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
  • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
  • C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular 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
  • 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
  • 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
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/102—Aliphatic fractions
  • C10M2203/1025—Aliphatic fractions used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
  • C10M2205/022—Ethene
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/028—Overbased salts thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/283—Esters of polyhydroxy 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/287—Partial esters
  • C10M2207/289—Partial esters containing free hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
  • C10M2219/046—Overbasedsulfonic acid salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/045—Metal containing thio derivatives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/02—Pour-point; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/04—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
  • C10N2030/52—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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/54—Fuel economy
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • 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
  • C10N2070/00—Specific manufacturing methods for lubricant compositions
  • C10N2070/02—Concentrating of additives

Definitions

• the present invention relates to a lubricating composition for a marine engine, in particular for a four-stroke or two-stroke marine engine, the use of which promotes fuel economy and exhibiting good engine cleanliness properties, in particular crankcase cleanliness.
• the consumption gains in the NEDC cycle (New European Driving Cycle) according to European directive 70/220 / EEC are cold (urban cycle) of 5%, hot (extra-urban cycle) of 1.5% , for average gains of 2.5%.
• NEDC cycle New European Driving Cycle
• hot extra-urban cycle
• the formulation of a “fuel-eco” lubricant must not be to the detriment of the other performances of the lubricant.
• the resistance to wear, demulsion, neutralization capacity, and the cleanliness of the engine (piston and / or crankcase) must not be altered.
• lubricating compositions for marine engines which comprise at least one base oil, an overbased sulphonate detergent, at least one phenate detergent containing sulfur, and other additives such as antioxidants, anti-wear additives, extreme pressure additives, corrosion inhibitors, foam inhibitors, viscosity index improvers, etc.
• additives such as antioxidants, anti-wear additives, extreme pressure additives, corrosion inhibitors, foam inhibitors, viscosity index improvers, etc.
• compositions comprising at least one base oil, overbased alkali metal salts and various additives such as dispersants, detergents, antioxidants, anti-wear additives, extreme pressure additives, etc.
• the document US, 449,208 describes the synthesis of a low volatility polyfunctional additive obtained from the reaction of an alcohol (compound a), an acid or ester derivative bearing a hydroxyphenyl group (compound b) and an ester or an acyl halide (compound c).
• the product obtained can be used as antioxidants in liquid fuels or as an anti-friction additive in a lubricating composition.
• WO2011005741 discloses a marine engine lubricant comprising a base oil, a hydrogenated copolymer comprising an olefinic block and a vinyl aromatic block and a star copolymer of a diene and a hydrogenated vinyl aromatic.
• the aim of the present invention is to provide a lubricating composition for a marine engine which makes it possible to reduce the consumption of fuel oil while keeping intact the cleanliness of the engine, in particular of the crankcase.
• the objective of the present invention is to obtain reductions in fuel oil consumption of at least 0.5% compared to a reference oil without additives of the same grade (that is to say of kinematic viscosity at 100 ° C of the same order of magnitude), preferably at least 0.7%, more preferably at least 0.8%>, even more preferably at least 0.9%, still more preferably at at least 1%, still more preferably at least 2%, still more preferably at least 3%.
• the objective of the present invention is to obtain reductions in fuel oil consumption as described above, while maintaining good engine cleanliness, in particular good crankcase cleanliness, illustrated by a quantity of deposits according to the test.
• Continuous ECBT less than 600 mg, preferably less than 550 mg, more preferably less than 500 mg, even more preferentially less than 450 mg, even more preferably less than 400 mg, even more preferably less than 350 mg, even more preferably less at 300 mg.
• the hydrogenated styrene / isoprene copolymer has an amount by mass of hydrogenated isoprene units, relative to the mass of copolymer, of between 50% and 95%.
• the detergents are chosen from carboxylates, sulfonates and / or phenates, taken alone or as a mixture, in particular calcium carboxylates, calcium sulfonates and / or calcium phenates.
• the lubricating composition has a BN determined according to standard ASTM D-2896, from 5 to 100 mg of KOH / g, preferably from 7 to 80 mg of KOH / g, more preferably from 10 to 60 mg of KOH / g.
