WO2020260569A1 - Lubricant composition for preventing corrosion and/or tribo-corrosion of metal parts in an engine - Google Patents

Lubricant composition for preventing corrosion and/or tribo-corrosion of metal parts in an engine Download PDF

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Publication number
WO2020260569A1
WO2020260569A1 PCT/EP2020/068004 EP2020068004W WO2020260569A1 WO 2020260569 A1 WO2020260569 A1 WO 2020260569A1 EP 2020068004 W EP2020068004 W EP 2020068004W WO 2020260569 A1 WO2020260569 A1 WO 2020260569A1
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Prior art keywords
engine
carbon atoms
corrosion
lubricating composition
weight
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PCT/EP2020/068004
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French (fr)
Inventor
Anne Neville
Erfan ABEDI ESFAHANI
Ardian MORINA
Catherine AMBLARD
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Total Marketing Services
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Priority to US17/619,486 priority Critical patent/US20220411712A1/en
Application filed by Total Marketing Services filed Critical Total Marketing Services
Priority to CN202080047734.9A priority patent/CN114364771A/en
Priority to EP20734060.5A priority patent/EP3990589A1/en
Priority to KR1020227003474A priority patent/KR20220050132A/en
Priority to JP2021577877A priority patent/JP2022538645A/en
Publication of WO2020260569A1 publication Critical patent/WO2020260569A1/en

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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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/38—Heterocyclic nitrogen compounds
    • C10M133/44—Five-membered ring containing nitrogen and carbon only
    • C10M133/46—Imidazoles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/38—Heterocyclic nitrogen compounds
    • C10M133/44—Five-membered ring containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C10M133/58—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • C10M2215/224—Imidazoles
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/30—Heterocyclic compounds
    • C10M2215/305—Heterocyclic compounds 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
    • 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
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • 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

Definitions

  • TITLE Lubricating composition to prevent corrosion and / or tribocorrosion of metal parts in an engine
  • the present invention relates to novel lubricating compositions, in particular for engines, in particular useful for preventing corrosion and / or tribocorrosion of metal parts in an engine, and in particular in a two-stroke engine, such as a two-stroke marine engine.
  • the present invention also relates to a method of passivation of metal parts of an engine, in particular of a two-stroke engine, such as a two-stroke marine engine.
  • SO 3 sulfur oxides
  • H 2 SO 4 sulfuric acid
  • Other acids such as nitric acid, compounds bearing one or more carboxylic acid functions, or combinations of these acids, can also be responsible for the corrosion and / or tribocorrosion of engine parts.
  • Acid corrosion occurs in the tribological system in the segment-piston-liner area. In this area, on a lubricated engine, the friction observed is of the reciprocating slip type.
  • cylinder oils which provide lubrication of the piston-cylinder assembly
  • system oils which provide lubrication of the piston-cylinder assembly. all moving parts other than those of the piston-cylinder assembly.
  • the lubricating compositions for engines, and in particular for marine engines, currently used comprise a base oil to which dispersants and overbased detergents are added.
  • These overbased detergents generally comprise a core of CaCC> 3 calcium carbonate coated with a layer of surfactant. Calcium carbonate reacts with sulfuric acid to form, in particular, calcium sulphate (CaSC> 4). The decrease in sulfuric acid in the medium allows parts to be protected against corrosion and / or tribocorrosion.
  • the lubricating compositions used must be sufficiently basic (in particular to neutralize the acid), which implies increasing the amount of detergents included in these compositions.
  • BN Basicity Indexes
  • the increase in the amount of detergents in these lubricating compositions leads to an increase in the number of particles of CaCC> 3 and CaSC responsible for the wear of the surfaces by polishing (or abrasive wear) of the metal parts of the engine, and in particular of the parts.
  • two-stroke engine cylinders such as two-stroke marine engines.
  • the use of the lubricating compositions currently available does not completely protect the metal parts of the engine from corrosion and / or tribocorrosion, and in particular the metal parts of the two-stroke engine against tribocorrosion, when the friction is of reciprocating slip type.
  • An objective of the present invention is to provide lubricating compositions making it possible to improve the protection of the metal parts of an engine, typically of a two-stroke engine, in particular of a two-stroke marine engine, against corrosion and / or tribocorrosion.
  • the present invention relates more particularly to the supply of cylinder oils for two-stroke engines, in particular for two-stroke marine engines.
  • Another objective of the present invention is to provide lubricating compositions exhibiting a reduced Basicity Index.
  • R 1 represents an alkyl group, linear or branched, comprising from 1 to 16 carbon atoms, preferably from 1 to 12 carbon atoms, advantageously from 2 to 8 carbon atoms, optionally substituted at the end of the chain by a group chosen from among NH 2 , OH or SH, or R 1 represents an alkenyl group, linear or branched, comprising from 2 to 16 carbon atoms, preferably from 2 to 12 carbon atoms, advantageously from 2 to 8 carbon atoms, optionally end-substituted chain with a group chosen from NH 2 , OH or SH.
  • R 1 represents an alkyl or alkenyl group, linear or branched, comprising from 2 to 8 carbon atoms, preferably from 2 to 6 carbon atoms, advantageously from 2 to 4 carbon atoms and being substituted at the end of the chain by the -NH 2 group.
  • R 2 represents an alkyl group, linear or branched, comprising from 1 to 36 carbon atoms, preferably from 4 to 28 carbon atoms, advantageously from 8 to 24 carbon atoms, or R 2 represents an alkenyl group, linear or branched , comprising from 2 to 36 carbon atoms, preferably from 4 to 28 carbon atoms, advantageously from 8 to 24 carbon atoms.
  • R 1 represents an alkyl group, linear or branched, comprising from 1 to 12 carbon atoms, preferably from 2 to 8 carbon atoms, more preferably from 2 to 6 carbon atoms or even from 2 to 4 carbon atoms, said R 1 group being preferably substituted at the end of the alkyl chain by an -NH 2 group; and or
  • R 2 represents an alkyl or alkenyl group, linear or branched, comprising from 4 to 28 carbon atoms, preferably from 8 to 24 carbon atoms.
  • R 2 represents an alkenyl group, linear or branched, comprising from 4 to 28 carbon atoms, preferably from 8 to 24 carbon atoms.
  • the R 2 group represents an alkenyl group comprising at least one double bond.
  • said double bond is located at C-8, C-9 of the alkenyl group relative to the imidazoline function.
  • the base oil included in the lubricating composition is chosen from oils of mineral, synthetic or vegetable origin as well as their mixtures.
  • the mineral or synthetic oils generally used in the application belong to one of the classes defined in the API classification as summarized in the table below.
  • Group 1 mineral oils can be obtained by distillation of selected naphthenic or paraffinic crudes, followed by purification of these distillates by processes such as solvent extraction, solvent or catalytic dewaxing, hydrotreatment or hydrogenation.
  • Group 2 and 3 oils are obtained by more stringent purification processes, for example a combination of hydrotreatment, hydrocracking, hydrogenation and catalytic dewaxing.
  • Group 4 and 5 synthetic bases include poly-alphas olefins, polybutenes, polyisobutenes, alkylbenzenes.
  • base oils can be used alone or as a mixture.
  • Mineral oil can be combined with synthetic oil.
  • Cylinder oils for 2-stroke marine diesel engines have a viscosimetric grade SAE-40 to SAE-60, generally SAE-50 equivalent to a kinematic viscosity at 100 ° C between 16.3 and 21 .9 mm 2 / s.
  • Grade 40 oils have a kinematic viscosity at 100 ° C of between 12.5 and 16.3 mm 2 / s.
  • Grade 50 oils have a kinematic viscosity at 100 ° C of between 16.3 and 21.9 mm 2 / s.
  • Grade 60 oils have a kinematic viscosity at 100 ° C of between 21.9 and 26.1 mm 2 / s.
  • cylinder oils for two-stroke marine diesel engines having a kinematic viscosity at 100 ° C. of between 18 and 21.5, preferably between 19 and 21.5 mm 2 / s.
  • This viscosity can be obtained by mixing additives and base oils, for example containing Group 1 mineral bases such as Neutral Solvent bases (for example 500 NS or 600 NS) and Brightstock. Any other combination mineral, synthetic or vegetable bases having, mixed with the additives, a viscosity compatible with the SAE-50 grade can be used.
  • Group 1 mineral bases such as Neutral Solvent bases (for example 500 NS or 600 NS) and Brightstock. Any other combination mineral, synthetic or vegetable bases having, mixed with the additives, a viscosity compatible with the SAE-50 grade can be used.
  • a conventional formulation of cylinder lubricant for slow 2-stroke marine diesel engines is of grade SAE-40 to SAE-60, preferably SAE-50 (according to the SAE J300 classification) and comprises at least 50% by mass of oil of lubricating base of mineral and / or synthetic origin, suitable for use in marine engines, for example, API Group 1 class, i.e. obtained by distillation of selected crudes followed by the purification of these distillates by processes such as solvent extraction, solvent or catalytic dewaxing, hydrotreatment or hydrogenation.
  • Their Viscosity Index (VI) is between 80 and 120; their sulfur content is greater than 0.03% and their saturated content is less than 90%.
  • the lubricating composition according to the invention comprises at least 50% by mass of base oil (s) relative to the total mass of the composition.
  • the lubricating composition according to the invention comprises at least 60% by mass, or even at least 70% by mass, of base oil (s) relative to the total mass of the composition.
  • the lubricating composition according to the invention comprises from 60 to 99.9% by mass of base oils, preferably from 70 to 98% by mass of base oils, relative to the total mass. of the composition.
  • the lubricating composition according to the invention further comprises at least one additive chosen from detergents, dispersants and mixtures thereof.
  • the detergents used in the lubricating compositions according to the present invention are well known to those skilled in the art.
