EP3562921B1 - Schmiermittelzusammensetzung mit n-alkyliertem dianilin - Google Patents

Schmiermittelzusammensetzung mit n-alkyliertem dianilin Download PDF

Info

Publication number
EP3562921B1
EP3562921B1 EP17826048.5A EP17826048A EP3562921B1 EP 3562921 B1 EP3562921 B1 EP 3562921B1 EP 17826048 A EP17826048 A EP 17826048A EP 3562921 B1 EP3562921 B1 EP 3562921B1
Authority
EP
European Patent Office
Prior art keywords
lubricating composition
lubricating
oil
alkylated
composition
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.)
Active
Application number
EP17826048.5A
Other languages
English (en)
French (fr)
Other versions
EP3562921A1 (de
Inventor
Jason J. HANTHORN
Yanshi Zhang
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.)
Lubrizol Corp
Original Assignee
Lubrizol Corp
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 Lubrizol Corp filed Critical Lubrizol Corp
Publication of EP3562921A1 publication Critical patent/EP3562921A1/de
Application granted granted Critical
Publication of EP3562921B1 publication Critical patent/EP3562921B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
    • 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
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution 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
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • 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
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • 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
    • C10M2207/283—Esters of polyhydroxy 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy 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
    • 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
    • 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
    • C10M2215/02—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
    • C10M2215/26—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
    • C10M2217/06—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
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
    • 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
    • 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
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • 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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]
    • 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
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

