WO2021229517A1 - Composition d'huile lubrifiante comprenant des modificateurs de viscosité de polyméthacrylate en peigne et de copolymère d'oléfine à base d'éthylène - Google Patents

Composition d'huile lubrifiante comprenant des modificateurs de viscosité de polyméthacrylate en peigne et de copolymère d'oléfine à base d'éthylène Download PDF

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Publication number
WO2021229517A1
WO2021229517A1 PCT/IB2021/054137 IB2021054137W WO2021229517A1 WO 2021229517 A1 WO2021229517 A1 WO 2021229517A1 IB 2021054137 W IB2021054137 W IB 2021054137W WO 2021229517 A1 WO2021229517 A1 WO 2021229517A1
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Prior art keywords
lubricating oil
oil composition
dispersant
ethylene
olefin copolymer
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PCT/IB2021/054137
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English (en)
Inventor
Hisanari Onouchi
Isao Tanaka
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Chevron Japan Ltd.
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Priority to CA3182688A priority Critical patent/CA3182688A1/fr
Priority to KR1020227042844A priority patent/KR20230011331A/ko
Priority to EP21727244.2A priority patent/EP4150035A1/fr
Priority to CN202180034987.7A priority patent/CN115551976A/zh
Priority to JP2022568926A priority patent/JP2023525328A/ja
Publication of WO2021229517A1 publication Critical patent/WO2021229517A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • 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
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • 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
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54—Fuel economy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • 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 disclosed technology relates to lubricating oils for internal combustion engines, particularly lubricating oils for spark-ignited engines.
  • Engine oil is blended with various additives to satisfy performance requirements.
  • a challenge in engine oil formulation is to simultaneously achieve wear, deposit, and varnish control while also achieving improved fuel economy.
  • a lubricating oil composition comprising: a) a major amount of an oil of lubricating viscosity; b) a non-dispersant comb polymethacrylate (PMA) in an amount of 0.4 wt. % to 1.9 wt. %, based on the total weight of the lubricating oil composition; and c) a non-dispersant ethylene-based olefin copolymer in an amount of 0.01 wt. % to 0.36 wt. %, based on the total weight of the lubricating oil composition.
  • PMA non-dispersant comb polymethacrylate
  • Another aspect of the present disclosure provides a method for reducing wear in an internal combustion engine comprising lubricating the engine with a lubricating oil composition, the lubricating oil composition including: a) a major amount of an oil of lubricating viscosity; b) a non-dispersant comb polymethacrylate (PMA) in an amount of 0.4 wt. % to 1.9 wt. %, based on the total weight of the lubricating oil composition; and c) a non-dispersant ethylene-based olefin copolymer in an amount of 0.01 wt. % to 0.36 wt. %, based on the total weight of the lubricating oil composition.
  • PMA non-dispersant comb polymethacrylate
  • a “major amount” means in excess of 50 wt. % of a composition.
  • a “minor amount” means less than 50 wt. % of a composition, expressed in respect of the stated additive and in respect of the total mass of all the additives present in the composition, reckoned as active ingredient of the additive or additives.
  • Active ingredients or “actives” refers to additive material that is not diluent or solvent.
  • ppm means parts per million by weight, based on the total weight of the lubricating oil composition.
  • KV Kinematic Viscosity
  • HTHS High Temperature High Shear
  • Metal refers to alkali metals, alkaline earth metals, or mixtures thereof.
  • An oil soluble or dispersible material means that an amount of the material needed to provide the desired level of activity or performance can be incorporated by being dissolved, dispersed or suspended in an oil of lubricating viscosity. Usually, this means that at least about 0.001% by weight of the material can be incorporated in a lubricating oil composition.
  • sulfated ash refers to the non-combustible residue resulting from detergents and metallic additives in lubricating oil. Sulfated ash may be determined in accordance with ASTM D874.
  • Total Base Number refers to the amount of base equivalent to milligrams of KOH in one gram of sample. Thus, higher TBN numbers reflect more alkaline products, and therefore a greater alkalinity. TBN is determined in accordance with ASTM D2896.
  • SSI Shear Stability Index
  • Olefins refers to a class of unsaturated aliphatic hydrocarbons having one or more carbon-carbon double bonds, obtained by a number of processes. Those containing one double bond are called mono-alkenes, and those with two double bonds are called dienes, alkyldienes, or diolefins. Alpha olefins are particularly reactive because the double bond is between the first and second carbons. Examples are 1-octene and 1-octadecene, which are used as the starting point for medium -biodegradable surfactants. Linear and branched olefins are also included in the definition of olefins.
