WO2019018329A1 - Composition lubrifiante à faible teneur en agent dispersant - Google Patents

Composition lubrifiante à faible teneur en agent dispersant Download PDF

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Publication number
WO2019018329A1
WO2019018329A1 PCT/US2018/042372 US2018042372W WO2019018329A1 WO 2019018329 A1 WO2019018329 A1 WO 2019018329A1 US 2018042372 W US2018042372 W US 2018042372W WO 2019018329 A1 WO2019018329 A1 WO 2019018329A1
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WIPO (PCT)
Prior art keywords
weight
lubricating composition
weight percent
group
composition
Prior art date
Application number
PCT/US2018/042372
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English (en)
Inventor
Joanne L. Jones
Yanshi Zhang
Original Assignee
The Lubrizol Corporation
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 The Lubrizol Corporation filed Critical The Lubrizol Corporation
Priority to US16/631,660 priority Critical patent/US20200199479A1/en
Priority to EP18749704.5A priority patent/EP3655511A1/fr
Priority to CN201880052298.7A priority patent/CN111032838A/zh
Priority to CA3069970A priority patent/CA3069970A1/fr
Publication of WO2019018329A1 publication Critical patent/WO2019018329A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • 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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/12—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
    • 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
    • C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
    • C10M157/04—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential at least one of them being a nitrogen-containing compound
    • 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
    • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
    • 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
    • C10M2205/024—Propene
    • 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/141—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings monocarboxylic
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
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    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • C10M2217/042—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds between the nitrogen-containing monomer and an aldehyde or ketone
    • 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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • 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
    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2221/041—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds involving sulfurisation of macromolecular compounds, e.g. polyolefins
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/09—Complexes with metals
    • 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
    • C10M2290/00—Mixtures of base materials or thickeners or additives
    • C10M2290/02—Mineral base oils; Mixtures of fractions
    • 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
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/45—Ash-less or low ash content
    • 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
    • C10N2030/78—Fuel contamination
    • 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
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/09—Treatment with nitrogen containing compounds

Definitions

  • the disclosed technology relates to lubricants for compression ignition internal combustion engines, particularly those demonstrating at least one of improved seals performance, reduced deposit formation, and excellent durability.
  • Lubrication of internal combustion engines has been a practice for many decades, yet continual improvement in lubricant technology is ongoing as new engines and new standards have been developed.
  • Formulations directed to spark ignition engines and compression ignition engines must address limits placed on sulfated ash, phosphorus, and sulfur content (“SAPS"), and restrictions in these components often lead to upper limits on the amount of metal-containing additives that can be included in the lubricant.
  • SAPS sulfated ash, phosphorus, and sulfur content
  • Reduction in metal containing additives is necessary to reduce the impact of metal ash on exhaust aftertreatment devices and to reduce the emission of particulate matter.
  • ZDDP for wear and oxidation protection and overbased metal detergents for cleanliness and acid control.
  • ZDDP has been the industry standard for reducing valve train wear, protecting against liner wear, and reducing oxidation leading to corrosive wear.
  • the zinc contributes to an increase in sulfated ash in the lubricating oil and the phosphorus causes inactivation of oxidation catalysts used in exhaust after-treatment devices.
  • Ashless dispersants are often utilized to provide cleanliness, including sludge and soot control.
  • Polyisobutylene succinimide dispersants have been widely used to supplement detergents in providing deposit control. These succinimide dispersants often contribute to seals degradation and can have a negative impact on low temperature viscometrics, especially in modern fuel economy lubricants.
  • WO/PCT Patent Publication 2014-193543 discloses lubricant compositions for heavy duty diesel engines comprising oxyalkylated hydrocarbyl phenol compounds.
  • the disclosed technology provides a lubricant composition with a reduced level of ashless dispersant, i.e. a low dispersant lubricating composition; such compositions are suitable for reducing deposit formation in compression ignition internal combustion engines, while maintaining cleanliness.
  • the disclosed technology further provides a lubricant composition with a reduced concentration of zinc-containing additives.
  • the present invention provides a low dispersant lubricating composition
  • a low dispersant lubricating composition comprising (a) an oil of lubricating viscosity, (b) about 0.5 weight percent to 3.0 weight percent of an oxyalkylated hydrocarbyl-substituted phenol compound, (c) about 0.01 weight percent to 2.6 weight percent of a polyalkenylsuccinimide dispersant, and (d) about 0.05 weight percent to 2.0 weight percent of a polyolefin dispersant viscosity modifier, and wherein the lubricating composition contains zinc in an amount less than about 700 ppm by weight of the composition.
  • the present invention provides a low dispersant lubricating composition
  • a low dispersant lubricating composition comprising (a) an oil of lubricating viscosity, (b) 0.5 weight percent to 3.0 weight percent of an oxyalkylated hydrocarbyl phenol compound according to the formula:
  • each R 2 is independently hydrogen or a hydrocarbyl group of 1 to 6 carbon atoms
  • the invention further provides a method of lubricating a light-duty vehicle equipped with a compression-ignition internal combustion engine with a low dispersant lubricating composition
  • a low dispersant lubricating composition comprising (a) an oil of lubricating viscosity, (b) about 0.5 weight percent to 3.0 weight percent of an oxyalkylated hydrocarbyl-substituted phenol compound, (c) about 0.01 weight percent to 2.6 weight percent of a polyalkenylsuccinimide dispersant, and (d) about 0.05 weight percent to 2.0 weight percent of a polyolefin dispersant viscosity modifier , and wherein the lubricating composition contains zinc in an amount less than about 700 ppm by weight of the composition.
  • a light duty vehicle, especially a light-duty diesel vehicle is understood to be any vehicle with a gross weight of less than about 8,500 pounds (or approximately 3900 kg).
  • the invention further provides a method of reducing deposit formation in a light-duty compression ignition internal combustion engine by operating the engine with a lubricant composition
  • a lubricant composition comprising (a) an oil of lubricating viscosity, (b) an 0.5 weight percent to 3.0 weight percent of an oxyalkylated hydrocarbyl-substituted phenol compound, (c) 0.01 weight percent to 2.6 weight percent of a polyalkenylsuccinimide dispersant, and (d) 0.05 weight percent to 2.0 weight percent of a polyolefin dispersant viscosity modifier , and wherein the lubricating composition contains zinc in an amount less than 700 ppm by weight of the composition.
  • the invention further provides a method of improving the retention of base number, i.e., total base number (TBN), further into an engine oil drain interval.
  • TBN retention may assist in mitigating the effects of acid build-up in an engine oil lubricant composition.
  • the disclosed technology provides a low zinc lubricating composition, a method for lubricating an internal combustion engine with a low zinc lubricating composition, and the use as disclosed above.
  • the lubricating composition comprises an oil of lubricating viscosity.
  • oils include natural and synthetic oils, oil derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined, refined, re-refined oils or mixtures thereof.
  • a more detailed description of unrefined, refined and re-refined oils is provided in International Publication WO2008/147704, paragraphs [0054] to [0056] (a similar disclosure is provided in US Patent Application 2010/197536, see [0072] to [0073]).
  • Synthetic oils may also be produced by Fischer-Tropsch reactions and typically may be hydroisomerised Fischer-Tropsch hydrocarbons or waxes.
  • oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to-liquid oils.
  • Oils of lubricating viscosity may also be defined as specified in the April 2008 version of "Appendix E - API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils", section 1.3 Sub-heading 1.3. "Base Stock Categories”. The API Guidelines are also summarized in US Patent US 7,285,516 (see column 11, line 64 to column 12, line 10).
  • the oil of lubricating viscosity may be an API Group II, Group III, or Group IV oil, or mixtures thereof.
  • the five base oil groups are as follows:
  • the amount of the oil of lubricating viscosity present is typically the balance remaining after subtracting from 100 weight % (weight %) the sum of the amount of the compound of the invention and the other performance additives.
  • the lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant. If the lubricating composition of the invention (comprising the additives disclosed herein) is in the form of a concentrate which may be combined with additional oil to form, in whole or in part, a finished lubricant), the ratio of the of these additives to the oil of lubricating viscosity and/or to diluent oil include the ranges of 1 :99 to 99: 1 by weight, or 80:20 to 10:90 by weight.
  • the base oil has a kinematic viscosity at 100°C from 2 mm 2 /s (centi Stokes - cSt) to 16 mm 2 /s, from 3 mm 2 /s to 10 mm 2 /s, or even from 4 mm 2 /s to 8 mm 2 /s.