  • the detergents commonly used in the formulation of lubricating compositions are anionic compounds comprising a long lipophilic hydrocarbon chain and a hydrophilic head.
  • the associated cation is a metallic cation of an alkali or alkaline earth metal.
  • the detergents are preferably chosen from alkali metal or alkaline-earth metal salts of carboxylic acids, sulphonates, salicylates, naphthenates, as well as salts of phenates.
  • the alkali metals and alkaline earth metals are preferably calcium, magnesium, sodium or barium. These metal salts can contain the metal in an approximately stoichiometric amount. In this case, we speak of non-overbased or "neutral” detergents, although they also provide a certain basicity. These “neutral” detergents typically have a BN, measured according to ASTM D2896, less than 150 mg KOH / g, or less than 100, or even less than 80 mg KOH / g.
  • neutral detergents can partly contribute to the BN of the lubricants according to the present invention.
  • BN is high, for example greater than 150 mg KOH / g, typically between 200 and 700 mg KOH / g, generally between 250 and 450 mg KOH / g.
  • the excess metal providing the overbased character to the detergent is in the form of metal salts insoluble in oil, for example carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate.
  • the metals of these insoluble salts may be the same as those of the oil soluble detergents or they may be different. They are preferably chosen from calcium, magnesium, sodium or barium.
  • the overbased detergents are thus in the form of micelles composed of insoluble metal salts held in suspension in the lubricating composition by the detergents in the form of oil-soluble metal salts.
  • Overbased detergents comprising a single type of detergent soluble metal salt will generally be named after the nature of the hydrophobic chain of the latter detergent.
  • overbased detergents will be said to be of mixed type if the micelles comprise several types of detergents, which differ from one another by the nature of their hydrophobic chain.
  • the oil-soluble metal salts will preferably be carboxylates, phenates, sulfonates, salicylates, and mixed phenate - sulfonate and / or salicylate detergents of calcium, magnesium, sodium or barium.
  • the insoluble metal salts providing the overbased character are carbonates of alkali metals and alkaline earth metals, preferably calcium carbonate.
  • the detergents used in the lubricating compositions according to the present invention are detergents overbased on calcium carbonate chosen from carboxylates, phenates, sulphonates, salicylates and mixed phenates - sulphonates - salicylates detergents.
  • the lubricating composition according to the invention can comprise from 3 to 40%, preferably from 5% to 30%, advantageously from 10% to 25% by mass of detergent (s) relative to the total mass of the composition lubricant.
  • Dispersants are well known additives used in the formulation of lubricating compositions, in particular for application in the marine field. Their primary role is to maintain in suspension the particles initially present or appearing in the lubricating composition during its use in the engine. They prevent their agglomeration by playing on steric hindrance. They can also exhibit a synergistic effect on neutralization.
  • the dispersants used as lubricant additives contain a polar group, associated with a relatively long hydrocarbon chain, generally containing from 50 to 400 carbon atoms.
  • the polar group typically contains at least one nitrogen or oxygen element.
  • the compounds derived from succinic acid are dispersants that are particularly used as lubricating additives.
  • succinimides obtained by condensation of succinic anhydrides and amines
  • succinic esters obtained by condensation of succinic anhydrides and alcohols or polyols are used.
  • These compounds can then be treated with various compounds, including sulfur, oxygen, formaldehyde, carboxylic acids and compounds containing boron or zinc to produce, for example, borated succinimides or zinc blocked succinimides.
  • Mannich bases obtained by polycondensation of phenols substituted with alkyl groups, formaldehyde and primary or secondary amines, are also compounds used as dispersants in lubricants.
  • the dispersants according to the invention are chosen from succinimides, such as polyisobutylene bis-succinimides, optionally borated or blocked with zinc.
  • the lubricating composition according to the invention may comprise from 0.01 to 10%, preferably from 0.1% to 5%, advantageously from 0.5% to 3% by mass of dispersant (s) relative to the total mass of the lubricating composition.
  • the lubricating composition can also comprise at least one antiwear additive.
  • the antiwear additive is zinc di-thiophosphate or DTPZn.
  • DTPZn zinc di-thiophosphate
  • these categories are also found various phosphorus, sulfur, nitrogen, chlorine and boron compounds.
  • antiwear additives there is a wide variety of antiwear additives, but the most widely used category is that of phospho-sulfur additives such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates or DTPZn.
  • phospho-sulfur additives such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates or DTPZn.
  • Amine phosphates, polysulfides, especially sulfur olefins, are also commonly used anti-wear additives.
  • antiwear and extreme pressure additives of nitrogenous and sulfur type are also usually encountered, such as for example metal dithiocarbamates, in particular molybdenum dithiocarbamate.
  • Glycerol esters are also antiwear additives. Mention may be made, for example, of mono, di- and trioleates, monopalmitates and monomyristates.
  • the lubricating composition comprises, relative to the total weight of the lubricating composition:
  • the lubricating composition comprises, relative to the total weight of the lubricating composition:
  • detergent optionally from 3 to 40% by weight, preferably from 5 to 30% by weight, more preferably from 10 to 25% by weight, of detergent (s).
  • the lubricating composition can also comprise all types of functional additives suitable for their use, for example anti-foam additives which can be, for example, polar polymers such as polymethylsiloxanes, polyacrylates, anti-oxidant additives, for example of the phenolic or amine type. and / or anti-rust additives, for example organometallic compounds or thiadiazoles. These are known to those skilled in the art.
  • anti-foam additives can be, for example, polar polymers such as polymethylsiloxanes, polyacrylates, anti-oxidant additives, for example of the phenolic or amine type.
  • anti-rust additives for example organometallic compounds or thiadiazoles.
  • the compound of formula (A) is the following compound (I):
  • the lubricating composition comprises, relative to the total weight of the lubricating composition: - from 50 to 96.9% by weight, preferably from 60 to 95% by weight, more preferably from 70 to 90% by weight, of base oil (s),
  • detergent (s) comprising at least one overbased detergent of phenate or sulphonate type
  • dispersant (s) optionally from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, more preferably from 0.5 to 3% by weight, of dispersant (s).
  • the lubricating composition comprises, relative to the total weight of the lubricating composition:
  • dispersant (s) chosen from succinimides, and
  • detergent optionally from 3 to 40% by weight, preferably from 5 to 30% by weight, more preferably from 10 to 25% by weight, of detergent (s).
  • the present invention also relates to the use of the lubricating composition according to the invention for the lubrication of at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine.
  • the use of the lubricating composition according to the invention makes it possible to prevent and / or reduce corrosion and / or tribocorrosion of said metal part of said engine.
  • the present invention also relates to a method of lubricating at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine, comprising bringing said part of an engine into contact. with the lubricating composition according to the invention.
  • the present invention also relates to the use of a compound of formula (A) according to the invention in a lubricating composition comprising at least one base oil for preventing and / or reducing corrosion and / or tribocorrosion of at least one.
  • metal part of an engine such as a two-stroke engine and in particular a two-stroke marine engine.
  • the present invention also relates to a method of preventing and / or reducing corrosion and / or tribocorrosion of at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine. time, comprising lubricating said metal part with a lubricating composition according to the invention.
  • the present invention also relates to the use of the lubricating composition according to the invention for the passivation of at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine.
  • the present invention also relates to a process for passivation of at least one metal part of an engine comprising at least one step of bringing said metal part into contact with the lubricating composition according to the invention.
  • the present invention also relates to the use of a compound of formula (A) according to the invention in a lubricating composition comprising at least one base oil for the passivation of at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine.
  • the metal part according to the invention is a cylinder or a piston.
  • the metal part is made of cast iron.
  • the engine according to the invention is a two-stroke engine.
  • the engine is a two-stroke marine engine.
  • the engine is an engine consuming heavy fuel oil.
  • heavy fuel oil is understood to mean the heavy cuts resulting from the distillation of petroleum, optionally containing additives.
  • the term “corrosion” means an alteration of a material, preferably metallic, by chemical reaction with an oxidant.
  • this oxidant is an acid.
  • this acid is sulfuric acid H2SO4.
  • titanium corrosion means a process leading to the degradation and wear of a metallic material under the combined action of friction and corrosion as defined above.
  • the compound of formula (A) defined in the present invention is used in a cylinder lubricating composition for reducing acid tribocorrosion on the cylinders and pistons of a two-stroke engine, such as a two-stroke marine engine. .
  • Figure 1 shows the depth profiles of the cast iron trays obtained after a tribological test conducted in the presence of the composition according to the invention CL and the comparative composition CC.
  • compositions of Table 2 (LC: lubricating composition according to the invention; CC: comparative lubricating composition) were prepared by mixing the dispersant and / or detergents and the additive in a base oil at 60 ° C.
  • the tribological tests were carried out on a reciprocating Biceri tribometer using steel rods (EN31) with a diameter of 6 mm and a radius of curvature of 50 mm, and cast iron plates (FT 25) polished with 800 grit sandpaper SiC.
  • the steel rods were also polished to obtain a roughness Ra of between 50 and 100 nm.
  • the areas of the cast iron plates outside the friction area have been covered with a resin. This resin is removed at the end of the tests. In this way, the areas covered by the resin are not corroded during the tests and serve as a standard for measuring the depth of wear marks due to corrosion phenomena.
  • the lubricating composition Before each test, the lubricating composition is heated to 100 ° C and brought into contact with a 5M sulfuric acid solution (27% by mass) at room temperature by means of a "T" assembly.
  • the lubricating composition arrives through the main channel and the acid solution is supplied through a channel perpendicular to the main channel.
  • the corrosion products are removed with an ethylenediaminetetraacetic acid (EDTA) solution, and the wear of the cast iron plates is analyzed by white light interferometry, which makes it possible to obtain a 3D profile of the wear scar produced by corrosion and / or tribocorrosion.
