Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
  • C10M149/12—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M149/14—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds a condensation reaction being involved
  • C10M149/22—Polyamines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
  • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
  • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
• • 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
  • C10M133/54—Amines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/04—Mixtures of base-materials and additives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/04—Mixtures of base-materials and additives
  • C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds 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
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
• • 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
  • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
  • C10M2215/26—Amines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
• • 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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/52—Base number [TBN]
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • 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
• • 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

• the present invention relates to the prevention and/or reduction of metal losses of parts of an engine, in particular of a marine engine. More particularly, the present invention relates to the prevention and/or reduction of metal losses of parts of a marine engine due to contacts of these parts with an acidic medium.
• the present invention relates to the use of one or more soluble fatty amines in a lubricating composition to prevent and/or reduce metal losses from engine parts, in particular a marine engine.
• the present invention also relates to a method for preventing and/or reducing metal losses from parts of an engine, in particular a marine engine, in which said parts are brought into contact with one or more fatty amines soluble in a lubricating composition.
• the combustion of fuel oils generates the formation of acid gases, in particular sulphur oxides (SO 2 , SO 3 ).
• acid gases are among other things part of the combustion residues of fuel oils; these residues are in contact with the lubricating oil, and therefore also in contact with the engine parts.
• these acid gases hydrolyse into sulphurous acid (HSO 3 ) or sulphuric acid (H 2 SO 4 ), which in turn are in contact with the engine parts.
• lubricating oils are classified into two categories: cylinder oils on the one hand, providing lubrication to the piston-cylinder assembly, and system oils on the other hand, providing lubrication to all moving parts other than those of the piston-cylinder assembly. More specifically, it is within the piston-cylinder assembly that combustion residues containing acidic gases come into contact with the lubricating oil.
• the neutralization of these acids is carried out by reaction with the basic sites included in the lubricant.
• the neutralization capacity of an oil is measured by its BN or Base Number in English, characterizing its basicity. It is measured according to the ASTM D- 2896 standard and is expressed in equivalent weight of potash per gram of oil or mg of KOH/g of oil.
• the BN is a classic criterion for adjusting the basicity of cylinder oils to the sulfur content of the fuel oil used, in order to be able to neutralize all of the sulfur contained in the fuel, and capable of being transformed into sulfuric acid by combustion and hydrolysis. More specifically, marine oils available on the market have a BN ranging from 5 to 130 mg KOH/g of oil.
• detergents that are overbased with insoluble metal salts, in particular metal carbonates.
• Detergents mainly of the anionic type, are for example metal soaps of the salicylate, phenate, sulfonate, carboxylate type, etc. which form micelles where the particles of insoluble metal salts are kept in suspension.
• the usual overbased detergents intrinsically have a BN classically between 150 and 700 mg of potash per gram of detergent.
• Some BN can also be provided by non-overbased or “neutral” detergents with BN typically less than 150 mg of potash per gram of detergent.
• the applicant replaced part of the detergents providing all of the BN of the lubricating composition with compounds providing BN and forming little or no ash during the combustion of fuel oil.
• the applicant therefore developed lubricating compositions in which part of the detergents providing the BN of the lubricating composition is replaced by amine compounds.
• WO 2009/153453 describes a cylinder lubricating composition having a BN greater than or equal to 40 milligrams of potash per gram of lubricant and comprising a base oil, an alkali metal or alkaline earth metal detergent overbased with metal carbonate salts, a neutral detergent and a fatty amine and/or oil-soluble fatty amine derivative having a BN of between 150 and 600 milligrams of potash per gram of lubricant.
• WO 2014/180843 describes a cylinder lubricating composition having a BN greater than or equal to 50 milligrams of potash per gram of lubricant comprising a base oil, an alkali metal or alkaline detergent earthy, overbased with metal carbonate salts, a neutral detergent and a fatty amine mixture having four amine units.
• EP 2 486 113 describes a marine engine lubricating oil comprising a monoamine comprising a base oil, a detergent and a monoamine disubstituted by a hydrogen atom or a hydrocarbon group having 1 to 50 carbon atoms.
• WO 2011/042552 describes a lubricating composition for engines comprising a base oil, a detergent and a monoamine disubstituted by a hydrocarbon group comprising from 1 to 50 carbon atoms and by a hydrogen atom or a hydrocarbon group comprising from 1 to 50 carbon atoms.