  • the base oil comprises at least 30 weight % of Group II or
  • the base oil comprises at least 60 weight % of Group II or Group III base oil, or at least 80 weight % of Group II or Group III base oil.
  • the lubricant composition comprises less than 20 weight % of Group IV (i.e., polyalphaolefin) base oil.
  • the base oil comprises less than 10 weight % of Group IV base oil.
  • the lubricating composition is substantially free of (i.e., contains less than 0.5 weight %) of Group IV base oil.
  • Ester base fluids which are characterized as Group V oils, have high levels of solvency as a result of their polar nature. Addition of low levels (typically less than 10 weight %) of ester to a lubricating composition may significantly increase the resulting solvency of the base oil mixture.
  • Esters may be broadly grouped into two categories: synthetic and natural. An ester base fluid would have a kinematic viscosity at 100°C suitable for use in an engine oil lubricant, such as between 2 cSt and 30 cSt, or from 3 cSt to 20 cSt, or even from 4 cSt to 12 cSt.
  • Synthetic esters may comprise esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, and alkenyl malonic acids) with any of variety of monohydric alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, and propylene glycol).
  • dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
  • esters include those made from C5 to C12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol. Esters can also be monoesters of mono-carboxylic acids and monohydric alcohols.
  • Natural (or bio-derived) esters refer to materials derived from a renewable biological resource, organism, or entity, distinct from materials derived from petroleum or equivalent raw materials. Natural esters include fatty acid triglycerides, hydrolyzed or partially hydrolyzed triglycerides, or transesterified triglyceride esters, such as fatty acid methyl ester (or FAME). Suitable triglycerides include, but are not limited to, palm oil, soybean oil, sunflower oil, rapeseed oil, olive oil, linseed oil, and related materials. Other sources of triglycerides include, but are not limited to, algae, animal tallow, and zooplankton. Methods for producing biolubricants from natural triglycerides is described in, e.g., United States patent application 2011/0009300A1.
  • the lubricating composition comprises at least 2 weight % of an ester base fluid. In one embodiment, the lubricating composition of the invention comprises at least 4 weight %of an ester base fluid, or at least 7 weight % of an ester base fluid, or even at least 10 weight % of an ester base fluid.
  • the lubricating composition may comprise an oxyalkylated hydrocarbyl phenol represented by Formula 1 :
  • each R 2 is independently hydrogen or a hydrocarbyl group of 1 to 6 carbon atoms
  • R 5 is a hydrocarbyl group of 1 to 24 carbon atoms; each R 4 is independently a hydrocarbyl group of 1 to 220, or 20 to 220, wherein at least one R 4 contains 25 to 200, or 35 to 180 or 40 to 180 to 60 to 180 or 40 to 96 carbon atoms;
  • n 1 to 10;
  • the oxyalkylated hydrocarbyl phenol of Formula 1 is selected such that one
  • R 2 group is methyl, and the second R 2 group is hydrogen;
  • R 5 is a hydrocarbyl group of 1 to 24 carbon atoms;
  • each R 4 is a hydrocarbyl group of 25 to 200, or 35 to 180 or 40 to 180 to 60 to 180 or 40 to 96 carbon atoms;
  • the oxyalkylated hydrocarbyl phenol of Formula 1 is selected such that one
  • R 2 is methyl, and the second R 2 is hydrogen;
  • R 5 is a hydrocarbyl group of 1 to 24 carbon atoms;
  • R 4 is a hydrocarbyl group of 1 to 220 or 20 to 220 carbon atoms, wherein at least one R 4 comprises a polyalk(en)yl group containing 25 to 200, or 35 to 180 or 40 to 180 to 60 to 180 or 40 to 96 carbon atoms;
  • n 2 to 8; and
  • m 1.
  • the oxyalkylated hydrocarbyl phenol of Formula 1 is selected such that one
  • R 2 is methyl, and the second R 2 is hydrogen;
  • R 5 is a hydrocarbyl group of 1 to 24 carbon atoms; each a hydrocarbyl group of 1 to 220 or 20 to 220 carbon atoms comprises a polyisobutenyl group containing 25 to 200, or 35 to 180 or 40 to 180 to 60 to 180 or 40 to 96 carbon atoms;
  • n 2 to 8 (or 3 to 5); and
  • m 1.
  • R 4 group of each of the formulae above may be located in the para- position relative to the oxyalkylated group, and the resultant formula is represented by the structure:
  • variables R 2 to R 5 , and n are defined previously.
  • the oxyalkylated hydrocarbyl phenol of the present invention is represented by Formula 1(a), wherein R 4 is a polyolefinic group such as a polypropenyl or a polyisobutenyl group (typically a polyisobutenyl group), and variables R 2 , R 3 , R 5 , and n are defined previously.
  • the polyisobutenyl group has a number average molecular weight of 350 to 2500, or 550 to 2300, or 750 to 1150. In one embodiment, the polyisobutenyl group has a number average molecular weight of 950-1000.
  • the polypropenyl group may have a number average molecular weight of 740 to 1200, or 800-850. In one embodiment, the polypropenyl group has a number average molecular weight of 825.
  • the oxyalkylated hydrocarbyl phenol of the present invention is represented by Formula 1(b):
  • R 4 is a polyolefinic group such as a polypropenyl or a polyisobutenyl group (typically a polyisobutenyl group), and variables R 2 , R 3 , R 5 , and n, are defined previously.
  • the polyisobutenyl group may have a number average molecular weight of 350 to 2500, or 550 to 2300, or 750 to 1150. In one embodiment, the polyisobutenyl group has a number average molecular weight of 950-1000.
  • the oxyalkylated group of the oxyalkylated hydrocarbyl phenol has the formula wherein R 1 is an ethylene, propylene, butylene group, or mixtures thereof; and n may independently be from 1 to 50, or 1 to 20, or 1 to 10, or 2 to 5.
  • the oxyalkylated group of the oxyalkylated hydrocarbyl phenol may be either a homopolymer or copolymer or oligomers thereof. If the oxyalkylated group is in the form of a copolymer, or oligomer thereof, the oxyalkylated group may have either random or block architecture.
  • the oxyalkylated group (or R 1 is a propylene, or butylene group i.e., the oxyalkylated group does not require an ethylene group.
  • the oxyalkylate group may be a copolymer, or oligomer thereof with either propylene or butylene oxide i.e., blocks of (i) -CH 2 CH 2 0- with (ii) -CH 2 CH 2 CH 2 CH 2 0- or -CH 2 CH(CH 3 )CH 2 0- or -CH 2 CH(CH 3 )0-.
  • the oxyalkylated group is based upon propylene oxide.
  • the oxyalkylated hydrocarbyl phenol is prepared by reacting a hydrocarbyl substituted phenol with an alkylene oxide (typically ethylene oxide, propylene oxide or butylene oxide), optionally in the presence of a base catalyst. Typically the reaction occurs in the presence of a base catalyst.
  • alkylene oxide typically ethylene oxide, propylene oxide or butylene oxide
  • the base catalyst may include, but is not limited to, sodium chloroacetate, sodium hydride or potassium hydroxide
  • the aliphatic hydrocarbyl group (also represented by R 4 ) is linear or branched, typically with at least one branching point.
  • the aliphatic hydrocarbyl group typically has one, although it may in some embodiments be desirable to have to R 4 groups, with the second group being methyl. If a second R 4 group is present and is methyl, then the oxyalkylated hydrocarbyl phenol is a cresol.
  • the oxyalkylated hydrocarbyl phenol of the present invention is present in an amount ranging from 0.01 weight % to 5 weight %, or 0.05 to 3.5 weight %, or 0.1 to 2.5 weight % of the lubricating composition.
  • the oxyalkylated hydrocarbyl phenol is present in an amount from 0.25 to 2 weight % of the lubricating composition.
  • the lubricating compositions of the present invention comprises a polyalkenylsuccinimide dispersant.
  • the dispersant may be borated using one or more of a variety of agents selected from the group consisting of the various forms of boric acid (including metaboric acid, HB0 2 , orthoboric acid, H 3 B0 3 , and tetraboric acid, H2B4O7), boric oxide, boron trioxide, and alkyl borates.
  • the borating agent is boric acid which may be used alone or in combination with other borating agents. Methods of preparing borated dispersants are known in the art.
  • the borated dispersant may be prepared in such a way that the borated dispersant contains 0.1 weight % to 2.5 weight% boron, or 0.1 weight % to 2.0 weight % boron or 0.2 to 1.5 weight % boron or 0.3 to 1.0 weight % boron.
  • the succinimide dispersant may be a derivative of an aliphatic polyamine, or mixtures thereof.
