EP2373768B1 - Huile lubrifiante a base d'esters de polyols - Google Patents

Huile lubrifiante a base d'esters de polyols Download PDF

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Publication number
EP2373768B1
EP2373768B1 EP09775311.5A EP09775311A EP2373768B1 EP 2373768 B1 EP2373768 B1 EP 2373768B1 EP 09775311 A EP09775311 A EP 09775311A EP 2373768 B1 EP2373768 B1 EP 2373768B1
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EP
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Prior art keywords
carbon atoms
long
oil
oils
preferentially
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EP09775311.5A
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German (de)
English (en)
French (fr)
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EP2373768A1 (fr
Inventor
Laurent Germanaud
Karine Alfoss
Patrick Turello
Elise Bataille Gresser
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TotalEnergies Marketing Services SA
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Total Marketing Services SA
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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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/38—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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
    • C10M105/68—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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
    • C10M105/70—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen as ring hetero atom
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/74—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing phosphorus
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/76—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing silicon
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68—Esters
    • C10M129/74—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
    • 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
    • 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
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four 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
    • 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
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms 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
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl 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
    • 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
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • 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
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • 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
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • 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

Definitions

  • the present invention relates to oils based on polyol esters, obtainable from renewable resources, and useful as lubricating bases or lubricity additives, especially in four-stroke engine oils, hydraulic oils or transmissions, as well as industrial lubricants.
  • oils used as lubricating bases in engines or various bodies of vehicles or in industry are typically hydrocarbon oils derived from petroleum cuts.
  • Vegetable oils are a renewable alternative to these products. They contain mainly esters of glycerol or other polyols and natural fatty acids. However, the poor cold properties and low oxidation resistance of these products limit its use, especially in engine oil formulations. This is the case, for example, rapeseed oils or oleic sunflower oils.
  • the natural fatty acid esters that are liquid at room temperature are unsaturated compounds and are therefore sensitive to oxidation. Furthermore, saturated natural fatty acid esters such as lauric, myristic, palmitic or stearic acid are themselves solid at room temperature, which renders them unfit for use as a lubricating base.
  • compositions comprising an ester of a polyol and a mixture of fatty acids, wherein at least a portion (I) of the esterified fatty acids has a chain length of 5-12 carbon atoms and another part ( II) esterified fatty acids with a chain length of 16-22 carbon atoms.
  • These compositions have good low temperature properties, particularly good rheology after being stored for a prolonged period of time at low temperatures.
  • These compositions are suitable for use as a hydraulic fluid in low temperature applications.
  • the present invention proposes to solve this problem by providing oils comprising one or more polyol esters, called “mixed” esters, because, in the synthesis of these compounds, at least one alcohol function of each polyol has been esterified with a fatty acid. and at least one alcohol function of the same polyol has been esterified with a synthetic fatty acid.
  • Synthetic fatty acids are typically short chain saturated acids (typically having less than 12 carbon atoms) and naturally occurring fatty acids are typically unsaturated long chain acids (typically having at least 14 carbon atoms).
  • the synthetic fatty acids used to produce the oils according to the present invention may themselves have been obtained from renewable resources, such as, for example, heptanoic acid obtained by thermal cracking of castor oil, or cuts of C8-C10 fatty acids, resulting from the refining and distillation of natural oils such as for example copra.
  • renewable resources such as, for example, heptanoic acid obtained by thermal cracking of castor oil, or cuts of C8-C10 fatty acids, resulting from the refining and distillation of natural oils such as for example copra.
  • R 1, R 2, R 3, R 4 are aliphatic chains having from 1 to 4 carbon atoms.
  • the methyl esters of long-chain fatty acids comprising from 14 to 22 carbon atoms are predominantly mono-unsaturated, in the composition of fatty acid methyl esters, obtained from said oil by the implementation of the NF ISO standards. 5509 and NF ISO 5508, of said oil.
