EP3470499B1 - Utilisation des détergents dans les huiles lubrifiantes de moteur à combustion interne - Google Patents

Utilisation des détergents dans les huiles lubrifiantes de moteur à combustion interne Download PDF

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EP3470499B1
EP3470499B1 EP18195639.2A EP18195639A EP3470499B1 EP 3470499 B1 EP3470499 B1 EP 3470499B1 EP 18195639 A EP18195639 A EP 18195639A EP 3470499 B1 EP3470499 B1 EP 3470499B1
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detergent
lubricant
active ingredient
mass
tbn
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German (de)
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EP3470499A1 (fr
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Alexander Coxon
Alastair Cant
Malgorzata Maranska
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Infineum International Ltd
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Infineum International Ltd
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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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/28—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring
    • C10M135/30—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups; Derivatives 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • 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
    • C10N2030/06—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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/26—Two-strokes or two-cycle 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
    • C10N2060/10—Chemical after-treatment of the constituents of the lubricating composition by sulfur or a compound containing sulfur

Definitions

  • This invention relates to the lubrication of internal combustion engines.
  • EP-A-2 682 451 (“451") describes overbased sulphurised calcium phenate detergent additives having oxyalkylated phenolic functional groups from unreacted alkylphenol starting material and lubricating compositions (including MDCL's) comprising the same. See Abstract and paragraph 0046. These are stated to be for a range of internal combustion engines (spark-ignited or compression-ignited) such as motor vehicle engines and marine engines. The latter include two-stroke marine diesel engines and marine trunk piston engines. There is, however, no mention of the additives having antiwear properties; in fact, "451” refers to antiwear functionality being provided by different additives. See paragraph 0045. US2014/360451 discloses the use of sulfurized branched alkyl phenols to improve the anti-wear performance of lubricating oil compositions.
  • the present invention provides in one aspect the use of an oxyalkylated sulfurized alkylphenol detergent additive in an internal combustion engine lubricant for providing control of and/or improvement of the wear performance of the lubricant, such as when lubricating the engine cylinder of a marine diesel two-stroke cross-head engine.
  • the lubricant composition contains a major amount of an oil of lubricating viscosity.
  • oil of lubricating viscosity may range in viscosity from light distillate mineral oils to heavy lubricating oils. Generally, the viscosity of the oil ranges from 2 to 40, such as 3 to 15, mm 2 /sec, as measured at 100°C, and has a viscosity index of 80 to 100, such as 90 to 95.
  • the lubricating oil may comprise a major amount of the composition as defined above.
  • Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil); liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale also serve as useful base oils.
  • Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes)); alkybenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulphides and derivatives, analogues and homologues thereof.
  • Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of known synthetic lubricating oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, and the alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having a molecular weight of 1000 or diphenyl ether of polyethylene glycol having a molecular weight of 1000 to 1500); and mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C 3 -C 8 fatty acid esters and C 13 oxo acid diester of tetraethylene glycol.
  • polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide
  • alkyl and aryl ethers of polyoxyalkylene polymers e.g.
  • Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol).
  • dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linole
