EP3470499B1 - Verwendung von detergentien in schmiermitteln für verbrennungsmotoren - Google Patents

Verwendung von detergentien in schmiermitteln für verbrennungsmotoren Download PDF

Info

Publication number
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
Authority
EP
European Patent Office
Prior art keywords
detergent
lubricant
active ingredient
mass
tbn
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
EP18195639.2A
Other languages
English (en)
French (fr)
Other versions
EP3470499A1 (de
Inventor
Alexander Coxon
Alastair Cant
Malgorzata Maranska
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.)
Infineum International Ltd
Original Assignee
Infineum International Ltd
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 Infineum International Ltd filed Critical Infineum International Ltd
Publication of EP3470499A1 publication Critical patent/EP3470499A1/de
Application granted granted Critical
Publication of EP3470499B1 publication Critical patent/EP3470499B1/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
    • 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.

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 (14)

  1. Verwendung von oxyalkyliertem sulfurierten Alkylphenoldetergensadditiv in einem Verbrennungsmotorschmiermittel, um Steuerung und/oder Verbesserung der Verschleißleistung des Schmiermittels bereitzustellen.
  2. Verwendung nach Anspruch 1, bei der das Detergensadditiv durch Umsetzung von 10 bis 50, wie 15 bis 40 oder 20 bis 30, Masse-% Alkylencarbonat oxyalkyliert worden ist, bezogen auf aktiven Bestandteil des Detergensadditivs.
  3. Verwendung nach Anspruch 2, bei der das Alkylencarbonat Ethylencarbonat, Propylencarbonat oder Butylencarbonat ist.
  4. Verwendung nach einem der Ansprüche 1 bis 3, bei der das Detergens, falls es neutralisiert, teilweise neutralisiert oder überbasisch ist, ein Alkali- oder Erdalkalimetall umfasst, vorzugsweise Calcium.
  5. Verwendung nach einem der Ansprüche 1 bis 4, bei der die Oxyalkylgruppen die Formel

            -(R'O)n-

    aufweisen, in der R' Ethylen, Propylen, oder Butylen ist und n unabhängig von 1 bis 10 beträgt.
  6. Verwendung nach einem der Ansprüche 1 bis 5, bei der die Phenylgruppen des Alkylphenols mit einer oder mehreren Kohlenwasserstoffgruppen substituiert sind, die 9 bis 100, vorzugsweise 9 bis 70 oder 9 bis 50 Kohlenstoffatome aufweisen.
  7. Verwendung nach einem der Ansprüche 1 bis 6, bei der das Schmiermittel ein Schmiermittel für einen Zylinder eines Schiffsdiesels ist.
  8. Verwendung nach Anspruch 7, bei der das Schmiermittel die inneren Wände und das Kolbenringpaket des Motorzylinders schmiert.
  9. Verwendung nach einem der Ansprüche 7 und 8, bei der die Gesamtbasenzahl (TBN) des Schmiermittels im Bereich von 5 bis 160 liegt.
  10. Verwendung nach einem der Ansprüche 1 bis 6, bei der das Schmiermittel ferner überbasisches Sulfonatdetergens umfasst, vorzugsweise überbasisches Calciumsulfonatdetergens.
  11. Verwendung nach Anspruch 10, bei dem das Sulfonatdetergens eine TBN im Bereich von 250 bis 800 aufweist, bezogen auf aktiven Bestandteil.
  12. Verwendung nach einem der Ansprüche 7 bis 9, bei der das Schmiermittel ferner überbasisches Sulfonatdetergens, vorzugsweise überbasisches Calciumsulfonatdetergens aufweist, das eine TBN im Bereich von 250 bis 800 aufweist, bezogen auf aktiven Bestandteil, und in einer Konzentration von 20 bis 95, wie 30 bis 90 oder 40 bis 85, % als Prozentsatz bezogen auf die Masse an gesamten aktiven Bestandteil.
  13. Verwendung nach einem der Ansprüche 1 bis 12, bei der das Schmiermittel ferner nichtsulfuriertes oxyalkyliertes Alkylphenol umfasst, wie in einer Konzentration von 0,01 bis 10%, als Prozentsatz bezogen auf die Masse an gesamten aktiven Bestandteil.
  14. Verwendung nach einem der Ansprüche 1 bis 13, bei der das Schmiermittel ferner boriertes oder nichtboriertes Dispergiermitteladditiv umfasst, wie Polyalkenylsuccinimid.
EP18195639.2A 2017-10-16 2018-09-20 Verwendung von detergentien in schmiermitteln für verbrennungsmotoren Active EP3470499B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP17196562 2017-10-16