  • the oil comprises at least 30% by weight, preferably 35% by weight of tetraesters of formula (I), wherein at least two of R5, R6, R7, R8 are long olefinic chains comprising from 13 to 21 carbon atoms and / or tetraester corresponding to the general formula (II) wherein R9, R10, R11, R12 are aliphatic chains having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and R13 is a long olefinic chain having 13 to 21 carbon atoms.
  • the oil comprises at most 10%, preferably at most 7% by weight of tetraesters of formula (II).
  • the oil comprises at most 10%, preferably at most 7% by weight of tetraesters of formula (II).
  • the oil comprises at most 25% by weight of tetraester of formula (I) in which 3 groups R 5, R 6, R 7 and R 8 are long olefinic chains comprising from 13 to 21 carbon atoms.
  • the oil comprises at least 85% by weight of total or partial ester (s) obtained by reacting one or more polyols of formula (III) wherein R 1, R 2, R 3, R 4 are aliphatic chains having from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, with one or more long unsaturated fatty acids comprising from 14 to 22 carbon atoms and / or one or a plurality of short saturated fatty acids comprising from 7 to 12 carbon atoms.
  • R 1, R 2, R 3, R 4 are aliphatic chains having from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, with one or more long unsaturated fatty acids comprising from 14 to 22 carbon atoms and / or one or a plurality of short saturated fatty acids comprising from 7 to 12 carbon atoms.
  • the oil comprises at least 30% by weight of tetraesters of formula (I) having from 40 to 70 carbon atoms and at least 15% by weight, preferably at least 20% by weight of tetraesters of formula (I) having from 45 to 60 carbon atoms.
  • the oil has a hydroxyl number, measured according to standard NF T60-231, less than 10 mg of KOH / g.
  • the oil has an acid number, measured according to the NF ISO 660 standard, of less than 1 mg KOH / g.
  • the oil has an iodine value, measured according to standard NF ISO 3961, less than 50, preferably less than 40, even more preferably less than 30 g I 2/100 g.
  • the ratio between the number of moles of long fatty acids comprising from 14 to 22 carbon atoms and the number of moles of short fatty acids comprising from 7 to 12 carbon atoms, is between 1.5 and 2.5, preferably between 1.6 and 2, the ratio being determined on the composition of fatty acid methyl esters obtained from said oil by the implementation of standards NF ISO 5509 and NF ISO 5508.
  • the ratio, between the number of moles of long fatty acids comprising from 14 to 22 carbon atoms and the number of moles of short fatty acids comprising from 7 to 12 carbon atoms is between 0.4 and 1.1, preferably between 0.42 and 1, the ratio being determined on the composition of fatty acid methyl esters obtained from said oil by the implementation of standards NF ISO 5509 and NF ISO 5508.
  • the present invention also relates to lubricating compositions containing said oils. It relates in particular lubricant compositions for four-stroke engine containing the said oils and any type of base oil and additives suitable for this use.
  • the lubricating composition comprises from 10 to 99%, or from 10 to 70%, or from 10 to 40%, or from 10 to 50%, or from 15 to 30%, even more preferably from 15 to 25% by weight. an oil as defined above.
  • the lubricating composition comprises from 30 to 70% of one or more Group IV base oils having a kinematic viscosity at 100 ° C of 4 to 8 cSt.
  • the lubricating composition has a kinematic viscosity at 100 ° C is between 5.6 and 9.3 Cst (grade 20).
  • the lubricating composition has a kinematic viscosity at 100 ° C is between 9.3 and 12.5 Cst (grade 30).
  • the lubricating composition has a viscosity index greater than 160, preferably greater than 175.
  • the present invention also relates to the use of these mixed ester or mixed ester oils as a base oil or friction modifier in lubricating compositions, including engine lubricant, hydraulic, transmissions, and industrial lubricants. It relates to the use of such oils as single lubricating base for engine, hydraulic and transmission of public works vehicles or agricultural vehicles or as lubricant for four-stroke engines, preferably for light motor vehicle or heavy vehicle engine, preferably for motor petrol or diesel.