  • the exemplary embodiment relates to additives for lubricating compositions and finds particular application in connection with N-alkylated dianilines for improved deposit control as deposit boosters in internal combustion engines.
  • U.S. Pat No. 3,779,923 describes alkylated methylenedianiline tars as antioxidants in lubricant compositions.
  • the compounds are formed with a phosphorusbased catalyst.
  • U.S. Pat No. 8,242,066 describes aniline compounds useful as ashless TBN sources for lubricating oil compositions that are compatible with fluoroelastomeric engine seal materials.
  • U.S. Pat. Nos. 4,100,082 ; 4,200,545 ; 4,320,021 , and 4,663,063 ; 4,708.809 generally describe amino-phenol compounds as lubricating oil additives (e.g., dispersant/detergents).
  • US 2016/115418 A1 discloses a lubricating composition containing an oil of lubricating viscosity and an N-acylated aromatic amine compound as well as methods of lubricating an internal combustion engine by supplying said composition to said engine and the use of the N-acylated aromatic amine compound as a TBN booster.
  • MHT TEOST is a bench test that is designed to predict the deposit-forming tendencies of engine oil in the piston ring belt and upper piston crown area during service, and is one of the required test methods in Specification D 4485 to define API Category-Identified engine oils.
  • MDAs methylenedianiline compounds
  • a lubricating composition it would be desirable for a lubricating composition to be able to provide good deposit control, both in fired engine tests and in bench tests such as MHT TEOST, while also providing other performance properties.
  • the present invention provides a lubricating composition
  • a lubricating composition comprising: a) an oil of lubricating viscosity; b) at least 0.1 weight % of an N-alkylated dianiline compound; c) at least 0.1 weight % of an ashless antioxidant selected from a diarylamine antioxidant, a phenolic antioxidant, and combinations thereof; and d) at least 0.01 weight % of an overbased calcium detergent; wherein the lubricating composition comprises less than 0.15 weight percent of phosphorus; and wherein the N-alkylated dianiline is an N,N'-alkylated dianiline compound represented by the formula: wherein R 1 and R 2 are independently selected from alkyl groups of 1 to 24 carbon atoms, which alkyl groups are selected from acyclic alkyl groups, cyclic alkyl groups, and combinations thereof.
  • the present invention provides for the use of the lubricating composition of the invention for reducing deposit formation in an internal combustion engine. In a further aspect, the present invention provides for the use of the lubricating composition of the invention for lubricating an internal combustion engine.
  • the lubricating composition has a TBN of at least 4 mg KOH/g, as measured in accordance with ASTM D-2896.
  • the N-alkyl group is a cyclohexyl group.
  • the N-alkylated dianiline compound is at least 0.15 wt. %, or at least 0.2 wt. %, or at least 0.4 wt. % of the lubricating composition.
  • the N-alkylated dianiline compound is up to 4.0 weight percent of the lubricating composition, or up to 3 wt. %, or up to 1.5 wt. %, or up to 1.2 wt. % of the lubricating composition.
  • N-alkylated dianiline compound is selected from the group consisting of Structures A1, A-2, A-3, A-4, A-5, A-6 and A8 described below, and mixtures thereof.
  • the N-alkylated dianiline compound is selected from 4,4'-2-ethylhexylmethylenedianiline, 4,4'-cyclohexylmethylenedianiline, and mixtures thereof.
  • the oil of lubricating viscosity is at least 40 weight percent of the lubricating composition.
  • the ashless antioxidant is at least 0.2 wt. %, or at least 0.4 wt. %, or at least 0.6 wt. %, or up to 4 wt. %, or up to 1.2 wt. %, or up to 1 wt. % of the lubricating composition.
  • a ratio of the ashless antioxidant to the N-alkyl dianiline compound is from 20:1 to 1:20.
  • the ashless antioxidant includes a phenolic ester and a diarylamine.
  • the ashless antioxidant further includes a sulfurized olefin.
  • the overbased calcium detergent is selected from sulfonates, non-sulfur containing phenates, sulfur containing phenates, salixarates, salicylates, mixtures thereof, and borated equivalents thereof.
  • the overbased calcium detergent is present in an amount to deliver at least 2 mg KOH/g of total base number (TBN), as measured in accordance with ASTM D-2896, to the composition.
  • TBN total base number
  • the overbased calcium detergent is at least 0.1 wt. %, or at least 0.5 wt. %, or up to 3 wt. %, or up to 2 wt. % of the lubricating composition.
  • a ratio of calcium to magnesium in the lubricating composition, by weight, is at least 9:10.
  • the lubricating composition further includes a polyolefin succinimide dispersant, wherein the polyolefin of the polyolefin succinimide has a number average molecular weight of at least 300.
  • the lubricating composition further includes a zinc dialkyldithiophosphate.
  • the lubricating composition includes at least 0.02 weight percent of phosphorus.
  • the N-alkylated dianiline compound is a reaction product of a dianiline with at least one of an aldehyde and a ketone.
  • the lubrication composition includes at least 0.1 weight % of an N-alkylated dianiline compound, an oil of lubricating viscosity, at least 0.1 weight % of an ashless antioxidant, and at least 0.01 weight % of a calcium overbased detergent.
  • the ashless antioxidant is selected from diarylamine antioxidants, phenolic antioxidants, and mixtures thereof.
  • the exemplary lubricating composition includes less than 0.15 wt. % phosphorus.
  • the exemplary N-alkylated dianiline compound improves deposit performance, as measured by the MHT TEOST, while providing good TBN, without negatively impacting (and in some cases, improving) antioxidancy performance, when formulated for heavy duty diesel engine (HD) and passenger car engine applications.
  • HD heavy duty diesel engine
  • Cy MDA N,N'-dicyclohexyl methylenedianiline
  • N-alkylated dianiline compound the two aromatic rings are hydrocarbylene coupled by a methylene group.
  • N-alkylated methylenedianiline compounds can be readily prepared.
  • N-alkylated it is meant that an alkyl group is attached to the dianiline by one or both of the amine groups attached to the aromatic rings of the dianiline.
  • Each of these N-alkyl groups is selected from C 1 -C 24 alkyl groups, which alkyl groups are selected from acyclic alkyl groups, cyclic alkyl groups, and combinations thereof.
  • each amine group of the dianiline has no more than one alkyl group.
  • the exemplary N-alkylated methylenedianiline is an N, N'-alkylated methylenedianiline, where both amine groups are alkylated.
  • the exemplary N, N'-alkylated methylenedianiline contains no more than two aromatic rings linked by a methylene group. While methods of generating the N-alkylated dianiline compound may result in structures having more than two aromatic rings linked by hydrocarbylene groups, in the exemplary embodiment, a molar ratio of these N-alkylated polyaromatic aniline compounds to the N-alkylated dianiline compound in the lubricating composition may be no greater than 1:10.
  • N-alkylated dianiline compound of the present invention is a 4,4'-N-alkylated dianiline compound represented by the formula:
  • Representative acyclic alkyl groups of the general formula C n H 2 n +1 suitable for R 1 and R 2 include straight chain and branched chain alkyl groups, such as methyl, ethyl, n-propyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, stearyl, icosyl, docosyl, tetracosyl, 1-methylpropyl, 2,2-dimethylpropyl, isobutyl, isopentyl, isohexyl, 2-ethylhexyl, isoheptyl, 2-ethylheptyl, 2-propylheptyl, isooctyl, 2-ethyloctyl, 2-butyloctyl, 2-hexy
  • Representative cyclic alkyl groups of the general formula C n H 2 n -1 suitable for R 1 and R 2 include cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl and combinations thereof.
  • Example N-alkylated dianiline compounds include compounds of formulas A-1 to A-6, and A-8:
  • N-alkylated dianiline compound is selected from 4,4'-2-cyclohexylmethylenedianiline (CY-MDA) (Formula A-1), and 4,4'-2-ethylhexylmethylenedianiline (EHL-MDA) (Formula A-2).
  • CY-MDA 4,4'-2-cyclohexylmethylenedianiline
  • EHL-MDA 4,4'-2-ethylhexylmethylenedianiline
  • the N-alkylated dianiline compound is present in the lubricating composition at a concentration of at least 0.1 wt. % and may be up to 5 wt. %.
  • the concentration of the compound may be at least 0.15 wt. %, or at least 0.4 wt. %, or at least 1.5 wt. %, or up to 5.0 wt. %, or up to 2.5 wt. % of the lubricating composition.
  • the compound may also be present in a concentrate, alone or with other additives and with a lesser amount of oil. In a concentrate, the amount of the compound may be at least 2, or at least 3 times the concentration in the lubricating composition.
  • TBN is measured according to ASTM D2896 - 15, Standard Test Method for Base Number of Petroleum Products by Potentiometric Perchloric Acid Titration, ASTM International, West Conshohocken, PA, 2011, DOI: 10.1520/D2896-15.
  • the N-alkylated dianiline compound has a TBN of at least 50 mg of KOH/g, or at least 100 mg of KOH/g, as measured according to ASTM D2896.
  • the lubricating composition has a TBN of at least 4 mg KOH/g, as measured in accordance with ASTM D-2896.
  • the N-alkylated dianiline compound is particularly effective at improving deposit performance in lubricating compositions which are low in phosphorus.
  • the phosphorus content of the lubricating composition is up to 0.15 wt. %, such as up to 0.12 wt. %, or up to 0.11 wt. %, or up to 0.08 wt. %, or up to 0.05 wt. %, or up to 0.04 wt. %, or up to 0.02 wt. %.
  • the phosphorus content of the lubricating composition may be at least 0.01 wt. %, or at least 0.02 wt. %, or at least 0.03 wt. %.
  • Suitable additives for providing the lubricating composition with such low levels of phosphorus include zinc dialkyldithiophosphates (ZDDPs), as described below.
  • the exemplary compounds may be prepared, for example, from dianilines, such as 4,4'-methylenedianiline.
  • N-alkylated dianiline compounds are prepared by reacting a dianiline with one or more aldehydes or ketones in a 1:2 or excess molar ratio in an alcohol solvent, such as methanol or toluene.
  • the aldehyde or ketone can be of the general formula: , where corresponds to R 1 and R 2 above, at least one of R 5 and R 6 is not H.
  • the aldehyde or ketone may be a C 2 -C 12 aldehyde or ketone, such as a C 2 -C 9 aldehyde, or a C 2 -C 6 aldehyde or a C 3 -C 10 ketone, or C 3 -C 7 ketone.
  • Example ketones useful in forming the compound include methyl alkyl ketones and ethyl alkyl ketones of from 3-12 carbon atoms where the alkyl group may be alicyclic or cyclic.
  • Examples of such ketones include those in which the alkyl portions are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl and as well as the various isomeric forms thereof.
  • ketones include acetone, 2-butanone, 2-pentanone, 3-pentanone, 4-methyl-2-butanone, 2-hexanone, 4-methyl-2-hexanone, 4-heptanone, 5-methyl-2-hexanone, 5,6-dimethyl-2-hexanone, 5,5-dimethyl-2-hexanone, 4,5-dimethyl-2-hexanone, 4-ethyl-2-hexanone, 5-ethyl-2-hexanone, 4,5,5-trimethyl-2-hexanone, 2-heptanone, 3-heptanone, 5,5-dimethyl-2-heptanone, 4,5-dimethyl-2-heptanone, 5-ethyl-2-heptanone, 4-ethyl-2-heptanone, 2-octanone, 3-octanone, 4-octanone, 6-methyl-2-octanone, 7,7-dimethyl-2-octanone, 6-methyl-3-octan
  • 4,4'-methylenedianiline is reacted with an aldehyde/ketone in a 1:2 or excess molar ratio in a suitable solvent, such as toluene, at a temperature of over 100°C.
  • a suitable solvent such as toluene
  • Water formed in the reaction is removed.
  • the solvent is removed.
  • the product may be purified by redissolving it in a suitable solvent, such as methanol, and adding sodium borohydride.
  • the mixture is poured into water and the product extracted using ethyl acetate.
  • the solvent is removed yielding the purified product.