  • the term “averaged,” when referring to a value, is intended to mean an average, a geometric mean, or a median value.
  • Group numbers corresponding to columns within the Periodic Table of the elements use the “New Notation” convention as seen in the CRC Handbook of Chemistry and Physics, 81st Edition (2000-2001).
  • Natural oils include animal and vegetable oils, liquid petroleum oils and hydrorefined, solvent-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic- naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
  • Synthetic oils include hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(l -hexenes), poly(l-octenes), and poly(l-decenes); alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, and di(2-ethylhexyl)benzenes); polyphenols (e.g., biphenyls, terphenyls, and alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogues and homologues thereof.
  • hydrocarbon oils such as polymerized and interpolymerized olefins (e.g.
  • Another suitable class of synthetic oils comprises the esters of dicarboxylic acids (e.g., malonic acid, alkyl malonic acids, alkenyl malonic acids, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, fumaric acid, azelaic acid, suberic acid, sebacic acid, adipic acid, linoleic acid dimer, and phthalic acid) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, and propylene glycol).
  • dicarboxylic acids e.g., malonic acid, alkyl malonic acids, alkenyl malonic acids, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, fumaric acid, azelaic acid, suberic acid, sebacic acid
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di- «-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 C5 to C12 monocarboxylic acids and polyols, and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, andtripentaerythritol.
  • the base oil which may be used to make the present lubricating oil composition may be selected from any of the base oils in Groups I-V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines (API Publication 1509).
  • API American Petroleum Institute
  • Base Oil Interchangeability Guidelines API Publication 1509
  • Base oils suitable for use herein are any of the variety corresponding to API Group II, Group III, Group IV, and Group V oils and combinations thereof, preferably the Group III to Group V oils due to their exceptional volatility, stability, viscometric and cleanliness features.
  • the base oil constitutes the major component of the lubricating oil composition and is present is an amount ranging from greater than 50 to 99 wt. % (e.g., 70 to 95 wt. %, or 85 to 95 wt. %).
  • a base oil having a Kinematic Viscosity exceeding 6 mm 2 /s is needed.
  • the overall base oil could include a minor portion of a higher cut base oil, such as a 10 cSt polyalphaolefm.
  • the base oil has a Viscosity Index of at least 90 (e.g., at least 95, at least 105, at least 110, at least 115, or at least 120). If the Viscosity Index is less than 90, not only viscosity-temperature properties, heat and oxidation stability, and anti-volatilization are reduced, but also the coefficient of friction tends to be increased; and resistance against wear tends to be reduced.
  • the lubricating oil composition can be a multi-grade oil having a viscosity grade of SAE 0W-XX, wherein XX is any one of 8, 10, 12, 16, and 20. According to one preferred embodiment, the lubricating oil composition has a viscosity grade of SAE 0W-20.
  • the lubricating oil composition has a High Temperature High Shear (HTHS) viscosity at 150°C of 3.0 cP or less (e.g., 1.0 cP to 3.0 cP or 1.3 cP to 3.0 cP), 2.8 cP or less (e.g., 1.0 cP to 2.8 cP or 1.3 cP to 2.8 cP), 2.7 cP or less (e.g., 1.0 cP to 2.7 cP or 1.3 cP to 2.7 cP), 2.6 cP or less (e.g., 1.0 cP to 2.6 cP or 1.3 cP to 2.6 cP), such as 2.5 cP or less (e.g., 1.0 cP to 2.5 cP or 1.3 cP to 2.5 cP) or 2.0 cP or less (e.g., 1.0 cP to 2.0 cP or 1.3 cP to 2.0 cP).
  • HTHS High
  • the lubricating oil composition has a Viscosity Index of at least 135 (e.g., 135 to 400 or 135 to 250), at least 150 (e.g., 150 to 400 or 150 to 250), at least 165 (e.g., 165 to 400 or 165 to 250), at least 190 (e.g., 190 to 400 or 190 to 250), or at least 200 (e.g., 200 to 400 or 200 to 250). If the Viscosity Index of the lubricating oil composition is less than 135, it may be difficult to improve fuel efficiency while maintaining the desired HTHS viscosity at 150°C.