  • esters includes 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 polyol esters such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
  • Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicone oils and silicate oils comprise another useful class of synthetic lubricants; such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2-ethylhexyl)disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes.
  • oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexy
  • Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
  • Unrefined, refined and re-refined oils can be used in lubricants of the present invention.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations; petroleum oil obtained directly from distillation; or ester oil obtained directly from esterification and used without further treatment are unrefined oils.
  • the present invention preferably embraces Group I or Group II base stocks or oils.
  • the oil of lubricating viscosity in this invention contains 50 mass % or more of said basestocks. It may contain 60, such as 70, 80 or 90, mass % or more of said basestock or a mixture thereof.
  • the oil of lubricating viscosity may be substantially all of said basestock or a mixture thereof.
  • the invention is not however limited to use of the above-mentioned base stocks; thus it may, for example, include use of Group III, IV or V basestocks and of bright stock. They also include basestocks derived from hydrocarbons synthesised by the Fischer-Tropsch process.
  • synthesis gas containing carbon monoxide and hydrogen is first generated and then converted to hydrocarbons using a Fischer-Tropsch catalyst.
  • hydrocarbons typically require further processing in order to be useful as a base oil. For example, they may, by methods known in the art, be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed.
  • the syngas may, for example, be made from gas such as natural gas or other gaseous hydrocarbons by steam reforming, when the basestock may be referred to as gas-to-liquid (“GTL”) base oil; or from gasification of biomass, when the basestock may be referred to as biomass-to-liquid (“BTL” or “BMTL”) base oil; or from gasification of coal, when the basestock may be referred to as coal-to-liquid (“CTL”) base oil.
  • GTL gas-to-liquid
  • BTL biomass-to-liquid
  • CTL coal-to-liquid
  • the oil of lubricating viscosity in this invention contains 50 mass % or more of said basestocks. It may contain 60, such as 70, 80 or 90, mass % or more of said basestock or a mixture thereof.
  • the oil of lubricating viscosity may be substantially all of said basestock or a mixture thereof.
  • a detergent is an additive that is based on compounds comprising a polar moeity and a hydrophobic tail, sometimes referred to as surfactants. If the polar moeity of the surfactant is acidic then it can optionally be neutralised in the presence of a metal base to form detergents comprising metal salts.
  • a metal base Large amounts of a metal base are optionally included by reacting an excess of a metal compound, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide to give an overbased detergent which comprises neutralised surfactant as the outer layer of a metal base (e.g. carbonate) micelle.
  • a metal compound such as an oxide or hydroxide
  • an acidic gas such as carbon dioxide
  • the detergent may be a surfactant, partially neutralised surfactant, fully neutralised surfactant or overbased neutralised surfactant.
  • the detergent is preferably an alkali metal or alkaline earth metal additive such as a neutral or overbased oil-soluble or oil-dispersible calcium, magnesium, sodium or barium salt of a phenol, wherein any overbasing is provided by an oil-insoluble salt of the metal, e.g. carbonate, basic carbonate, acetate, formate, hydroxide or oxalate, which is stabilized in an oleaginous diluent by the oil-soluble salt of the surfactant.
  • the metal is calcium.
  • the TBN of the detergent may be low, i.e. less than 50 mg KOH/g, medium, i.e. 50 to 150 mg KOH/g, or high, i.e. over 150 mg KOH/g, on an active ingredients basis as determined by ASTM D2896.
  • the sulfurised alkylphenol detergent additive may have been oxyalkylated by reaction with 10 to 50, such as 15 to 40 or 20 to 30, % by mass of an alkylene carbonate relative to the detergent additive on an active ingredients basis.
  • the TBN of the lubricant is preferably in the range of 5 to 160, and the total detergent concentration in the additive package is preferably from greater than 50 up to 99, such as 60 to 98 or 70 to 95, as a percentage by mass of the total active ingredient.