  • N-alkylated dianiline compounds can also be prepared by reacting a methylenedianiline and one or more aldehydes or ketones in a 1:2 or excess molar ratio in the presence of hydrogen and a hydrogenation catalyst, such as platinum, palladium, cobalt or nickel, either as such or carried on a suitable support, such as carbon, in methanol solvent, as described, for example, in U.S. Pat. Nos. 2,045,574 and 3,779,923 .
  • a hydrogenation catalyst such as platinum, palladium, cobalt or nickel
  • reaction results in mono-substitution of each -NH 2 group, although there may be a small amount of di-substituted compounds present.
  • a lubricating composition may be prepared by adding the N-alkylated dianiline compound, ashless antioxidant, and overbased calcium detergent to an oil of lubricating viscosity, optionally in the presence of other performance additives (as described herein below), or by adding reagents for forming the N-alkylated dianiline compound to an oil of lubricating viscosity.
  • the lubricating composition may further include additional performance additives, such as antioxidants, additional dispersants, antiwear agents, and friction modifiers.
  • a method for forming a lubricating composition includes forming an N-alkylated dianiline compound and combining the N-alkylated dianiline compound with an oil of lubricating viscosity, an ashless antioxidant and an overbased calcium detergent, to provide a lubricating composition comprising less than 0.15 weight percent of phosphorus.
  • the lubricating composition includes at least 0.1 weight % of an ashless antioxidant(s) (AAO) selected from a diarylamine antioxidant, a phenolic antioxidant, and a mixture thereof.
  • AAO ashless antioxidant
  • the AAO may be present in the lubricating composition at a concentration of at least 0.2 wt. %, such as at least 0.3 wt. %., or up to 5 wt. %, or up to 2.5 wt. %, or up to 2 wt. %, or up to 1 wt. %.
  • a weight ratio of the AAO to the N-alkylated dianiline compound may be at least 1:20 or up to 20:1.
  • Exemplary phenolic antioxidants useful herein include alkylated diphenylamine antioxidants, such as C 1 -C 24 monoalkylated, dialkylated and polyalkylated diphenylamines, as described, for example, in U.S. Pat. Nos. 2,943,112 ; 4,824,601 ; 5,672,752 ; 6,204,412 ; 6,315,925 ; 6,355,839 , and U.S. Pub. Nos. 2015/0307803 and 2016/0017252 .
  • Particularly useful are monoalkylated and dialkylated diphenylamines in which the alkyl group(s) include(s) at least 6 carbon atoms, such as at least 8, or at least 9 carbon atoms.
  • Exemplary phenolic antioxidants that may be used include C 7 -C 9 branched alkyl esters of 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-benzenepropanoic acid, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol, 2,4-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 2-tert-butyl-4-methoxyphenol, 3-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-4-alkylphenols such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-alkoxy
  • Phenol-based antioxidants often contain a secondary butyl and/or a tertiary butyl group as a steric hindering group.
  • the phenol group may be further substituted with a hydrocarbyl group (e.g., a 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, 4,4'-methylenebis-(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, 4-butyl-2,6-di-tert-butylphenol, 4-dodecyl-2,6-di-tert-butylphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), as described, for example, in U.S.
  • the hindered phenol antioxidant may be an ester, such as those described in U.S. Pat. No. 6,559,105 , such as an alkyl alcohol esters of 3-(4-hydroxy-3,5-di-tert-butyl-phenyl)propionic acid.
  • an alkyl alcohol esters of 3-(4-hydroxy-3,5-di-tert-butyl-phenyl)propionic acid is sold as Irganox TM L-135, obtainable from Ciba.
  • the phenolic antioxidant where present in the lubricating composition, may be at least 0.5 wt. %, or at least 1.5 wt. %, or at least 2.5 wt. %, and may be up to 5 wt. %, such as up to 4 wt. %, or up to 3 wt. % of the lubricating composition.
  • alkylated diphenylamines useful herein include those of the general formula: where each of R 7 , R 8 , R 9 and R 10 , is selected from H and C 8 -C 24 or C 8 -C 12 alkyl groups, and wherein at least one of R 7 , R 8 , R 9 , and R 10 is not H. In one embodiment, R 8 and R 10 (and optionally also R 9 ) are not H. Para-substitution by the alkyl group is common.
  • Example alkylated diphenylamines include dinonyl diphenylamine, nonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine, dodecyl diphenylamine, decyl diphenylamine, and mixtures thereof.
  • diarylamine antioxidants include alkylated phenylnaphthylamines of the general form: where each of R 7 , R 8 are as defined above and at least one of R 7 and R 8 is not H.
  • Example alkylated phenylnaphthylamines include octyl, dioctyl, nonyl, dinonyl, decyl and dodecyl phenylnaphthylamines, such as N-(Dodecylphenyl)naphthalen-1-amine:
  • a ratio of the diarylamine to the N-alkyl dianiline compound is from 20:1 to 1:20.
  • the alkylated diarylamine where present in the lubricating composition, may be at least 0.2 wt. %, or at least 0.4 wt. %, or at least 0.5 wt. %, or at least 1.0 wt. %, or at least 2.5 wt. %, and may be up to 5 wt. %, such as up to 2.5 wt. %, or up to 1.5 wt. % of the lubricating composition.
  • phenolic and/or alkylated diarylamine antioxidants may be employed.
  • the combined amount of ashless antioxidant may be at least 0.8 wt. %, or at least 1.5 wt. %, or at least 3 wt. %, and may be up to 5 wt. %, such as up to 4 wt. %, or up to 3.5 wt. % of the lubricating composition.
  • the lubricating composition includes at least 0.01 weight % of an overbased calcium detergent.
  • the lubricating composition includes an alkaline earth metal overbased detergent in an amount sufficient to deliver at least 2 mg KOH/g of total base number (TBN), as measured in accordance with ASTM D-2896-15, to the lubricating composition.
  • the overbased calcium detergent may be chosen from sulfonates, non-sulfur containing phenates, sulfur containing phenates, salixarates, salicylates, and mixtures thereof, or borated equivalents thereof.
  • the overbased detergent may be borated with a borating agent such as boric acid.
  • the overbased calcium-containing detergent may also include "hybrid" detergents formed with mixed surfactant systems including phenate and/or sulfonate components, e.g., phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, sulfonates/phenates/salicylates, as described, for example, in U.S. Pat. Nos. 6,429,178 ; 6,429,179 ; 6,153,565 ; and 6,281,179 . Where a hybrid sulfonate/phenate detergent is employed, the hybrid detergent can be considered equivalent to amounts of distinct phenate and sulfonate detergents introducing like amounts of phenate and sulfonate soaps, respectively.
  • phenate/salicylates e.g., phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, as described, for example
  • Example overbased calcium-containing detergents include calcium salts of sulfonates, phenates (including sulfur-containing and non-sulfur containing phenates), salixarates and salicylates. Such overbased sulfonates, salixarates, phenates and salicylates may have a total base number of 120 to 700, or 250 to 600, or 300 to 500 (on an oil free basis).
  • Overbased calcium sulfonates, salixarates, phenates and salicylates typically have a total base number of 120 to 700 TBN. Overbased sulfonates typically have a total base number of 120 to 700, or 250 to 600, or 300 to 500 (on an oil free basis).
  • overbased it is meant that the calcium is in excess of stoichiometric amounts with respect to the soap counterion (e.g., sulfonate).
  • the overbased calcium detergent may have a metal: counterion ratio of at least 3:1, or at least 4:1, or at least 6:1.
  • Example sulfonate detergents include linear and branched alkylbenzene sulfonate detergents, and mixtures thereof, which may have a metal ratio of at least 8, as described, for example, in U.S. Pub. No. 2005065045 .
  • Linear alkyl benzenes may have the benzene ring attached anywhere on the linear chain, usually at the 2, 3, or 4 position, or be mixtures thereof.
  • Linear alkylbenzene sulfonate detergents may be particularly useful for assisting in improving fuel economy.
  • the alkylbenzene sulfonate detergent may be a branched alkylbenzene sulfonate, a linear alkylbenzene sulfonate, or mixtures thereof.
  • the lubricating composition may be free of linear alkylbenzene sulfonate detergent.
  • the sulfonate detergent may be a calcium salt of one or more oil-soluble alkyl toluene sulfonate compounds as disclosed in U.S. Pub. No.20080119378 .
  • the lubricating composition includes at least 0.01 wt. % of overbased calcium detergent.
  • the lubricating composition may include at least 0.1 wt. %, or at least 0.5 wt. %, of overbased calcium detergent, and in some embodiments, up to 3 wt. %, or up to 2 wt. % overbased calcium detergent(s).
  • the lubricating composition may include the oil of lubricating viscosity as a minor or major component thereof, such as at least 5 wt. %, or at least 10 wt. %, or at least 20 wt. %, or at least 30 wt. %, or at least 40 wt. %, or at least 60 wt. %, or at least 80 wt. %, or up to 98 wt. %, or up to 95 wt. %, of the lubricating composition.
  • the oil of lubricating viscosity as a minor or major component thereof, such as at least 5 wt. %, or at least 10 wt. %, or at least 20 wt. %, or at least 30 wt. %, or at least 40 wt. %, or at least 60 wt. %, or at least 80 wt. %, or up to 98 wt. %, or up to 95
  • the amount of the oil of lubricating viscosity present may be typically the balance remaining after subtracting from 100 wt. %, the sum of the amount of the compound and antioxidant, as described above and any other performance additives.
  • Suitable oils include natural and synthetic oils, oil derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined, refined, re-refined oils or mixtures thereof. Unrefined, refined and re-refined oils, and natural and synthetic oils are described, for example, in WO 2008/147704 and U.S. Pub. No. 2010/197536 .
  • Synthetic oils may also be produced by Fischer-Tropsch reactions and typically may be hydroisomerized 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 procedures.
  • Oils of lubricating viscosity may also be defined as specified in 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 U.S. Pat. No. 7,285,516 .
  • the five base oil groups are as follows: Group I (sulfur content >0.03 wt. %, and/or ⁇ 90 wt. % saturates, viscosity index 80-120); Group II (sulfur content ⁇ 0.03 wt. %, and >90 wt.
  • the exemplary oil of lubricating viscosity includes an API Group I, Group II, Group III, Group IV, Group V oil, or mixtures thereof. In some embodiments, the oil of lubricating viscosity is an API Group I, Group II, Group III, or Group IV oil, or mixtures thereof.
  • the oil of lubricating viscosity is an API Group I, Group II, or Group III oil, or mixture thereof.
  • the oil of lubricating viscosity may be an API Group II, Group III mineral oil, a Group IV synthetic oil, or mixture thereof.
  • at least 5 wt. %, or at least 10 wt. %, or at least 20 wt. %, or at least 40 wt. % of the lubricating composition is a polyalphaolefin (Group IV).
  • the lubricating composition disclosed herein may have a SAE viscosity grade of XW-Y, wherein X may be 0, 5, 10 or 15; and Y may be 16, 20, 30 or 40.
  • the oil of lubricating viscosity may have a kinematic viscosity of up to 12 mm 2 /s or up to 8 mm 2 /s (cSt) at 100 °C and can be at least 12 mm 2 /s at 100 °C, and in other embodiments at least 3.5 mm 2 /s.
  • kinematic viscosity is determined at 100 °C by ASTM D445-14, "Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (and Calculation of Dynamic Viscosity)," ASTM International, West Conshohocken, PA, 2003, DOI: 10.1520/D0445-14 and may be referred to as KV_100.
  • the viscosity grade of the oil depends on the end use. For passenger car and diesel engines, the viscosity grade may be SAE-5W-30, SAE 10W-30 or SAE 15W-40.