  • the lubricating oil composition has a Kinematic Viscosity at 100°C in a range of 3 mm 2 /s to 12 mm 2 /s (e.g., 3 mm 2 /s to 11 mm 2 /s, 5 mm 2 /s to 9 mm 2 /s, or 6 mm 2 /s to 8 mm 2 /s).
  • the lubricating oil composition has an Apparent Viscosity at temperatures ranging from 35°C to -5°C, measured by a Cold Cranking Simulator (CCS), of 3600 mPa s to 3900 mPa s.
  • CCS Cold Cranking Simulator
  • the lubricating oil composition has an apparent viscosity of 3600 mPa s to 3700 mPa s, 3700 mPa s to 3800 mPa s, or 3800 mPa s to 3900 mPa s.
  • the level of sulfur in the lubricating oil composition is less than or equal to about 0.7 wt. %, based on the total weight of the lubricating oil composition.
  • the lubricating oil composition can have a level of sulfur of about 0.01 wt. % to 0.5 wt.%, 0.01 wt. %to 0.4 wt.%, 0.01 wt. %to 0.3 wt.%, 0.01 wt. %to 0.2 wt.%, or 0.01 wt. %to 0.10 wt. %.
  • the level of sulfur in the lubricating oil composition is less than or equal to about 0.60 wt.
  • % less than or equal to about 0.50 wt. %, less than or equal to about 0.40 wt. %, less than or equal to about 0.30 wt. %, less than or equal to about 0.20 wt. %, or less than or equal to about 0.10 wt. %, based on the total weight of the lubricating oil composition.
  • the level of phosphorus in the lubricating oil composition is less than or equal to about 0.08 wt. %, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.08 wt. %. In one embodiment, the level of phosphorus in the lubricating oil composition is less than or equal to about 0.07 wt. %, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.07 wt. %.
  • the level of phosphorus in the lubricating oil composition is less than or equal to about 0.05 wt. %, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.05 wt. %.
  • the level of sulfated ash produced by the lubricating oil composition is less than or equal to about 1.00 wt. % as determined by ASTM D874, e.g., a level of sulfated ash of from about 0.10 wt. % to about 1.00 wt. % as determined by ASTM D874. In one embodiment, the level of sulfated ash produced by the lubricating oil composition is less than or equal to about 0.80 wt. % as determined by ASTM D874, e.g., a level of sulfated ash of from about 0.10 wt. % to about 0.80 wt. % as determined by ASTM D874.
  • the level of sulfated ash produced by the lubricating oil composition is less than or equal to about 0.60 wt. % as determined by ASTM D874, e.g., a level of sulfated ash of from about 0.10 wt. % to about 0.60 wt. % as determined by ASTM D874.
  • the present lubricating oil composition may have a total base number (TBN) of 4 to 15 mg KOH/g (e.g., 5 mg KOH/g to 12 mg KOH/g, 6 mg KOH/g to 12 mg KOH/g, or 8 mg KOH/g to 12 mg KOH/g).
  • TBN total base number
  • Viscosity modifiers are present in the lubricating oil composition to impart high and low temperature operability.
  • the viscosity modifiers increase the viscosity of the lubricating oil composition at elevated temperatures, which increases film thickness, while having limited effect on viscosity at low temperatures.
  • Viscosity modifiers may be used to impart that sole function or may be multifunctional. Multifunctional viscosity modifiers can also function as a dispersant.
  • suitable viscosity modifiers are polymers and copolymers of methacrylate, butadiene, olefins, or alkylated styrenes.
  • Other suitable viscosity modifiers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (copolymers of various chain length acrylates, for example).
  • the viscosity modifiers can be present in the lubricating oil composition in a total amount of 0.001 wt. % to 10 wt. %, based on the total weight of the lubricating oil composition.
  • the viscosity modifiers can be present in a total amount of 0.01 wt. % to 8 wt. %, 0.1 wt. % to 5 wt. %, 0.4 wt. % to 4 wt. %, 0.6 wt. % to 3 wt. %, 0.7 wt. % to 2 wt. %, 1 wt. % to 1.5 wt. %, or 1.05 wt. % to 1.44 wt.%, based on the total weight of the lubricating oil composition.
  • the viscosity modifiers are present in a total amount of 1.0 wt. % to 1.2 wt. %, 1.3 wt. % to 1.4 wt. %, or 1.4 wt. % to 1.5 wt. %, based on the total weight of the lubricating oil composition.