  • the aliphatic polyamine may be aliphatic polyamine such as an ethylenepolyamine, a propylenepolyamine, a butyl enepolyamine, or mixtures thereof.
  • the aliphatic polyamine may be ethylenepolyamine.
  • the aliphatic polyamine may be selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms, and mixtures thereof.
  • the succinimide dispersant may be a derivative of an aromatic amine, an aromatic polyamine, or mixtures thereof.
  • the aromatic amine may be 4-aminodiphenylamine (ADPA) (also known as N-phenylphenylenediamine), derivatives of ADPA (as described in United States Patent Publications 2011/0306528 and 2010/0298185), a nitroaniline, an aminocarbazole, an amino-indazolinone, an aminopyrimidine, 4-(4-nitrophenylazo)aniline, or combinations thereof.
  • ADPA 4-aminodiphenylamine
  • the dispersant is derivative of an aromatic amine wherein the aromatic amine has at least three non-continuous aromatic rings.
  • the succinimide dispersant may be a derivative of a polyether amine or polyether polyamine.
  • Typical polyether amine compounds contain at least one ether unit and will be chain terminated with at least one amine moiety.
  • the polyether polyamines can be based on polymers derived from C2-C6 epoxides such as ethylene oxide, propylene oxide, and butylene oxide. Examples of polyether polyamines are sold under the Jeffamine® brand and are commercially available from Hunstman Corporation located in Houston, Texas.
  • the dispersant is based upon a polyisobutylene succinimide dispersant, wherein the polyisobutylene of the borated polyisobutylene succinimide has a number average molecular weight of 350 to 5000, or 550 to 3000 or 750 to 2500 or 350 to 2200, or 350 to 1350, or 350 to 1150 or 350 to 750 or 550 to 2200 or 550 to 1350 or 750 to 2200.
  • Suitable polyisobutylenes for use in the succinimide dispersant may include those formed from polyisobutylene or highly reactive polyisobutylene having at least about 50 mol %, such as about 60 mol %, and particularly from about 70 mol % to about 90 mol % or greater than 90 mol%, terminal vinylidene content.
  • Suitable polyisobutenes may include those prepared using BF 3 catalysts.
  • the borated dispersant is derived from a polyolefin having number average molecular weight of 350 to 3000 Daltons and a vinylidene content of at least 50 mol %, or at least 70 mol %, or at least 90 mol %.
  • the dispersant is obtained from reaction of succinic anhydride by an "ene" or
  • the "ene” reaction mechanism and general reaction conditions are summarised in "Maleic Anhydride", pages, 147-149, Edited by B.C. Trivedi and B.C. Culbertson and Published by Plenum Press in 1982.
  • the dispersant prepared by a process that includes an “ene” reaction may be a polyisobutylene succinimide having a carbocyclic ring present on less than 50 mole %, or 0 to less than 30 mole %, or 0 to less than 20 mole %, or 0 mole % of the dispersant molecules.
  • the "ene” reaction may have a reaction temperature of 180 °C to less than 300 °C, or 200 °C to 250 °C, or 200 °C to 220 °C.
  • the dispersant may also be obtained from a chlorine-assisted process, often involving Diels-Alder chemistry, leading to formation of carbocyclic linkages.
  • the process is known to a person skilled in the art.
  • the chlorine-assisted process may produce a dispersant that is a polyisobutylene succinimide having a carbocyclic ring present on 50 mole % or more, or 60 to 100 mole % of the dispersant molecules.
  • Both the thermal and chlorine-assisted processes are described in greater detail in U.S. Patent 7,615,521, columns 4-5 and preparative examples A and B.
  • the dispersant may further comprise a polyolefin succinic acid ester, amide, or ester-amide.
  • a polyolefin succinic acid ester may be a polyisobutylene succinic acid ester of pentaerythritol, or mixtures thereof.
  • a polyolefin succinic acid ester-amide may be a polyisobutylene succinic acid reacted with an alcohol (such as pentaerythritol) and an amine (such as a diamine, typically diethyleneamine).
  • the dispersant is used alone or as part of a mixture of non-borated and borated dispersants. If a mixture of dispersants is used, there may be two to five, or two to three or two dispersants. [0049]
  • the dispersant is typically present at 0.1 weight % to 10 weight %, or 0.5 weight % to 7 weight %, or 0.8 weight % to 4.5 weight %, or 1.0 weight % to 4.5 weight % or 2.0 weight % to 4.0 weight % or 1.5 weight % to 3 weight % of the lubricating oil composition.
  • the lubricating composition may further comprise a polyalphaolefins (PAO) containing dispersant selected from the group consisting of a polyalphaolefin succimmide, a polyalphaolefin succinamide, a poiyalphaolefm acid ester, a poiyalphaolefm oxazoline, a poiyalphaolefm imidazoline, a poiyalphaolefm succinamide imidazoline, and combinations thereof
  • PAO polyalphaolefins
  • Polyalphaolefins (PAO) useful as feedstock in forming the PAO containing dispersants are those derived from oligomerization or polymerization of ethylene, propylene, and a-olefins.
  • Suitable a-olefms include 1-buteiie, 1-penteiie, 1-hexene, 1-hepteiie, 1-octene, 1 -nonene, 1 -decene, 1 -undecene, 1 -dodecene, 1 -tetradecene, and 1 -octadecene.
  • Feedstocks containing a mixture of two or more of the foregoing monomers as well as other hydrocarbons are typically employed when manufacturing PAOs commercially.
  • the PAO may take the form of dimers, trimers, tetramers, polymers, and the like.
  • the PAO may be reacted with maieic anhydride (MA) to form the polyalphaolefin succinic anhydride (PAO-SA) and subsequently the anhydride may reacted with one or more of polyamines, aminoalcohols, and alcohols/polyols to form polyalphaolefin succinimide, polyalphaolefin succinamide, polyalphaolefin succinic acid ester, polyalphaolefin oxazoline, polyalphaolefin imidazoline, polyalphaolefin-succinamide- imidazoline, and mixtures thereof.
  • MA maieic anhydride
  • PAO-SA polyalphaolefin succinic anhydride
  • PAO-SA polyalphaolefin succinic anhydride
  • the polyalkenyl succinimide dispersant may be present at 0.1 weight % to 10 weight %, or 0.5 weight % to 7 weight %, or 1 weight % to 5 weight %, or 1.5 weight % to 4 weight % of the lubricating oil composition.
  • any or all borated and non-borated dispersant may have a carbonyl to nitrogen ratio (CO:N ratio) of 5 : 1 to 1 : 10, 2: 1 to 1 : 10, or 2: 1 to 1 :5, or 2: 1 to 1 :2.
  • the dispersant may have a CO:N ratio of 2: 1 to 1 : 10, or 2: 1 to 1 :5, or 2: 1 to 1 :2, or 1 : 1.4 to 1 :0.6, or 0.9: l to 1.6: 1, or 0.95 : l to 1.5 : 1, or 1 : 1 to 1 :4.
  • the lubricating composition of the invention comprises a polyolefin dispersant viscosity modifier.
  • the dispersant viscosity modifier may be a functionalized ethylene-a-olefin copolymer.
  • the term "functionalized” means that the olefin polymer has been modified by the addition of a polar moiety.
  • the olefin polymer may be derived from isobutylene or isoprene.
  • the olefin polymer is prepared from ethylene and a higher olefin within the range of C3-C10 alpha-mono-olefins, for example, the olefin polymer may be prepared from ethylene and propylene.
  • the olefin polymer may be a polymer of 15 to 80 mole percent of ethylene, for example, 30 mol percent to 70 mol percent ethylene and from and from 20 to 85 mole percent of C3 to CIO mono-olefins, such as propylene, for example, 30 to 70 mol percent propylene or higher mono-olefins.
  • C3 to CIO mono-olefins such as propylene, for example, 30 to 70 mol percent propylene or higher mono-olefins.
  • Terpolymer variations of the olefin copolymer may also be used and may contain up to 15 mol percent of a non-conjugated diene or triene. Non-conjugated dienes or trienes may have 5 to about 14 carbon atoms.
  • the non- conjugated diene or triene monomers may be characterized by the presence of a vinyl group in the structure and can include cyclic and bicycle compounds.
  • Representative dienes include 1,4-hexadiene, 1,4-cyclohexadiene, dicyclopentadiene, 5-ethyldiene-2-norbornene, 5- methylene-2-norbornene, 1,5-heptadiene, and 1,6-octadiene.
  • the olefin copolymer may be a copolymer of ethylene, propylene, and butylene.