Publications (2)

Publication Number Publication Date
EP3470499A1 EP3470499A1 (de) 2019-04-17
EP3470499B1 true EP3470499B1 (de) 2021-01-13

Family

ID=60117569

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18195639.2A Active EP3470499B1 (de) 2017-10-16 2018-09-20 Verwendung von detergentien in schmiermitteln für verbrennungsmotoren

Country Status (3)

Country Link
EP (1) EP3470499B1 (de)
JP (1) JP2019073703A (de)
CN (1) CN109666525B (de)

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 (de) 1959-08-24
NL255193A (de) 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 (de) 2012-06-07 2021-03-31 Infineum International Limited Schmierung für einen Schiffsmotor
EP2682451B1 (de) * 2012-07-06 2015-11-18 Infineum International Limited Detergensmodifizierung
US20140360451A1 (en) * 2013-06-06 2014-12-11 James C. Dodd Marine Engine Lubrication
CA3007127A1 (en) * 2015-12-15 2017-06-22 The Lubrizol Corporation Sulfurized catecholate detergents for lubricating compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
JP2019073703A (ja) 2019-05-16
EP3470499A1 (de) 2019-04-17
CN109666525A (zh) 2019-04-23
CN109666525B (zh) 2022-05-17

Similar Documents

Publication Publication Date Title
CA2686115C (en) Overbased metal hydroxybenzoate detergent
US9347019B2 (en) Lubricating oil composition
US11142719B2 (en) Lubricating oil composition
EP2913384B1 (de) Schmierölzusammensetzung
US9109182B2 (en) Lubricating oil composition
EP2371932B1 (de) Schmierölzusammensetzung
US10167440B2 (en) Marine engine lubrication
EP2290038B1 (de) Schmierölzusammensetzung
CA2799378A1 (en) A method of reducing the rate of depletion of basicity of a lubricating oil composition in an engine
EP3378924B1 (de) Schiffsmotorschmierung
EP3470499B1 (de) Verwendung von detergentien in schmiermitteln für verbrennungsmotoren
EP3018191A1 (de) Schmierung für einen Schiffsmotor

Legal Events

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

Free format text: STATUS: EXAMINATION IS IN PROGRESS

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

17P Request for examination filed

Effective date: 20180920

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

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

INTG Intention to grant announced

Effective date: 20201007

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: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602018011782

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1354569

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210215

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1354569

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210113

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

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

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: 20210113

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: 20210413

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: 20210513

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: 20210113

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: 20210414

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: 20210113

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: 20210413

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

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: 20210113

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: 20210113

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: 20210113

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: 20210113

Ref country code: SE

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: 20210113

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

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: 20210513

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602018011782

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: 20210113

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: 20210113

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: 20210113

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: DK

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: 20210113

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: 20210113

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: 20210113

26N No opposition filed

Effective date: 20211014

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

Ref country code: ES

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: 20210113

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: 20210113

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: 20210113

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20210930

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

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: 20210513

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: 20210113

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: 20210920

Ref country code: IE

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

Effective date: 20210920

Ref country code: FR

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

Effective date: 20210930

Ref country code: BE

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

Effective date: 20210930

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: 20210930

Ref country code: CH

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

Effective date: 20210930

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: 20210113

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: 20180920

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

Ref country code: IT

Payment date: 20230912

Year of fee payment: 6

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: 20210113

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

Ref country code: NL

Payment date: 20240813

Year of fee payment: 7

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: 20210113

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

Ref country code: DE

Payment date: 20240808

Year of fee payment: 7

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

Ref country code: GB

Payment date: 20240808

Year of fee payment: 7