  • comb PMA non dispersant comb polymethacrylate
  • OCP non-dispersant ethylene based olefin copolymer
  • the non-dispersant comb polymethacrylate (comb PMA) is a comb-shaped polymer and thus is a macromolecule in which the main chain has one long branch per repeat unit.
  • the non-dispersant comb PMA has a weight average molecular weight (Mw) of 300,000 g/mol to 600,000 g/mol, 350,000 g/mol to 550,000 g/mol, 375,000 g/mol to 500,000 g/mol, or 390,000 g/mol to 460,000 g/mol.
  • Mw weight average molecular weight
  • the non-dispersant comb PMA has a number average molecular weight (Mn) of 35,000 g/mol to 105,000 g/mol, 45,000 g/mol to 95,000 g/mol, 55,000 g/mol to 85,000 g/mol, or 65,000 g/mol to 75,000 g/mol. In another embodiment, the non-dispersant comb PMA has a number average molecular weight (Mn) of 150,000 g/mol to 250,000 g/mol or 200,000 g/mol to 215,000 g/mol.
  • the non-dispersant comb PMA has a Shear Stability Index (SSI) of 0.1 to 1.0, 0.2 to 0.9, or 0.3 to 0.8.
  • SSI Shear Stability Index
  • the non-dispersant comb PMA of the lubricating oil composition can be described as set forth in US 2017/0298287AI and JP2019014802, the disclosures of which is incorporated herein by reference.
  • the non-dispersant comb PMA can be provided by Viscoplex® Viscosity Index Improver 3-201 and/or 3-162, which are available from Evonik.
  • the non-dispersant comb PMA is provided by the compound referred to as Viscoplex® 3-201, which includes, as a main resin component, a comb PMA.
  • This non-dispersant comb PMA has a weight average molecular weight (Mw) of
  • the compound has at least a constituent unit derived from a macromonomer having a Mn of 500 or more.
  • the non-dispersant comb PMA is present in an amount of 19 wt. %, based on the total weight of the compound.
  • the non-dispersant comb PMA is provided by the compound referred to as Viscoplex® 3-162, which also includes, as a main resin component, a comb PMA.
  • This non-dispersant comb PMA has a weight average molecular weight (Mw) of 399,292 g/mol, a number average molecular weight (Mn) of 205,952 g/mol, a Mw/Ms of 1 .94, and a Shear Stability Index (SSI) of 0.6.
  • the non-dispersant combPMA is typically present in an amount of 0.4 wt. % to 2.0 wt. %, 0.5 wt. % to 1.9 wt. %, 0.6 wt. % to 1.8 wt. %, 0.77 wt. % to 1.5 wt. %, or 0.76 wt. % to 1 .33 wt. %, based on the total weight of the lubricating oil composition.
  • the non-dispersant combPMA is present in an amount of 0.4 wt. % to 1.9 wt. %, based on the total weight of the lubricating oil composition.
  • the lubricating oil composition also includes a non-dispersant ethylene-based olefin copolymer (OCP) as a viscosity modifier.
  • OCP non-dispersant ethylene-based olefin copolymer
  • the non-dispersant ethylene- based olefin copolymer has a weight average molecular weight (Mw) of 50,000 g/mol to 200,000 g/mol, 70,000 g/mol to 180,000 g/mol, or 90,000 g/mol to 160,000 g/mol.
  • the non-dispersant ethylene-based olefin copolymer could have a weight average molecular weight of 95,000 g/mol to 105,000 g/mol, 110,000 g/mol to 115,000 g/mol, or 145,000 g/mol to 150,000 g/mol.
  • the non-dispersant ethylene-based olefin copolymer has a number average molecular weight (Mn) of 20,000 g/mol to 100,000 g/mol, 30,000 g/mol to 90,000 g/mol, or 35,000 g/mol to 85,000 g/mol.
  • non-dispersant ethylene-based olefin copolymer can be described as follows, and as set forth in US 2013/0203640, the disclosure of which is incorporated herein by reference.
  • the non-dispersant ethylene -based olefin copolymer is an ethylene propylene copolymer. In one embodiment, the non-dispersant ethylene-based olefin copolymer has a total ethylene content of 35 wt. % to 70 wt. % or 40 wt. % to 65 wt. %, based on the total weight of the non-dispersant ethylene-based olefin copolymer. In another embodiment, the non dispersant ethylene -based olefin copolymer has a total ethylene content of 45 wt. % to 60 wt. %, based on the total weight of the non-dispersant ethylene-based olefin copolymer.