  • EDTA ethylenediaminetetraacetic acid
  • Figure 1 shows the depth profiles of the cast iron plates obtained after a tribological test as described above and carried out in the presence of the lubricating composition according to the invention CL, and of the comparative composition CC.

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  • General Chemical & Material Sciences (AREA)
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  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Inorganic Chemistry (AREA)

Abstract

Disclosed is a lubricant composition comprising: - at least one base oil; and - 0.1 to 30% by weight of an imidazoline compound of formula (A) which is defined such that: - R1 represents a linear or branched alkyl or alkenyl group comprising 1 to 16 carbon atoms, optionally substituted, at the end of the chain, by a group selected from among NH2, OH and SH; and - R2 represents a linear or branched alkyl or alkenyl group comprising 1 to 36 carbon atoms.

Description

TITRE : Composition lubrifiante pour prévenir la corrosion et/ou la tribocorrosion des pièces métalliques dans un moteur TITLE: Lubricating composition to prevent corrosion and / or tribocorrosion of metal parts in an engine
La présente invention concerne de nouvelles compositions lubrifiantes, notamment pour moteur, notamment utiles pour prévenir la corrosion et/ou la tribocorrosion des pièces métalliques dans un moteur, et notamment dans un moteur deux-temps, tel qu’un moteur marin deux-temps. La présente invention concerne également un procédé de passivation de pièces métalliques d’un moteur, notamment d’un moteur deux temps, tel qu’un moteur marin deux-temps. The present invention relates to novel lubricating compositions, in particular for engines, in particular useful for preventing corrosion and / or tribocorrosion of metal parts in an engine, and in particular in a two-stroke engine, such as a two-stroke marine engine. The present invention also relates to a method of passivation of metal parts of an engine, in particular of a two-stroke engine, such as a two-stroke marine engine.
Depuis 201 1 , la présence de corrosion excessive, voire incontrôlée, devient prépondérante lorsque les moteurs sont opérés à très faible charge (25% et moins de la charge maximale). Cette corrosion excessive est également présente avec les derniers designs moteurs existants car de plus en plus sévères. Même si dans un futur proche (2020), les taux de soufre des combustibles pour moteurs marins seront abaissés afin de respecter la réglementation (émissions de SOx), la problématique de corrosion reste entière pour de nombreux opérateurs de moteurs et plus particulièrement pour les moteurs deux-temps. Since 201 1, the presence of excessive corrosion, even uncontrolled, becomes preponderant when the engines are operated at very low load (25% and less of the maximum load). This excessive corrosion is also present with the latest existing engine designs because they are increasingly severe. Even if in the near future (2020), the sulfur levels in marine engine fuels will be lowered in order to comply with regulations (SOx emissions), the problem of corrosion remains unresolved for many engine operators and more particularly for engines. two-stroke.
La combustion des fiouls génère la formation de gaz acides, notamment des oxydes de soufre (SO3, formé par oxydation du SO2), qui sont en contact avec les pièces métalliques du moteur. En présence d’eau, SO3 s’hydrolyse en acide sulfurique H2SO4, responsable de la corrosion des pièces du moteur. D’autres acides, comme l’acide nitrique, les composés portant une ou plusieurs fonctions acide carboxylique, ou les combinaisons de ces acides, peuvent également être responsables de la corrosion et/ou la tribocorrosion des pièces du moteur. The combustion of fuel oils generates the formation of acid gases, in particular sulfur oxides (SO 3 , formed by oxidation of SO 2 ), which are in contact with the metal parts of the engine. In the presence of water, SO 3 hydrolyzes to sulfuric acid H 2 SO 4 , responsible for the corrosion of engine parts. Other acids, such as nitric acid, compounds bearing one or more carboxylic acid functions, or combinations of these acids, can also be responsible for the corrosion and / or tribocorrosion of engine parts.
La corrosion acide se situe dans le système tribologique dans la zone segment- piston-chemise. Dans cette zone, sur un moteur lubrifié, le frottement observé est du type glissement alternatif. Acid corrosion occurs in the tribological system in the segment-piston-liner area. In this area, on a lubricated engine, the friction observed is of the reciprocating slip type.
Dans le cas des moteurs marins, notamment les moteurs marins deux-temps, les compositions lubrifiantes sont classées en deux catégories : les huiles cylindre, qui assurent la lubrification de l’ensemble piston-cylindre, et les huiles système, qui assurent la lubrification de toutes les parties en mouvement autres que celles de l’ensemble piston-cylindre. Lorsque le moteur est en marche, l’huile cylindre est répandue sur le cylindre et forme un film fin et huileux entre le piston et la paroi du cylindre. Ce film joue trois rôles : In the case of marine engines, especially two-stroke marine engines, the lubricating compositions are classified into two categories: cylinder oils, which provide lubrication of the piston-cylinder assembly, and system oils, which provide lubrication of the piston-cylinder assembly. all moving parts other than those of the piston-cylinder assembly. When the engine is running, cylinder oil is spread over the cylinder and forms a thin, oily film between the piston and the cylinder wall. This film plays three roles:
- assurer la séparation entre les deux surfaces afin d’éviter une usure d’adhérence, - ensure the separation between the two surfaces in order to avoid adhesion wear,
- neutraliser les gouttes d’acide sulfurique formées dans la chambre de combustion avant qu’elles n’atteignent le cylindre et ne provoquent son usure par corrosion et/ou la tribocorrosion, et - neutralize the drops of sulfuric acid formed in the combustion chamber before they reach the cylinder and cause wear by corrosion and / or tribocorrosion, and
- disperser tout dépôt qui pourrait se former sur chaque surface afin de les conserver propres. - disperse any deposit that could form on each surface in order to keep them clean.
Les compositions lubrifiantes pour moteurs, et notamment pour moteurs marins, actuellement utilisées comprennent une huile de base à laquelle sont ajoutés des dispersants et des détergents surbasés. Ces détergents surbasés comprennent généralement un noyau de carbonate de calcium CaCC>3 enrobé par une couche de tensioactif. Le carbonate de calcium réagit avec l’acide sulfurique pour former notamment du sulfate de calcium (CaSC>4). La baisse de l’acide sulfurique dans le milieu permet une protection des pièces contre la corrosion et/ou la tribocorrosion. The lubricating compositions for engines, and in particular for marine engines, currently used comprise a base oil to which dispersants and overbased detergents are added. These overbased detergents generally comprise a core of CaCC> 3 calcium carbonate coated with a layer of surfactant. Calcium carbonate reacts with sulfuric acid to form, in particular, calcium sulphate (CaSC> 4). The decrease in sulfuric acid in the medium allows parts to be protected against corrosion and / or tribocorrosion.
Afin d’assurer cette protection, les compositions lubrifiantes utilisées doivent être suffisamment basiques (notamment pour neutraliser l’acide), ce qui implique d’augmenter la quantité de détergents compris dans ces compositions. In order to ensure this protection, the lubricating compositions used must be sufficiently basic (in particular to neutralize the acid), which implies increasing the amount of detergents included in these compositions.
Ainsi, les compositions lubrifiantes actuellement sur le marché présentent des Indices de Basicité (BN) supérieurs à 70. Thus, the lubricating compositions currently on the market have Basicity Indexes (BN) greater than 70.
Cependant, l’augmentation de la quantité de détergents dans ces compositions lubrifiantes entraîne une augmentation du nombre de particules de CaCC>3 et CaSC responsables de l’usure des surfaces par polissage (ou usure abrasive) des pièces métalliques du moteur, et notamment des cylindres de moteur deux-temps, tel que les moteurs marin deux-temps. D’autre part, l’emploi des compositions lubrifiantes actuellement disponibles ne protège pas complètement les pièces métalliques du moteur de la corrosion et/ou de la tribocorrosion, et en particulier les pièces métalliques du moteur deux-temps contre la tribocorrosion, lorsque le frottement est de type glissement alternatif. However, the increase in the amount of detergents in these lubricating compositions leads to an increase in the number of particles of CaCC> 3 and CaSC responsible for the wear of the surfaces by polishing (or abrasive wear) of the metal parts of the engine, and in particular of the parts. two-stroke engine cylinders, such as two-stroke marine engines. On the other hand, the use of the lubricating compositions currently available does not completely protect the metal parts of the engine from corrosion and / or tribocorrosion, and in particular the metal parts of the two-stroke engine against tribocorrosion, when the friction is of reciprocating slip type.
Il existe donc un intérêt à fournir des compositions lubrifiantes permettant d’améliorer la protection des pièces métalliques d’un moteur, notamment d’un moteur deux-temps, tel qu’un moteur marin deux-temps, contre la corrosion et/ou la tribocorrosion. There is therefore an interest in providing lubricating compositions making it possible to improve the protection of the metal parts of an engine, in particular of an engine. two-stroke, such as a two-stroke marine engine, against corrosion and / or tribocorrosion.
Il existe également un intérêt à fournir des compositions lubrifiantes permettant de réduire leur Indice de Basicité. There is also an interest in providing lubricating compositions making it possible to reduce their Basicity Index.
Un objectif de la présente invention est de fournir des compositions lubrifiantes permettant d’améliorer la protection des pièces métalliques d’un moteur, typiquement d’un moteur deux-temps, notamment d’un moteur marin deux-temps, contre la corrosion et/ou la tribocorrosion. An objective of the present invention is to provide lubricating compositions making it possible to improve the protection of the metal parts of an engine, typically of a two-stroke engine, in particular of a two-stroke marine engine, against corrosion and / or tribocorrosion.
La présente invention vise plus particulièrement la fourniture d’huiles cylindre pour moteur deux-temps, en particulier pour moteur marin deux-temps. The present invention relates more particularly to the supply of cylinder oils for two-stroke engines, in particular for two-stroke marine engines.