• the lubricating composition has a kinematic viscosity measured according to the ASTM D7279 standard at 100 ° C is between 5.6 and 26.1 cSt, preferably between 9.3 and 21.9 cSt, more preferably between 12.5 and 16.3 cSt.
• the lubricating base oils are chosen from group 1 or group 2 base oils, taken alone or as a mixture.
• the lubricating composition further comprises an antiwear additive, preferably a zinc dithiophosphate.
• the invention also relates to the use of a lubricating composition as defined above for the lubrication of 4-stroke or 2-stroke marine engines.
• a lubricating composition as defined above makes it possible to reduce the fuel consumption of 4-stroke or 2-stroke marine engines.
• a lubricating composition as defined above makes it possible to reduce the fuel consumption of 4-stroke or 2-stroke marine engines and while maintaining good engine cleanliness, preferably good crankcase cleanliness.
• the invention also relates to the use of 0.5 to 2% by mass of at least one ester of glycerol, the ester of glycerol being a mixed ester of glycerol with at least one fatty acid comprising from 8 to 24 carbon atoms.
• a lubricating composition for a 2-stroke or 4-stroke marine engine comprising at least one lubricating base oil, 0.2 to 5% by mass of at least one linear copolymer ethylene and propylene, 0.3 to 8% by mass of at least one hydrogenated styrene / isoprene copolymer, 4 to 15% by mass of at least one detergent, to improve engine cleanliness of 4-stroke marine engines or 2-stroke, preferably the crankcase cleanliness of 4-stroke or 2-stroke marine engines.
• the lubricating composition according to the invention contains at least one olefin copolymer (OCP). These olefin copolymers are traditionally copolymers based on ethylene units and on propylene units.
• OCP olefin copolymer
• the olefin copolymer according to the invention is an ethylene / propylene copolymer.
• the olefin copolymer according to the invention is in linear form.
• the olefin copolymer according to the invention is in the form of blocks or in random form.
• the olefin copolymer according to the invention advantageously has a content of ethylene units, ranging from 5% to 75% by mass, relative to the mass of olefin copolymer, of preferably from 10% to 60%, more preferably from 15% to 55%, even more preferably from 20% to 50%, even more preferably from 30% to 40%.
• the olefin copolymer according to the invention advantageously has a weight average molecular mass M W of between 10,000 and 500,000 daltons, preferably between 50,000 and 400,000, more preferably between 100,000 and 200,000, even more preferably between 150 000 and 180,000.
• the olefin copolymer according to the invention advantageously has a number-average molecular mass M n of between 10,000 and 500,000 daltons, preferably between 50,000 and 200,000, more preferably between 80,000 and 150,000, even more preferably between 90 000 and 130,000.
• the olefin copolymer according to the invention advantageously has a polydispersity index of between 1 and 4, preferably between 1.2 and 3, more preferably between 1.5 and 2, even more preferably between 1.6 and 1.9.
• the amount of olefin copolymer in the lubricating composition according to the invention is from 0.2% to 5% by mass, relative to the total mass of the lubricating composition, preferably 0.3% to 4%, even more preferably from 0.5% to 2%.
• This quantity is understood as a quantity of dry polymer material.
• the olefin copolymer used in the context of the present invention is sometimes found in dilution in a mineral or synthetic oil (most often a group 1 oil according to the API classification).
• the lubricating composition according to the invention also contains at least one copolymer based on styrene and hydrogenated isoprene.
• the hydrogenated styrene / isoprene copolymer according to the invention is in linear or star form, preferably in star form.
• the hydrogenated styrene / isoprene copolymer according to the invention is in the form of blocks or in random form.
• the hydrogenated styrene / isoprene copolymer according to the invention advantageously has a content of hydrogenated isoprene units, ranging from 50% to 95% by mass, relative to the mass of hydrogenated styrene / isoprene copolymer, preferably from 60% to 90%, more preferably from 70% to 85%, even more preferably from 75% to 80%.
• the hydrogenated styrene / isoprene copolymer according to the invention advantageously has a content of styrene units, ranging from 5% to 50% by mass, relative to the mass of hydrogenated styrene / isoprene copolymer, preferably from 10% to 40%, more preferably from 15% to 30%, even more preferably from 20% to 25%.