  • the lubricating oil composition can include more than one non-dispersant ethylene - based olefin copolymer.
  • the lubricating oil composition includes a combination of a first ethylene-a-olefin copolymer (a) and a second ethylene-a-olefin copolymer (b).
  • the lubricating oil composition typically contains about 30 wt. % to about 70 wt. % of the first ethylene-a-olefin copolymer (a) and about 70 wt. % to about 30 wt.
  • the lubricating oil composition contains about 40 wt. % to about 60 wt. % of the first ethylene-a-olefin copolymer (a) and about 60 wt. % to about 40 wt. % of the second ethylene-a-olefin copolymer (b) based upon the total amount of (a) and (b) in the composition. In a particular embodiment, the lubricating oil composition contains about 50 wt. % to about 54 wt.
  • the weight average molecular weight of the first ethylene-a-olefin copolymer in one embodiment is typically about 60,000 g/mol to about 120,000 g/mol. In another embodiment, the weight average molecular weight of the first ethylene-a-olefin copolymer is typically about 70,000 g/mol to about 110,000 g/mol.
  • the weight average molecular weight of the second ethylene-a-olefin copolymer in one embodiment is typically about 60,000 g/mol to about 120,000 g/mol. In another embodiment, the weight average molecular weight of the second ethylene-a-olefin copolymer is typically about 70,000 g/mol to about 110,000 g/mol.
  • the at least one non-dispersant ethylene-based olefin copolymer is typically present in an amount of 0.01 wt. % to 1.5 wt. %, 0.05 wt. % to 1.0 wt. %, 0.08 wt. % to 0.4 wt. %, 0.1 wt. % to 0.5 wt. %, or 0.15 wt. % to 0.4 wt. %, based on the total weight of the lubricating oil composition.
  • the at least one non-dispersant ethylene-based olefin copolymer is present in an amount of 0.01 wt. % to 0.36 wt. %, based on the total weight of the lubricating oil composition.
  • the lubricating oil composition of the present disclosure may contain one or more additional performance additives that can impart or improve any desirable property of the lubricating oil composition.
  • additional performance additives Any additive known to those of skill in the art may be used in the lubricating oil composition disclosed herein. Some suitable additives have been described by R.M. Mortier et al. “Chemistry and Technology of Lubricants,” 3rd Edition, Springer (2010) and L.R. Rudnik “Lubricant Additives: Chemistry and Applications,” Second Edition, CRC Press (2009).
  • the lubricating oil composition may contain antioxidants, anti -wear agent, metal detergents, dispersants, additional friction modifiers, corrosion inhibitors, demulsifiers, additional viscosity modifiers, pour point depressants, foam inhibitors, and others.
  • the concentration of each of the additives in the lubricating oil composition when used, may range from 0.001 wt. %to 10 wt. % (e.g., 0.01 wt. %to 5 wt. % or 0.05 wt. % to 2.5 wt. %), based on the total weight of the lubricating oil composition. Further, the total amount of additives in the lubricating oil composition may range from 0.001 wt. % to 20 wt. % (e.g., 0.01 wt. % to 15 wt. % or 0.1 wt. % to 10 wt. %), based on the total weight of the lubricating oil composition.
  • Antioxidants retard the oxidative degradation of base oils during service. Such degradation may result in deposits on metal surfaces, the presence of sludge, or a viscosity increase in the lubricating oil composition.
  • Useful antioxidants include hindered phenols, aromatic amines, and sulfurized alkylphenols and alkali and alkaline earth metal salts thereof.
  • the hindered phenol antioxidant may contain a secondary butyl and/or a tertiary butyl group as a sterically hindering group.
  • the phenol group may be further substituted with a hydrocarbyl group and/or a bridging group linking to a second aromatic group.
  • hindered phenol antioxidants examples include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert- butylphenol, 2,2’-methylenebis(6-tert-butyl-4-methylphenol), 4,4’-bis(2,6-di-tert- butylphenol) and 4,4’-methylenebis(2,6-di-tert-butylphenol).
  • the hindered phenol antioxidant may be an ester or an addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, wherein the alkyl group may contain from 1 to 18 carbon atoms.