  • the present invention relates to a process for producing mixed ester based oils according to the invention.
  • the process further comprises a third step of neutralization with acetic anhydride unreacted hydroxyl groups.
  • the mixture of unsaturated long fatty acid methyl esters comprising from 14 to 22 carbon atoms used in step (i) to transesterify the polyol comprises at least 85%, preferably at least 90% by weight, still more preferably at least 95% by weight of mono-unsaturated fatty-chain methyl esters, said percentage being determined by NF ISO5508.
  • the mono-unsaturated methyl esters comprise from 16 to 22 carbon atoms, preferably 18 carbon atoms.
  • the polyols are chosen from pentaerythritol and neopentylglycol.
  • R 1, R 2, R 3 and R 4 are preferably aliphatic chains containing from 1 to 4 carbon atoms
  • the methyl esters of long-chain fatty acids comprising from 14 to 22 carbon atoms are predominantly mono-unsaturated, in the composition of fatty acid methyl esters, determined according to standard NF ISO 5509 and NF ISO 5508, of said oil.
  • the oils according to the invention contain at least 30% by weight, preferably 35%, even more preferably at least 40% by weight of tetraesters of formula (I), where at least two of the groups R5, R6, R7, R8 are long olefinic chains comprising from 13 to 21 carbon atoms and / or tetraester corresponding to the general formula (II) wherein R9, R10, R11, R12 are aliphatic chains having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and R13 is a long olefinic chain having 13 to 21 carbon atoms.
  • a minimum content of tetraesters of this type gives a sufficiently high viscosity to be able to use the oils containing them as a lubricating composition, especially for the applications more particularly targeted by the present invention, namely industrial lubricants and automotive lubricants, in particular particular engine, hydraulic and transmissions.
  • the oils according to the invention contain at most 10%, preferably at most 9%, preferably at most 7%, preferably at most 6%, even more preferably at most 5% by weight of tetraesters of formula ( II).
  • this type of ester if it ensures a sufficient viscosity, however, has at least 4 unsaturations. Too high a content of this type of esters can lead to low resistance to oxidation, which can penalize their use in lubricating compositions, especially in engine lubricants.
  • oils according to the invention preferably contain at most 25%, or at most 20% or at most 15% by weight of tetraesters of formula (I) where 3 groups R5, R6, R7, R8 are long olefinic chains having from 13 to 21 carbon atoms.
  • the oils according to the invention preferably contain at least 85%, or at least 90% by weight of total or partial ester (s) obtained by reaction of one or more polyols of formula (III).
  • R1, R2, R3, R4 are aliphatic chains having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, with one or more long unsaturated fatty acids comprising 14 to 22 carbon atoms and / or of short saturated fatty acids having 7 to 12 carbon atoms.
  • the percentages by weight of the various esters and tetraesters of polyols present in the oils according to the invention are determined from their GC (gas chromatography) analysis.
  • the oils according to the invention comprise at least 30% by weight of tetraesters of formula (I) containing from 40 to 70 carbon atoms and at least 15% by weight, preferably at least 20% by weight of tetraesters of formula (I) having from 45 to 60 carbon atoms.
  • the mass percentage of tetraesters having a given number of carbon atoms is determined by GPC analysis (gas chromatography) of the oils according to the invention, according to the method described in the examples below.
  • the oils according to the invention have a hydroxyl number, measured according to standard NF T60-231, less than 10 mg of KOH / g.
  • the hydroxyl number makes it possible to quantify the non-esterified hydroxyl functions in the oils.
  • a limited content of such free hydroxyl functions, correlated with a low hydroxyl number, makes it possible to have oils having suitable viscometric properties for use in lubricating compositions.
  • the formation of the hydrogen bond between the molecules mentioned above is minimized and leads to very high viscosity increases.