• Fatty amines of formula (I) included in a lubricating composition are known as such in the applications WO 2009/153453 And WO 2014/180843 filed by the applicant. The applicant has now discovered a new use for these fatty amines.
• the applicant has surprisingly observed that the fatty amines according to the invention not only make it possible to provide organic BN to the lubricating composition while providing little or no ash during the combustion of fuel oil, but also make it possible to prevent and/or reduce metal losses from engine parts, in particular in a marine engine, when these parts are brought into contact with acids resulting from the combustion of fuel oil. More specifically, the applicant has unexpectedly discovered that these fatty amines soluble in a lubricating composition in the presence of a large excess of sulfuric acid make it possible to reduce and/or decrease metal losses from parts directly in contact with said lubricating composition and the large excess of sulfuric acid. This limitation and/or reduction of metal losses from parts is probably due to the passivation of all or part of the surface of the metal parts by said fatty amines.
• metal losses from engine parts means metal losses resulting from the attack of these parts by acids and not metal losses generated by friction of one metal part against another.
• fatty amine of formulas (I), (III) and/or (IV) makes it possible to prevent and/or reduce metal losses from parts in a marine engine, two-stroke or four-stroke during the combustion of any type of fuel oil.
• fatty amine of formulas (I), (III) and/or (IV) makes it possible to prevent and/or reduce metal losses from parts in hot parts, in particular the piston ring-liner (SPC) zone, of a two-stroke or four-stroke marine engine, during the combustion of any type of fuel oil.
• SPC piston ring-liner
• the fuel oil has a sulfur content of less than 3.5% by weight relative to the total weight of the fuel oil.
• fatty amine according to the invention is meant an amine of formula (I), (III) or (IV) comprising one or more hydrocarbon groups, saturated or unsaturated, linear or branched, and optionally comprising at least one heteroatom chosen from nitrogen, sulfur or oxygen, preferably oxygen.
• severe fatty amines according to the invention is meant a mixture of fatty amines of which at least one fatty amine is of formulas (I), (III) and/or (IV).
• the fatty amines of formula (I) according to the invention are mainly obtained from carboxylic acids. These acids are dehydrated in the presence of ammonia to give nitriles, and then undergo catalytic hydrogenation to lead in particular to fatty amines.
• the fatty amine of formula (I) is obtained from at least one carboxylic acid, preferably from at least one fatty acid.
• the alkyl group of the fatty amine of formula (I) has a number of carbon atoms corresponding to the number of carbon atoms in the carbon chain of the carboxylic acid, preferably corresponding to the number of carbon atoms in the carbon chain of the fatty acid.
• the same fatty amine of formula (I) may be substituted by several alkyl groups obtained from several carboxylic acids, identical or different, preferably obtained from several fatty acids, identical or different.
• the alkyl group is obtained from a fatty acid chosen from caprylic, pelargonic, capric, undecylenic, lauric, tridecylenic, myristic, pentadecylic, palmitic, margaric, stearic, nonadecylic, arachic, heneicosanoic, behenic, tricosanoic, lignoceric, pentacosanoic, cerotic, heptacosanoic, montanic, nonacosanoic, melissic, hentriacontanoic, laceroic acids, and their derivatives or unsaturated fatty acids such as palmitoleic, oleic, erucic, nervonic, linoleic, a-linolenic, c-linolenic, di-homo-c-linolenic, arachidonic, eico
• the fatty acids are derived from the hydrolysis of triglycerides present in vegetable and animal oils, such as coconut oil, palm oil, olive oil, peanut oil, rapeseed oil, sunflower oil, soybean oil, cottonseed oil, linseed oil, beef tallow.
• vegetable and animal oils such as coconut oil, palm oil, olive oil, peanut oil, rapeseed oil, sunflower oil, soybean oil, cottonseed oil, linseed oil, beef tallow.
• Natural oils may have been genetically modified so as to enrich their content of certain fatty acids, for example rapeseed oil or high oleic sunflower oil.
• the fatty amine of formula (I) according to the invention is preferably obtained from natural, plant or animal resources.
• the treatments making it possible to obtain fatty amines from oils natural can lead to mixtures of primary, secondary and tertiary polyamines.
• the mixture of fatty amines of formula (I) is in a purified form, that is to say comprising mainly a single type of amine of formula (Ia), (Ib) or (Ic), for example mainly diamines of formula (Ia), triamines of formula (Ib) or mainly tetramines of formula (Ic).