  • the polymer may be prepared by polymerizing a mixture of monomers comprising ethylene, propylene and butylene. These polymers may be referred to as copolymers or terpolymers.
  • the terpolymer may comprise from about 5 mol % to about 20 mol %, or from about 5 mol % to about 10 mol % structural units derived from ethylene; from about 60 mol % to about 90 mol %, or from about 60 mol % to about 75 mol structural units derived from propylene; and from about 5 mol % to about 30 mol %, or from about 15 mol % to about 30 mol % structural units derived from butylene.
  • the butylene may comprise any isomers or mixtures thereof, such as n-butylene, iso-butylene, or a mixture thereof.
  • the butylene may comprise butene-1.
  • butylene may comprise butene-1 as well as butene-2 and butadiene.
  • the butylene may comprise a mixture of butene-1 and isobutylene wherein the weight ratio of butene-1 to isobutylene is about 1 :0.1 or less.
  • the butylene may comprise butene-1 and be free of or essentially free of isobutylene.
  • the olefin copolymer may be a copolymer of ethylene and butylene.
  • the polymer may be prepared by polymerizing a mixture of monomers comprising ethylene and butylene wherein, the monomer composition is free of or substantially free of propylene monomers (i.e., contains less than 1 weight percent of intentionally added monomer).
  • the copolymer may comprise 30 to 50 mol percent structural units derived from butylene; and from about 50 mol percent to 70 mol percent structural units derived from ethylene.
  • the butylene may comprise a mixture of butene-1 and isobutylene wherein the weight ratio of butene-1 to isobutylene is about 1 :0.1 or less.
  • the butylene may comprise butene-1 and be free of or essentially free of isobutylene.
  • the olefin polymers useful in the present invention in particular, the ethylene- a-olefin copolymers have a number average molecular weight ranging from 4500 to 500,000, for example, 5000 to 100,000, or 7500 to 60,000, or 8000 to 45,000.
  • the olefin polymers are functionalized by modifying the polymer by the addition of a polar moiety.
  • the functionalized copolymer is the reaction product of an olefin polymer grafted with an acylating agent.
  • the acylating agent may be an ethylenically unsaturated acylating agent.
  • Useful acylating agents are typically ⁇ , ⁇ unsaturated compounds having at least one ethylenic bond (prior to reaction) and at least one, for example two, carboxylic acid (or its anhydride) groups or a polar group which is convertible into said carboxyl groups by oxidation or hydrolysis.
  • the acylating agent grafts onto the olefin polymer to give two carboxylic acid functionalities.
  • useful acylating agents include maleic anhydride, chlormaleic anhydride, itaconic anhydride, or the reactive equivalents thereof, for example, the corresponding dicarboxylic acids, such as maleic acid, fumaric acid, cinnamic acid, (meth)acrylic acid, the esters of these compounds and the acid chlorides of these compounds.
  • the functionalized ethyl ene-a-olefin copolymer comprises an olefin copolymer grafted with the acyl group which is further functionalized with a hydrocarbyl amine, a hydrocarbyl alcohol group, amino- or hydroxy- terminated polyether compounds, and mixtures thereof.
  • Amine functional groups are be added to the olefin polymer by reacting the olefin copolymer (typically, an ethylene-a-olefin copolymer, such as an ethylene-propylene copolymer) with an acylating agent (typically maleic anhydride) and a hydrocarbyl amine having a primary or secondary amino group.
  • the hydrocarbyl amine may be selected from aromatic amines, aliphatic amines, and mixtures thereof.
  • Aromatic amines useful for providing the polar moiety of the functionalized ethylene-a-olefin copolymer also include those which can be represented by the general structure H 2 -Ar or T- H-Ar, where T may be alkyl or aromatic, Ar is an aromatic group, including nitrogen-containing or amino-substituted aromatic groups and Ar groups including any of the following structures:
  • Aromatic amines may also include those amines wherein a carbon atom of the aromatic ring structure is attached directly to the amino nitrogen.
  • the amines may be monoamines or polyamines.
  • the aromatic ring will typically be a mononuclear aromatic ring (i.e., one derived from benzene) but can include fused aromatic rings, especially those derived from naphthalene.
  • aromatic amines include aniline, N-alkylanilines such as N- methylaniline and N-butylaniline, di-(para-methylphenyl)amine, 4 aminodiphenylamine, ⁇ , ⁇ -dimethylphenylenediamine, naphthylamine, 4-(4-nitrophenyl- , azo)aniline (disperse orange 3), sulphamethazine, 4-phenoxyaniline, S-nitro ⁇ aniline, 4-aminoacetanilide (N-(4- aminophenyl)acetamide)), 4-amino-2-hydroxy-benzoic acid phenyl ester (phenyl amino salicylate), N-(4-amino-phenyl)-benzamide, various benzyHamines such as 2,5- dimethoxybenzylamine, 4-phenylazoaniline, and substituted versions of these.
  • N-alkylanilines such as N- methylaniline and N-butylaniline
  • aromatic amines include amino-substituted aromatic compounds and amines in which the amine nitrogen is a part of an aromatic ring, such as 3 aminoquinoline, 5-aminoquinoline, and 8-aminoquinoline.
  • aromatic amines such as 2-aminobenzimidazole, which contains one secondary amino group attached directly to the aromatic ring and a primary amino group attached to the imidazole ring.
  • Other amines include N-(4-anilinophenyl)-3-aminobutanamide or 3 amino propyl imidazole.
  • Yet other amines include 2,5-dimethoxybenzylamine.
  • Suitable amines include 3-amino-N- (4-anilinophenyl)-N-isopropyl butanamide, and N-(4-anilinophenyl)-3- ⁇ (3-aminopropyl)- (coco ⁇ alkyl ⁇ amino ⁇ butanamide.
  • Other aromatic amines which can be used include various aromatic amine dye intermediates containing multiple aromatic rings linked by, for example, amide structures. Examples include materials of the general structure:
  • Rviii and Rix are independently alkyl or alkoxy groups such as methyl, methoxy, or ethoxy.
  • Rviii and Rix are both -OCH3 and the material is known as Fast Blue RR [CAS# 6268-05-9].
  • Rix is -OCH3 and Rviii is -CH3, and the material is known as Fast Violet B [99-21-8]. When both Rviii and Rix are ethoxy, the material is Fast Blue BB [120-00-3].
  • U.S. Patent 5,744,429 discloses other aromatic amine compounds, particularly aminoalkylphenothiazines. N-aromatic substituted acid amide compounds, such as those disclosed in U.S. Patent Application 2003/0030033 Al, may also be used for the purposes of this invention. Suitable aromatic amines include those in which the amine nitrogen is a substituent on an aromatic carboxyclic compound, that is, the nitrogen is not sp2 hybridized within an aromatic ring.
  • a useful aromatic amine may also comprise an amine formed by reacting an aldehyde with 4-aminodiphenylamine.
  • the resultant amine may be described as an alkylene coupled amine having at least 4 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.
  • an aliphatic aldehyde examples include formaldehyde (or a reactive equivalent thereof such as formalin or paraformaldehyde), ethanal or propanal.
  • the aldehyde may be formaldehyde or benzaldehyde.
  • this aromatic amine may also be prepared by the methodology described in Berichte der Deutschen Chemischenmaschine (1910), 43, 728-39.
  • the aromatic amine includes 4 aminodiphenylamine, aldehyde (typically formaldehyde) coupled 4 aminodiphenylamine, nitro-aniline (3- nitro- aniline), disperse orange-3 (D03), or mixtures thereof.
  • the hydrocarbyl amine component may comprise at least one aliphatic amine containing at least one amino group capable of condensing with said acyl group to provide a pendant group and at least one additional group comprising at least one nitrogen, oxygen, or sulfur atom.
  • Suitable aliphatic amines include polyethylene polyamines (such as tetraethylene pentamine (TEPA), triethylene tetra amine (TETA), pentaethylene hexamine (PEHA), and polyamine bottoms), ⁇ , ⁇ -dimethylaminopropylamine (DMAPA), N- (aminopropyl)morpholine, ⁇ , ⁇ -diIsostearylaminopropylamine, ethanolamine, and combinations thereof.
  • TEPA tetraethylene pentamine
  • TETA triethylene tetra amine
  • PEHA pentaethylene hexamine
  • DMAPA ⁇ , ⁇ -dimethylaminopropylamine
  • N- (aminopropyl)morpholine N- (aminopropyl)morpholine
  • ⁇ , ⁇ -diIsostearylaminopropylamine ethanolamine, and combinations thereof.