  • the oils according to the invention have an acid number, measured according to the NF ISO 660 standard, of less than 1 mg KOH / g.
  • the acid number in mg KOH / gram of product makes it possible to quantify the unreacted fatty acids (the higher the index, the more unreacted fatty acids).
  • a low acid number thus also reveals a limited content of unreacted hydroxyl and thus makes it possible to obtain oils having viscometric properties more suitable for use in lubricating compositions.
  • the oils according to the invention have an iodine number, measured according to the NF ISO 3961 standard, less than 50, preferably less than 40, even more preferably less than 30, or less than 15, or even less than 10, grams of I2 per 100 grams of oil.
  • the iodine number is related to the presence of unsaturations and therefore to the sensitivity to oxidation. The lower the index, the less unsaturations, so the better the resistance to oxidation. Oils with a low iodine number will therefore be useful in applications where the oxidation resistance parameter is important, for example in engine lubricating compositions.
  • the oils according to the invention have a ratio, between the number of moles of long fatty acids comprising from 14 to 22 carbon atoms and the number of moles of short fatty acids comprising from 7 to 12 carbon atoms. , between 1.50 and 2.50, preferably between 1.60 and 2.00, more preferably between 1.61 and 1.90. This ratio is determined on the composition of fatty acid methyl esters obtained from said oil by the implementation of standards NF ISO 5509 and NF ISO 5508.
  • oils according to this variant can be used for example as lubricating bases in industrial lubricant applications.
  • oils have the viscosity required for application in the field of industrial lubricants, as well as good cold properties. However, their resistance to oxidation is limited. Their viscosity at 100 ° C. according to ASTM D 445 is preferably between 4 and 10 mm 2 / s, preferentially between 6 and 9 mm 2 / s, more preferably between 8 and 9 mm 2 / s.
  • Their dynamic viscosity at -25 ° C. measured according to the ASTM D5293 standard, is typically less than 4300, preferably less than 3500 mPa.s.
  • the oils according to the invention have a ratio, obtained from their composition of fatty acid methyl esters according to the standard NF ISO 5509 and NF ISO 5508, between the number of moles of long-chain fatty acids comprising from 14 to 22 carbon atoms and the number of moles of short fatty acids comprising from 7 to 12 carbon atoms, which is between 0.4 and 1.49, preferentially between 0.4 and 1.20, and even more preferably between 0.42 and 1.10, or between 0.42 and 1.00.
  • oils having these long fatty acid / short fatty acid molar ratio values have the thermaloxidative properties required for application as a lubricating base in engine lubricating compositions. Examples below detail these properties in the ICOT high temperature oxidation test and MCT test, which quantifies the tendency for hot surface deposits to form.
  • the viscosity of said oils is also suitable for this use, in particular for formulating oils of grade 20 or 30 according to the classification SAE (Society of Automotive Engineers).
  • They preferably have a kinematic viscosity at 100 ° C., measured according to the ASTM D445 standard, of between 4 and 8 mm 2 / s, preferably between 4 and 6.5 mm 2 / s.
  • Their viscosity number according to ASTM D2270 is preferably greater than or equal to 150, preferably greater than or equal to 155.
  • the present invention also relates to lubricating compositions comprising an oil according to the invention as described above.
  • compositions comprising oils according to the invention which have a ratio between the number of moles of long fatty acids comprising from 14 to 22 carbon atoms and the number of moles of short fatty acids comprising from 7 to 12 carbon atoms, is between 0.4 and 1.49, preferably between 0.4 and 1.20, still more preferably between 0.42 and 1.10, or between 0.42 and 1, 00. This ratio is determined on the composition of fatty acid methyl esters obtained from said oil by the implementation of standards NF ISO 5509 and NF ISO 5508.
  • Said lubricant compositions preferably comprise from 10 to 99%, or from 10 to 70%, or from 10 to 40%, from 10 to 50%, or from 15 to 30%, even more preferentially from 15 to 25% of such oils.