• the hydrogenated styrene / isoprene copolymer according to the invention advantageously has a weight average molecular mass M W of between 100,000 and 800,000 daltons, preferably between 200,000 and 700,000, more preferably between 300,000 and 600,000, even more preferably. between 400,000 and 500,000.
• the hydrogenated styrene / isoprene copolymer according to the invention advantageously has a number-average molecular mass Mn of between 50,000 and 800,000 daltons, preferably between 100,000 and 600,000, more preferably between 200,000 and 500,000, even more preferably between 300,000 and 400,000.
• the hydrogenated styrene / isoprene copolymer according to the invention advantageously has a polydispersity index of between 1 and 4, preferably between 1.2 and 3, more preferably between 1.4 and 2, even more preferably between 1.5 and 1, 8.
• the amount of copolymer of styrene and of hydrogenated isoprene in the lubricating composition according to the invention is from 0.3% to 8% by mass, relative to the total mass of the lubricating composition, preferably from 0.5% to 5%.
• This quantity is understood as a quantity of dry polymer material.
• the copolymer of styrene and of hydrogenated isoprene used in the context of the present invention is sometimes found in dilution in a mineral or synthetic oil (most often a group 1 oil according to the API classification).
• the lubricating composition according to the invention also contains, at least one ester of glycerol, the ester of glycerol being a mixed ester of glycerol with at least one fatty acid comprising from 8 to 24 carbon atoms and at least one carboxylic acid also comprising a hydroxyphenyl function.
• glycerol ester is meant a reaction product between glycerol and one or more carboxylic acids taken alone or as a mixture.
• Glycerol esters are known in the field of lubricants as being friction modifiers. The Applicant has noticed that this additive has an influence on the cleanliness of the engine, and in particular the crankcase cleanliness of the engine.
• the glycerol ester according to the invention is most often a mixed ester, that is to say a reaction product between glycerol and several (at least two) carboxylic acids different from one another.
• the glycerol ester according to the invention is a mixture of monoesters, diesters and / or triesters of glycerol with one or more carboxylic acids taken alone or as a mixture. Since the preferred glycerol esters are mixed esters, the glycerol ester according to the invention is preferably a mixture of glycerol diesters and / or triesters with at least two different carboxylic acids.
• the carboxylic acids used for reaction with glycerol are, for example, fatty acids, derived from oils of vegetable origin. These fatty acids are saturated, monounsaturated and / or polyunsaturated fatty acids. These fatty acids comprise from 6 to 24 carbon atoms, preferably from 6 to 22 carbon atoms, more preferably from 8 to 20 carbon atoms. Preferably, the carboxylic acids used for the reaction with glycerol are used in the form of a mixture of fatty acids.
• the mixture of fatty acids mainly comprises saturated, monounsaturated and / or polyunsaturated fatty acids comprising between 8 to 20 carbon atoms, preferably predominantly saturated, monounsaturated and / or polyunsaturated fatty acids comprising between 10 to 18 carbon atoms, even more preferably predominantly saturated, monounsaturated and / or polyunsaturated fatty acids having between 12 to 16 carbon atoms.
• predominantly within the meaning of the present invention is meant that the sum of saturated, monounsaturated and / or polyunsaturated fatty acids comprising between 8 to 20 carbon atoms represents more than 50% by weight of the total weight of the mixture of fatty acids.
• Fatty acids can come from vegetable oils such as rapeseed, sunflower, soybean, linseed, olive, palm, castor, wood, corn, squash, grape seed, jojoba, sesame, walnut, hazelnut, almond, shea, macadamia, cotton, alfalfa, rye, safflower, peanut, coconut and copra, taken alone or in mixtures.
• vegetable oils such as rapeseed, sunflower, soybean, linseed, olive, palm, castor, wood, corn, squash, grape seed, jojoba, sesame, walnut, hazelnut, almond, shea, macadamia, cotton, alfalfa, rye, safflower, peanut, coconut and copra, taken alone or in mixtures.
• coconut oil is used.
• the carboxylic acids used for reaction with glycerol can also be carboxylic acids comprising an alkyl chain comprising between 1 and 6 carbon atoms linked to the acid function; the alkyl chain further comprising another function, preferably a substituted or unsubstituted hydroxyphenyl function.