  • the polar moiety added to the functionalized ethylene-a-olefin copolymer may be derived from a hydrocarbyl alcohol group, containing at least one hydroxy group capable of condensing with said acyl group to provide a pendant group and at least one additional group comprising at least one nitrogen, oxygen, or sulfur atom.
  • the alcohol functional groups may be added to the olefin polymer by reacting the olefin copolymer with an acylating agent (typically maleic anhydride) and a hydrocarbyl alcohol.
  • the hydrocarbyl alcohol may be a polyol compound.
  • Suitable hydrocarbyl polyols include ethylene glycol and propylene glycol, trimethylol propane (TMP), pentaerythritol, and mixtures thereof.
  • the polar moiety added to the functionalized ethylene-a-olefin copolymer may be amine-terminated polyether compounds, hydroxy- terminated polyether compounds, and mixtures thereof.
  • the hydroxy terminated or amine terminated polyether may be selected from the group comprising polyethylene glycols, polypropylene glycols, mixtures of one or more amine terminated polyether compounds containing units derived from ethylene oxides, propylene oxides, butylene oxides or some combination thereof, or some combination thereof.
  • Suitable polyether compounds include Synalox® line of polyalkylene glycol compounds, the UCONTM OSP line of polyether compounds available from Dow Chemical, Jeffamine® line of polyether amines available from Huntsman.
  • the lubricating compositions of the present invention comprise 0.05 weight % to 2 weight %, or 0.08 weight % to 1.8 weight %, or 0.1 to 1.2 weight % of the functionalized ethylene-a-olefin copolymer as described herein.
  • the invention provides a lubricating composition further comprising a metal containing detergent.
  • the metal-containing detergent may be an overbased detergent. Overbased detergents, otherwise referred to as overbased or superbased salts, are characterized by a metal content in excess of that which would be necessary for neutralization according to the stoichiometry of the metal and the particular acidic organic compound reacted with the metal.
  • the overbased metal -containing detergent is selected from the group consisting of non-sulfur containing phenates, sulfur containing phenates, sulfonates, salixarates, salicylates, and mixtures thereof, or borated equivalents thereof.
  • the overbased detergent may be borated with a borating agent such as boric acid.
  • the metal-containing detergent includes calcium salts, magnesium salts, sodium salts, or mixtures thereof of one or more sulfonates.
  • Other useful metals may include titanium and zirconium.
  • Overbased sulfonates typically have a total base number of 250 to 600, or 300 to 500. Overbased detergents are known in the art.
  • the sulfonate detergent may be predominantly a linear alkylbenzene sulfonate detergent having a metal ratio of at least about 8 as is described in paragraphs [0026] to [0037] of US Patent Publication 2005065045 (and granted as US 7,407,919).
  • the linear alkylbenzene sulfonate detergent may be particularly useful for assisting in improving fuel economy.
  • the linear alkyl group may be attached to the benzene ring anywhere along the linear chain of the alkyl group, but often in the 2, 3 or 4 position of the linear chain, and in some instances, predominantly in the 2 position, resulting in the linear alkylbenzene sulfonate detergent.
  • Overbased sulfonate detergents are known in the art.
  • the overbased calcium sulfonate detergent may be present in an amount to deliver at least 500 ppm calcium by weight and no more than 3000 ppm calcium by weight, or at least 1000 ppm calcium by weight, or at least 2000 ppm calcium by weight, or no more than 2500 ppm calcium by weight to the lubricating composition.
  • the overbased magnesium sulfonate detergent may be present in an amount to deliver no more than 500 ppm by weight of magnesium to the lubricating composition, or no more than 330 ppm by weight, or no more than 125 ppm by weight, or no more than 45 ppm by weight.
  • the overbased a magnesium sulfonate detergent may be present in an amount to deliver at least 200 ppm by weight of magnesium, or at least 450 ppm by weight magnesium, or at least 700 ppm by weight magnesium to the lubricating composition.
  • both calcium and magnesium containing sulfonate detergents may be present in the lubricating composition.
  • Calcium and magnesium sulfonate detergents may be present such that the weight ratio of calcium to magnesium is 10: 1 to 1 : 10, or 8:3 to 4:5, or 1 : 1 to 1 :3.
  • the detergent may comprise a mixture of calcium and magnesium containing detergents.
  • the detergent may provide, in one embodiment, 800 to 1300 ppm calcium and 450 to 800 ppm magnesium and in another embodiment 900 to 1200 ppm calcium and 500 to 750 ppm magnesium.
  • the overbased detergent may be present at 0.1 weight % to 15 weight %, or
  • the lubricating composition may further comprise an alkali or alkaline earth metal salicylate detergent or salixarate detergent or mixture thereof.
  • the metal containing salicylate or salixarate detergent may be an overbased detergent.
  • Useful salicylate and salixarate detergents may include calcium salts, magnesium salts, sodium salts or mixtures thereof.
  • Other useful metals may include titanium and zirconium.
  • the overbased metal salicylate detergent may be present at 0.1 weight % to 15 weight %, or 0.1 weight % to 10 weight %, or 0.2 weight % to 8 weight %, or 0.2 weight % to 3 weight %.
  • the overbased metal salixarate detergent may be present at 0.1 weight % to 15 weight %, or 0.1 weight % to 10 weight %, or 0.2 weight % to 8 weight %, or 0.2 weight % to 3 weight %.
  • the lubricating composition may free or substantially free of a metal containing salicylate detergent or metal containing salixarate detergent or both.
  • the lubricating composition comprises less than 0.2 weight. % or 0.1 weight. % or 0.05 weight. % or 0.01 weight. % of a metal containing salicylate detergent, metal containing salixarate detergent or both.
  • the lubricating composition is free or substantially free of a metal containing sulfur coupled alkyl phenol compound.
  • a metal containing sulfur coupled alkyl phenol compound Such compounds may be exemplified by alkali and alkaline earth metal containing phenate detergents, such as magnesium phenate detergents, calcium phenate detergents and sodium phenate detergents and further including overbased metal containing phenate detergents, all of which are known in the art.
  • the lubricating composition comprises less than 0.2 weight. % or 0.1 weight. % or 0.05 weight. % or 0.01 weight. % or 0.005 weight % of a metal containing sulfur coupled alkyl phenol compound.
  • the lubricating composition is free of or substantially free of a metal containing saligenin detergent, such as magnesium saligenin detergent, calcium saligenin detergents and sodium saligenin detergents and further including overbased metal containing saligenin detergents, all of which are known in the art.
  • the lubricating composition comprises less than 0.2 weight. % or 0.1 weight. % or 0.05 weight. % or 0.01 weight. % or 0.005 weight % of a metal containing saligenin detergent.
  • the total amount of soap contributed by the detergent may be from about 0.08 or 1.0 to less than 0.9 or 0.7 or 0.5 or 0.4 or 0.3 or 0.25 weight. % with respect to the lubricating composition.
  • the lubricating composition may be free or substantially free of phenate soap.
  • the soap may substantially consist of sulfonate soap.
  • the term "soap" means the surfactant portion of a detergent and does not include a metal base, such as calcium carbonate.
  • the soap term may also be referred to as a detergent substrate.
  • the sulfonate detergents described herein, the soap or substrate may be a neutral salt of an alkylbenzenesulfonic acid.
  • Metal-containing detergents also contribute sulfated ash to a lubricating composition.
  • Sulfated ash may be determined by ASTM D874.
  • the lubricating composition of the invention comprises a metal-containing detergent in an amount to deliver at least 0.4 weight. % sulfated ash to the total composition.
  • the metal-containing detergent is present in an amount to deliver at least 0.6 weight. % sulfated ash, or at least 0.75 weight. % sulfated ash, or even at least 0.9 weight. % sulfated ash to the lubricating composition.
  • Antioxidants provide and/or improve the anti-oxidation performance of organic compositions, including lubricant compositions that contain organic components, by preventing or retarding oxidative and thermal decomposition.
  • Suitable antioxidants may be catalytic or stoichiometric in activity and include any compound capable of inhibiting or decomposing free radicals, including peroxide.
  • Ashless antioxidants of the invention may comprise one or more of arylamines, diarylamines, alkylated arylamines, alkylated diaryl amines, phenols, hindered phenols, sulfurized olefins, or mixtures thereof.
  • the lubricating composition includes an antioxidant, or mixtures thereof.
  • the antioxidant may be present at 0.05 weight % to 15 weight %, or 0.1 weight % to 10 weight %, or 0.5 weight % to 5 weight %, or 0.5 weight % to 3 weight %, or 0.3 weight % to 1.5 weight % of the lubricating composition.