Un autre objectif de la présente invention est de fournir des compositions lubrifiantes présentant un Indice de Basicité réduit. Another objective of the present invention is to provide lubricating compositions exhibiting a reduced Basicity Index.
D’autres objectifs encore apparaîtront à la lecture de la description de l’invention qui suit. Still other objects will become apparent from the following description of the invention.
Ces objectifs sont remplis par la présente invention qui concerne une composition lubrifiante comprenant : These objectives are fulfilled by the present invention which relates to a lubricating composition comprising:
- au moins une huile de base ; et - at least one base oil; and
- de 0,1 à 30 %, préférentiellement de 0,5 % à 20 %, avantageusement de 1 % à 10 % en masse d’un composé imidazoline de formule (A) : - from 0.1 to 30%, preferably from 0.5% to 20%, advantageously from 1% to 10% by mass of an imidazoline compound of formula (A):
Figure imgf000004_0001
dans laquelle :
Figure imgf000004_0001
in which :
- R1 représente un groupement alkyle, linéaire ou ramifié, comprenant de 1 à 16 atomes de carbone, préférentiellement de 1 à 12 atomes de carbone, avantageusement de 2 à 8 atomes de carbone, optionnellement substitué en bout de chaîne par un groupement choisi parmi NH2, OH ou SH, ou R1 représente un groupement alcényle, linéaire ou ramifié, comprenant de 2 à 16 atomes de carbone, préférentiellement de 2 à 12 atomes de carbone, avantageusement de 2 à 8 atomes de carbone, optionnellement substitué en bout de chaîne par un groupement choisi parmi NH2, OH ou SH. De préférence, R1 représente un groupement alkyle ou alcényle, linéaire ou ramifié, comprenant de 2 à 8 atomes de carbone, préférentiellement de 2 à 6 atomes de carbone, avantageusement de 2 à 4 atomes de carbone et étant substitué en bout de chaîne par le groupement -NH2. - R 1 represents an alkyl group, linear or branched, comprising from 1 to 16 carbon atoms, preferably from 1 to 12 carbon atoms, advantageously from 2 to 8 carbon atoms, optionally substituted at the end of the chain by a group chosen from among NH 2 , OH or SH, or R 1 represents an alkenyl group, linear or branched, comprising from 2 to 16 carbon atoms, preferably from 2 to 12 carbon atoms, advantageously from 2 to 8 carbon atoms, optionally end-substituted chain with a group chosen from NH 2 , OH or SH. Preferably, R 1 represents an alkyl or alkenyl group, linear or branched, comprising from 2 to 8 carbon atoms, preferably from 2 to 6 carbon atoms, advantageously from 2 to 4 carbon atoms and being substituted at the end of the chain by the -NH 2 group.
- R2 représente un groupement alkyle, linéaire ou ramifié, comprenant de 1 à 36 atomes de carbone, préférentiellement de 4 à 28 atomes de carbone, avantageusement de 8 à 24 atomes de carbone, ou R2 représente un groupement alcényle, linéaire ou ramifié, comprenant de 2 à 36 atomes de carbone, préférentiellement de 4 à 28 atomes de carbone, avantageusement de 8 à 24 atomes de carbone. Selon un mode de réalisation, R1 représente un groupement alkyle, linéaire ou ramifié, comprenant de 1 à 12 atomes de carbone, de préférence de 2 à 8 atomes de carbone, de préférence encore de 2 à 6 atomes de carbone voire de 2 à 4 atomes de carbone, ledit groupement R1 étant de préférence substitué en bout de chaîne alkyle par un groupement -NH2 ; et/ou - R 2 represents an alkyl group, linear or branched, comprising from 1 to 36 carbon atoms, preferably from 4 to 28 carbon atoms, advantageously from 8 to 24 carbon atoms, or R 2 represents an alkenyl group, linear or branched , comprising from 2 to 36 carbon atoms, preferably from 4 to 28 carbon atoms, advantageously from 8 to 24 carbon atoms. According to one embodiment, R 1 represents an alkyl group, linear or branched, comprising from 1 to 12 carbon atoms, preferably from 2 to 8 carbon atoms, more preferably from 2 to 6 carbon atoms or even from 2 to 4 carbon atoms, said R 1 group being preferably substituted at the end of the alkyl chain by an -NH 2 group; and or
Selon un mode de réalisation, R2 représente un groupement alkyle ou alcényle, linéaire ou ramifié, comprenant de 4 à 28 atomes de carbone, de préférence de 8 à 24 atomes de carbone. De préférence, R2 représente un groupement alcényle, linéaire ou ramifié, comprenant de 4 à 28 atomes de carbone, de préférence de 8 à 24 atomes de carbone. According to one embodiment, R 2 represents an alkyl or alkenyl group, linear or branched, comprising from 4 to 28 carbon atoms, preferably from 8 to 24 carbon atoms. Preferably, R 2 represents an alkenyl group, linear or branched, comprising from 4 to 28 carbon atoms, preferably from 8 to 24 carbon atoms.
De préférence, le groupement R2 représente un groupement alcényle comprenant au moins une double liaison. De manière préférentielle, ladite double liaison est située en C-8, C-9 du groupement alcényle par rapport à la fonction imidazoline. Preferably, the R 2 group represents an alkenyl group comprising at least one double bond. Preferably, said double bond is located at C-8, C-9 of the alkenyl group relative to the imidazoline function.
Selon un mode de réalisation particulier de l’invention, l’huile de base comprise dans la composition lubrifiante est choisie parmi des huiles d’origine minérale, synthétique ou végétale ainsi que leurs mélanges. According to a particular embodiment of the invention, the base oil included in the lubricating composition is chosen from oils of mineral, synthetic or vegetable origin as well as their mixtures.
Les huiles minérales ou synthétiques généralement utilisées dans l’application appartiennent à l’une des classes définies dans la classification API telle que résumée dans le tableau ci-dessous. The mineral or synthetic oils generally used in the application belong to one of the classes defined in the API classification as summarized in the table below.
[Table 1 ] [Table 1]
Figure imgf000005_0001
Figure imgf000006_0001
Figure imgf000005_0001
Figure imgf000006_0001
Tableau 1 : Classification API des huiles de base Table 1: API classification of base oils
Les huiles minérales de Groupe 1 peuvent être obtenues par distillation de bruts naphténiques ou paraffiniques sélectionnés, suivie d’une purification de ces distillais par des procédés tels que l’extraction au solvant, le déparaffinage au solvant ou catalytique, l’hydrotraitement ou l’hydrogénation. Group 1 mineral oils can be obtained by distillation of selected naphthenic or paraffinic crudes, followed by purification of these distillates by processes such as solvent extraction, solvent or catalytic dewaxing, hydrotreatment or hydrogenation.
Les huiles des Groupes 2 et 3 sont obtenues par des procédés de purification plus sévères, par exemple une combinaison parmi l’hydrotraitement, l’hydrocraquage, l’hydrogénation et le déparaffinage catalytique. Group 2 and 3 oils are obtained by more stringent purification processes, for example a combination of hydrotreatment, hydrocracking, hydrogenation and catalytic dewaxing.
Les exemples de bases synthétiques de Groupe 4 et 5 incluent les poly-alphas oléfines, les polybutènes, les polyisobutènes, les alkylbenzènes. Examples of Group 4 and 5 synthetic bases include poly-alphas olefins, polybutenes, polyisobutenes, alkylbenzenes.
Ces huiles de base peuvent être utilisées seules ou en mélange. Une huile minérale peut être combinée avec une huile synthétique. These base oils can be used alone or as a mixture. Mineral oil can be combined with synthetic oil.
Les huiles cylindres pour moteurs marins diesel 2-temps ont un grade viscosimétrique SAE-40 à SAE-60, généralement SAE-50 équivalent à une viscosité cinématique à 100°C comprise entre 16.3 et 21 .9 mm2/s. Cylinder oils for 2-stroke marine diesel engines have a viscosimetric grade SAE-40 to SAE-60, generally SAE-50 equivalent to a kinematic viscosity at 100 ° C between 16.3 and 21 .9 mm 2 / s.
Les huiles de grade 40 ont une viscosité cinématique à 100°C comprise entre 12,5 et 16,3 mm2/s. Grade 40 oils have a kinematic viscosity at 100 ° C of between 12.5 and 16.3 mm 2 / s.
Les huiles de grade 50 ont une viscosité cinématique à 100°C comprise entre 16,3 et 21 ,9 mm2/s. Grade 50 oils have a kinematic viscosity at 100 ° C of between 16.3 and 21.9 mm 2 / s.
Les huiles de grade 60 ont une viscosité cinématique à 100°C comprise entre 21 ,9 et 26,1 mm2/s. Grade 60 oils have a kinematic viscosity at 100 ° C of between 21.9 and 26.1 mm 2 / s.
Selon les usages de la profession, on préfère formuler des huiles cylindres pour moteurs marins diesel deux-temps ayant une viscosité cinématique à 100°C comprise entre 18 et 21 ,5, préférentiellement entre 19 et 21 ,5 mm2/s. According to the uses of the profession, it is preferred to formulate cylinder oils for two-stroke marine diesel engines having a kinematic viscosity at 100 ° C. of between 18 and 21.5, preferably between 19 and 21.5 mm 2 / s.
Cette viscosité peut être obtenue par mélange d’additifs et d’huiles de base, par exemple contenant des bases minérales de Groupe 1 telles des bases Neutral Solvant (par exemple 500 NS ou 600 NS) et le Brightstock. Toute autre combinaison de bases minérales, synthétiques ou d’origine végétale ayant, en mélange avec les additifs, une viscosité compatible avec le grade SAE-50 peut être utilisée. This viscosity can be obtained by mixing additives and base oils, for example containing Group 1 mineral bases such as Neutral Solvent bases (for example 500 NS or 600 NS) and Brightstock. Any other combination mineral, synthetic or vegetable bases having, mixed with the additives, a viscosity compatible with the SAE-50 grade can be used.