  • the base oil may be a blend of two or more fractions having different oligomer distributions. A fraction rich in lower oligomers is typically blended with a fraction rich in higher oligomers to achieve the desired oligomer distribution. However, any combination of fractions which will yield a composite having the required distribution of oligomers is acceptable.
  • the fractions employed for such blending may be different distillation cuts from the same process or may be obtained from entirely different oligomerization processes. A single fraction may be used to produce different multigrade oils, e.g. SAE 10W-30 and SAE 15W-40 oils.
  • the composite obtained after blending can be hydrogenated or the individual fractions can be hydrogenated before they are blended.
  • the viscosity grade may be from SAE-40 to SAE-60, which corresponds to a KV_100 of 12.5 to 26 mm 2 /s.
  • SAE-50 grade oils for example, have a KV_100 of 16.3-21.9 mm 2 /s.
  • Cylinder oils for 2-stroke marine diesel engines may be formulated to achieve a KV_100 of 19 to 21.5 mm 2 /s.
  • This viscosity can be obtained by a mixture of additives and base oils, for example containing mineral bases of Group I such as Neutral Solvent (for example 500 NS or 600 NS) and Bright Stock bases. Any other combination of mineral or synthetic bases or bases of vegetable origin having, in mixture with the additives, a viscosity compatible with the grade SAE 50 can be used.
  • an oil formulation suited to use as a cylinder lubricant for low-speed 2-stroke marine diesel engines contains 18 to 25 wt. % of a Group I base oil of a BSS type (distillation residue, with a KV_100 of 28 - 32 mm 2 /s, with a density at 15°C of 895 - 915 kg/m 3 ), and 50 to 60 wt. % of a Group I base oil of a SN 600 type (distillate, with a density at 15 °C of 880 - 900 kg/m 3 , with a KV_100 of about 12 mm 2 /s).
  • the lubricating composition may contain synthetic ester base fluids.
  • Synthetic esters may have a kinematic viscosity measured at 100°C of 2.5 mm 2 /s to 30 mm 2 /s.
  • the lubricating composition comprises less than 50 wt. % of a synthetic ester base fluid with a KV_100 of at least 5.5 mm 2 /s, or at least 6 mm 2 /s, or at least 8 mm 2 /s.
  • Exemplary synthetic oils include poly-alpha olefins, polyesters, polyacrylates, and poly-methacrylates, and co-polymers thereof.
  • Example synthetic esters include esters of a dicarboxylic acid (e.g., selected from phthalic acid, succinic acid, alkyl succinic acids, 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 an alcohol (e.g., selected from butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, and propylene glycol).
  • a dicarboxylic acid e.g., selected from phthalic acid, succinic acid, alkyl succinic acids, alkenyl
  • 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 useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and from polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol. Esters can also be monoesters, such as are available under the trade name Priolube 1976 TM (C 18 -alkyl-COO-C 20 alkyl).
  • Synthetic ester base oils may be present in the lubricating composition in an amount less than 50 wt. % of the composition, or less than 40 weight %, or less than 35 weight %, or less than 28 weight %, or less than 21 weight %, or less than 17 weight %, or less than 10 weight %, or less than 5 weight % of the composition.
  • the lubricating composition is free of, or substantially free of, a synthetic ester base fluid having a KV_100 of at least 5.5 mm 2 /s.
  • Example natural oils include animal and vegetable oils, such as long chain fatty acid esters. Examples include linseed oil, sunflower oil, sesame seed oil, beef tallow oil, lard oil, palm oil, castor oil, cottonseed oil, corn oil, peanut oil, soybean oil, olive oil, whale oil, menhaden oil, sardine oil, coconut oil, palm kernel oil, babassu oil, rape oil, and soya oil.
  • the amount of the oil of lubricating viscosity present is typically the balance remaining after subtracting from 100 weight % the sum of the amount of the exemplary N-alkylated methylenedianiline compound and the other performance additives.
  • the lubricating composition may further include one or more of the following additional performance additives: antioxidants (different from above), dispersants, viscosity modifiers, antiwear/antiscuffing agents, metal deactivators, friction modifiers, extreme pressure agents, foam inhibitors, demulsifiers, pour point depressants, corrosion inhibitors, seal swelling agents, TBN boosters, and the like.
  • additional performance additive(s) may be suited to providing the performance properties of a fully formulated lubricating composition, e.g., a passenger car or HD engine lubricant.
  • the lubricating composition optionally further includes at least one detergent, in addition to the overbased calcium detergent discussed above.
  • exemplary detergents useful herein include overbased metal-containing detergents, where the metal is other than calcium.
  • the metal of the metal-containing detergent may be zinc, sodium, barium, or magnesium.
  • the lubricating composition includes an alkaline earth metal overbased detergent in an amount sufficient to deliver at least 2 mg KOH/g of total base number (TBN), as measured in accordance with ASTM D-2896-15, to the lubricating composition.
  • the overbased metal-containing detergent may be chosen from sulfonates, non-sulfur containing phenates, sulfur containing phenates, salixarates, salicylates, and mixtures thereof, or borated equivalents thereof.
  • the overbased detergent may be borated with a borating agent such as boric acid.
  • the overbased metal-containing detergent may also include "hybrid" detergents formed with mixed surfactant systems including phenate and/or sulfonate components, e.g., phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, sulfonates/phenates/salicylates, as described, for example, in U.S. Pat. Nos. 6,429,178 ; 6,429,179 ; 6,153,565 ; and 6,281,179 . Where a hybrid sulfonate/phenate detergent is employed, the hybrid detergent can be considered equivalent to amounts of distinct phenate and sulfonate detergents introducing like amounts of phenate and sulfonate soaps, respectively.
  • phenate/salicylates e.g., phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, sulfon
  • Example overbased metal-containing detergents include zinc, sodium, and magnesium salts of sulfonates, phenates (including sulfur-containing and non-sulfur containing phenates), salixarates and salicylates.
  • Such overbased sulfonates, salixarates, phenates and salicylates may have a total base number of 120 to 700, or 250 to 600, or 300 to 500 (on an oil free basis).
  • an overbased metal-containing detergent may be a zinc, sodium, or magnesium salt of a sulfonate, a phenate, sulfur-containing phenate, salixarate or salicylate.
  • Overbased sulfonates, salixarates, phenates and salicylates typically have a total base number of 120 to 700 TBN.
  • Overbased sulfonates typically have a total base number of 120 to 700, or 250 to 600, or 300 to 500 (on an oil free basis).
  • the overbased metal-containing detergent may be alkali metal or alkaline earth metal salts.
  • the overbased detergent may be sodium salts, calcium salts, magnesium salts, or mixtures thereof of the phenates, sulfur-containing phenates, sulfonates, salixarates and salicylates.
  • the overbased detergent is a calcium detergent, a magnesium detergent or mixtures thereof.
  • the overbased calcium 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 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 lubricating composition is essentially free of (i.e., contains less than 10 ppm) magnesium resulting from the overbased detergent.
  • the overbased 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 detergents may be present in the lubricating composition. Calcium and magnesium 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 overbased detergent is free of or substantially free of sodium.
  • the overbased sulfonate detergent may have a metal ratio of 12 to less than 20, or 12 to 18, or 20 to 30, or 22 to 25.
  • Example sulfonate detergents include linear and branched alkylbenzene sulfonate detergents, and mixtures thereof, which may have a metal ratio of at least 8, as described, for example, in U.S. Pub. No. 2005065045 .
  • Linear alkyl benzenes may have the benzene ring attached anywhere on the linear chain, usually at the 2, 3, or 4 position, or be mixtures thereof.
  • Linear alkylbenzene sulfonate detergents may be particularly useful for assisting in improving fuel economy.
  • the alkylbenzene sulfonate detergent may be a branched alkylbenzene sulfonate, a linear alkylbenzene sulfonate, or mixtures thereof.
  • the lubricating composition may be free of linear alkylbenzene sulfonate detergent.
  • the sulfonate detergent may be a metal salt of one or more oil-soluble alkyl toluene sulfonate compounds as disclosed in U.S. Pub. No. 20080119378 .
  • the lubricating composition may include at least 0.01 wt. % or at least 0.1 wt. %, detergent, and in some embodiments, up to 2 wt. %, or up to 1 wt. % detergent.
  • the lubricating composition optionally further includes at least one antioxidant, in addition to the AAOs listed above.
  • antioxidants useful herein include sulfurized olefins.
  • suitable olefins that may be sulfurized to form the sulfurized olefin include propylene, butylene, isobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, undecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, and mixtures thereof.
  • hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof and their dimers, trimers and tetramers are especially useful olefins.
  • the olefin may be a Diels-Alder adduct of a diene such as 1,3-butadiene and an unsaturated ester, such as, butyl acrylate.
  • Another class of sulfurized olefin includes fatty acids and their esters.
  • the fatty acids are often obtained from vegetable oil or animal oil; and typically contain 4 to 22 carbon atoms. Examples of suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid, and mixtures thereof.
  • the fatty acids may be obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil or mixtures thereof.
  • the lubricating composition may include at least 0.1 wt. % or at least 0.5 wt. %, or at least 1 wt. % antioxidant, and in some embodiments, up to 3 wt. %, or up to 2.75 wt. %, or up to 2.5 wt. %, or up to 1.2 wt. % of such additional antioxidants.
  • the lubricating composition optionally further includes at least one dispersant other than the exemplary compound.
  • exemplary dispersants include succinimide dispersants, Mannich dispersants, succinamide dispersants, and polyolefin succinic acid esters, amides, and ester-amides, and mixtures thereof.
  • the succinimide dispersant may be derived from an aliphatic polyamine, or mixtures thereof.
  • the aliphatic polyamine may be an ethylenepolyamine, a propylenepolyamine, a butylenepolyamine, or a mixture thereof.
  • the aliphatic polyamine may be an ethylenepolyamine.
  • the aliphatic polyamine may be chosen from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms, and mixtures thereof.
  • the dispersant may be a polyolefin succinic acid ester, amide, or ester-amide.
  • a polyolefin succinic acid ester-amide may be a polyisobutylene succinic acid reacted with an alcohol (such as pentaerythritol) and a polyamine as described above.
  • Example polyolefin succinic acid esters include polyisobutylene succinic acid esters of pentaerythritol and mixture thereof.
  • the dispersant may be an N-substituted long chain alkenyl succinimide.
  • An example of an N-substituted long chain alkenyl succinimide is polyisobutylene succinimide.
  • the polyisobutylene from which polyisobutylene succinic anhydride is derived has a number average molecular weight of at least 300, or at least 350, or at least 500, or at least 550, or at least 750, and can be up to 5000, or up to 3000, or up to 2500.
  • Such succinimides can be formed, for example, from high vinylidene polyisobutylene and maleic anhydride.
  • Succinimide dispersants and their preparation are disclosed, for example, in U.S. Pat. Nos. 3,172,892 , 3,219,666 , 3,316,177 , 3,340,281 , 3,351,552 , 3,381,022 , 3,433,744 , 3,444,170 , 3,467,668 , 3,501,405 , 3,542,680 , 3,576,743 , 3,632,511 , 4,234,435 , Re 26,433 , and 6,165,235 , and 7,238,650 and EP Patent Application 0 355 895 A .