  • the lubricant may further comprise an overbased sulfonate (preferably calcium) detergent, for example having a TBN in the range of 250 to 800 on an active ingredients basis and, for example, in a concentration of 20 to 95, such as 30 to 90 or 40 to 85, % as a percentage by mass of the total active ingredient.
  • an overbased sulfonate (preferably calcium) detergent for example having a TBN in the range of 250 to 800 on an active ingredients basis and, for example, in a concentration of 20 to 95, such as 30 to 90 or 40 to 85, % as a percentage by mass of the total active ingredient.
  • the lubricant may further comprise a non-sulfurized oxyalkylated alkylphenol such as in a concentration of 0.01 to 10% as a percentage by mass of the total active ingredient.
  • the lubricant may further comprise a borated or non-borated dispersant additive, such as a polyalkenyl succinimide.
  • the invention is applicable to lubricants for a range of internal combustion engines (spark-ignited or compression-ignited) such as motor vehicle engines and marine engines. Of the latter, there may be mentioned two-stroke marine diesel cross-head engines and marine trunk piston engines.
  • Cross-head engines are slow engines with a high to very high power range. They include two separately-lubricated parts: the piston/cylinder assembly lubricated, with total-loss lubrication, by a highly viscous oil (an MDCL); and the crankshaft lubricated by a less viscous lubricant, usually referred to as a system oil.
  • the MDCL lubricates the inner walls of the engine cylinder and the piston ring pack.
  • Marine cylinder lubricants are routinely formulated with high base number metal detergents as the main additive constituents to neutralise the acid produced from the high sulfur fuels used in operation of the engines.
  • a dispersant is an additive whose primary function is to hold solid and liquid contaminations in suspension, thereby passivating them and reducing engine deposits at the same time as reducing sludge depositions.
  • a dispersant maintains in suspension oil-insoluble substances that result from oxidation during use of the lubricant, thus preventing sludge flocculation and precipitation or deposition on metal parts of the engine.
  • Dispersants are usually "ashless", being non-metallic organic materials that form substantially no ash on combustion. They comprise a long hydrocarbon chain with a polar head, the polarity being derived from inclusion of e.g. an O, P, or N atom.
  • the hydrocarbon is an oleophilic group that confers oil-solubility, having, for example 40 to 500 carbon atoms.
  • ashless dispersants may comprise an oil-soluble polymeric backbone.
  • a preferred class of olefin polymers is constituted by polybutenes, specifically polyisobutenes (PIB) or poly-n-butenes, such as may be prepared by polymerization of a C 4 refinery stream.
  • PIB polyisobutenes
  • poly-n-butenes such as may be prepared by polymerization of a C 4 refinery stream.
  • Dispersants include, for example, derivatives of long chain hydrocarbon-substituted carboxylic acids, examples being derivatives of high molecular weight hydrocarbyl-substituted succinic acid.
  • a noteworthy group of dispersants is constituted by hydrocarbon-substituted succinimides, made, for example, by reacting the above acids (or derivatives) with a nitrogen-containing compound, advantageously a polyalkylene polyamine, such as a polyethylene polyamine.
  • reaction products of polyalkylene polyamines with alkenyl succinic anhydrides such as described in US-A-3,202,678 ; - 3,154,560 ; - 3,172,892 ; - 3,024,195 ; - 3,024,237 , - 3,219,666 ; and - 3,216,936 .
  • Hydrocarbon-substituted succinimides such as those described above may be post-treated to improve their properties, such as through boration (as described in USA-3,087,936 and - 3,254,025 ).
  • boration may be accomplished by treating an acyl nitrogen-containing dispersant with a boron compound selected from boron oxide, boron halides, boron acids and esters of boron acids.
  • Sulfonate detergents are metal salts and may contain a substantially stoichiometric amount of the metal when they are usually described as normal or neutral salts and would typically have a total base number or TBN (as may be measured by ASTM D2896) of from 0 to 80.
  • TBN total base number
  • Large amounts of a metal base can be included by reaction of an excess of a metal compound, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide.