Typiquement, une formulation classique de lubrifiant cylindre pour moteurs diesels marins 2-temps lents est de grade SAE-40 à SAE-60, préférentiellement SAE- 50 (selon la classification SAE J300) et comprend au moins 50 % en masse d’huile de base lubrifiante d’origine minérale et/ou synthétique, adaptée à l’utilisation en moteur marin, par exemple, de classe API Groupe 1 c'est-à-dire obtenue par distillation de bruts sélectionnés suivi de la purification de ces distillais par des procédés tels l’extraction au solvant, le déparaffinage au solvant ou catalytique, l’hydrotraitement ou l’hydrogénation. Leur Indice de Viscosité (VI) est compris entre 80 et 120 ; leur teneur en soufre est supérieure à 0.03 % et leur teneur en saturé est inférieure à 90 %. Typically, a conventional formulation of cylinder lubricant for slow 2-stroke marine diesel engines is of grade SAE-40 to SAE-60, preferably SAE-50 (according to the SAE J300 classification) and comprises at least 50% by mass of oil of lubricating base of mineral and / or synthetic origin, suitable for use in marine engines, for example, API Group 1 class, i.e. obtained by distillation of selected crudes followed by the purification of these distillates by processes such as solvent extraction, solvent or catalytic dewaxing, hydrotreatment or hydrogenation. Their Viscosity Index (VI) is between 80 and 120; their sulfur content is greater than 0.03% and their saturated content is less than 90%.
De manière avantageuse, la composition lubrifiante selon l’invention comprend au moins 50 % en masse d’huile(s) de base par rapport à la masse totale de la composition. Advantageously, the lubricating composition according to the invention comprises at least 50% by mass of base oil (s) relative to the total mass of the composition.
De manière plus avantageuse, la composition lubrifiante selon l’invention comprend au moins 60 % en masse, voire au moins 70 % en masse, d’huile(s) de base par rapport à la masse totale de la composition. More advantageously, the lubricating composition according to the invention comprises at least 60% by mass, or even at least 70% by mass, of base oil (s) relative to the total mass of the composition.
De manière plus particulièrement avantageuse, la composition lubrifiante selon l’invention comprend de 60 à 99,9% en masse d’huiles de base, de préférence de 70 à 98 % en masse d’huiles de base, par rapport à la masse totale de la composition. More particularly advantageously, the lubricating composition according to the invention comprises from 60 to 99.9% by mass of base oils, preferably from 70 to 98% by mass of base oils, relative to the total mass. of the composition.
De préférence, la composition lubrifiante selon l’invention comprend en outre au moins un additif choisi parmi des détergents, des dispersants et leurs mélanges. Preferably, the lubricating composition according to the invention further comprises at least one additive chosen from detergents, dispersants and mixtures thereof.
Les détergents utilisés dans les compositions lubrifiantes selon la présente invention sont bien connus de l’homme de métier. The detergents used in the lubricating compositions according to the present invention are well known to those skilled in the art.
Dans le cadre de la présente invention, les détergents communément utilisés dans la formulation de compositions lubrifiantes sont des composés anioniques comportant une longue chaîne hydrocarbonée lipophile et une tête hydrophile. Le cation associé est un cation métallique d’un métal alcalin ou alcalino-terreux. In the context of the present invention, the detergents commonly used in the formulation of lubricating compositions are anionic compounds comprising a long lipophilic hydrocarbon chain and a hydrophilic head. The associated cation is a metallic cation of an alkali or alkaline earth metal.
Les détergents sont préférentiellement choisis parmi les sels de métaux alcalins ou alcalino-terreux d’acides carboxyliques, sulfonates, salicylates, naphténates, ainsi que les sels de phénates. The detergents are preferably chosen from alkali metal or alkaline-earth metal salts of carboxylic acids, sulphonates, salicylates, naphthenates, as well as salts of phenates.
Les métaux alcalins et alcalino terreux sont préférentiellement le calcium, le magnésium, le sodium ou le baryum. Ces sels métalliques peuvent contenir le métal en quantité approximativement stoechiométrique. Dans ce cas, on parle de détergents non surbasés ou « neutres », bien qu’ils apportent également une certaine basicité. Ces détergents « neutres » ont typiquement un BN, mesuré selon ASTM D2896, inférieur à 150 mg KOH/g, ou inférieur à 100, ou encore inférieur à 80 mg KOH/g. The alkali metals and alkaline earth metals are preferably calcium, magnesium, sodium or barium. These metal salts can contain the metal in an approximately stoichiometric amount. In this case, we speak of non-overbased or "neutral" detergents, although they also provide a certain basicity. These “neutral” detergents typically have a BN, measured according to ASTM D2896, less than 150 mg KOH / g, or less than 100, or even less than 80 mg KOH / g.
Ce type de détergents dits neutres peut contribuer pour partie au BN des lubrifiants selon la présente invention. On emploiera par exemple des détergents neutres de type carboxylates, sulfonates, salicylates, phénates, naphténates de métaux alcalins et alcalino terreux, par exemple de calcium, sodium, magnésium, baryum. This type of so-called neutral detergents can partly contribute to the BN of the lubricants according to the present invention. Neutral detergents of the carboxylates, sulfonates, salicylates, phenates, naphthenates of alkali and alkaline earth metals, for example of calcium, sodium, magnesium, barium type, will be employed.
Lorsque le métal est en excès (en quantité supérieure à la quantité stoechiométrique), on a affaire à des détergents dits surbasés. Leur BN est élevé, par exemple supérieur à 150 mg KOH/g, typiquement compris entre 200 et 700 mg KOH/g, généralement compris entre 250 et 450 mg KOH/g. When the metal is in excess (in an amount greater than the stoichiometric amount), we are dealing with so-called overbased detergents. Their BN is high, for example greater than 150 mg KOH / g, typically between 200 and 700 mg KOH / g, generally between 250 and 450 mg KOH / g.
Le métal en excès apportant le caractère surbasé au détergent se présente sous la forme de sels métalliques insolubles dans l’huile, par exemple carbonate, hydroxyde, oxalate, acétate, glutamate, préférentiellement carbonate. The excess metal providing the overbased character to the detergent is in the form of metal salts insoluble in oil, for example carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate.
Dans un même détergent surbasé, les métaux de ces sels insolubles peuvent être les mêmes que ceux des détergents solubles dans l’huile ou bien être différents. Ils sont préférentiellement choisis parmi le calcium, le magnésium, le sodium ou le baryum. In the same overbased detergent, the metals of these insoluble salts may be the same as those of the oil soluble detergents or they may be different. They are preferably chosen from calcium, magnesium, sodium or barium.
Les détergents surbasés se présentent ainsi sous forme de micelles composées de sels métalliques insolubles maintenues en suspension dans la composition lubrifiante par les détergents sous forme de sels métalliques solubles dans l’huile. The overbased detergents are thus in the form of micelles composed of insoluble metal salts held in suspension in the lubricating composition by the detergents in the form of oil-soluble metal salts.
Les détergents surbasés comportant un seul type de sel métallique soluble détergent seront généralement nommés d’après la nature de la chaîne hydrophobe de ce dernier détergent. Overbased detergents comprising a single type of detergent soluble metal salt will generally be named after the nature of the hydrophobic chain of the latter detergent.
Ainsi, ils seront dits de type carboxylate, phénate, salicylate, sulfonate, naphténate selon que ce détergent est respectivement un carboxylate, phénate, salicylate, sulfonate, ou naphténate. Thus, they will be said to be of the carboxylate, phenate, salicylate, sulfonate, naphthenate type depending on whether this detergent is a carboxylate, phenate, salicylate, sulfonate or naphthenate respectively.
Les détergents surbasés seront dits de type mixte si les micelles comprennent plusieurs types de détergents, différents entre eux par la nature de leur chaîne hydrophobe. The overbased detergents will be said to be of mixed type if the micelles comprise several types of detergents, which differ from one another by the nature of their hydrophobic chain.
Pour une utilisation dans les compositions lubrifiantes selon la présente invention, les sels métalliques solubles dans l’huile seront préférentiellement des carboxylates, des phénates, des sulfonates des salicylates, et des détergents mixtes phénate - sulfonate et /ou salicylates de calcium, magnésium, sodium ou baryum. For use in the lubricating compositions according to the present invention, the oil-soluble metal salts will preferably be carboxylates, phenates, sulfonates, salicylates, and mixed phenate - sulfonate and / or salicylate detergents of calcium, magnesium, sodium or barium.
Les sels de métaux insolubles apportant le caractère surbasé sont des carbonates de métaux alcalins et alcalino terreux, préférentiellement le carbonate de calcium. The insoluble metal salts providing the overbased character are carbonates of alkali metals and alkaline earth metals, preferably calcium carbonate.
De préférence, les détergents utilisés dans les compositions lubrifiantes selon la présente invention sont des détergents surbasés au carbonate de calcium choisis parmi les carboxylates, les phénates, les sulfonates, les salicylates et les détergents mixtes phénates - sulfonates - salicylates. Preferably, the detergents used in the lubricating compositions according to the present invention are detergents overbased on calcium carbonate chosen from carboxylates, phenates, sulphonates, salicylates and mixed phenates - sulphonates - salicylates detergents.
De manière avantageuse, la composition lubrifiante selon l’invention peut comprendre de 3 à 40 %, préférentiellement de 5 % à 30 %, avantageusement de 10 % à 25 % en masse de détergent(s) par rapport à la masse totale de la composition lubrifiante. Advantageously, the lubricating composition according to the invention can comprise from 3 to 40%, preferably from 5% to 30%, advantageously from 10% to 25% by mass of detergent (s) relative to the total mass of the composition lubricant.