  • the exemplary dispersants may also be post-treated by conventional methods by a reaction with any of a variety of agents.
  • agents such as boric acid, urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, such as terephthalic acid, hydrocarbonsubstituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds.
  • the post-treated dispersant is borated.
  • the post-treated dispersant is reacted with dimercaptothiadiazoles.
  • the post-treated dispersant is reacted with phosphoric or phosphorous acid. In one embodiment the post-treated dispersant is reacted with terephthalic acid and boric acid (as described in U.S. Pub. No. 2009/0054278 .
  • Dispersant viscosity modifiers are dispersants which provide both dispersancy and viscosity modification.
  • Example DVMs are made from polymers such as an olefin polymer (e.g., ethylene propylene copolymer) and/or vinyl aromatic polymers (e.g., polystyrene) that have been radically grafted with an ethylenically unsaturated carboxylic acid material, such as maleic anhydride which is functionalized with one or more amines and/ or a pendent functional group which has sulfonate functionality.
  • DVMs of this type are disclosed, for example, in U.S. Pat. Nos.
  • the lubricating composition may include at least 0.01 wt. %, or at least 0.1 wt. %, or at least 0.5 wt. %, or at least 1 wt. % dispersant, and in some embodiments, up to 20 wt. %, or up to 15 wt. %, or up to 10 wt. %, or up to 6 wt. % or up to 3 wt. % dispersant.
  • the lubricating composition optionally further includes at least one antiwear agent.
  • suitable antiwear agents suitable for use herein include titanium compounds, tartrates, tartrimides, oil soluble amine salts of phosphorus compounds, sulfurized olefins, metal dihydrocarbyldithiophosphates (such as zinc dialkyldithiophosphates (ZDDPs)), phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides.
  • the antiwear agent may in one embodiment include a tartrate or tartrimide, as described in U.S. Pub. Nos. 2006/0079413 ; 2006/0183647 ; and 2010/0081592 .
  • 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 as disclosed in U.S. Pub. No. 20050198894 .
  • the lubricating composition may include at least 0.01 wt. %, or at least 0.1 wt. %, or at least 0.5 wt. % antiwear agent, and in some embodiments, up to 3 wt. %, or up to 1.5 wt. %, or up to 0.9 wt. antiwear agent.
  • the lubricating composition is free or substantially free of phosphorus-containing antiwear agents.
  • phosphorus-containing antiwear agents are present, if at all, in an amount which enables the lubricating composition to have no more than 0.15 wt. % phosphorus, or up to 1.1 wt. % phosphorus, or up to 0.8 wt. % phosphorus.
  • C3/6 mixed secondary ZDDP's may be present at up to 1.2 wt. %, or up to 1 wt. %, or up to 0.5 wt. %.
  • the lubricating composition may include one or more oil-soluble titanium compounds, which may function as antiwear agents, friction modifiers, antioxidants, deposit control additives, or more than one of these functions.
  • Example oil-soluble titanium compounds are disclosed in U.S. Pat. No. 7,727,943 and U.S. Pub. No. 2006/0014651 .
  • Example oil soluble titanium compounds include titanium (IV) alkoxides, such as titanium (IV) isopropoxide and titanium (IV) 2-ethylhexoxide.
  • Such alkoxides may be formed from a monohydric alcohol, a vicinal 1,2-diol, a polyol, or mixture thereof.
  • the monohydric alkoxides may have 2 to 16, or 3 to 10 carbon atoms.
  • the titanium compound comprises the alkoxide of a vicinal 1,2-diol or polyol.
  • 1,2-vicinal diols include fatty acid mono-esters of glycerol, where the fatty acid may be, for example, oleic acid.
  • Other example oil soluble titanium compounds include titanium carboxylates, such as titanium neodecanoate.
  • the amount of oil-soluble titanium compounds is included as part of the antiwear agent.
  • the lubricating composition may include an extreme pressure agent.
  • Example extreme pressure agents that are soluble in the oil include sulfur- and chlorosulfur-containing EP agents, dimercaptothiadiazole or CS 2 derivatives of dispersants (typically succinimide dispersants), derivative of chlorinated hydrocarbon EP agents and phosphorus EP agents.
  • EP agents include chlorinated wax; sulfurized olefins (such as sulfurized isobutylene), hydrocarbylsubstituted 2,5-dimercapto-1,3,4-thiadiazoles and oligomers thereof, organic sulfides and polysulfides, such as dibenzyl disulfide, bis-(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, sulfurized terpene, and sulfurized Diels-Alder adducts; phosphosulfurized hydrocarbons such as the reaction product of phosphorus sulfide with turpentine or methyl oleate; phosphorus esters, such as di-hydrocarbon and tri-hydrocarbon phosphites, e.g., dibutyl phosphite, diheptyl phosphite
  • the lubricating composition may include at least 0.01 wt. %, or at least 0.1 wt. %, or at least 0.5 wt. % extreme pressure agent, and in some embodiments, up to 3 wt. %, or up to 1.5 wt. %, or up to 0.9 wt. % of the extreme pressure agent.
  • the lubricating composition may include a foam inhibitor.
  • Foam inhibitors that may be useful in the lubricant composition include polysiloxanes; copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including fluorinated polysiloxanes, trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers.
  • the lubricating composition may include a viscosity modifier.
  • Viscosity modifiers also sometimes referred to as viscosity index improvers or viscosity improvers
  • Viscosity modifiers useful in the lubricant composition are usually polymers, including polyisobutenes, polymethacrylates (PMA) and polymethacrylic acid esters, diene polymers, polyalkylstyrenes, esterified styrene-maleic anhydride copolymers, hydrogenated alkenylarene-conjugated diene copolymers and polyolefins also referred to as olefin copolymer or OCP.
  • PMAs are prepared from mixtures of methacrylate monomers having different alkyl groups.
  • the alkyl groups may be either straight chain or branched chain groups containing from 1 to 18 carbon atoms.
  • Most PMAs are viscosity modifiers as well as pour point depressants.
  • the viscosity modifier is a polyolefin comprising ethylene and one or more higher olefin, such as propylene.
  • the lubricating composition may include at least 0.01 wt. %, or at least 0.1 wt. %, or at least 0.3 wt. %, or at least 0.5 wt. % polymeric viscosity modifiers, and in some embodiments, up to 10 wt. %, or up to 5 wt. %, or up to 2.5 wt. % polymeric viscosity modifiers.
  • the lubricating composition may include a corrosion inhibitor.
  • Corrosion inhibitors/metal deactivators that may be useful in the exemplary lubricating composition include fatty amines, octylamine octanoate, condensation products of dodecenyl succinic acid or anhydride, and a fatty acid such as oleic acid with a polyamine, derivatives of benzotriazoles (e.g., tolyltriazole), 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles and 2-alkyldithiobenzothiazoles.
  • benzotriazoles e.g., tolyltriazole
  • 1,2,4-triazoles 1,2,4-triazoles
  • benzimidazoles 2-alkyldithiobenzimidazoles
  • 2-alkyldithiobenzothiazoles 2-alkyldithiobenzothiazoles.
  • the lubricating composition may include a pour point depressant.
  • Pour point depressants that may be useful in the exemplary lubricating composition include polyalphaolefins, esters of maleic anhydride-styrene copolymers, polymethacrylates, polyacrylates, and polyacrylamides.
  • the lubricating composition may include a friction modifier.
  • Friction modifiers that may be useful in the exemplary lubricating composition include fatty acid derivatives such as amines, esters, epoxides, fatty imidazolines, condensation products of carboxylic acids and polyalkylene-polyamines and amine salts of alkylphosphoric acids.
  • the friction modifier may be an ash-free friction modifier.
  • Such friction modifiers are those which typically do not produce any sulfated ash when subjected to the conditions of ASTM D 874 (see ASTM D874 - 13a, "Standard Test Method for Sulfated Ash from Lubricating Oils and Additives," ASTM International, West Conshohocken, PA, 2013).
  • fatty alkyl or “fatty” in relation to friction modifiers means a carbon chain having 8 to 30 carbon atoms, typically a straight carbon chain.
  • the amount of the ash-free friction modifier in a lubricant may be 0.1 to 3 wt. % (or 0.12 to 1.2 or 0.15 to 0.8 wt. %).
  • the material may also be present in a concentrate, alone or with other additives and with a lesser amount of oil. In a concentrate, the amount of material may be two to ten times the above concentration amounts.
  • the ash-free friction modifier is a fatty ester, amide, or imide of various hydroxy-carboxylic acids, such as tartaric acid, malic acid lactic acid, glycolic acid, and mandelic acid.
  • suitable materials include tartaric acid di(2-ethylhexyl) ester (i.e., di(2-ethylhexyl)tartrate), di(C 8 -C 10 ) tartrate, di(C 12 - 15 ) tartrate, di-oleyl tartrate, oleyl tartrimide, and oleyl maleimide.
  • the ash-free friction modifier may be chosen from long chain fatty acid derivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines such as condensation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fatty phosphonates; fatty phosphites; borated phospholipids, borated fatty epoxides; glycerol esters; borated glycerol esters; fatty amines; alkoxylated fatty amines; borated alkoxylated fatty amines; hydroxyl and polyhydroxy fatty amines including tertiary hydroxy fatty amines; hydroxy alkyl amides; metal salts of fatty acids; metal salts of alkyl salicylates; fatty oxazolines; fatty e
  • Friction modifiers may also encompass materials such as sulfurized fatty compounds and olefins, sunflower oil or soybean oil monoester of a polyol and an aliphatic carboxylic acid.
  • the friction modifier may be a long chain fatty acid ester.
  • the long chain fatty acid ester may be a mono-ester and in another embodiment the long chain fatty acid ester may be a triglyceride.
  • Molybdenum compounds are also known as friction modifiers.
  • the exemplary molybdenum compound does not contain dithiocarbamate moieties or ligands.
  • Nitrogen-containing molybdenum materials include molybdenum-amine compounds, as described in U.S. Pat. No. 6,329,327 , and organomolybdenum compounds made from the reaction of a molybdenum source, fatty oil, and a diamine as described in U.S. Pat. No. 6,914,037 .
  • Other molybdenum compounds are disclosed in U.S. Pub. No. 20080280795 .
  • a primary, secondary or tertiary amine represented by the formula NR 29 R 30 R 31 , where each
  • Suitable amines include monoalkyl (or alkenyl) amines such as tetradecylamine, stearylamine, oleylamine, beef tallow alkylamine, hardened beef tallow alkylamine, and soybean oil alkylamine; dialkyl(or alkenyl)amines such as N-tetradecylmethylamine, N-pentadecylmethylamine, N-hexadecylmethylamine, N-stearylmethylamine, N-oleylmethylamine, N-cocoyl methylamine, N-beef tallow alkyl methylamine, N-hardened beef tallow alkyl methylamine, N-soybean oil alkyl methylamine, ditetradecylamine, dipentadecylamine, dihexadecylamine, distearylamine, dioleylamine, bis(2-hexyldecyl)amine, bis(2-octyld
  • Examples of the compound containing the hexavalent molybdenum atom include molybdenum trioxides or hydrates thereof (MoO 3 .nH 2 O), molybdenum acid (H 2 MoO 4 ), alkali metal molybdates (Q 2 MoO 4 ) wherein Q represents an alkali metal, such as sodium or potassium, ammonium molybdates ((NH4) 2 MoO 4 or heptamolybdate (NH 4 )6[Mo 7 O 24 ].4H 2 O), MoOCl 4 , MoO 2 Cl 2 , MoO 2 Br 2 , Mo 2 O 3 Cl 6 , and the like.
  • MoO 3 .nH 2 O molybdenum trioxides or hydrates thereof
  • H 2 MoO 4 molybdenum acid
  • Q 2 MoO 4 alkali metal molybdates
  • Q represents an alkali metal, such as sodium or potassium, ammonium molybdates ((NH4) 2 MoO
  • the lubricating composition comprises molybdenum amine compound.