• the alkyl chain can be linear or branched.
• the alkyl chain is linear.
• the alkyl chain comprises between 1 and 4 carbon atoms.
• the alkyl chain is a propyl chain.
• the hydroxyphenyl function is preferably a substituted hydroxyphenyl function.
• the hydroxyphenyl function is substituted by at least one linear or branched alkyl group comprising between 1 and 6 carbon atoms.
• the hydroxyphenyl function is substituted by at least one linear or branched alkyl group comprising between 1 and 4 carbon atoms.
• the carboxylic acid used to react with glycerol is an alkyl carboxylic acid comprising a hydroxyphenyl function substituted by t -butyl units.
• the hydroxyl function of the hydroxyphenyl is in the para position relative to the alkyl carboxylic acid group which reacts with glycerol, and the t -butyl units are located in the meta position.
• the ester of glycerol according to the invention is an ester mixed glycerol, preferably a mixed ester of at least one fatty acid and at least one carboxylic acid comprising a hydroxyphenyl function, as defined above.
• the amount of glycerol ester in the lubricating composition according to the invention is from 0.5% to 2% by mass, relative to the total mass of the lubricating composition, preferably from 1% to 1.5%. This quantity is understood as a quantity of product dry matter.
• the glycerol ester used in the context of the present invention is sometimes found in dilution in a mineral or synthetic oil of the paraffinic type (most often an oil comprising aliphatic cycloparaffinic hydrocarbons).
• the detergents used in the lubricating compositions according to the present invention are well known to those skilled in the art.
• Detergents commonly used in the formulation of lubricating compositions are typically anionic compounds having 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 according to the invention are chosen from alkali metal or alkaline earth metal salts of carboxylic acids, sulphonates, salicylates, naphthenates and phenates taken alone or as a mixture.
• Detergents are named after the nature of the hydrophobic chain, carboxylate, sulfonate, salicylate, naphthenate or phenate.
• the alkali metals and alkaline earth metals are preferably calcium, magnesium, sodium or barium, more preferably calcium.
• the detergents used will not be overbased (or neutral) or overbased.
• the excess metal imparting the overbased character to the detergent is in the form of oil-insoluble metal salts.
• 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. These micelles can contain one or more types of insoluble metal salts, stabilized by one or more types of detergents.
• the overbased detergents will be said to be of mixed type if the micelles comprise several types of detergents, which are different from one another by the nature of their hydrophobic chain.
• the preferred detergents are the carboxylates, the sulphonates and / or the phenates, taken alone or as a mixture, in particular the carboxylates, the sulphonates and / or the calcium phenates.
• the amount of detergents in the lubricating composition according to the invention is from 4% to 15% by mass, relative to the total mass of the lubricating composition, preferably from 5% to 10%.
• the BN (Base Number measured according to ASTM D-2896) of the lubricating compositions according to the present invention is provided by neutral or overbased detergents based on alkali or alkaline earth metals.
• the BN value of the lubricating compositions according to the present invention can vary from 5 to 100 mg of KOH / g, preferably from 7 to 80 mg of KOH / g, more preferably from 10 to 60 mg of KOH / g.
• the BN value will be chosen as a function of the conditions of use of the lubricating compositions and in particular according to the sulfur content of the fuel oil used.
• the value of BN will be high and preferably between 20 and 80 mg of KOH / g, more preferably between 30 and 65 mg of KOH / g.
• the value of BN is low and preferably between 5 and 20 mg of KOH / g, more preferably between 10 and 15 mg KOH / g.
• additives will be referred to as the additives described above, that is to say a) at least one olefin copolymer, b) at least one copolymer of styrene and of hydrogenated isoprene, c) at least one glycerol ester and d) at least one detergent as defined above.
• the base oils used for the formulation of the lubricating compositions according to the present invention can be 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.