• the mixture of fatty amines mainly comprises tetramines of formula (Ic).
• R 1 or R 2 represents a saturated alkyl group
• said saturated alkyl is obtained from a saturated fatty acid or from a unsaturated fatty acid which has undergone hydrogenation, in particular of all of its double bonds.
• the fatty amine mixture of formula (I) does not comprise fatty amines other than fatty amines corresponding to formula (IIc).
• the fatty amine is a mixture of polyalkylamines of formulas (III) and/or (IV)
• the mixtures of polyalkylamines comprise at least 5% by weight of compounds having a pure linear structure, since these compounds have been shown to have an acceptable viscosity profile.
• the mixtures of polyalkylamines comprise at least 4% by mass (%m/m), preferably at least 5%m/m, preferably at least 6%m/m, preferably more than 7%m/m, preferably more than 7.5%m/m, preferably more than 10%m/m, preferably more than 20%m/m of branched compounds of which at least one of n or z is greater than or equal to 1.
• n For products of formula (III), this means that for branched products, n must be greater than or equal to 1.
• the fatty amine is a mixture of polyalkylamines of formulas (III) and/or (IV)
• n, o, p or z is equal to 0
• the hydrogen atom present at the end of the chain is covalently bonded to the corresponding secondary nitrogen atom.
• the fatty amine is a mixture of polyalkylamines of formulas (III) and/or (IV)
• the mixture comprises compounds of formulas (III) and/or (IV) in which n, o, p and z, when they are different from 0, are equal to 1 or 2, preferably, when n, o, p and z are different from 0 they are equal to 1.
• the mixture essentially comprises compounds of formulas (III) and/or (IV) for which n, o, p or z independently represent 0, 1 or 2, preferably n, o, p or z independently represent 0 or 1.
• the mixture essentially comprises compounds of formulas (III) and/or (IV) and their derivatives for which n, o, p and z independently represent 0, 1 or 2, preferably, n, o, p and z independently represent 0 or 1.
• each R group is, independently of one another, an alkyl group, linear or branched, comprising from 14 to 22 carbon atoms, preferably from 14 to 20 carbon atoms, preferably from 16 to 20 carbon atoms.
• the fatty amines of formula (III) and (IV) according to the invention are mainly obtained from carboxylic acids. These acids are dehydrated in the presence of ammonia to give nitriles, and then undergo catalytic hydrogenation to lead in particular to fatty amines.
• the fatty amines of formula (III) and (IV) are obtained from at least one carboxylic acid, preferably from at least one fatty acid.
• the alkyl group of the fatty amines of formula (III) and (IV) has a number of carbon atoms corresponding to the number of carbon atoms in the carbon chain of the carboxylic acid, preferably corresponding to the number of carbon atoms in the carbon chain of the fatty acid.
• the same fatty amine of formula (I) may be substituted by several alkyl groups obtained from several carboxylic acids, identical or different, preferably obtained from several fatty acids, identical or different.
• the same fatty amine of formula (I) can be substituted by several alkyl groups obtained from several acids.
• R groups may be different, they are, in a preferred embodiment, identical, such compounds being produced more economically. Regardless of whether they are identical or not, one or both R groups, independently, are derived from chemical or natural raw material such as natural oils and fats. In particular, if a natural raw material is used, this means that each R group may have a particular distribution in the length of the carbon chain.
• R is derived from oil or fat of animal or vegetable origin such as tallow, coconut oil and palm oil.
• the preparation of the di-alkyl fatty polyalkylamines according to the invention comprises a hydrogenation step, it may be advantageous, in the process for preparing the products of the invention, to use hydrogenated R groups.
• the R group is a hydrogenated tallow group.
• the R group of the raw material is unsaturated and is (partially) hydrogenated during the process of preparing the fatty polyalkylamine.
• the alkyl group R is obtained from a fatty acid chosen from caprylic, pelargonic, capric, undecylenic, lauric, tridecylenic, myristic, pentadecylic, palmitic, margaric, stearic, nonadecylic, arachic, heneicosanoic, behenic, tricosanoic, lignoceric, pentacosanoic, cerotic, heptacosanoic, montanic, nonacosanoic, melissic, hentriacontanoic, laceroic acids, and their derivatives or unsaturated fatty acids such as palmitoleic, oleic, erucic, nervonic, linoleic, a-linolenic,
• the fatty acids are derived from the hydrolysis of triglycerides present in vegetable and animal oils, such as coconut oil, palm oil, olive oil, peanut oil, rapeseed oil, sunflower oil, soybean oil, cottonseed oil, linseed oil, beef tallow.