  • the diarylamine or alkylated diarylamine may be a phenyl-a-naphthylamine
  • the alkylated diphenylamine may include di-nonylated diphenylamine, nonyl diphenylamine, octyl diphenylamine, di-octylated diphenylamine, di-decylated diphenylamine, decyl diphenylamine and mixtures thereof.
  • the diphenylamine may include nonyl diphenylamine, dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine, or mixtures thereof.
  • the alkylated diphenylamine may include nonyl diphenylamine, or dinonyl diphenylamine.
  • the alkylated diarylamine may include octyl, di-octyl, nonyl, di-nonyl, decyl or di-decyl phenylnapthylamines.
  • Diarylamines of the invention may also be represented by Formula 2:
  • Ri and R 2 are moieties which, together with the carbon atoms to which they are bonded, are joined together to form a 5-, 6-, or 7-membered ring (such as a carbocyclic ring or cyclic hydrocarbylene ring);
  • R 3 and R 4 are independently hydrogen, hydrocarbyl groups, or are moieties which, taken together with the carbon atoms to which they are bonded, form a 5-, 6-, or 7-membered ring (such as a carbocyclic ring or cyclic hydrocarbylene ring);
  • R 5 and R 6 are independently hydrogen, hydrocarbyl groups, or are moieties (typically hydrocarbyl moieties) which, taken together with the carbon atoms to which they are attached, form a ring, or represent a zero-carbon or direct linkage between the rings; and
  • R 7 is hydrogen or a hydrocarbyl group
  • the diarylamine is a N-phenyl-naphthylamine (PNA).
  • PNA N-phenyl-naphthylamine
  • the diarylamine may be represented by Formula (2a):
  • R 3 and R 4 are defined as above.
  • diarylamine compounds include those having the general Formula (2b):
  • compounds of Formula (2) further comprise an N- allyl group, for example the compound of Formula (2c):
  • the diarylamine is a dihydroacridan derivative of Formula
  • Ri, R 2 , R 3 , and R 4 are defined above; R 8 and R are independently hydrogen or a hydrocarbyl group of 1 to 20 carbon atoms.
  • the diarylamine of Formula (2) is chosen such that R5 and
  • R 6 represent a direct (or zero-carbon) link between the aryl rings.
  • the result is a carbazole of Formula (2g):
  • the diarylamine antioxidant of the invention may be present on a weight basis of the lubrication composition at 0.1% to 10%, 0.35% to 5%, or even 0.5% to 2%.
  • the phenolic antioxidant may be a simple alkyl phenol, a hindered phenol, or coupled phenolic compounds.
  • the hindered phenol antioxidant often contains a secondary butyl and/or a tertiary butyl group as a sterically hindering group.
  • the phenol group may be further substituted with a hydrocarbyl group (typically linear or branched alkyl) and/or a bridging group linking to a second aromatic group.
  • hindered phenol antioxidants examples include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert- butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, 4-dodecyl- 2,6-di-tert-butylphenol, or butyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate.
  • the hindered phenol antioxidant may be an ester and may include, e.g., IrganoxTM L-135 from Ciba.
  • Coupled phenols often contain two alkylphenols coupled with alkylene groups to form bisphenol compounds.
  • suitable coupled phenol compounds include 4,4'- methylene bis-(2,6-di-tert-butyl phenol), 4-methyl-2,6-di-tert-butylphenol, 2,2'-bis-(6-t- butyl-4-heptylphenol); 4,4'-bis(2,6-di-t-butyl phenol), 2,2'-methylenebis(4-methyl-6-t- butylphenol), and 2,2'-methylene bis(4-ethyl-6-t-butylphenol).
  • Phenols of the invention also include polyhydric aromatic compounds and their derivatives.
  • suitable polyhydric aromatic compounds include esters and amides of gallic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, l,4-dihydroxy-2- naphthoic acid, 3,5-dihydroxynaphthoic acid, 3,7-dihydroxy naphthoic acid, and mixtures thereof.
  • the phenolic antioxidant comprises a hindered phenol.
  • the hindered phenol is derived from 2,6-ditertbutyl phenol.
  • the lubricating composition of the invention comprises a phenolic antioxidant in a range of 0.01 weight % to 5 weight %, or 0.1 weight % to 4 weight
  • Sulfurized olefins are well known commercial materials, and those which are substantially nitrogen-free, that is, not containing nitrogen functionality, are readily available.
  • the olefinic compounds which may be sulfurized are diverse in nature. They contain at least one olefinic double bond, which is defined as a non-aromatic double bond; that is, one connecting two aliphatic carbon atoms. These materials generally have sulfide linkages having 1 to 10 sulfur atoms, for instance, 1 to 4, or 1 or 2.
  • the lubricating composition of the invention comprises a sulfurized olefin in a range 0.2 weight percent to 2.5 weight percent, or 0.5 weight percent to 2.0 weight percent, or 0.7 weight percent to 1.5 weight percent.
  • the ashless antioxidants of the invention may be used separately or in combination.
  • two or more different antioxidants are used in combination, such that there is at least 0.1 weight percent of each of the at least two antioxidants and wherein the combined amount of the ashless antioxidants is 0.5 to 5 weight percent.
  • the invention provides a lubricating composition further comprising a molybdenum compound.
  • the molybdenum compound may be selected from the group consisting of molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, amine salts of molybdenum compounds, and mixtures thereof.
  • the molybdenum compound may provide the lubricating composition with 0 to 1000 ppm, or 5 to 1000 ppm, or 10 to 750 ppm, or 5 ppm to 300 ppm, or 20 ppm to 250 ppm of molybdenum.
  • the invention provides a lubricating composition further comprising a friction modifier.
  • friction modifiers include long chain fatty acid derivatives of amines, fatty esters, or epoxides; fatty imidazolines such as condensation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; or fatty alkyl tartramides.
  • fatty as used herein, can mean having a C8-22 linear alkyl group.
  • the lubricating composition of the invention further includes an anti-wear agent, typically a phosphorus-containing anti-wear agent.
  • an anti-wear agent typically a phosphorus-containing anti-wear agent.
  • suitable phosphorus-containing anti-wear agents include metal dialkyl dithiophosphates, organo-phosphates, phosphites, phosphonates, amine salted alkylphosphoric acid compounds, and mixtures thereof.
  • the invention provides a lubricating composition which further includes a metal dialkyldithiophosphate.
  • the metal dialkyldithiophosphate may be a zinc dialkyldithiophosphate (ZDDP), or mixtures thereof.
  • Zinc dialkyldithiophosphates are known in the art.
  • the zinc dialkyldithiophosphate may be present at 0 weight % to 3 weight %, or 0.1 weight % to 1.5 weight %, or 0.5 weight % to 0.9 weight % of the lubricating composition, such that the total zinc contributed to the lubricant composition does not exceed 0.06 weight percent of the composition.
  • the ZDDP may be present in an amount to provide 0.05 weight % or 0.03 weight % zinc to the lubricating composition.
  • the zinc dialkyldithiophosphate may be derived from primary alcohols, secondary alcohols, or combinations thereof. Typically they are derived from primary and secondary alcohols containing 3 to 12 carbon atoms and combinations thereof. In one embodiment the zinc alkyldithiophosphate comprises at least 25 mol % secondary alkyl groups, or at least 40 mol % secondary alkyl groups, or at least 75 mol % secondary alkyl groups, or at least 90 mol % secondary alkyl groups
  • the phosphorus-containing anti-wear agent may be a metal free organo- phosphorus anti-wear agent.
  • the organo-phosphorus agent may contain sulfur or may be sulfur-free.
  • Sulfur-free phosphorus-containing antiwear agents may be phosphites, phosphonates, alkylphosphate esters, amine or ammonium phosphate salts, or mixtures thereof.
  • Phosphorus esters such as the dihydrocarbon and trihydrocarbon phosphites, e.g., dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite; dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite and polypropylene substituted phenol phosphite; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol diacid; amine salts of alkyl and dialkylphosphoric acids or derivatives including, for example, the amine salt of a reaction product of a dialkyldithiophosphoric acid with propylene oxide and subsequently followed by a further reaction with P2O5; and mixtures thereof (as described in US 3,197,405).
  • the amine salt of a sulfur-free phosphorus-containing compound may be salts of primary amines, secondary amines, tertiary amines, or mixtures thereof
  • Amine phosphate salts may be derived from mono- or di- hydrocarbyl phosphoric acid (typically alkyl phosphoric acid), or mixtures thereof.
  • the alkyl of the mono- or di- hydrocarbyl phosphoric acid may comprise linear or branched alkyl groups of 3 to 36 carbon atoms.