  • organomolybdenum compounds may be the reaction products of fatty oils, mono-alkylated alkylene diamines and a molybdenum source. Materials of this sort are generally made in two steps, a first step involving the preparation of an aminoamide/glyceride mixture at high temperature, and a second step involving incorporation of the molybdenum.
  • fatty oils examples include cottonseed oil, groundnut oil, coconut oil, linseed oil, palm kernel oil, olive oil, corn oil, palm oil, castor oil, rapeseed oil (low or high erucic acids), soyabean oil, sunflower oil, herring oil, sardine oil, and tallow. These fatty oils are generally known as glyceryl esters of fatty acids, triacylglycerols or triglycerides.
  • Examples of some mono-alkylated alkylene diamines that may be used include methylaminopropylamine, methylaminoethylamine, butylaminopropylamine, butylaminoethylamine, octylaminopropylamine, octylaminoethylamine, dodecylaminopropylamine, dodecylaminoethylamine, hexadecylaminopropylamine, hexadecylaminoethylamine, octadecyl-aminopropylamine, octadecylaminoethylamine, isopropyloxypropyl-1,3-diaminopropane, and octyloxypropyl-1,3-diaminopropane.
  • Mono-alkylated alkylene diamines derived from fatty acids may also be used. Examples include N-coco alkyl-1,3-propanediamine (Duomeen ® C), N-tall oil alkyl-1,3-propanediamine (Duomeen ® T) and N-oleyl-1,3-propanediamine (Duomeen ® O), all commercially available from Akzo Nobel.
  • Duomeen ® C N-coco alkyl-1,3-propanediamine
  • Duomeen ® T N-tall oil alkyl-1,3-propanediamine
  • Duomeen ® O N-oleyl-1,3-propanediamine
  • Sources of molybdenum for incorporation into the fatty oil/diamine complex are generally oxygen-containing molybdenum compounds include, similar to those above, ammonium molybdates, sodium molybdate, molybdenum oxides and mixtures thereof.
  • One suitable molybdenum source comprises molybdenum trioxide (MoO 3 ).
  • Nitrogen-containing molybdenum compounds which are commercially available include, for example, Sakuralube ® 710 available from Adeka which is a molybdenum amine compound, and Molyvan ® 855, available from R.T. Vanderbilt.
  • the nitrogen-containing molybdenum compound may be present in the lubricant composition at 0.005 to 2 wt. % of the composition, or 0.01 to 1.3 wt. %, or 0.02 to 1.0 wt. % of the composition.
  • the molybdenum compound may provide the lubricant composition with 0 to 1000 ppm, or 5 to 1000 ppm, or 10 to 750 ppm 5 ppm to 300 ppm, or 20 ppm to 250 ppm of molybdenum.
  • Demulsifiers useful herein include trialkyl phosphates, and various polymers and copolymers of ethylene glycol, ethylene oxide, propylene oxide, and mixtures thereof.
  • Seal swell agents useful herein include sulfolene derivatives such as Exxon Necton-37 TM (FN 1380) and Exxon Mineral Seal Oil TM (FN 3200).
  • Useful TBN boosters are anthranilate ester (esters of anthranilic acid) as described, for example, in U.S. Pub. No. 20140187458 , such as decyl anthranilate.
  • An engine lubricant in different embodiments may have a composition as illustrated in Table 1. All additives are expressed on an oil-free basis.
  • the exemplary N-alkylated dianiline compound tends to be more effective in low magnesium lubricating compositions.
  • a ratio of calcium to magnesium by weight may be at least 90:10 and in one embodiment, up to 10:90.
  • Calcium can be provided by overbased detergents, such as calcium sulfonates, as discussed above.
  • the lubricating composition includes less than 500 ppm magnesium, or less than 200 ppm magnesium, or less than 100 ppm magnesium. Table 1: Example Lubricating Composition Additive Embodiments (wt.
  • the lubricating composition described herein may be used for reducing deposit formation in an internal combustion engine.
  • the lubricating composition described herein may also be used for lubricating an internal combustion engine.
  • the end use of the lubricating composition described herein includes use as a cylinder lubricant for an internal combustion engine, such as in a passenger car or a heavy, medium, or light duty diesel vehicle, but may also find use as an engine oil for 2-stroke marine diesel engines, small engines such as motorcycle and 2-stroke oil engines, as a driveline lubricant, including gear and automatic transmission oils, and for other industrial oils, such as hydraulic lubricants.
  • An exemplary method (not covered by the present invention) of lubricating a mechanical device includes supplying the exemplary lubricating composition to the device.
  • the lubricating composition is added to the lubricating system of an internal combustion engine, which then delivers the lubricating composition to the cylinder of the engine, during its operation.
  • the internal combustion engine may be a gasoline fuelled engine, a dieselfuelled engine, such as a 2-stroke marine diesel engine, or a natural gas fuelled engine, a mixed gasoline/alcohol fuelled engine, or a biodiesel fuelled engine.
  • the internal combustion engine may be a 2-stroke or 4-stroke engine.
  • the internal combustion engine may be a passenger car internal combustion engine.
  • the passenger car internal combustion engine may have a reference mass not exceeding 2610 kg.
  • the passenger car engine may be operated on unleaded gasoline. Unleaded gasoline is well known in the art and is defined by British Standard BS EN 228:2008 (entitled “Automotive Fuels - Unleaded Petrol - Requirements and Test Methods").
  • the internal combustion engine may also be a heavy duty diesel internal combustion engine.
  • the heavy duty diesel internal combustion engine may have a "technically permissible maximum laden mass" over 3,500 kg.
  • the engine may be a compression ignition engine or a positive ignition natural gas (NG) or LPG (liquefied petroleum gas) engine.
  • NG positive ignition natural gas
  • LPG liquefied petroleum gas
  • the lubricating composition may be suitable for use as a cylinder lubricant irrespective of the sulfur, phosphorus or sulfated ash (ASTM D-874) content of the fuel.
  • the sulfur content of the lubricating composition which is particularly suited to use as an engine oil lubricant, may be 1 wt. % or less, or 0.8 wt. % or less, or 0.5 wt. % or less, or 0.3 wt. % or less.
  • the sulfur content may be in the range of 0.001 wt. % to 0.5 wt. %, or 0.01 wt. % to 0.3 wt. %.
  • the phosphorus content may be 0.2 wt.
  • the phosphorus content may be 100 ppm to 1000 ppm, or 200 ppm to 600 ppm.
  • the total sulfated ash content may be 2 wt. % or less, or 1.5 wt. % or less, or 1.1 wt. % or less, or 1 wt. % or less, or 0.8 wt.
  • the sulfated ash content may be 0.05 wt. % to 0.9 wt. %, or 0.1 wt. % to 0.2 wt. % or to 0.45 wt. %.
  • Example 2 The process of Example 1 is repeated, using 2-ethylhexanal (2.1 eq.) in place of cyclohexanone as the ketone.
  • TABLE 2 Diamine Compounds Example Ketone/Aldehyde Amine cyclohexanone MDA 2-ethylhexanal MDA 3-pentanone MDA 4-methyl cyclohexanone MDA methyl isobutyl ketone MDA 4-tert-butyl cyclohexanone MDA 3,3,5-trimethyl cyclohexanone MDA
  • N,N'-dialkylmethylenedianiline compounds prepared according to Examples 1 and 2 are evaluated in various formulations.
  • Lubricating compositions suitable as 5W-30 engine lubricants are prepared using a baseline formulation as shown in TABLE 3. All concentrations are on an oil free (i.e., active basis).
  • TABLE 3 Baseline Lubricating Composition B1 Component Baseline B1 Base Oil Balance to 100% Calcium alkylsulfonates (overbased detergent) 0.9 Secondary Zinc dialkyldithiophosphate (ZDDP) 0.86 Diarylamine antioxidant 1 0.9 Phenol antioxidant 2 0.35 Polyisobutylene succinimide dispersant 3 2.12 Ethylene-propylene copolymer (viscosity modifier) 0.7 Additional performance additives (friction modifiers, corrosion inhibitors, foam inhibitors, pour point depressants, etc.) 0.51 % Phosphorus 0.075 1.
  • compositions L1 and L2 are added to the baseline composition, as shown in TABLE 4, to form lubricating compositions L1 and L2, respectively.
  • TABLE 4 Lubricating Oil Composition Formulations Composition B1 L1 L2 B1 100 99.5 99.5 A-1 0.5 A-2 0.5 % Phosphorus 0.075 0.075 0.075 D2896 TBN (mg KOH/kg) 7.5 9.1 8.7
  • Lubricating compositions B1, L1, and L2 are evaluated in the following oxidation bench tests:
  • Lubricating compositions suitable as 5W-30 engine lubricants are prepared using a baseline formulation (B2) as shown in TABLE 6. All concentrations are on an oil-free (i.e., active) basis.
  • B2 Baseline lubricating composition B2 Component Baseline B2 Base Oil Balance to 100% Calcium alkylsulfonates (overbased detergent) 0.9 Zinc dialkyldithiophosphate (ZDDP) 0.43 Antioxidants 1 1.73 Polyisobutylene succinimide dispersant 2 2.65 Polymeric Viscosity Modifier 0.7 Additional performance additives (friction modifiers, corrosion inhibitors, foam inhibitors, pour point depressants, etc.) 0.61 % Phosphorus 0.038 1. Combination of diarylamine and hindered phenol 2. Combination of Polyisobutylene succinimide dispersants with Mn ranging from 1600-2300
  • Lubricating compositions B2, L3, L4, L5, and C1 are evaluated in the oxidation bench tests, as described above. The results obtained are shown in TABLE 8.
  • Lubricating compositions suitable as 15W-40 engine lubricants are prepared using a baseline formulation (B3) as shown in TABLE 9. All concentrations are on an oil-free (i.e., active basis).
  • B3 Baseline lubricating composition B3 Component Baseline B3 Base Oil Balance to 100% Calcium alkylsulfonate and calcium sulfur-coupled alkylphenol (overbased detergent) 2.7 Zinc dialkyldithiophosphate (ZDDP) 1.15 Antioxidants (combination of diarylamine and hindered phenol) 1.25 2200 Mn polyisobutylene succinimide, TBN ⁇ 55 (ashless dispersant) 3.6 Polymeric Viscosity Modifier 0.9 Additional performance additives (corrosion inhibitor, foam inhibitors, pour point depressant, and surfactant etc.) 0.86 % Phosphorus 0.11
  • composition B3 L6 L7 B3 100 99.5 99.5 A-2 0.5 A-1 0.5 % Phosphorus 0.11 0.11 0.11 TBN mg of KOH/g (D2896) 11.8 12.7 13.2
  • Lubricating compositions B3, L6, and L7 are evaluated in the oxidation bench tests, as described above. The results obtained are shown in TABLE 11.
  • 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. By predominantly hydrocarbon character, it is meant that at least 70% or at least 80% of the atoms in the substituent are hydrogen or carbon.
  • hydrocarbyl groups examples include:
  • alkyl groups include n-butyl, iso-butyl, sec-butyl, n-pentyl, amyl, neopentyl, n-hexyl, n-heptyl, secondary heptyl, n-octyl, secondary octyl, 2-ethyl hexyl, n-nonyl, secondary nonyl, undecyl, secondary undecyl, dodecyl, secondary dodecyl, tridecyl, secondary tridecyl, tetradecyl, secondary tetradecyl, hexadecyl, secondary hexadecyl, stearyl, icosyl, docosyl, tetracosyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyloctyl, 2-hexydecyl, 2-octylde
  • aryl groups include phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, benzylphenyl, styrenated phenyl, p-cumylphenyl, ⁇ -naphthyl, ⁇ -naphthyl groups, and mixtures thereof.
  • Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents, such as pyridyl, furyl, thienyl and imidazolyl.
  • substituents such as pyridyl, furyl, thienyl and imidazolyl.
  • no more than two, and in one embodiment, no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group. In some embodiments, there are no non-hydrocarbon substituents in the hydrocarbyl group.
  • Representative aliphatic groups may contain 4 to 14 carbon atoms, 6 to 12 carbon atoms, or 8 to 10 carbon atoms.
  • suitable alkyl groups include butyl, isobutyl, pentyl, isopentyl, neopentyl, hexyl, amyl, heptyl, octyl, iso-octyl, 2-ethylhexyl, nonyl, decyl, iso-decyl, undecyl, dodecyl, 2-propylheptyl, tridecyl, isotridecyl, tetradecyl, 4-methyl-2-pentyl, propyl heptyl, and combinations thereof.
  • Hydrocarbylene groups are the divalent equivalents of hydrocarbyl groups, such as alkylene groups.
  • each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade.
  • the amount of each chemical component is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, unless otherwise indicated. It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined. Similarly, the ranges and amounts for each element of the invention may be used together with ranges or amounts for any of the other elements.