  • said compositions comprise from 30 to 70% of one or more Group IV base oils with a kinematic viscosity at 100 ° C. of between 4 and 8 mm 2 / s.
  • these compositions have a kinematic viscosity at 100 ° C. of between 5.6 and 9.3 mm 2 / s, which corresponds to oils of grade 20 according to the SAE classification.
  • these lubricating compositions have a kinematic viscosity at 100 ° C. of between 9.3 and 12.5 mm 2 / s, which corresponds to oils of grade 30 according to the SAE classification.
  • Their viscosity index is preferably greater than 160, even more preferably greater than 175.
  • the present invention also relates to the use of the oils described above as a friction modifying additive and as a lubricating base in lubricating compositions.
  • oils according to the invention having a ratio, between the number of moles of long fatty acids comprising from 14 to 22 carbon atoms and the number of moles of short fatty acids comprising from 7 to 12 carbon atoms, between 1.50 and 2.50, preferably between 1.60 and 2.00, even more preferentially between 1.61 and 1.90, as lubricating base, for hydraulic lubricant, transmissions, and for industrial lubricants.
  • This ratio is determined on the composition of fatty acid methyl esters obtained from said oil by the implementation of standards NF ISO 5509 and NF ISO 5508.
  • oils according to the invention having a ratio, between the number of moles of long fatty acids comprising from 14 to 22 carbon atoms and the number of moles of short fatty acids. comprising from 7 to 12 carbon atoms, is between 0.4 and 1.49, preferably between 0.4 and 1.20, still more preferably between 0.42 and 1.10, or between 0.42 and 1 , 00, as a lubricating base for engine lubricant, hydraulic, transmission, and for industrial lubricants.
  • This ratio is determined on the composition of fatty acid methyl esters obtained from said oil by the implementation of standards NF ISO 5509 and NF ISO 5508.
  • the present invention also relates to the use of lubricant composition as described above as lubricant for four-stroke engine , preferably for light motor vehicle or heavy vehicle engine.
  • the process according to the invention also comprises a third step of neutralization with acetic anhydride of the unreacted hydroxyl groups.
  • the mixture of unsaturated long fatty acid methyl esters comprising from 14 to 22 carbon atoms used in step (i) to transesterify the polyol comprises at least 85%, preferably at least less than 90% by weight, still more preferably at least 95% by weight of mono-unsaturated methyl esters, said percentage being determined by NF ISO5508.
  • the mixture of unsaturated long fatty acid methyl esters used in step i to transesterify the polyol comprises at least 80%, preferably at least 85%, preferably at least 90% by weight, still more preferably at least 95% by weight. % by weight of mono-unsaturated methyl esters comprising from 16 to 22 carbon atoms, preferably 18 carbon atoms, said percentage being determined by NF ISO5508.
  • the polyols are chosen from pentaerythritol and neopentylglycol.
  • the present invention also relates to products that can be obtained by the processes described above.
  • the mass percentage of the different fatty acid methyl esters in the oil is then obtained. Knowing the molar mass of these different methyl esters, can thus calculate the molar ratios between these different esters present in the oil analyzed.
  • short fatty acids defined as fatty acids comprising from 7 to 12 carbon atoms. These short fatty acids are in principle exclusively saturated. For the calculation of the characteristic molar ratio of the oils according to the invention, account will however be taken of methyl esters of all fatty acids comprising from 7 to 12 carbon atoms.
  • the separation of the different species is done by increasing number of carbon.
  • the column is calibrated by passing a mixture of reference triglycerides of known composition.
  • the polyol esters of the oils according to the invention emerge at the same time as the triglycerides of the same number of carbon.
  • partial esters that is to say the esters comprising one or more non-esterified OH functions, the tetraesters having three short chains and one long chain (3C81C18), the tetraesters comprising four short chains (4C8), can not to be separated by this method, because of their too close carbon number.