  • Suitable aromatic amine antioxidants include diary lamines such as alkylated diphenylamines (e.g., dioctyl diphenylamine, dinonyl diphenylamine), phenyl-alpha- naphthalene and alkylated phenyl-alpha-naphthalenes.
  • diary lamines such as alkylated diphenylamines (e.g., dioctyl diphenylamine, dinonyl diphenylamine), phenyl-alpha- naphthalene and alkylated phenyl-alpha-naphthalenes.
  • the lubricating oil composition includes an aminic antioxidant.
  • Mannich bases are made from the reaction of an alkylphenols, formaldehyde, and a polyalkylene polyamines. Molecular weights of the alkylphenol may range from 800 to 2500.
  • the lubricating oil composition includes molybdenum dithiocarbamate (MoDTC).
  • Molybdenum dithiocarbamate (MoDTC) is an organomolybdenum compound represented by the following structure (1): wherein R 1 , R 2 , R 3 , and R 4 are independently of each other, linear or branched alkyl groups having from 4 to 18 carbon atoms (e.g., 8 to 13 carbon atoms).
  • the lubricating oil composition includes molybdenum dithiophosphate (MoDTP).
  • MoDTP is an organomolybdenum compound represented by the following structure (2): wherein R 5 , R 6 , R 7 , and R 8 are independently of each other, linear or branched alkyl groups having from 4 to 18 carbon atoms (e.g., 8 to 13 carbon atoms).
  • Molybdenum carboxylates are described in U.S. Pat. RE 38,929, and U.S. Pat. No. 6,174,842, which are incorporated herein by reference.
  • Molybdenum carboxylates can be derived from any oil soluble carboxylic acid.
  • Typical carboxylic acids include naphthenic acid, 2-ethylhexanoic acid, and linolenic acid.
  • Commercial sources of carboxylates produce from these particular acids are MOLYBDENUM NAP-ALL, MOLYBDENUM HEX-CEM, and MOLYBDENUM LIN-ALL respectively.
  • a manufacturer of these products is OMG OM Group.
  • the molybdenum amine is a molybdenum-succinimide complex.
  • Suitable molybdenum-succinimide complexes are described, for example, in U.S. Patent No. 8,076,275. These complexes are prepared by a process comprising reacting an acidic molybdenum compound with an alkyl or alkenyl succinimide of a polyamine of structure (3), (4), or mixtures thereof:
  • succinimides that can be used to prepare the molybdenum-succinimide complex are disclosed in numerous references and are well known in the art. Certain fundamental types of succinimides and the related materials encompassed by the term of art “succinimide” are taught in U.S. Patent Nos. 3,172,892; 3,219,666; and 3,272,746.
  • succinimide is understood in the art to include many of the amide, imide, and amidine species which may also be formed. The predominant product however is a succinimide and this term has been generally accepted as meaning the product of a reaction of an alkyl or alkenyl substituted succinic acid or anhydride with a nitrogen-containing compound.
  • R is hydrocarbyl (e.g., Ci to Cio alkyl) and x is at least 3, Ci to Cio mercaptans, inorganic sulfides and polysulfides, thioacetamide, and thiourea.
  • the molybdenum containing compound is used in an amount that provides molybdenum to the lubricating oil composition in an amount of 50 ppm to 1200 ppm, 50 ppm to 1000 ppm, 50 ppm to 800 ppm, 50 ppm to 600 ppm, 50 ppm to 400 ppm, or 50 ppm to 200 ppm.
  • the molybdenum containing compound can promote the formation of a molybdenum containing lubricating film on a metal surface of the engine.
  • the lubricating oil composition includes MoDTC in an amount ranging from 0.6 wt. % to 0.8 wt. %, based on the total weight of the lubricating composition.
  • Corrosion inhibitors protect lubricated metal surfaces against chemical attack by water or other contaminants.
  • Suitable corrosion inhibitors include polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, thiadiazoles, and anionic alkyl sulfonic acids.
  • pour point depressants lower the minimum temperature at which a fluid will flow or can be poured.
  • Suitable pour point depressants include C8 to Cl 8 dialkyl fumarate/vinyl acetate copolymers, polyalkylmethacrylates, and the like.
  • Foam Inhibitors include C8 to Cl 8 dialkyl fumarate/vinyl acetate copolymers, polyalkylmethacrylates, and the like.