  • the hydrocarbyl group of the linear or branched hydrocarbylphosphoric acid may contain 4 to 30, or 8 to 20 carbon atoms.
  • Examples of a suitable hydrocarbyl group of the hydrocarbyl phosphoric acid may include isopropyl, n-butyl, sec-butyl, amyl, 4-methyl-2- pentyl (i.e.
  • the phosphate is a mixture of mono- and di- (2-ethyl)hexylphosphate.
  • Suitable primary amines include ethylamine, propylamine, butylamine, 2-ethylhexyl amine, octylamine, and dodecylamine, as well as such fatty amines as n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n- octadecyl amine and oleyamine.
  • fatty amines include commercially available fatty amines such as "Armeen.RTM.” amines (products available from Akzo Chemicals, Chicago, 111.), such as Armeen C, Armeen O, Armeen O L, Armeen T, Armeen H T, Armeen S and Armeen S D, wherein the letter designation relates to the fatty group, such as coco, oleyl, tallow, or stearyl groups.
  • the phosphorus anti-wear agent may be present in the lubricant composition in amount of 0.01 to 5 weight %, or 0.1 to 3.2 weight %, or 0.35 to 1.8 weight %, or 0.5 to 1.5 weight %, or 0.5 to 0.9 weight %. In one embodiment, the phosphorus anti-wear agent may be present in an amount to provide 0.01 weight % to 0.15 weight % phosphorus, or 0.01 to 0.08 weight % phosphorus, or 0.025 to 0.065 weight % phosphorus to the composition.
  • Other Performance Additives may be present in the lubricant composition in amount of 0.01 to 5 weight %, or 0.1 to 3.2 weight %, or 0.35 to 1.8 weight %, or 0.5 to 1.5 weight %, or 0.5 to 0.9 weight %.
  • the phosphorus anti-wear agent may be present in an amount to provide 0.01 weight % to 0.15 weight % phosphorus, or 0.01 to 0.08 weight % phosphorus, or 0.025 to 0.0
  • compositions of the invention may optionally comprise one or more additional additives.
  • additional additives may include one or more metal deactivators, viscosity modifiers, detergents, friction modifiers, antiwear agents, corrosion inhibitors, dispersants different from the borated dispersant of the invention, dispersant viscosity modifiers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, pour point depressants, seal swelling agents, and any combination or mixture thereof.
  • metal deactivators viscosity modifiers
  • detergents dispersants different from the borated dispersant of the invention
  • dispersant viscosity modifiers dispersant viscosity modifiers
  • extreme pressure agents antioxidants
  • foam inhibitors demulsifiers
  • pour point depressants pour point depressants
  • seal swelling agents and any combination or mixture thereof.
  • fully- formulated lubricating oil will contain one or more of these performance additives, and often a package of multiple performance additives.
  • the lubricating composition further comprises an anti-wear agent (different from the phosphorus-containing anti-wear agent above), a friction modifier, a viscosity modifier, a corrosion inhibitor or a combination thereof, where each of the additives listed may be a mixture of two or more of that type of additive.
  • the invention provides a lubricating composition further comprising an ashless antiwear agent, a friction modifier, a viscosity modifier (typically an olefin copolymer such as an ethylene-propylene copolymer), or a combination thereof, where each of the additives listed may be a mixture of two or more of that type of additive.
  • the lubricating composition further comprises an ashless antiwear agent different from the phosphorus antiwear agent described above.
  • suitable antiwear agents include hydroxy-carboxylic acid derivatives such as esters, amides, imides or amine or ammonium salt, sulfurized olefins, thiocarbamate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-coupled thio- carbamates, and bis(S-alkyldithiocarbamyl) disulphides.
  • the ashless antiwear agent comprises a compound derived from a hydroxycarboxylic acid.
  • the ashless antiwear agent is derived from at least one of hydroxy-polycarboxylic acid di-ester, a hydroxy-polycarboxylic acid di -amide, a hydroxy-polycarboxylic acid imide, and a hydroxy-polycarboxylic acid ester amide.
  • the ashless antiwear agent is derived from a hydroxy-polycarboxylic acid imide.
  • a suitable a hydroxycarboxylic acid examples include citric acid, tartaric acid, lactic acid, glycolic acid, hydroxy -propionic acid, hydroxyglutaric acid, or mixtures thereof.
  • ashless antiwear agent is derived from tartaric acid, citric acid, hydroxy-succinic acid, dihydroxy mono-acids, mono-hydroxy diacids, or mixtures thereof.
  • the ashless antiwear agent includes a compound derived from tartaric acid or citric acid.
  • the ashless antiwear agent includes a compound derived from tartaric acid.
  • US Patent Application 2005/198894 discloses suitable hydroxycarboxylic acid compounds, and methods of preparing the same.
  • US-2006-0079413 U.S. Patent Application No. 60/867,402; and British Patent 2 105743 A. all disclose examples of suitable tartaric acid derivatives.
  • the antiwear agent may in one embodiment include a tartrate or tartrimide as disclosed in International Publication WO 2006/044411 or Canadian Patent CA 1 183 125.
  • the tartrate or tartrimide may contain alkyl- ester groups, where the sum of carbon atoms on the alkyl groups is at least 8.
  • the antiwear agent may in one embodiment include a citrate.
  • the ashless phosphorus-free antiwear agent is present at 0.1 to 5 weight %, 0.1 weight % to 3 weight %, or 0.2 to 3 or 0.1 weight % to 1.5 weight %, or 0.5 weight % to 1.1 weight % of the lubricating composition.
  • Friction modifiers may also encompass materials such as sulfurized fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil or monoester of a polyol and an aliphatic carboxylic acid.
  • the friction modifier is selected from the group consisting of long chain fatty acid derivatives of amines, long chain fatty esters, or long chain fatty epoxides; fatty imidazolines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; and fatty alkyl tartramides.
  • the friction modifier may be present at 0.05 weight % to 6 weight %, or 0.05 weight % to 4 weight %, or 0.1 weight % to 2 weight % of the lubricating composition.
  • the friction modifier may be a long chain fatty acid ester.
  • the long chain fatty acid ester may be a mono-ester or a diester or a mixture thereof, and in another embodiment the long chain fatty acid ester may be a triglyceride.
  • Other performance additives such as corrosion inhibitors include those described in paragraphs 5 to 8 of US Application US05/038319, published as WO2006/047486, octyl octanamide, condensation products of dodecenyl succinic acid or anhydride and a fatty acid such as oleic acid with a polyamine.
  • the corrosion inhibitors include the Synalox® (a registered trademark of The Dow Chemical Company) corrosion inhibitor.
  • the Synalox® corrosion inhibitor may be a homopolymer or copolymer of propylene oxide.
  • the Synalox® corrosion inhibitor is described in more detail in a product brochure with Form No. 118-01453-0702 AMS, published by The Dow Chemical Company.
  • the product brochure is entitled "SYNALOX Lubricants, High-Performance Polyglycols for Demanding Applications.”
  • the lubricating composition may further include metal deactivators, including derivatives of benzotriazoles (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles, or 2-alkyldithiobenzothiazoles; foam inhibitors, including copolymers of ethyl acrylate and 2-ethylhexylacrylate and copolymers of ethyl acrylate and 2-ethylhexylacrylate and vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers; and pour point depressants, including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides.
  • metal deactivators including derivatives of benzotriazoles (typically tolyltri
  • pour point depressants that may be useful in the compositions of the invention further include polyalphaolefins, esters of maleic anhydride-styrene, poly(meth)acrylates, polyacrylates or polyacrylamides.
  • the lubricating composition may have a composition as described in the following table:
  • Dispersant Viscosity Modifier 0.05 to 3 0.1 to 2 0.2 to 1.6
  • Metal dialkyldithiophosphate O to 1 0.01 to 0.8 0.1 to 0.6
  • Friction Modifier O to 6 0.1 to 2.4 0.2 to 1.5
  • Viscosity Modifier O to 10 0.5 to 8 1 to 6
  • the present invention provides a surprising ability to control damage to an engine in operation due to wear and deposit formation. This is accomplished while maintaining fuel economy performance, low sulfated ash levels, seals compatibility, corrosion control, and other limitations, required by increasingly stringent government regulations.
  • the invention provides for a method of lubricating an internal combustion engine comprising supplying to the internal combustion engine a lubricating composition as disclosed herein.
  • the lubricant is added to the lubricating system of the internal combustion engine, which then delivers the lubricating composition to the critical parts of the engine, during its operation, that require lubrication
  • the lubricating compositions described above may be utilized in an internal combustion engine.