Les dispersants sont des additifs bien connus employés dans la formulation de compositions lubrifiantes, notamment pour application dans le domaine marin. Leur rôle premier est de maintenir en suspension les particules présentes initialement ou apparaissant dans la composition lubrifiante au cours de son utilisation dans le moteur. Ils préviennent leur agglomération en jouant sur l’encombrement stérique. Ils peuvent présenter également un effet synergique sur la neutralisation. Dispersants are well known additives used in the formulation of lubricating compositions, in particular for application in the marine field. Their primary role is to maintain in suspension the particles initially present or appearing in the lubricating composition during its use in the engine. They prevent their agglomeration by playing on steric hindrance. They can also exhibit a synergistic effect on neutralization.
Dans le cadre de la présente invention, les dispersants utilisés comme additifs pour lubrifiant contiennent un groupement polaire, associé à une chaîne hydrocarbonée relativement longue, contenant généralement de 50 à 400 atomes de carbone. Le groupement polaire contient typiquement au moins un élément azote ou oxygène. In the context of the present invention, the dispersants used as lubricant additives contain a polar group, associated with a relatively long hydrocarbon chain, generally containing from 50 to 400 carbon atoms. The polar group typically contains at least one nitrogen or oxygen element.
Les composés dérivés de l’acide succinique sont des dispersants particulièrement utilisés comme additifs de lubrification. On utilise en particulier les succinimides, obtenues par condensation d’anhydrides succiniques et d’amines, les esters succiniques obtenus par condensation d’anhydrides succiniques et d’alcools ou polyols. The compounds derived from succinic acid are dispersants that are particularly used as lubricating additives. In particular, succinimides, obtained by condensation of succinic anhydrides and amines, succinic esters obtained by condensation of succinic anhydrides and alcohols or polyols are used.
Ces composés peuvent être ensuite traités par divers composés, notamment soufre, oxygène, formaldéhyde, acides carboxyliques et composés contenant du bore ou du zinc pour produire par exemple des succinimides boratées ou des succinimides bloqués au zinc. These compounds can then be treated with various compounds, including sulfur, oxygen, formaldehyde, carboxylic acids and compounds containing boron or zinc to produce, for example, borated succinimides or zinc blocked succinimides.
Les bases de Mannich, obtenues par polycondensation de phénols substitués par des groupements alkyls, de formaldéhyde et d’amines primaires ou secondaires, sont également des composés utilisés comme dispersants dans les lubrifiants. De préférence, les dispersants selon l’invention sont choisis parmi les succinimides, tels que les polyisobutylènes bis-succinimides, éventuellement boratés ou bloqués au zinc. Mannich bases, obtained by polycondensation of phenols substituted with alkyl groups, formaldehyde and primary or secondary amines, are also compounds used as dispersants in lubricants. Preferably, the dispersants according to the invention are chosen from succinimides, such as polyisobutylene bis-succinimides, optionally borated or blocked with zinc.
De manière avantageuse, la composition lubrifiante selon l’invention peut comprendre de 0,01 à 10 %, préférentiellement de 0,1 % à 5 %, avantageusement de 0,5 % à 3 % en masse de dispersant(s) par rapport à la masse totale de la composition lubrifiante. Advantageously, the lubricating composition according to the invention may comprise from 0.01 to 10%, preferably from 0.1% to 5%, advantageously from 0.5% to 3% by mass of dispersant (s) relative to the total mass of the lubricating composition.
La composition lubrifiante peut comprendre en outre au moins un additif anti usure. The lubricating composition can also comprise at least one antiwear additive.
De préférence, l’additif anti-usure est le di-thiophosphate de zinc ou DTPZn. On trouve également dans cette catégorie divers composés phosphorés, soufrés, azotés, chlorés et borés. Preferably, the antiwear additive is zinc di-thiophosphate or DTPZn. In this category are also found various phosphorus, sulfur, nitrogen, chlorine and boron compounds.
Il existe une grande variété d’additifs anti-usure, mais la catégorie la plus utilisée est celle des additifs phospho-soufrés comme les alkylthiophosphates métalliques, en particulier les alkylthiophosphates de zinc, et plus spécifiquement les dialkyldithiophosphates de zinc ou DTPZn. There is a wide variety of antiwear additives, but the most widely used category is that of phospho-sulfur additives such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates or DTPZn.
Les phosphates d’amines, les polysulfures, notamment les oléfines soufrées, sont également des additifs anti-usure couramment employés. Amine phosphates, polysulfides, especially sulfur olefins, are also commonly used anti-wear additives.
On rencontre également usuellement dans les compositions lubrifiantes des additifs anti-usure et extrême pression de type azotés et soufrés, tels que par exemple les dithiocarbamates métalliques, en particulier le dithiocarbamate de molybdène. Les esters de glycérol sont également des additifs anti-usure. On peut citer par exemple les mono, les di- et trioléates, les monopalmitates et les monomyristates. In lubricating compositions, antiwear and extreme pressure additives of nitrogenous and sulfur type are also usually encountered, such as for example metal dithiocarbamates, in particular molybdenum dithiocarbamate. Glycerol esters are also antiwear additives. Mention may be made, for example, of mono, di- and trioleates, monopalmitates and monomyristates.
Selon un mode de réalisation particulier, la composition lubrifiante comprend, par rapport au poids total de la composition lubrifiante : According to a particular embodiment, the lubricating composition comprises, relative to the total weight of the lubricating composition:
- de 50 à 96,9% en poids, de préférence de 60 à 95% en poids, de préférence encore de 70 à 90% en poids, d’huile(s) de base, - from 50 to 96.9% by weight, preferably from 60 to 95% by weight, more preferably from 70 to 90% by weight, of base oil (s),
- de 0,1 à 30% en poids, de préférence de 0,5 à 20% en poids, de préférence encore de 1 à 10% en poids, d’un ou plusieurs composés imidazoline de formule (A), et - 0.1 to 30% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight, of one or more imidazoline compounds of formula (A), and
- de 3 à 40% en poids, de préférence de 5 à 30% en poids, de préférence encore de 10 à 25% en poids, de détergent(s), et - from 3 to 40% by weight, preferably from 5 to 30% by weight, more preferably from 10 to 25% by weight, of detergent (s), and
- éventuellement de 0,01 à 10% en poids, de préférence de 0,1 à 5% en poids, de préférence encore de 0,5 à 3% en poids, de dispersant(s). Selon un mode de réalisation particulier, la composition lubrifiante comprend, par rapport au poids total de la composition lubrifiante : - optionally from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, more preferably from 0.5 to 3% by weight, of dispersant (s). According to a particular embodiment, the lubricating composition comprises, relative to the total weight of the lubricating composition:
- de 60 à 99% en poids, de préférence de 60 à 95% en poids, de préférence encore de 70 à 90% en poids, d’huile(s) de base, - from 60 to 99% by weight, preferably from 60 to 95% by weight, more preferably from 70 to 90% by weight, of base oil (s),
- de 0,1 à 30% en poids, de préférence de 0,5 à 20% en poids, de préférence encore de 1 à 10% en poids, d’un ou plusieurs composés imidazoline de formule (A), et - 0.1 to 30% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight, of one or more imidazoline compounds of formula (A), and
- de 0,01 à 10% en poids, de préférence de 0,1 à 5% en poids, de préférence encore de 0,5 à 3% en poids, de dispersant(s), et - from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, more preferably from 0.5 to 3% by weight, of dispersant (s), and
- éventuellement de 3 à 40% en poids, de préférence de 5 à 30% en poids, de préférence encore de 10 à 25% en poids, de détergent(s). - optionally from 3 to 40% by weight, preferably from 5 to 30% by weight, more preferably from 10 to 25% by weight, of detergent (s).
La composition lubrifiante peut également comprendre tous types d’additifs fonctionnels adaptés à leur utilisation, par exemple des additifs anti mousse pouvant être par exemple des polymères polaires tels que les polyméthylsiloxanes, les polyacrylates, des additifs anti-oxydants par exemple de type phénolique ou aminé et/ou des additifs anti-rouille, par exemple des composés organo-métalliques ou thiadiazoles. Ceux-ci sont connus de l'homme du métier. The lubricating composition can also comprise all types of functional additives suitable for their use, for example anti-foam additives which can be, for example, polar polymers such as polymethylsiloxanes, polyacrylates, anti-oxidant additives, for example of the phenolic or amine type. and / or anti-rust additives, for example organometallic compounds or thiadiazoles. These are known to those skilled in the art.
Selon un mode de réalisation préféré de l’invention, le composé de formule (A) est le composé (I) suivant : According to a preferred embodiment of the invention, the compound of formula (A) is the following compound (I):
Figure imgf000011_0001
Figure imgf000011_0001
Selon un mode de réalisation particulier, la composition lubrifiante comprend, par rapport au poids total de la composition lubrifiante : - de 50 à 96,9% en poids, de préférence de 60 à 95% en poids, de préférence encore de 70 à 90% en poids, d’huile(s) de base, According to a particular embodiment, the lubricating composition comprises, relative to the total weight of the lubricating composition: - from 50 to 96.9% by weight, preferably from 60 to 95% by weight, more preferably from 70 to 90% by weight, of base oil (s),
- de 0,1 à 30% en poids, de préférence de 0,5 à 20% en poids, de préférence encore de 1 à 10% en poids, d’un ou plusieurs composés imidazolines dont au moins un composé de formule (I) définie ci-dessus, et - from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, more preferably from 1 to 10% by weight, of one or more imidazoline compounds including at least one compound of formula (I ) defined above, and
- de 3 à 40% en poids, de préférence de 5 à 30% en poids, de préférence encore de 10 à 25% en poids, de détergent(s) comprenant au moins un détergent surbasé de type phénate ou sulphonate, et - from 3 to 40% by weight, preferably from 5 to 30% by weight, more preferably from 10 to 25% by weight, of detergent (s) comprising at least one overbased detergent of phenate or sulphonate type, and
- éventuellement de 0,01 à 10% en poids, de préférence de 0,1 à 5% en poids, de préférence encore de 0,5 à 3% en poids, de dispersant(s). - optionally from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, more preferably from 0.5 to 3% by weight, of dispersant (s).