  • Any mixing or dispersing equipment known to a person of ordinary skill in the art may be used for blending, mixing, or solubilizing the ingredients used to form the lubricating oil composition.
  • the blending, mixing, or solubilizing may be carried out with a blender, an agitator, a disperser, a mixer (e.g., planetary mixers and double planetary mixers), a homogenizer (e.g., Gaulin homogenizers and Rannie homogenizers), a mill (e.g., colloid mill, ball mill, and sand mill), or any other mixing or dispersing equipment known in the art.
  • a blender e.g., planetary mixers and double planetary mixers
  • a homogenizer e.g., Gaulin homogenizers and Rannie homogenizers
  • a mill e.g., colloid mill, ball mill, and sand mill
  • any other mixing or dispersing equipment known in the art e.g., colloid mill
  • the lubricating oil composition disclosed herein may be suitable for use as a motor oil (an engine oil or crankcase oil) in a spark-ignited internal combustion engine.
  • the lubricating oil composition is preferably used in engines or crankcases requiring a viscosity grade of SAE 0W-20, OW-16, or OW-12.
  • the lubricating oil composition can be used to lubricate an engine comprising a valve train system which includes roller follower rocker arms.
  • the wt. % of ingredients (a) - (h) includes any diluent and/or solvent that may be present and thus is not an active basis.
  • PMA (Viscoplex® 3-201) is a compound containing 19 wt. % non-dispersant comb-shaped polymethacrylate having a Mw of 420,000 g/mol and a Mw/Mn of 5.92.
  • 2 0CP1 is a concentrate containing 10 wt% of a non-dispersant ethylene -propylene copolymer having an ethylene content of 57 wt. %, Mw of about 100,000, Mn of about 40,000, and a SSI of 24.
  • OCP 2 is a concentrate containing 8.75 wt% of a non-dispersant ethylene -propylene copolymer having an ethylene content of 57 wt. %, Mw of 112,000, Mn of 49,000, and a SSI of 35.
  • 4 OCP 3 is a concentrate containing 8.8 wt. % of a non-dispersant ethylene -propylene copolymer having an ethylene content of 49 wt. %, a Mw of 146,000, a Mn of 84,000 Mn, and a SSI of 50.
  • Table 4 provides the average %torque change at the oil temperatures of 60° C, 80° C, and 100° C for the Invention Example Compositions
  • Table 5 provides the average % torque change at the oil temperatures of 60° C, 80° C, and 100° C for the Comparative Example Compositions.

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

Abstract

L'invention concerne une composition d'huile lubrifiante, par exemple une composition présentant une viscosité de grade SAE 0W-20 ou inférieur, comprenant : (a) une grande quantité d'une huile de viscosité lubrifiante, (b) un polyméthacrylate (PMA) en peigne non dispersant, et (c) un copolymère d'oléfine à base d'éthylène non dispersant. L'invention concerne également un procédé de réduction de l'usure dans un moteur à combustion interne par lubrification du moteur à l'aide de la composition d'huile lubrifiante.
PCT/IB2021/054137 2020-05-14 2021-05-14 Composition d'huile lubrifiante comprenant des modificateurs de viscosité de polyméthacrylate en peigne et de copolymère d'oléfine à base d'éthylène WO2021229517A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CA3182688A CA3182688A1 (fr) 2020-05-14 2021-05-14 Composition d'huile lubrifiante comprenant des modificateurs de viscosite de polymethacrylate en peigne et de copolymere d'olefine a base d'ethylene
KR1020227042844A KR20230011331A (ko) 2020-05-14 2021-05-14 콤(comb) 폴리메타크릴레이트와 에틸렌계 올레핀 공중합체 점도 조절제를 포함하는 윤활유 조성물
EP21727244.2A EP4150035A1 (fr) 2020-05-14 2021-05-14 Composition d'huile lubrifiante comprenant des modificateurs de viscosité de polyméthacrylate en peigne et de copolymère d'oléfine à base d'éthylène
CN202180034987.7A CN115551976A (zh) 2020-05-14 2021-05-14 包括梳状聚甲基丙烯酸酯和基于乙烯的烯烃共聚物粘度改性剂的润滑油组合物
JP2022568926A JP2023525328A (ja) 2020-05-14 2021-05-14 櫛型ポリメタクリレート及びエチレン系オレフィンコポリマー粘度調整剤を含む潤滑油組成物

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KR20230011331A (ko) 2023-01-20

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