• Saturated content Sulfur content Viscosity index (VI) Group 1 Mineral oils ⁇ 90% > 0.03% 80 ⁇ VI ⁇ 120 Group 2 Hydrocracked oils ⁇ 90% ⁇ 0.03% 80 ⁇ VI ⁇ 120 Group 3 Hydro-isomerized oils ⁇ 90% ⁇ 0.03% ⁇ 120 Group 4
• PAO Poly-alpha-olefins
• Group 1 mineral oils can be obtained by distillation of selected naphthenic or paraffinic crudes and then by purification of these distillates by processes such as solvent extraction, solvent or catalytic dewaxing, hydrotreatment or hydrogenation.
• the Group 1 mineral bases are, for example, bases called Neutral Solvant (such as 150NS, 330NS, 500NS or 600NS) or Brightstock.
• the oils of Groups 2 and 3 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.
• the lubricating compositions according to the invention have an SAE-20, SAE-30, SAE-40, SAE-50 or SAE-60 viscosimetric grade according to the SAEJ300 classification.
• Grade 20 oils have a kinematic viscosity at 100 ° C between 5.6 and 9.3 cSt.
• Grade 30 oils have a kinematic viscosity at 100 ° C between 9.3 and 12.5 cSt.
• Grade 40 oils have a kinematic viscosity at 100 ° C between 12.5 and 16.3 cSt.
• Grade 50 oils have a kinematic viscosity at 100 ° C between 16.3 and 21.9 cSt.
• Grade 60 oils have a kinematic viscosity at 100 ° C between 21.9 and 26.1 cSt.
• the amount of base oil in the lubricating composition according to the invention is 30% to 80% by mass, relative to the total mass of the lubricating composition, preferably 40% to 70%, more preferably 50% at 60%.
• viscosity index such as polyisobutylenes (PIB).
• composition according to the invention can comprise at least one optional additive, in particular chosen from those commonly used by those skilled in the art.
• the optional additive may be an antiwear additive and / or a dispersant additive and / or an anti-foam additive or a mixture thereof.
• Anti-wear additives protect friction surfaces by forming a protective film adsorbed on these surfaces.
• antiwear additives Mention may thus be made of phospho-sulfur additives, such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates (or ZnDTP).
• the alkyl groups of these zinc dialkyldithiophosphates preferably contain from 1 to 18 carbon atoms.
• Amine phosphates and polysulphides, in particular sulfur-containing olefins are also commonly used anti-wear additives.
• anti-wear additives of nitrogenous and sulfur type such as, for example, metal dithiocarbamates, in particular molybdenum dithiocarbamates.
• the preferred antiwear additive is ZnDTP.
• the amount of antiwear additive in the lubricant according to the invention is 0.1% to 5% by mass, relative to the total mass of the lubricant composition, preferably 0.2% to 4%, plus preferably from 0.5% to 2%, even more preferably from 0.4% to 1%.
• Dispersants are well known additives used in the formulation of lubricating composition, 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.
• 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 element nitrogen, oxygen or phosphorus.
• the compounds derived from succinic acid are dispersants which are particularly used as lubricating additives. Use is made in particular of dispersants of the succinimide family, obtained by condensation of succinic anhydrides and amines, succinic esters obtained by condensation of succinic anhydrides and alcohols or polyols.
• These compounds can then be treated with various compounds in particular sulfur, oxygen, formaldehyde, carboxylic acids and compounds containing boron or zinc to produce, for example, borated succinimides or succinimides blocked with 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.
• At least 0.1% by mass of a dispersant additive relative to the total mass of the lubricating composition is used.
• a dispersant from the succinimide PIB family for example borated or blocked with zinc, can be used.
• 0.1% to 5% by mass of a dispersant additive is used relative to the total mass of the lubricating composition, preferably from 0.2% to 4%, more preferably from 0.5% to 2 %, even more preferably from 0.4% to 1%.
• the lubricating composition according to the present invention may also contain any functional additives suitable for their use, for example anti-foam additives to counter the effect of detergents, which may for example be polar polymers such as polymethylsiloxanes, polyacrylates, anti-oxidant additives and / or anti rust, for example organometallic or thiadiazole detergents, pour point depressants (also called Pour Point Depressant in English terminology or PPD). These are known to those skilled in the art. These additives are generally present at a content by mass of 0.1 to 5% relative to the total mass of the lubricating composition.