Landscapes

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

Claims (15)

  1. Schmierzusammensetzung, die Folgendes umfasst:
    a) ein Öl mit Schmierviskosität;
    b) wenigstens 0,1 Gew.-% einer N-alkylierten Dianilinverbindung;
    c) wenigstens 0,1 Gew.-% eines aschefreien Antioxidans, das aus einem Diarylaminantioxidans, einem phenolischen Antioxidans und Kombinationen davon ausgewählt ist, und
    d) wenigstens 0,01 Gew.-% eines überbasischen Calciumdetergens;
    wobei die Schmiermittelzusammensetzung weniger als 0,15 Gewichtsprozent Phosphor umfasst; und
    wobei das N-alkylierte Dianilin eine N,N'-alkylierte Dianilinverbindung ist, die durch die folgende Formel dargestellt wird:
    Figure imgb0034
    wobei R1 und R2 unabhängig aus Alkylgruppen mit 1 bis 24 Kohlenstoffatomen ausgewählt sind, wobei die Alkylgruppen aus acyclischen Alkylgruppen, cyclischen Alkylgruppen und Kombinationen davon ausgewählt sind.
  2. Schmiermittelzusammensetzung nach Anspruch 1, wobei die Schmiermittelzusammensetzung eine TBN von wenigstens 4 mg KOH/g, gemessen gemäß ASTM D-2896, aufweist.
  3. Schmiermittelzusammensetzung nach Anspruch 1 oder 2, wobei die N-Alkylgruppe eine Cyclohexylgruppe ist.
  4. Schmiermittelzusammensetzung nach einem der vorhergehenden Ansprüche, wobei die N-alkylierte Dianilinverbindung wenigstens 0,15 Gew.-% oder wenigstens 0,2 Gew.-% oder wenigstens 0,4 Gew.-% der Schmiermittelzusammensetzung beträgt oder bis zu 4,0 Gewichtsprozent der Schmiermittelzusammensetzung oder bis zu 3 Gew.-% oder bis zu 1,5 Gew.-% oder bis zu 1,2 Gew.-% % der Schmiermittelzusammensetzung beträgt.
  5. Schmiermittelzusammensetzung nach einem der vorhergehenden Ansprüche, wobei die N-alkylierte Dianilinverbindung aus der Gruppe ausgewählt ist, die aus Folgendem besteht:
    Figure imgb0035
    Figure imgb0036
    Figure imgb0037
    Figure imgb0038
    Figure imgb0039
    Figure imgb0040
    Figure imgb0041
     und Gemischen davon.
  6. Schmiermittelzusammensetzung nach Anspruch 5, wobei die N-alkylierte Dianilinverbindung aus 4,4'-2-Ethylhexylmethylendianilin, 4,4'-Cyclohexylmethylendianilin und Gemischen davon ausgewählt ist.
  7. Schmiermittelzusammensetzung nach einem der vorhergehenden Ansprüche, wobei das Öl mit Schmierviskosität wenigstens 40 Gewichtsprozent der Schmiermittelzusammensetzung beträgt.
  8. Schmiermittelzusammensetzung nach einem der vorhergehenden Ansprüche, wobei das aschefreie Antioxidans wenigstens 0,2 Gew.-% oder wenigstens 0,4 Gew.-% oder wenigstens 0,6 Gew.-% oder bis zu 4 Gew.-% oder bis zu 1,2 Gew.-% oder bis zu 1 Gew.-% der Schmiermittelzusammensetzung beträgt.
  9. Schmiermittelzusammensetzung nach einem der vorhergehenden Ansprüche, wobei ein Verhältnis des aschefreien Antioxidans zu der N-Alkyldianilinverbindung von 20 : 1 bis 1 : 20 beträgt und/oder wobei ein Gewichtsverhältnis von Calcium zu Magnesium in der Schmiermittelzusammensetzung wenigstens 9 : 10 beträgt.
  10. Schmiermittelzusammensetzung nach einem der vorhergehenden Ansprüche, wobei das aschefreie Antioxidans einen Phenolester und ein Diarylamin und optional ein geschwefeltes Olefin umfasst.
  11. Schmiermittelzusammensetzung nach einem der vorhergehenden Ansprüche, wobei das überbasische Calciumdetergens aus Sulfonaten, nicht schwefelhaltigen Phenaten, schwefelhaltigen Phenaten, Salixaraten, Salicylaten, Gemischen davon und borierten Äquivalenten davon ausgewählt ist.
  12. Schmiermittelzusammensetzung nach einem der vorhergehenden Ansprüche, wobei das überbasische Calciumdetergens wenigstens 0,1 Gew.-% oder wenigstens 0,5 Gew.-% oder bis zu 3 Gew.-% oder bis zu 2 Gew.-% der Schmiermittelzusammensetzung beträgt.
  13. Schmiermittelzusammensetzung nach einem der vorhergehenden Ansprüche, die ferner ein Polyolefinsuccinimiddispergiermittel umfasst, wobei die Polyolefingruppe eine zahlenmittlere Molekülmasse von wenigstens 300 aufweist.
  14. Verwendung der Schmiermittelzusammensetzung nach einem der Ansprüche 1-13 zum Verringern einer Ablagerungsbildung in einem Verbrennungsmotor.
  15. Verwendung der Schmiermittelzusammensetzung nach einem der Ansprüche 1-13 zum Schmieren eines Verbrennungsmotors.
EP17826048.5A 2016-12-27 2017-12-13 Schmiermittelzusammensetzung mit n-alkyliertem dianilin Active EP3562921B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201662439246P 2016-12-27 2016-12-27
PCT/US2017/066103 WO2018125569A1 (en) 2016-12-27 2017-12-13 Lubricating composition including n-alkylated dianiline

Publications (2)

Publication Number Publication Date
EP3562921A1 EP3562921A1 (de) 2019-11-06
EP3562921B1 true EP3562921B1 (de) 2022-04-27

Family

ID=60937905

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17826048.5A Active EP3562921B1 (de) 2016-12-27 2017-12-13 Schmiermittelzusammensetzung mit n-alkyliertem dianilin

Country Status (7)

Country Link
US (1) US20190367833A1 (de)
EP (1) EP3562921B1 (de)
CN (1) CN110114447A (de)
CA (1) CA3046788A1 (de)
DK (1) DK3562921T3 (de)
ES (1) ES2914785T3 (de)
WO (1) WO2018125569A1 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200277541A1 (en) * 2019-02-28 2020-09-03 Afton Chemical Corporation Lubricating compositions for diesel particulate filter performance
CA3173362A1 (en) * 2020-03-11 2021-09-16 Chevron Oronite Company Llc Lubricating oil compositions with improved oxidative performance comprising alkylated diphenylamine antioxidant and carboxylate detergents
JP2023517064A (ja) * 2020-03-11 2023-04-21 シェブロン・オロナイト・カンパニー・エルエルシー スルホン酸塩洗浄剤による酸化性能の向上
CN115702347A (zh) 2020-06-01 2023-02-14 路博润公司 表面绝缘电阻兼容性测试系统和方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160115418A1 (en) * 2013-05-22 2016-04-28 The Lubrizol Corporation Lubricating Composition