  • the engine components may have a surface of steel or aluminum (typically a surface of steel), and may also be coated for example with a diamond-like carbon (DLC) coating.
  • DLC diamond-like carbon
  • An aluminum surface may be comprised of an aluminum alloy that may be a eutectic or hyper-eutectic aluminum alloy (such as those derived from aluminum silicates, aluminum oxides, or other ceramic materials).
  • the aluminum surface may be present on a cylinder bore, cylinder block, or piston ring having an aluminum alloy, or aluminum composite.
  • the internal combustion engine may be fitted with an emission control system or a turbocharger.
  • emission control system examples include diesel particulate filters (DPF), or systems employing selective catalytic reduction (SCR).
  • the internal combustion engine of the present invention is distinct from a gas turbine.
  • individual combustion events translate from a linear reciprocating force into a rotational torque through the rod and crankshaft.
  • a gas turbine which may also be referred to as a jet engine
  • a continuous combustion process generates a rotational torque continuously without translation, and can also develop thrust at the exhaust outlet.
  • the lubricant composition for an internal combustion engine may be suitable for any engine lubricant irrespective of the sulfur, phosphorus or sulfated ash (ASTM D-874) content.
  • the sulfur content of the engine oil lubricant may be 1 weight % or less, or 0.8 weight % or less, or 0.5 weight % or less, or 0.3 weight % or less. In one embodiment, the sulfur content may be in the range of 0.001 weight % to 0.5 weight %, or 0.01 weight % to 0.3 weight %.
  • the phosphorus content may be 0.2 weight % or less, or 0.12 weight % or less, or 0.1 weight % or less, or 0.085 weight % or less, or 0.08 weight % or less, or even 0.06 weight % or less, 0.055 weight % or less, or 0.05 weight % or less. In one embodiment the phosphorus content may be 100 ppm to 1000 ppm, or 200 ppm to 600 ppm.
  • the total sulfated ash content may be 2 weight % or less, or 1.5 weight % or less, or 1.1 weight % or less, or 1 weight % or less, or 0.8 weight % or less, or 0.5 weight % or less, or 0.4 weight % or less. In one embodiment, the sulfated ash content may be 0.05 weight % to 0.9 weight %, or 0.1 weight % to 0.2 weight % or to 0.45 weight %.
  • the lubricating composition may be an engine oil, wherein the lubricating composition may be characterized as having at least one of (i) a sulfur content of 0.5 weight % or less, (ii) a phosphorus content of 0.1 weight % or less, (iii) a sulfated ash content of 1.5 weight % or less, or combinations thereof.
  • a series of 0W-30 diesel engine lubricants in Group III and Group IV base oils of lubricating viscosity are prepared containing the additives described above as well as conventional additives including polymeric viscosity modifier, overbased detergents, antioxidants (combination of phenolic ester and diarylamine), zinc dialkyldithiophosphate (ZDDP), as well as other performance additives as follows (Table 1).
  • the phosphorus, zinc and ash contents of each of the examples are also presented in the table in part to show that each example has a similar amount of these materials and so provide a proper comparison between the comparative and invention examples.
  • EP DVM 4 0.32 0.32 0 0
  • Ashless AW agent 9 0.05 0.05 0 0
  • alkyl group is derived from ⁇ 1000 Mn polyisobutylene
  • the Additional Additives used in the examples include pourpoint depressants, anti-foam agents, corrosion inhibitors, and includes some amount of diluent oil
  • Engine Cleanliness Test The lubricant formulations of Table 1 were subjected to a series of performance evaluations including engine test VW TDI CEC-L-78-T-99 test, also known as the PV1452 test. This test is regarded as an industry standard and is a severe assessment of a lubricant's performance capabilities. The test employs a 4-cyiinder, 1.9 liter, 81 kW passenger car diesel engine, which is a direct injection compression-ignition engine in which a turbocharger system is used to increase the power output of the unit. The industry test procedure consists of a repeating cycle of hot and cold running conditions. This involves a 30 minute idle period at zero load followed by 180 minutes at full load and 4150 rpm.
  • the pistons are rated against what is known as the DIN rating system.
  • the ni271 three piston-ring grooves and the two piston lands that lie between the grooves are rated on a merit scale for deposits and given a score out of 100 by a method known to those skilled in the art.
  • the five scores are then averaged to give the overall piston cleanliness merit rating.
  • the scores for each of the four pistons are then averaged to afford the overall piston cleanliness for the test.
  • the lubricating compositions were subjected to panel coker tests.
  • the oil sample is splashed onto a metal panel held at 325° € in a cycle of splashing and baking for 3.5 hours.
  • the panel is weighed to determine amount of deposit formation and a visible rating is carried out, where 100% indicates no deposits and 0 indicates heavy black varnish.
  • Sludge Test The lubricant formulations were evaluated in the MB M271 SL Sludge Engine Test. This test is an industry standard for evaluating a lubricating composition to mitigate sludge in internal combustion engines.
  • Nitration/Oxidation test The lubricant formulations were evaluated in a nitration/oxidation bench test which assesses the oxidation and nitration resistance of crankcase engine oil formulations. The formulation is treated with nitric acid and iron naphthanoate prior to administering 50 cc/min of NOx gas whilst heating to 145° C. for 22 hours. A JR. spectroscopic method is used to determine degree of sample nitration and oxidation. Additionally, TBN (ASTM D2896 and D4739) and TAN (ASTM 1)664) are measured SOT and EOT to determine TBN retention and TAN escalation profiles.
  • Friction and Wear test The lubricant formulations were evaluated under TE- 77 friction and wear testing. Tests were run at each of a higher temperature and load (147°C and 616N) and at a lower temperature and load (100°C and 100N). TE- 77— High T, high load
  • PV3344 VW seals test This is an industry standard test designed to quantify the adverse effect of a lubricating oil has on fluorelastomeric seal materials. These materials are commonly used as seals in internal combustion engines. These must be passed in order to receive a VW engine oil approval. The particular seals tests below use the AK6 elastomer which is known to be challenging due to oil changes employed and the particular sensitivity to commonly used engine oil components.
  • hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • hydrocarbyl groups include:
  • hydrocarbon substituents that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic- substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);
  • aliphatic e.g., alkyl or alkenyl
  • alicyclic e.g., cycloalkyl, cycloalkenyl
  • aromatic-, aliphatic-, and alicyclic- substituted aromatic substituents as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);
  • substituted hydrocarbon substituents that is, substituents containing non- hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulphoxy);
  • hetero substituents that is, substituents which, while having a predominantly hydrocarbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms.
  • Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl.
  • substituents as pyridyl, furyl, thienyl and imidazolyl.
  • no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in the hydrocarbyl group.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

La technologie de l'invention concerne des lubrifiants pour moteurs à combustion interne à allumage par compression, en particulier ceux présentant au moins des performances d'étanchéité améliorées, une formation de dépôts réduite et une excellente durabilité. La présente invention concerne une composition lubrifiante à faible teneur en agent dispersant comprenant (a) une huile de viscosité lubrifiante, (b) d'environ 0,5 pour cent en poids à 3,0 pour cent en poids d'un composé phénol substitué par un hydrocarbyle oxyalkylé, (c) d'environ 0,01 pour cent en poids à 2,6 pour cent en poids d'un agent dispersant polyalcénylsuccinimide, et (d) d'environ 0,05 pour cent en poids à 2,0 pour cent en poids d'un modificateur de viscosité à agent dispersant polyoléfinique, et la composition lubrifiante contenant du zinc en une proportion inférieure à environ 700 ppm en poids de la composition.
PCT/US2018/042372 2017-07-17 2018-07-17 Composition lubrifiante à faible teneur en agent dispersant WO2019018329A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US16/631,660 US20200199479A1 (en) 2017-07-17 2018-07-17 Low Disperant Lubricant Composition
EP18749704.5A EP3655511A1 (fr) 2017-07-17 2018-07-17 Composition lubrifiante à faible teneur en agent dispersant
CN201880052298.7A CN111032838A (zh) 2017-07-17 2018-07-17 低分散剂润滑剂组合物
CA3069970A CA3069970A1 (fr) 2017-07-17 2018-07-17 Composition lubrifiante a faible teneur en agent dispersant

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US201762533306P 2017-07-17 2017-07-17
US62/533,306 2017-07-17

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CN (1) CN111032838A (fr)
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US11851628B2 (en) * 2021-12-21 2023-12-26 Afton Chemical Corporation Lubricating oil composition having resistance to engine deposits

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EP3655511A1 (fr) 2020-05-27
CN111032838A (zh) 2020-04-17

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