• the essential additives as defined above contained in the lubricating compositions according to the present invention can be incorporated into the lubricating composition as separate additives, in particular by separately adding them to the base oils.
• a subject of the invention is also a concentrate according to claim 11.
• the additive concentrate will be formulated in such a way as to comply with the pumpability limits of the pumps usually used.
• the additive concentrate may further comprise at least one optional additive as described above and chosen from antiwear additives and / or dispersant additives and / or anti-foam additives or their mixtures, in particular anti- wear and tear such as ZnDTP.
• the amount of olefin copolymer in the additive concentrate is 2 to 20% by mass, relative to the total mass of concentrate, preferably 5 to 15%, more preferably 8 to 12%.
• the amount of hydrogenated styrene / isoprene copolymer in the additive concentrate is 5 to 30% by mass, relative to the total mass of concentrate, preferably 10 to 25%, more preferably 15 to 20%.
• the amount of glycerol ester in the additive concentrate is 0.5 to 10% by mass, relative to the total mass of concentrate, preferably 1 to 8%, more preferably 2 to 5%.
• the amount of detergent in the additive concentrate is 10 to 70% by mass, relative to the total mass of concentrate, preferably 20 to 60%, more preferably 30 to 50%.
• the concentrates according to the invention are diluted 4 to 5 times in a base oil or in a mixture of base oils in order to obtain the lubricating compositions according to the invention.
• the lubricating composition according to the invention can be used in 4-stroke or 2-stroke marine engines.
• the lubricating composition is suitable for fast or semi-fast 4-stroke engines, which operate respectively with distillates and bunker or heavy fuel oils.
• the observed fuel economy also applies to distillates used in fast 4-stroke engines.
• Fast 4-stroke engines are used for the propulsion of small-tonnage ships and as a unit for generating electricity on larger ships.
• Semi-fast 4-stroke engines are used for the propulsion of many ships, such as freighters, tankers, ferries, and even some container ships. They can furthermore be used as power generation units on board large ships or in diesel-electric power stations.
• the lubricating composition is suitable for 4-stroke engines and for 2-stroke engines as cylinder oil or system oil, in particular as system oil.
• Another subject of the invention relates to a method of lubricating a marine engine, said method comprising a step of bringing the engine into contact with the lubricating composition as described above or obtained from the additive concentrate as described above. .
• Another subject of the invention relates to a method for reducing fuel oil consumption comprising bringing the lubricating composition as defined above or obtained from the concentrate as defined above into contact with a marine engine.
• the “fuel eco” or fuel-saving properties of the lubricating compositions are then evaluated and validated by a test carried out on a test bench equipped with a MAN 5L16 / 24 engine.
• the particular characteristics of this engine have been described in the publication entitled "INNOVATOR-4C, The cuttting-edge MAN B&W 5L16 / 24 test engine", by D. Lanboc, V. Doyen and J. Christensen, CIMAC Congress 2004, KYOTO (Paper 124 ).
• thermal resistance of these compositions was also measured using the continuous ECBT test, where the mass of deposits (in mg) generated under determined conditions is measured. The lower this mass, the better the thermal resistance.
• the test uses aluminum beakers that simulate the shape of pistons. These beakers are placed in a glass container, maintained at a controlled temperature of around 60 ° C.
• the lubricant is placed in these containers, themselves equipped with a wire brush, partially immersed in the lubricant. This brush is driven in a rotary motion at a speed of 1000 revolutions per minute, which creates a projection of lubricant on the lower surface of the beaker.
• the beaker is maintained at a temperature of 310 ° C by an electric heating resistance, regulated by a thermocouple.
• Table III Compositions L 1 L 2 L 3 L4 L 5 L 6 Fuel reduction (%) 0.5 0.2 0.5 0.2 0.7 0.7 ECBT (mg) 365 335 355 330 600 430
• the mass of the deposits of the lubricating composition L 5 is large compared to that of the lubricating composition L 6 .
• the addition of the glycerol ester ensures satisfactory crankcase cleanliness.
• Additivation by a combination of a hydrogenated styrene / isoprene copolymer, an olefin copolymer and a glycerol ester therefore makes it possible to formulate a “fuel eco” marine lubricant while maintaining good crankcase cleanliness.

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