• vegetable and animal oils such as coconut oil, palm oil, olive oil, peanut oil, rapeseed oil, sunflower oil, soybean oil, cottonseed oil, linseed oil, beef tallow.
• Natural oils may have been genetically modified so as to enrich their content with certain fatty acids, for example rapeseed oil or high oleic sunflower oil.
• compositions of fatty dialkyl polyalkylamine derivatives of formulae (III) and/or (IV) according to the invention comprise compounds for which one or more NH moieties of the fatty polyalkylamine of the invention are methylated, alkoxylated, or both. It has been found that such compounds have advantageous solubility, particularly in lubricating oils.
• the alkoxylated derivatives are butoxylated, propoxylated and/or ethoxylated. If two or more alkoxylating agents are used, they may be used in any order, for example EO-PO-EO, and the different alkoxy units may be polyhedral in nature and/or present randomly.
• a primary -NH 2 group is alkoxylated with one or more alkylene oxides in a conventional manner to form a -NH-AO-H group, where AO represents one or more alkyleneoxy units.
• the resulting -NH-AO-H group may be further alkoxylated to form -N(AO-H) 2 units.
• alkylene oxide i.e. more than 8 moles of alkylene oxides per mole of polyalkylamine
• the secondary amines if present, are alkoxylated.
• all the primary and secondary amine functions of the di-alkyl polyamine of formulas (III) and/or (IV) are alkoxylated.
• the fatty di-alkyl polyalkylamines are derived by methylation of one or more NH functions in a manner known to those skilled in the art, for example by reaction with formic acid and formaldehyde.
• one or more OH functions of the alkoxylated fatty di-alkyl polyalkylamines are methylated in a conventional manner.
• mixtures of polyalkylamines of formula (IV) are preferred. Where appropriate, mixtures of polyalkylamines of formulas (III) and/or (IV) are used.
• the branched polyalkylamines of the invention can be produced by any synthetic route known to those skilled in the art.
• a method Conventional production process may be from a diamine and involves two or more cycles, preferably two for economic reasons, each cycle comprising a cyanoethylation step and a hydrogenation step. This process is hereinafter referred to as a two-step process.
• one equivalent of di-alkyl diamine may react in a single step with two or more equivalents of acrylonitrile, followed by hydrogenation.
• optional additional cycles involving cyanoethylation and hydrogenation steps may be considered.
• Such a one-step process may be advantageous since it requires fewer intermediate steps.
• an acid catalyst is used such as HCl or acetic acid.
• increasing the reaction temperature during cyanoethylation also helps to increase branching in this process.
• the temperature of a subsequent cyanoethylation step is higher than the temperature of a previous cyanoethylation step, allowing a compound with the desired branching to be obtained.
• more than one mole of acrylonitrile per mole of initial polyamine is used, which also allows the branching of the expected product to be increased to the desired level.
• a solvent is used.
• Preferred solvents include C 1-4 alcohols and C 2-4 diols. Ethanol is preferably used, as it allows particular ease of handling. Surprisingly, it has been shown that C 1-4 alcohols and C 2-4 diols are not simple solvents but also have co-catalytic activity during the cyanoethylation step.
• the amount of solvent employed can vary over a wide range. For economic reasons, the amount employed is preferably minimal.
• the amount of solvent, in particular in the cyanoethylation step is preferably less than 50, 40, 30 or 25% by weight relative to the liquid reaction mixture.
• the amount of solvent, in particular in the cyanoethylation step is preferably greater than 0.1, 0.5, 1, 5 or 10% by weight relative to the liquid reaction mixture.
• the mixture of fatty dialkyl polyalkylamines of formulas (III) and/or (IV) according to the invention is characterized by a BN measured according to the ASTM D-2896 standard of between 150 and 350 mg KOH/g of amine, preferably between 170 and 340 and even more preferably between 180 and 320.
• the weight percentage of the di-alkyl polyalkylamine mixture relative to the total weight of the lubricating composition is chosen so that the BN provided by these compounds represents a contribution of between 5 and 60 mgKOH/g of lubricant, preferably between 10 and 30 mgKOH/g of lubricant, of the total BN of said cylinder lubricant, measured according to the ASTM D-2896 standard.
