant out of 10% total dispersant). The formulations were adjusted to equivalent HTHS viscosity (3.2) and tested in HFRR to indicate wear protection. As can be seen in Figure 9, increased levels of the carboxylic functionalized polymer dispersant with aromatic functionality enables higher base oil viscosity, which leads to lower HFRR wear scars at equivalent HTHS.

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Abstract

L'invention porte sur des huiles lubrifiantes pour moteur comprenant une huile de base d'huile lubrifiante en tant que constituant principal, présentant une viscosité d'huile de base à 100°C de 4,5 à 7,5 cSt et un dispersant de type polymère carboxylique fonctionnalisé, présentant une fonctionnalité amine aromatique, en tant que constituant mineur, les huiles lubrifiantes pour moteur présentant une viscosité dans un simulateur de démarrage à froid à -30°C inférieure à 8500 mPa.s. Les huiles lubrifiantes pour moteur peuvent fournir une protection améliorée contre l'usure du moteur à une efficacité de carburant équivalente ou une efficacité de carburant améliorée à une protection équivalente contre l'usure du moteur par rapport à une huile lubrifiante pour moteur contenant un dispersant en tant que constituant mineur autre que le polymère carboxylique fonctionnalisé présentant une fonctionnalité amine aromatique. L'invention concerne également des procédés de fabrication de l'huile lubrifiante pour moteur. Les huiles lubrifiantes pour moteur sont utiles dans les moteurs à combustion interne comprenant les moteurs à injection directe, les moteurs à essence et les moteurs au diesel.
EP17754537.3A 2016-08-03 2017-08-03 Huile lubrifiante pour moteur pour une protection améliorée contre l'usure et une efficacité améliorée du carburant Withdrawn EP3494200A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201662370371P 2016-08-03 2016-08-03
US15/667,066 US20180037841A1 (en) 2016-08-03 2017-08-02 Lubricating engine oil for improved wear protection and fuel efficiency
PCT/US2017/045207 WO2018026982A1 (fr) 2016-08-03 2017-08-03 Huile lubrifiante pour moteur pour une protection améliorée contre l'usure et une efficacité améliorée du carburant

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EP3494200A1 true EP3494200A1 (fr) 2019-06-12

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US (1) US20180037841A1 (fr)
EP (1) EP3494200A1 (fr)
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