Family Cites Families (72)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2045574A (en) 1936-06-30 Process for the catalytic
US2943112A (en) 1957-11-06 1960-06-28 Pennsalt Chemicals Corp Alkylation of diphenylamine
US3444170A (en) 1959-03-30 1969-05-13 Lubrizol Corp Process which comprises reacting a carboxylic intermediate with an amine
DE1248643B (de) 1959-03-30 1967-08-31 The Lubrizol Corporation, Cleveland, Ohio (V. St. A.) Verfahren zur Herstellung von öllöslichen aeylierten Aminen
NL253735A (de) * 1959-07-13
US3110671A (en) * 1960-07-05 1963-11-12 Universal Oil Prod Co Stabilized lubricants
US3197405A (en) 1962-07-09 1965-07-27 Lubrizol Corp Phosphorus-and nitrogen-containing compositions and process for preparing the same
DE1271877B (de) 1963-04-23 1968-07-04 Lubrizol Corp Schmieroel
US3381022A (en) 1963-04-23 1968-04-30 Lubrizol Corp Polymerized olefin substituted succinic acid esters
USRE26433E (en) 1963-12-11 1968-08-06 Amide and imide derivatives of metal salts of substituted succinic acids
GB1052380A (de) 1964-09-08
US3316177A (en) 1964-12-07 1967-04-25 Lubrizol Corp Functional fluid containing a sludge inhibiting detergent comprising the polyamine salt of the reaction product of maleic anhydride and an oxidized interpolymer of propylene and ethylene
DE1595234A1 (de) 1965-04-27 1970-03-05 Roehm & Haas Gmbh Verfahren zur Herstellung oligomerer bzw. polymerer Amine
US3340281A (en) 1965-06-14 1967-09-05 Standard Oil Co Method for producing lubricating oil additives
US3433744A (en) 1966-11-03 1969-03-18 Lubrizol Corp Reaction product of phosphosulfurized hydrocarbon and alkylene polycarboxylic acid or acid derivatives and lubricating oil containing the same
US3501405A (en) 1967-08-11 1970-03-17 Rohm & Haas Lubricating and fuel compositions comprising copolymers of n-substituted formamide-containing unsaturated esters
US3576743A (en) 1969-04-11 1971-04-27 Lubrizol Corp Lubricant and fuel additives and process for making the additives
US3632511A (en) 1969-11-10 1972-01-04 Lubrizol Corp Acylated nitrogen-containing compositions processes for their preparationand lubricants and fuels containing the same
US3779923A (en) 1972-01-20 1973-12-18 Du Pont Alkylated methylenedianiline tars
US4320021A (en) 1975-10-14 1982-03-16 The Lubrizol Corporation Amino phenols useful as additives for fuels and lubricants
US4200545A (en) 1976-01-28 1980-04-29 The Lubrizol Corporation Amino phenol-detergent/dispersant combinations and fuels and lubricants containing same
US4100082A (en) 1976-01-28 1978-07-11 The Lubrizol Corporation Lubricants containing amino phenol-detergent/dispersant combinations
US4234435A (en) 1979-02-23 1980-11-18 The Lubrizol Corporation Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation
US4370246A (en) * 1981-04-27 1983-01-25 Chevron Research Company Antioxidant combinations of molybdenum complexes and aromatic amine compounds
US4708809A (en) 1982-06-07 1987-11-24 The Lubrizol Corporation Two-cycle engine oils containing alkyl phenols
GB8332797D0 (en) 1983-12-08 1984-01-18 Ciba Geigy Ag Antioxidant production
CA1265506A (en) 1984-11-21 1990-02-06 Kirk Emerson Davis Alkyl phenol and amino compound compositions and two- cycle engine oils and fuels containing same
US4863623A (en) 1988-03-24 1989-09-05 Texaco Inc. Novel VI improver, dispersant, and anti-oxidant additive and lubricating oil composition containing same
GB8818711D0 (en) 1988-08-05 1988-09-07 Shell Int Research Lubricating oil dispersants
US6117825A (en) 1992-05-07 2000-09-12 Ethyl Corporation Polyisobutylene succinimide and ethylene-propylene succinimide synergistic additives for lubricating oils compositions
US5264140A (en) 1992-06-01 1993-11-23 Texaco Inc. Antioxidant-dispersant VI improver additive and lubricating oil composition containing same
US5409623A (en) 1992-09-02 1995-04-25 Texaco Inc. Functionalized graft co-polymer as a viscosity and index improver, dispersant, and anti-oxidant additive and lubricating oil composition containing same
US5672752A (en) 1995-09-13 1997-09-30 The Bfgoodrich Company Liquid alkylated diphenylamine antioxidant
GB9611318D0 (en) 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
GB9611428D0 (en) 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
GB9611316D0 (en) 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
GB9611424D0 (en) 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
SG65759A1 (en) 1997-06-06 1999-06-22 Ciba Sc Holding Ag Nonylated diphenylamines
US6165235A (en) 1997-08-26 2000-12-26 The Lubrizol Corporation Low chlorine content compositions for use in lubricants and fuels
US6107258A (en) 1997-10-15 2000-08-22 Ethyl Corporation Functionalized olefin copolymer additives
US6107257A (en) 1997-12-09 2000-08-22 Ethyl Corporation Highly grafted, multi-functional olefin copolymer VI modifiers
US6204412B1 (en) 1999-04-16 2001-03-20 The B. F. Goodrich Company Method of manufacturing alkylated diphenylamine compositions and products thereof
US6329327B1 (en) 1999-09-30 2001-12-11 Asahi Denka Kogyo, K.K. Lubricant and lubricating composition
US6559105B2 (en) 2000-04-03 2003-05-06 The Lubrizol Corporation Lubricant compositions containing ester-substituted hindered phenol antioxidants
EP1518920A1 (de) * 2001-05-11 2005-03-30 Infineum International Limited Schmierölzusammensetzungen
US6355839B1 (en) 2001-08-31 2002-03-12 Chevron U.S.A., Inc. Alkylation of diphenylamine with polyisobutylene oligomers
DE60203639T2 (de) 2001-11-05 2006-01-19 The Lubrizol Corp., Wickliffe Schmiermittelzusammensetzung mit verbesserter Brennstoffersparnis
US6645921B2 (en) 2002-02-08 2003-11-11 Ethyl Corporation Molybdenum-containing lubricant additive compositions, and processes for making and using same
US7238650B2 (en) 2002-06-27 2007-07-03 The Lubrizol Corporation Low-chlorine, polyolefin-substituted, with amine reacted, alpha-beta unsaturated carboxylic compounds
US7285516B2 (en) 2002-11-25 2007-10-23 The Lubrizol Corporation Additive formulation for lubricating oils
US7696136B2 (en) 2004-03-11 2010-04-13 Crompton Corporation Lubricant compositions containing hydroxy carboxylic acid and hydroxy polycarboxylic acid esters
WO2005103093A2 (en) 2004-04-19 2005-11-03 The Lubrizol Corporation Dispersant viscosity modifiers based on maleic anhydride-styrene copolymers
US7615519B2 (en) 2004-07-19 2009-11-10 Afton Chemical Corporation Additives and lubricant formulations for improved antiwear properties
US7651987B2 (en) 2004-10-12 2010-01-26 The Lubrizol Corporation Tartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereof
US7807611B2 (en) 2004-10-12 2010-10-05 The Lubrizol Corporation Tartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereof
AU2006216990B2 (en) 2005-02-18 2010-06-03 The Lubrizol Corporation Multifunctional dispersants
CN102229842A (zh) 2005-03-28 2011-11-02 卢布里佐尔公司 钛化合物和络合物作为润滑剂中的添加剂
CA2643358A1 (en) 2006-02-21 2007-08-30 Shell Internationale Research Maatschappij B.V. Lubricating oil composition
US20080119378A1 (en) 2006-11-21 2008-05-22 Chevron Oronite Company Llc Functional fluids comprising alkyl toluene sulfonates
CA2681312C (en) 2007-04-04 2015-10-27 The Lubrizol Corporation A synergistic combination of a hindered phenol and nitrogen containing detergent for biodiesel fuel to improve oxidative stability
WO2008147704A1 (en) 2007-05-24 2008-12-04 The Lubrizol Corporation Lubricating composition containing ashfree antiwear agent based on hydroxypolycarboxylic acid derivative and a molybdenum compound
JP2009024123A (ja) 2007-07-23 2009-02-05 Showa Shell Sekiyu Kk バイオ燃料対応ディーゼルエンジン用潤滑油組成物。
US7960322B2 (en) 2007-10-26 2011-06-14 Chevron Oronite Company Llc Lubricating oil compositions comprising a biodiesel fuel and an antioxidant
EP2291497B1 (de) * 2008-05-13 2013-07-10 The Lubrizol Corporation Methode zur minimierung von turboschlamm mit aminischen antioxidantien
CN102089415A (zh) * 2008-07-14 2011-06-08 科聚亚公司 用于稳定润滑剂组合物的液态添加剂
US8242066B2 (en) 2008-12-23 2012-08-14 Infineum International Limited Aniline compounds as ashless TBN sources and lubricating oil compositions containing same
KR101736517B1 (ko) 2009-07-08 2017-05-16 더루우브리졸코오포레이션 분산제 점도 조정제
CA2767803A1 (en) 2009-07-08 2011-01-13 The Lubrizol Corporation Dispersant viscosity modifiers
US9222051B2 (en) 2011-05-31 2015-12-29 The Lubrizol Corporation Lubricating composition with improved TBN retention
EP2920282B1 (de) 2012-11-19 2021-10-20 The Lubrizol Corporation Alkylen-gekoppelte phenole zur verwendung in biodieselmotoren
US9890346B2 (en) 2014-07-21 2018-02-13 Lanxess Solutions Us Inc. Selective alkylation method for producing p, p′-di-alkylated diphenylamine antioxidants
WO2016044262A1 (en) 2014-09-15 2016-03-24 The Lubrizol Corporation Dispersant viscosity modifiers with sulfonate functionality

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160115418A1 (en) * 2013-05-22 2016-04-28 The Lubrizol Corporation Lubricating Composition

Also Published As

Publication number Publication date
EP3562921A1 (de) 2019-11-06
US20190367833A1 (en) 2019-12-05
ES2914785T3 (es) 2022-06-16
DK3562921T3 (da) 2022-06-07
CA3046788A1 (en) 2018-07-05
WO2018125569A1 (en) 2018-07-05
CN110114447A (zh) 2019-08-09

Similar Documents

Publication Publication Date Title
EP3562921B1 (de) Schmiermittelzusammensetzung mit n-alkyliertem dianilin
EP3562922B1 (de) Schmiermittelzusammensetzung mit alkyliertem naphthylamin
EP3487968B1 (de) Tetraederförmige boratverbindungen für vollständig formulierte schmiermittelzusammensetzungen
US10196578B2 (en) Motorcycle engine lubricant
EP3262144B1 (de) Aromatische tetraederförmige boratverbindungen für schmierzusammensetzungen
EP2235147B1 (de) Verwendung zum erhöhen der kraftstoffeffizienz in einen schiffdieselmotor
US9663744B2 (en) Dispersant viscosity modifiers
US11427780B2 (en) Total base number boosters for marine diesel engine lubricating compositions
EP3307858B1 (de) Michael-addukt-aminoester als booster der gesamtbasenzahl für schmiermittelzusammensetzungen für schiffsdieselmotoren
CN107109282B (zh) 具有密封相容性的润滑组合物
US10260019B2 (en) Hydroxyaromatic succinimide detergents for lubricating compositions
EP3472274B1 (de) Schmierölzusammensetzungen mit einem polyisobutylen-substituiertem phenol
AU2016226303A1 (en) Novel organic friction modifiers
CN106574202B (zh) 碱性无灰添加剂
US10975323B2 (en) Sulfurized catecholate detergents for lubricating compositions
WO2024158648A1 (en) Lubricating composition with phenolic antioxidant and low active sulfur
EP3390591B1 (de) Schmiermittelzusammensetzungen mit geschwefelten catecholat-detergenzien
EP3390592B1 (de) Geschützte mercaptophenole für schmierzusammensetzungen

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20190713

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20210322

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C10N 60/14 20060101ALI20211028BHEP

Ipc: C10N 40/25 20060101ALI20211028BHEP

Ipc: C10N 30/00 20060101ALI20211028BHEP

Ipc: C10N 30/10 20060101ALI20211028BHEP

Ipc: C10N 30/04 20060101ALI20211028BHEP

Ipc: C10N 20/04 20060101ALI20211028BHEP

Ipc: C10N 10/04 20060101ALI20211028BHEP

Ipc: C10M 163/00 20060101ALI20211028BHEP

Ipc: C10M 133/12 20060101AFI20211028BHEP

INTG Intention to grant announced

Effective date: 20211123

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1486952

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220515

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602017056647

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

Effective date: 20220603

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2914785

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20220616

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1486952

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220427

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220829

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220728

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220827

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602017056647

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

26N No opposition filed

Effective date: 20230130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230517

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221213

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221231

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221213

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221231

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20231227

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20231227

Year of fee payment: 7

Ref country code: NL

Payment date: 20231226

Year of fee payment: 7

Ref country code: IT

Payment date: 20231220

Year of fee payment: 7

Ref country code: FR

Payment date: 20231227

Year of fee payment: 7

Ref country code: DK

Payment date: 20231229

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20231227

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20171213

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20240102

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20231229

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220427