  • the resulting overbased detergent comprises neutralised detergent as an outer layer of a metal base (e.g. carbonate) micelle.
  • Such overbased sulfonate detergents may have a TBN of 150 or greater, and typically of from 250 to 800 or more on an active ingredient basis.
  • Sulfonate detergents that may be used include oil-soluble neutral and overbased sulfonates of a metal, particularly the alkali or alkaline earth metals, e.g. sodium, potassium, lithium, calcium and magnesium.
  • a metal particularly the alkali or alkaline earth metals, e.g. sodium, potassium, lithium, calcium and magnesium.
  • the most commonly-used metals are calcium and magnesium, which may both be present in detergents used in a lubricant.
  • Sulfonate Detergent A is an overbased calcium sulfonate detergent. It is characterised by a TBN of 500 - 600 on an active ingredients basis.
  • Sulfonate Detergent B is an overbased calcium sulfonate detergent. It is characterised by a TBN of 650 to 750 on an active ingredients basis.
  • Phenate Detergent A is an overbased sulfurized calcium phenate detergent derived from tetrapropenylphenol.
  • the detergent is synthesised according to well established single stage methods (i.e. sulfurization and overbasing stages are conducted simultaneously as described in EP 2682451 B1 ). It is characterised by a TBN of 400 to 450 on an active ingredients basis.
  • Phenate Detergent B is an overbased sulfurized calcium phenate detergent derived from tetrapropenylphenol.
  • the detergent is synthesised according to well established two stage methods (i.e. sulfurization and overbasing stages are conducted independently as described in EP 2682451 B1 and US 3,801,507 ). It has the same generalised structure as Phenate Detergent A. It is characterised by a TBN of 375 to 425 on an active ingredients basis.
  • Capped Phenate Detergent B is derived from Phenate Detergent B described above, which has been subsequently oxyalkylated by reaction with 10 to 50, such as 15 to 40 or 20 to 30, % by mass of an alkylene carbonate relative to the detergent additive on an active ingredients basis. It is characterised by a TBN of 325 to 375 on an active ingredients basis.
  • ZDDPs zinc dialkyl dithiophosphates
  • ZDDPs may be prepared in accordance with known techniques by first forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohols or a phenol with P 2 S 5 , and then neutralising the formed DDPA with a zinc compound.
  • DDPA dihydrocarbyl dithiophosphoric acid
  • a dithiophosphoric acid may be made by reaction with mixtures of primary and secondary alcohols.
  • multiple dithiophosphoric acids can be prepared where the hydrocarbyl groups on one acid are entirely secondary in character and the hydrocarbyl groups on the other acids are entirely primary in character.
  • any basic or neutral zinc compound could be used but the oxides, hydroxides and carbonates are most generally employed.
  • Commercial additives frequently contain an excess of zinc due to use of an excess of the basic zinc compound in the neutralisation reaction.
  • Two sets of MDCL formulations were prepared by blending various selections of the above components.
  • Each formulation in set 3 contained 3.920g of borated dispersant, 21.000g of Sulfonate Detergent A, and 0.280g of a wear inhibitor.
  • Reference formulation 3' contained 2.380g of Phenate Detergent A and had a package total of 28.00g; reference formulation 3" contained 2.290g of Phenate Detergent B and had a package total of 27.91g; invention (Inventive example) formulation 3 contained 2.540g of Capped Phenate Detergent B and had a package total of 28.16g.
  • Each formulation in set 4 contained 1.013g of non-borated dispersant and 11.152g of Sulfonate Detergent B.
  • Reference formulation 4' contained 9.127g of Phenate Detergent A and had a package total of 21.80g; reference formulation 4" contained 8.790g of Phenate Detergent B and had a package total of 21.46g;
  • invention (Inventive example) formulation 4 contained 9.730g of Capped Phenate Detergent B and a package total of 22.40g.
  • the HT-HFRR rig is run at elevated temperatures and the friction coefficient (Fc) is recorded.
  • the friction co-efficient decreases with increasing temperature due to the viscosity decrease of the MDCL, until a temperature at which oil film break-down begins and the friction coefficient (Fc) starts to increase with increasing temperature.