• the lubricating composition has a BN determined according to the ASTM D-2896 standard greater than or equal to 15 milligrams of potash per gram of lubricant, more preferably greater than or equal to 40 milligrams.
• the lubricating composition has a BN determined according to the ASTM D-2896 standard of between 40 and 120 milligrams of potash per gram of lubricant, preferably between 50 and 100 milligrams of potash per gram of lubricant.
• the lubricating composition also has a BN determined according to the ASTM D-2896 standard of between 15 and 40 milligrams of potash per gram of lubricant, preferably between 20 and 40 milligrams of potash per gram of lubricant.
• the mass percentage of fatty amine relative to the total weight of the cylinder lubricant is chosen so that the BN provided by this fatty amine represents a contribution of at least 2 milligrams of potash per gram of lubricant to the total BN of said cylinder lubricant, preferably at least 5 milligrams of potash per gram of lubricant to the total BN of said cylinder lubricant.
• the mass percentage of fatty amine of formulae (I), (III) and/or (IV) relative to the total weight of the cylinder lubricant is chosen so that the BN provided by this fatty amine represents a contribution of 2 to 30 milligrams of potash per gram of lubricant, more preferably of 5 to 25 milligrams of potash per gram of lubricant to the total BN of said cylinder lubricant.
• the fatty amine of formula (I) or the mixture of fatty amines of formulas (III) and/or (IV) or the mixture of fatty amines of formulas (I), (III) and/or (IV) is added in an amount of 0.1 to 15%, preferably 0.5 to 10%, preferably 0.5 to 8% or 3 to 10% by weight relative to the total weight of the lubricating composition.
• the fatty amine of formula (I) represents from 0.5 to 10%, preferably from 0.5 to 8% by weight relative to the total weight of the lubricating composition.
• the weight percentage of the mixture of di-alkyl polyalkylamine of formulas (III) and/or (IV) relative to the total weight of lubricant is between 0.1 and 15%, preferably between 0.5 and 10%, advantageously between 3 and 10%.
• the lubricating composition further comprises at least one neutral detergent.
• the detergents commonly used in the formulation of lubricating compositions are typically anionic compounds comprising a long lipophilic hydrocarbon chain and a hydrophilic head.
• the associated cation is typically a metal cation of an alkali or alkaline earth metal.
• the detergents are preferably chosen from alkali or alkaline earth metal salts of carboxylic acids, sulfonates, salicylates, naphthenates, as well as phenate salts.
• the alkali and alkaline earth metals are preferably calcium, magnesium, sodium or barium.
• These metal salts may contain the metal in approximately stoichiometric amounts. In this case, they are referred to as non-overbased or "neutral" detergents, although they also provide some basicity. These "neutral" detergents typically have a BN, measured according to ASTM D2896, of less than 150 mg KOH/g, or less than 100, or less than 80 mg KOH/g.
• neutral detergents can contribute in part to the BN of the lubricants according to the present invention.
• neutral detergents of the type carboxylates, sulfonates, salicylates, phenates, naphthenates of alkali and alkaline earth metals, for example calcium, sodium, magnesium, barium, will be used.
• BN is high, 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 oil-insoluble metal salts, e.g. carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate.
• oil-insoluble metal salts e.g. 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.
• Overbased detergents are thus presented in the form of micelles composed of insoluble metal salts held in suspension in the lubricating composition by detergents in the form of oil-soluble metal salts.
• These micelles may contain one or more types of insoluble metal salts, stabilized by one or more types of detergent.
• Overbased detergents containing only one type of detergent-soluble metal salt will generally be named after the nature of the hydrophobic chain of the latter detergent.
• carboxylate, phenate, salicylate, sulfonate, naphthenate type depending on whether this detergent is respectively a carboxylate, phenate, salicylate, sulfonate, or naphthenate.
• Overbased detergents will be said to be of mixed type if the micelles include several types of detergents, different from each other by the nature of their hydrophobic chain.
• the oil-soluble metal salts will preferably be carboxylates, phenates, sulfonates of salicylates, and mixed phenate-sulfonate and/or salicylates of calcium, magnesium, sodium or barium.
• the insoluble metal salts providing the overbased character are carbonates of alkali and alkaline earth metals, preferably calcium carbonate.
• the overbased detergents used in the lubricating compositions according to the present invention will preferably be carboxylates, phenates, sulfonates, salicylates and mixed phenate-sulfonate-salicylate detergents, overbased with calcium carbonate.