Selon un mode de réalisation particulier, la composition lubrifiante comprend, par rapport au poids total de la composition lubrifiante : According to a particular embodiment, the lubricating composition comprises, relative to the total weight of the lubricating composition:
- de 60 à 99% en poids, de préférence de 60 à 95% en poids, de préférence encore de 70 à 90% en poids, d’huile(s) de base, - from 60 to 99% by weight, preferably from 60 to 95% by weight, more preferably from 70 to 90% by weight, of base oil (s),
- de 0,1 à 30% en poids, de préférence de 0,5 à 20% en poids, de préférence encore de 1 à 10% en poids, d’un ou plusieurs composés imidazolines dont au moins un composé de formule (I) définie ci-dessus, et - from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, more preferably from 1 to 10% by weight, of one or more imidazoline compounds including at least one compound of formula (I ) defined above, and
- de 0,01 à 10% en poids, de préférence de 0,1 à 5% en poids, de préférence encore de 0,5 à 3% en poids, de dispersant(s) choisi(s) parmi les succinimides, et - from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, more preferably from 0.5 to 3% by weight, of dispersant (s) chosen from succinimides, and
- éventuellement de 3 à 40% en poids, de préférence de 5 à 30% en poids, de préférence encore de 10 à 25% en poids, de détergent(s). - optionally from 3 to 40% by weight, preferably from 5 to 30% by weight, more preferably from 10 to 25% by weight, of detergent (s).
La présente invention concerne également l’utilisation de la composition lubrifiante selon l’invention pour la lubrification d’au moins une pièce métallique d’un moteur, tel qu’un moteur deux-temps et notamment un moteur marin deux-temps. The present invention also relates to the use of the lubricating composition according to the invention for the lubrication of at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine.
De préférence, l’utilisation de la composition lubrifiante selon l’invention permet de prévenir et/ou diminuer la corrosion et/ou la tribocorrosion de ladite pièce métallique dudit moteur. Preferably, the use of the lubricating composition according to the invention makes it possible to prevent and / or reduce corrosion and / or tribocorrosion of said metal part of said engine.
La présente invention concerne également un procédé de lubrification d’au moins une pièce métallique d’un moteur, tel qu’un moteur deux-temps et notamment un moteur marin deux-temps, comprenant la mise en contact de ladite pièce d’un moteur avec la composition lubrifiante selon l’invention. La présente invention concerne également l’utilisation d’un composé de formule (A) selon l’invention dans une composition lubrifiante comprenant au moins une huile de base pour prévenir et/ou diminuer la corrosion et/ou la tribocorrosion d’au moins une pièce métallique d’un moteur, tel qu’un moteur deux-temps et notamment un moteur marin deux-temps. The present invention also relates to a method of lubricating at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine, comprising bringing said part of an engine into contact. with the lubricating composition according to the invention. The present invention also relates to the use of a compound of formula (A) according to the invention in a lubricating composition comprising at least one base oil for preventing and / or reducing corrosion and / or tribocorrosion of at least one. metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine.
La présente invention concerne également un procédé de prévention et/ou de diminution de la corrosion et/ou de la tribocorrosion d’au moins une pièce métallique d’un moteur, tel qu’un moteur deux-temps et notamment un moteur marin deux- temps, comprenant la lubrification de ladite pièce métallique avec une composition lubrifiante selon l’invention. The present invention also relates to a method of preventing and / or reducing corrosion and / or tribocorrosion of at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine. time, comprising lubricating said metal part with a lubricating composition according to the invention.
La présente invention concerne également l’utilisation de la composition lubrifiante selon l’invention pour la passivation d’au moins une pièce métallique d’un moteur, tel qu’un moteur deux-temps et notamment un moteur marin deux-temps. The present invention also relates to the use of the lubricating composition according to the invention for the passivation of at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine.
La présente invention concerne également un procédé de passivation d’au moins une pièce métallique d’un moteur comprenant au moins une étape de mise en contact de ladite pièce métallique avec la composition lubrifiante selon l’invention. The present invention also relates to a process for passivation of at least one metal part of an engine comprising at least one step of bringing said metal part into contact with the lubricating composition according to the invention.
La présente invention concerne également l’utilisation d’un composé de formule (A) selon l’invention dans une composition lubrifiante comprenant au moins une huile de base pour la passivation d’au moins une pièce métallique d’un moteur, tel qu’un moteur deux-temps et notamment un moteur marin deux-temps. The present invention also relates to the use of a compound of formula (A) according to the invention in a lubricating composition comprising at least one base oil for the passivation of at least one metal part of an engine, such as a two-stroke engine and in particular a two-stroke marine engine.
De préférence, la pièce métallique selon l’invention est un cylindre ou un piston.Preferably, the metal part according to the invention is a cylinder or a piston.
De façon avantageuse, la pièce métallique est en fonte. Advantageously, the metal part is made of cast iron.
De préférence, le moteur selon l’invention est un moteur deux temps. De préférence, le moteur est un moteur marin deux-temps. Preferably, the engine according to the invention is a two-stroke engine. Preferably, the engine is a two-stroke marine engine.
De préférence, le moteur est un moteur consommant du mazout lourd. Par « mazout lourd », on entend au sens de la présente invention les coupes lourdes issues de la distillation du pétrole, éventuellement additivées. Preferably, the engine is an engine consuming heavy fuel oil. For the purposes of the present invention, the term “heavy fuel oil” is understood to mean the heavy cuts resulting from the distillation of petroleum, optionally containing additives.
Au sens de la présente invention, on entend par « corrosion » une altération d’un matériau, de préférence métallique, par réaction chimique avec un oxydant. De préférence, cet oxydant est un acide. De manière préférentielle, cet acide est l’acide sulfurique H2SO4. For the purposes of the present invention, the term “corrosion” means an alteration of a material, preferably metallic, by chemical reaction with an oxidant. Of preferably, this oxidant is an acid. Preferably, this acid is sulfuric acid H2SO4.
Au sens de la présente invention, on entend par « tribocorrosion » un processus conduisant à la dégradation et à l'usure d’un matériau métallique sous l'action combinée du frottement et de la corrosion telle que définie ci-dessus. For the purposes of the present invention, the term "tribocorrosion" means a process leading to the degradation and wear of a metallic material under the combined action of friction and corrosion as defined above.
De manière avantageuse, le composé de formule (A) défini dans la présente invention est utilisé dans une composition lubrifiante cylindre pour diminuer la tribocorrosion acide sur les cylindres et pistons d’un moteur deux-temps, tel qu’un moteur marin deux-temps. Advantageously, the compound of formula (A) defined in the present invention is used in a cylinder lubricating composition for reducing acid tribocorrosion on the cylinders and pistons of a two-stroke engine, such as a two-stroke marine engine. .
FIGURES FIGURES
[Fig 1] La Figure 1 représente les profils de profondeur des plateaux en fonte obtenus après un test tribologique conduit en présence de la composition selon l’invention CL et de la composition comparative CC. [Fig 1] Figure 1 shows the depth profiles of the cast iron trays obtained after a tribological test conducted in the presence of the composition according to the invention CL and the comparative composition CC.
La présente invention va maintenant être décrite à l’aide d’exemples non limitatifs. The present invention will now be described with the aid of non-limiting examples.
Exemple 1 : Compositions lubrifiantes Example 1: Lubricating compositions
Les compositions du tableau 2 (CL : composition lubrifiante selon l’invention ; CC : composition lubrifiante comparative) ont été préparées en mélangeant le dispersant et/ou les détergents et l’additif dans une huile de base à 60 °C. The compositions of Table 2 (LC: lubricating composition according to the invention; CC: comparative lubricating composition) were prepared by mixing the dispersant and / or detergents and the additive in a base oil at 60 ° C.
[Table 2] [Table 2]
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000014_0001
Figure imgf000015_0001
comparative comparative
Exemple 2 : Résultats des tests de profondeur d’usure Example 2: Results of the wear depth tests
Les tests tribologiques ont été réalisés sur un tribomètre Biceri alternatif en utilisant des tiges en acier (EN31 ) de 6 mm de diamètre et de rayon de courbure de 50 mm, et des plateaux en fonte (FT 25) polis avec du papier abrasif 800 grit SiC. Les tiges en acier ont également été polies pour obtenir une rugosité Ra comprise entre 50 et 100 nm. De plus, les zones des plateaux en fonte extérieures à la zone de friction ont été recouvertes par une résine. Cette résine est retirée à la fin des tests. De cette manière, les zones recouvertes par la résine ne sont pas corrodées pendant les tests et servent d’étalon pour mesurer la profondeur des marques d’usure dues aux phénomènes de corrosion. The tribological tests were carried out on a reciprocating Biceri tribometer using steel rods (EN31) with a diameter of 6 mm and a radius of curvature of 50 mm, and cast iron plates (FT 25) polished with 800 grit sandpaper SiC. The steel rods were also polished to obtain a roughness Ra of between 50 and 100 nm. In addition, the areas of the cast iron plates outside the friction area have been covered with a resin. This resin is removed at the end of the tests. In this way, the areas covered by the resin are not corroded during the tests and serve as a standard for measuring the depth of wear marks due to corrosion phenomena.