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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)

Claims (14)

  1. Utilisation d'un additif détergent alkyphénol sulfuré alcoxylé dans un lubrifiant pour moteur à combustion interne pour permettre le contrôle et/ou l'amélioration de la performance d'usure du lubrifiant.
  2. Utilisation selon la revendication 1, dans laquelle l'additif détergent a été alcoxylé par réaction avec 10 à 50, tels que 15 à 40, ou 20 à 30, % en masse d'un carbonate d'alkylène par rapport à l'additif détergent sur la base des ingrédients actifs.
  3. Utilisation selon la revendication 2, dans laquelle le carbonate d'alkylène est le carbonate d'éthylène, le carbonate de propylène ou le carbonate de butylène.
  4. Utilisation selon l'une quelconque des revendications 1 à 3, dans laquelle le détergent, s'il est neutralisé, partiellement neutralisé ou surbasique, comprend un métal alcalin ou alcalino-terreux, de préférence le calcium.
  5. Utilisation selon l'une quelconque des revendications 1 à 4, dans laquelle les groupes alcoxy répondent à la formule

            -(R'O)n-

    dans laquelle R' est l'éthylène, le propylène ou le butylène, et n vaut indépendamment 1 à 10.
  6. Utilisation selon l'une quelconque des revendications 1 à 5, dans laquelle les groupes phényle de l'alkylphénol sont substitués par un ou plusieurs groupes hydrocarbyle ayant 9 à 100, de préférence 9 à 70 ou 9 à 50, atomes de carbone.
  7. Utilisation selon l'une quelconque des revendications 1 à 6, dans laquelle le lubrifiant est un lubrifiant pour cylindre pour moteur diésel marin.
  8. Utilisation selon la revendication 7, dans laquelle le lubrifiant lubrifie les parois internes et l'ensemble de segments de piston du cylindre de moteur.
  9. Utilisation selon l'une quelconque des revendications 7 et 8, dans laquelle la valeur TBN du lubrifiant est située dans la plage allant de 5 à 160.
  10. Utilisation selon l'une quelconque des revendications 1 à 6, dans laquelle le lubrifiant comprend en outre un détergent surbasique sulfonate, de préférence de calcium.
  11. Utilisation selon la revendication 10, dans laquelle le détergent sulfonate a une valeur TBN située dans la plage allant de 250 à 800 sur la base des ingrédients actifs.
  12. Utilisation selon l'une quelconque des revendications 7 à 9, dans laquelle le lubrifiant comprend en outre un détergent surbasique sulfonate, de préférence de calcium, ayant une valeur TBN située dans la plage allant de 250 à 800 sur la base des ingrédients actifs, et à une concentration de 20 à 95, tels que 30 à 90, ou 40 à 85 %, en tant que pourcentage en masse du total des ingrédients actifs.
  13. Utilisation selon l'une quelconque des revendications 1 à 12, dans laquelle le lubrifiant comprend en outre un alkylphénol alcoxylé non sulfuré, tel qu'à une concentration de 0,01 à 10 % en tant que pourcentage en masse du total des ingrédients actifs.
  14. Utilisation selon l'une quelconque des revendications 1 à 13, dans laquelle le lubrifiant comprend en outre un additif dispersant boré ou non boré, tel qu'un polyalcényl-succinimide.
EP18195639.2A 2017-10-16 2018-09-20 Utilisation des détergents dans les huiles lubrifiantes de moteur à combustion interne Active EP3470499B1 (fr)

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Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1248643B (de) 1959-03-30 1967-08-31 The Lubrizol Corporation, Cleveland, Ohio (V. St. A.) Verfahren zur Herstellung von öllöslichen aeylierten Aminen
NL124842C (fr) 1959-08-24
NL255193A (fr) 1959-08-24
US3087936A (en) 1961-08-18 1963-04-30 Lubrizol Corp Reaction product of an aliphatic olefinpolymer-succinic acid producing compound with an amine and reacting the resulting product with a boron compound
US3154560A (en) 1961-12-04 1964-10-27 Monsanto Co Nu, nu'-azaalkylene-bis
US3216936A (en) 1964-03-02 1965-11-09 Lubrizol Corp Process of preparing lubricant additives
US3801507A (en) 1972-08-18 1974-04-02 Chevron Res Sulfurized metal phenates
GB9611318D0 (en) * 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
CN102690709B (zh) * 2011-03-24 2013-12-25 中国石油化工股份有限公司 一种燃气发动机润滑油组合物
GB2498635A (en) * 2011-12-21 2013-07-24 Infineum Int Ltd A method of reducing the rate of depletion of basicity of a lubricating oil composition for use in an engine
EP2719751B1 (fr) 2012-06-07 2021-03-31 Infineum International Limited Lubrification de moteur marin
EP2682451B1 (fr) 2012-07-06 2015-11-18 Infineum International Limited Modification de détergent
US20140360451A1 (en) * 2013-06-06 2014-12-11 James C. Dodd Marine Engine Lubrication
EP3390591A1 (fr) * 2015-12-15 2018-10-24 The Lubrizol Corporation Détergents de catécholate sulfuré pour compositions lubrifiantes

Non-Patent Citations (1)

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Title
None *

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JP2019073703A (ja) 2019-05-16
EP3470499A1 (fr) 2019-04-17
CN109666525B (zh) 2022-05-17

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