• the base oil included in the lubricating composition is chosen from oils of mineral, synthetic or vegetable origin as well as their mixtures.
• Group 1 mineral oils may be obtained by distillation of selected naphthenic or paraffinic crudes and then 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 severe purification processes, for example a combination of hydrotreating, hydrocracking, hydrogenation and catalytic dewaxing.
• Group 4 and 5 synthetic bases include polyalphaolefins, polybutenes, polyisobutenes, alkylbenzenes.
• base oils can be used alone or in a mixture.
• a mineral oil can be combined with a synthetic oil.
• Cylinder oils for 2-stroke marine diesel engines have a viscometric grade of 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 between 12.5 and 16.3 mm 2 /s.
• Grade 50 oils have a kinematic viscosity at 100°C between 16.3 and 21.9 mm 2 /s.
• Grade 60 oils have a kinematic viscosity at 100°C between 21.9 and 26.1 V.
• cylinder oils for 2-stroke marine diesel engines with 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 500NS or 600 NS) and Brightstock. Any other combination of mineral, synthetic or vegetable bases having, in mixture 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 500NS or 600 NS) and Brightstock.
• Neutral Solvent bases for example 500NS or 600 NS
• Brightstock any other combination of mineral, synthetic or vegetable bases having, in mixture with the additives, a viscosity compatible with the SAE-50 grade can be used.
• a conventional cylinder lubricant formulation for slow 2-stroke marine diesel engines is of SAE 40 to SAE60 grade, preferably SAE50 (according to SAE J300 classification) and comprises at least 50% by weight of lubricating base oil of mineral and/or synthetic origin, suitable for use in marine engines, for example, of API Group 1 class, i.e. obtained by distillation of selected crudes and then 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 may further comprise one or more thickening additives whose role is to increase the viscosity of the composition, both hot and cold, or viscosity index (VI) improving additives.
• thickening additives whose role is to increase the viscosity of the composition, both hot and cold, or viscosity index (VI) improving additives.
• these additives are most often low molecular weight polymers, of the order of 2000 to 50,000 daltons (Mn).
• PIB of the order of 2000 daltons
• poly-Acrylate or Poly Methacrylates of the order of 30000 daltons
• Olefin-copolymers Olefin and Alpha Olefin Copolymers
• EPDM Polybutenes
• High Molecular Weight Poly-Alphaolefins viscosity 100°C > 150
• Styrene-Olefin copolymers hydrogenated or not.
• the base oil(s) included in the lubricating composition according to the invention may be partially or totally substituted by these additives.
• the polymers used to partially or totally substitute one or more of the base oils are preferably the aforementioned PIB type thickeners (for example marketed under the name Indopol H2100).
• the lubricating composition may further comprise at least one anti-wear additive.
• the anti-wear additive is Zinc dithiophosphate or DTPZn. Also found in this category are various phosphorus, sulfur, nitrogen, chlorine and boron compounds.
• anti-wear additives there are a wide variety of anti-wear additives, but the most widely used category is phospho-sulfur additives such as metal alkylthiophosphates, particularly Zinc alkylthiophosphates, and more specifically Zinc dialkyldithiophosphates or DTPZn.
• phospho-sulfur additives such as metal alkylthiophosphates, particularly Zinc alkylthiophosphates, and more specifically Zinc dialkyldithiophosphates or DTPZn.
• Amine phosphates, polysulfides, especially sulfur olefins, are also commonly used anti-wear additives.
• anti-wear and extreme pressure additives of the nitrogen and sulfur type, such as for example metal dithiocarbamates, in particular molybdenum dithiocarbamate.
• Glycerol esters are also anti-wear additives. Examples include mono, di and trioleates, monopalmitates and monomyristates.
• the lubricating composition may further comprise at least one dispersant.
• Dispersants are well-known additives used in the formulation of lubricating compositions, particularly for application in the marine sector. 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 acting on the steric hindrance. They can also have a synergistic effect on neutralization.
• Dispersants used as lubricant additives typically 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, oxygen or phosphorus element.
• succinimides are used, obtained by condensation of succinic anhydrides and amines, succinic esters obtained by condensation of succinic anhydrides and alcohols or polyols.
• Mannich bases obtained by polycondensation of phenols substituted by alkyl groups, formaldehyde and primary or secondary amines, are also compounds used as dispersants in lubricants.
• a dispersant from the PIB succinimide family for example borated or zinc-blocked, can be used.