Avant chaque test, la composition lubrifiante est chauffée à 100 °C et mise en contact avec une solution d’acide sulfurique 5 M (27% en masse) à température ambiante grâce à un montage en « T ». La composition lubrifiante arrive par le canal principal et la solution d’acide est alimentée par un canal perpendiculaire au canal principal. Before each test, the lubricating composition is heated to 100 ° C and brought into contact with a 5M sulfuric acid solution (27% by mass) at room temperature by means of a "T" assembly. The lubricating composition arrives through the main channel and the acid solution is supplied through a channel perpendicular to the main channel.
Les conditions de ces tests sont les suivantes : The conditions for these tests are as follows:
- Température : 100 °C - Temperature: 100 ° C
- Pression : 0,67 GPa - Pressure: 0.67 GPa
- Vitesse : 0,02 m/s - Speed: 0.02 m / s
- Longueur de trace : 5 mm - Track length: 5 mm
- Durée : 6 h. - Duration: 6 h.
A la fin de chaque test, les produits de corrosion sont éliminés avec une solution d’acide éthylènediaminetétraacétique (EDTA), et l’usure des plateaux en fonte est analysée par interférométrie en lumière blanche, ce qui permet d’obtenir un profil en 3D de la cicatrice d’usure produite par corrosion et/ou tribocorrosion. At the end of each test, the corrosion products are removed with an ethylenediaminetetraacetic acid (EDTA) solution, and the wear of the cast iron plates is analyzed by white light interferometry, which makes it possible to obtain a 3D profile of the wear scar produced by corrosion and / or tribocorrosion.
Ces profils 3D permettent d’obtenir des profils de profondeur de la cicatrice d’usure. La Figure 1 représente les profils de profondeur des plateaux en fonte obtenus après un test tribologique tel que décrit ci-dessus et conduit en présence de la composition lubrifiante selon l’invention CL, et de la composition comparative CC. These 3D profiles provide depth profiles of the wear scar. Figure 1 shows the depth profiles of the cast iron plates obtained after a tribological test as described above and carried out in the presence of the lubricating composition according to the invention CL, and of the comparative composition CC.
Les résultats de ces tests montrent qu’en l’absence de composé de formule (I), le plateau en fonte se corrode au niveau des zones qui ne sont pas en contact avec la tige en acier (zones hors-contact), et une usure due à la tribocorrosion est également observée au niveau de la zone en contact avec la tige. La présence de composé de formule (I) améliore la protection contre la corrosion et la tribocorrosion. En effet, sans vouloir être lié par une quelconque théorie, les additifs permettent de créer une deuxième couche de protection qui vient s’ajouter à la neutralisation des gouttes d’acides par le détergent en formant une barrière physique entre la surface de la pièce métallique et l’huile de la composition lubrifiante, ce qui prévient les phénomènes de corrosion. The results of these tests show that in the absence of a compound of formula (I), the cast iron plate corrodes in the areas which are not in contact with the steel rod (non-contact areas), and a Wear due to tribocorrosion is also observed in the area in contact with the rod. The presence of compound of formula (I) improves protection against corrosion and tribocorrosion. Indeed, without wishing to be bound by any theory, the additives make it possible to create a second protective layer which is added to the neutralization of the acid drops by the detergent by forming a physical barrier between the surface of the metal part. and the oil of the lubricating composition, which prevents corrosion phenomena.

Claims

REVENDICATIONS
1. Composition lubrifiante comprenant : 1. Lubricating composition comprising:
- au moins une huile de base ; et - at least one base oil; and
- de 0,1 à 30 % en masse d’un composé imidazoline de formule (A) : - from 0.1 to 30% by mass of an imidazoline compound of formula (A):
Figure imgf000017_0001
Figure imgf000017_0001
défini tel que : defined as:
- R1 représente un groupement alkyle, linéaire ou ramifié, comprenant de 1 à 16 atomes de carbone, optionnellement substitué en bout de chaîne par un groupement choisi parmi NH2 ou SH, ou R1 représente un groupement alcényle, linéaire ou ramifié, comprenant de 2 à 16 atomes de carbone, optionnellement substitué en bout de chaîne par un groupement choisi parmi NH2 ou SH ; et- R 1 represents an alkyl group, linear or branched, comprising from 1 to 16 carbon atoms, optionally substituted at the end of the chain by a group chosen from NH 2 or SH, or R 1 represents an alkenyl group, linear or branched, comprising from 2 to 16 carbon atoms, optionally substituted at the end of the chain by a group chosen from NH 2 or SH; and
- R2 représente un groupement alkyle, linéaire ou ramifié, comprenant de 1 à 36 atomes de carbone, ou R2 représente un groupement alcényle, linéaire ou ramifié, comprenant de 2 à 36 atomes de carbone. - R 2 represents an alkyl group, linear or branched, comprising from 1 to 36 carbon atoms, or R 2 represents an alkenyl group, linear or branched, comprising from 2 to 36 carbon atoms.
2. Composition selon la revendication 1 , comprenant en outre au moins un additif choisi parmi des détergents, des dispersants et leurs mélanges. 2. Composition according to claim 1, further comprising at least one additive selected from detergents, dispersants and mixtures thereof.
3. Composition selon la revendication 2, dans laquelle : 3. Composition according to claim 2, in which:
- la quantité de détergent varie de 3 à 40 %, préférentiellement de 5 % à 30 %, avantageusement de 10 % à 25 % en masse, par rapport à la masse totale de la composition lubrifiante ; et/ou - the amount of detergent varies from 3 to 40%, preferably from 5% to 30%, advantageously from 10% to 25% by mass, relative to the total mass of the lubricating composition; and or
- la quantité de dispersant varie de 0,01 % à 10 %, préférentiellement de 0,1 % à 5 %, avantageusement de 0,5 % à 3 % en masse, par rapport à la masse totale de la composition lubrifiante. the amount of dispersant varies from 0.01% to 10%, preferably from 0.1% to 5%, advantageously from 0.5% to 3% by mass, relative to the total mass of the lubricating composition.
4. Composition selon la revendication 2 ou 3, dans laquelle les dispersants sont choisis parmi les succinimides, tels que les polyisobutylènes bis-succinimides, éventuellement boratés ou bloqués au zinc. 4. Composition according to claim 2 or 3, in which the dispersants are chosen from succinimides, such as polyisobutylene bis-succinimides, optionally borated or blocked with zinc.
5. Composition selon l’une quelconque des revendications 2 à 4, dans laquelle les détergents sont des détergents surbasés au carbonate de calcium choisis parmi les carboxylates, les phénates, les sulfonates, les salicylates et les détergents mixtes phénates - sulfonates - salicylates. 5. Composition according to any one of claims 2 to 4, in which the detergents are detergents overbased with calcium carbonate selected from carboxylates, phenates, sulphonates, salicylates and mixed phenates - sulphonates - salicylates detergents.
6. Composition selon l’une quelconque des revendications précédentes, dans laquelle le composé de formule (A) correspond au composé de formule (I) défini par la formule suivante : 6. Composition according to any one of the preceding claims, in which the compound of formula (A) corresponds to the compound of formula (I) defined by the following formula:
Figure imgf000018_0001
Figure imgf000018_0001
7. Utilisation d’un composé de formule (A) tel que défini dans les revendications 1 ou 6 dans une composition lubrifiante comprenant au moins une huile de base pour prévenir et/ou diminuer la corrosion et/ou la tribocorrosion d’au moins une pièce métallique d’un moteur, notamment un moteur deux-temps, par exemple un moteur marin deux-temps. 7. Use of a compound of formula (A) as defined in claims 1 or 6 in a lubricating composition comprising at least one base oil for preventing and / or reducing corrosion and / or tribocorrosion of at least one. metal part of an engine, in particular a two-stroke engine, for example a two-stroke marine engine.
8. Utilisation de la composition selon l’une quelconque des revendications 1 à 6 pour la prévention et/ou la diminution de la corrosion et/ou la tribocorrosion d’au moins une pièce métallique d’un moteur, notamment un moteur deux-temps, par exemple un moteur marin deux-temps. 8. Use of the composition according to any one of claims 1 to 6 for the prevention and / or reduction of corrosion and / or tribocorrosion of at least one metal part of an engine, in particular a two-stroke engine. , for example a two-stroke marine engine.
9. Utilisation selon la revendication 8 dans laquelle la pièce métallique est un cylindre, de préférence un cylindre en fonte. 9. Use according to claim 8 wherein the metal part is a cylinder, preferably a cast iron cylinder.
10. Procédé de passivation d’au moins une pièce métallique d’un moteur, notamment un moteur deux-temps, par exemple un moteur marin deux-temps, comprenant au moins une étape de mise en contact de ladite pièce métallique avec une composition lubrifiante définie selon l’une quelconque des revendications 1 à 6. 10. A method of passivation of at least one metal part of an engine, in particular a two-stroke engine, for example a two-stroke marine engine, comprising at least one step of bringing said metal part into contact with a lubricating composition. defined according to any one of claims 1 to 6.
PCT/EP2020/068004 2019-06-28 2020-06-26 Lubricant composition for preventing corrosion and/or tribo-corrosion of metal parts in an engine WO2020260569A1 (en)

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US17/619,486 US20220411712A1 (en) 2019-06-28 2020-01-28 Lubricant composition for preventing corrosion and/or tribo-corrosion of metal parts in an engine
CN202080047734.9A CN114364771A (en) 2019-06-28 2020-06-26 Lubricant composition for preventing corrosion and/or fretting corrosion of metal components in engines
EP20734060.5A EP3990589A1 (en) 2019-06-28 2020-06-26 Lubricant composition for preventing corrosion and/or tribo-corrosion of metal parts in an engine
KR1020227003474A KR20220050132A (en) 2019-06-28 2020-06-26 Lubricant composition for preventing corrosion and/or wear-corrosion of metal parts in engines
JP2021577877A JP2022538645A (en) 2019-06-28 2020-06-26 Lubricating composition for preventing corrosion and/or tribocorrosion of metal parts in engines

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