• the lubricating composition may further comprise all types of functional additives suitable for their use, for example anti-foam additives to counteract the effect of detergents, which may be for example polar polymers such as polymethylsiloxanes, polyacrylates, anti-oxidant and/or anti-rust additives, for example organo-metallic detergents or thiadiazoles. These are known to those skilled in the art.
• the lubricant compositions described refer to the compounds taken separately before mixing, it being understood that said compounds may or may not retain the same chemical form before and after mixing.
• the lubricants according to the present invention obtained by mixing the compounds taken separately are not in the form of an emulsion or a microemulsion.
• the use of one or more fatty amines of formulae (I), (III) and/or (IV) makes it possible to prevent and/or reduce metal losses from parts in a two-stroke or four-stroke marine engine during the combustion of any type of fuel oil.
• the use of one or more fatty amines of formulae (I), (III) and/or (IV) according to the invention makes it possible to prevent and/or reduce metal losses from parts in the hot parts, in particular the SPC zone, of a two-stroke or four-stroke marine engine, during the combustion of any type of fuel oil.
• the fuel oil has a sulfur content of less than 3.5% by weight relative to the total weight of the fuel oil.
• 200 g of the lubricating composition comprising one or more fatty amines according to the invention are introduced into a 700 mL test tube and this test tube is heated to 60°C with vigorous stirring for a period of approximately 30 minutes.
• a cast iron plate, previously sanded, cleaned and weighed, is immersed in the test tube thus heated and stirred, then a quantity of sulfuric acid diluted to 50% is gradually added over 1 hour 30 minutes so as to neutralize all or part of the total BN of said lubricating composition.
• the quantity of sulfuric acid diluted to 50% added to the lubricating composition is calculated according to the number of BN points to be neutralized.
• the rate of addition of the sulfuric acid diluted to 50% is calculated according to the total quantity of sulfuric acid to be added over a period of 1 hour 30 minutes.
• the lubricating composition thus acidified and comprising the plate is subsequently stirred for an additional 30 min in order to ensure that the BN neutralization reaction is complete.
• the plate immersed in the acidified lubricating composition is then removed from the test piece and weighed in order to determine the metallic losses of said cast iron plate due to attack by sulfuric acid.
• compositions L 1 to L 7 and L 9 to L 11 makes it possible to significantly reduce, or even avoid, the metal losses of a part directly placed in contact with sulfuric acid and this independently of the content of fatty amines in the lubricating composition, unlike the control composition which does not comprise fatty amines according to the invention.
• the metal losses of the parts do not exceed 4 mg when these parts are immersed in an acidic medium and respectively in the presence of different types of fatty amines according to the invention contained in the lubricating compositions, unlike the metal losses of the parts placed in contact with sulfuric acid and a lubricating composition not comprising fatty amines according to the invention which exceed 80 mg.
• the metal part loses little material, that is to say it loses 7 mg when it is in contact with fatty amines according to the invention contained in a lubricating composition, unlike a metal part placed in contact with a lubricating composition not comprising fatty amines according to the invention for which the metal losses amount to more than 115 mg.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Lubricants (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=54291489

Family Applications (1)

Country Status (12)

Families Citing this family (8)

Family Cites Families (20)

• 2015
  • 2015-08-03 FR FR1557492A patent/FR3039835B1/fr active Active
• 2016
  • 2016-08-03 KR KR1020187003438A patent/KR102665281B1/ko active Active
  • 2016-08-03 US US15/750,312 patent/US10738261B2/en active Active
  • 2016-08-03 RU RU2018103966A patent/RU2018103966A/ru not_active Application Discontinuation
  • 2016-08-03 JP JP2018506315A patent/JP6833813B2/ja active Active
  • 2016-08-03 BR BR112018002388-4A patent/BR112018002388A2/pt active Search and Examination
  • 2016-08-03 WO PCT/EP2016/068477 patent/WO2017021426A1/fr active Application Filing
  • 2016-08-03 ES ES16745760T patent/ES3014968T3/es active Active
  • 2016-08-03 EP EP16745760.5A patent/EP3331975B1/fr active Active
  • 2016-08-03 CN CN201680045002.XA patent/CN107922876B/zh active Active
  • 2016-08-03 DK DK16745760.5T patent/DK3331975T3/da active
  • 2016-08-03 SG SG11201800901UA patent/SG11201800901UA/en unknown

Also Published As

Similar Documents

Legal Events