  • This method identifies the different species present according to their carbon number. This method will therefore be used to calculate the mass percentage of polyol esters comprising from 40 to 70 carbon atoms, or from 45 to 60 carbon atoms, in the oils according to the invention.
  • the mass percentage of the species having retention times between those of the reference triglycerides of 40 and 70 carbon atoms, or of 45 and 60 carbon atoms, relative to the total of the chromatographable species, will be calculated.
  • the subject of the present invention is also lubricating compositions comprising oils based on polyol esters according to the present invention, whatever their application, whether they are intended, for example, for engine, hydraulic, transmission or applications applications. industrial.
  • the present invention relates to four-stroke lubricant compositions, including oils according to the present invention, and any type of additives or base oils suitable for use thereof.
  • the present invention relates to lubricating compositions for a four-cycle engine preferably comprising from 10 to 99%, or from 10 to 70%, or else from 10 to 40%, from 10 to 50%, or from 15 to 30%, still more preferably 15 to 25% of such oils.
  • said compositions comprise from 30 to 70% of one or more Group IV base oils with a kinematic viscosity at 100 ° C. of between 4 and 8 mm 2 / s.
  • Nonlimiting examples of additives that can be used in the lubricant compositions according to the invention are given below.
  • antioxidants commonly used are the antioxidants of the phenolic type, amines. Some of these additives, for example phospho-sulfur, can be ash generators.
  • Phenolic antioxidants may be ashless, or may be in the form of neutral or basic metal salts. Typically, these are compounds containing a sterically hindered hydroxyl group, for example when 2 phenol groups are in the o or p position of each other, or when the phenol is substituted by an alkyl group comprising at least 6 carbon atoms. .
  • Amino compounds are another class of antioxidants that can be used, optionally in combination with phenolics.
  • Typical examples are aromatic amines, of the formula R 8 R 9 R 10 N, where R 8 is an aliphatic group, or an optionally substituted aromatic group, R 9 is an optionally substituted aromatic group, R 10 is hydrogen, or an alkyl or aryl group, or a group of formula R11S (O) xR12, where R11 is alkylene, alkenylene, or aralkylene, and x is 0, 1 or 2.
  • Sulfurized alkyl phenols or their alkali and alkaline earth metal salts are also used as antioxidants.
  • Organic boron derivatives such as esters or succinimides can also be used as antioxidants.
  • antioxidants are oil-soluble copper compounds, for example copper thio or dithiophosphate, copper and carboxylic acid salts, copper dithiocarbamates, sulphonates, phenates, acetylacetonates. Copper salts I and II, succinic acid or anhydride are used.
  • alkyl polymethacrylates polyacrylates, polymers of esters of fumaric or maleic acid and of heavy alcohols, copolymers of different esters of acrylic, methacrylic, fumaric or maleic acid, or copolymers of fumaric acid esters and vinyl esters of fatty acids, copolymers of fumarates, vinyl esters of carboxylic acids, and alkylvinyl ethers, or mixtures thereof.
  • polyacrylamides, polyalkylsphenols, polyalkylnaphthalenes, alkylated polystyrene, etc. are especially present and not limited to condensation products of paraffins or halogenated waxes and aromatic compounds such as benzene, naphthalene, anthracene, phenols.
  • the lubricant compositions according to the invention have VI values, measured according to ASTM D2270, greater than or equal to 160, preferably greater than 175, and preferably greater than 180.
  • viscosity index improvers examples include polymeric esters, copolymer olefins (OCP), homopolymers or copolymers of styrene, butadiene or isoprene, polymethacrylates (PMA). They are conventionally present at levels of the order of 0 to 40%, preferably 0.01 to 15% by weight, in the lubricant compositions for four-stroke engine.
  • the preferred VI-improving polymers are selected from polymers and copolymers of methacrylates, olefins, styrene or dienes,
  • additives may be introduced individually into the lubricant compositions or in the form of additive packages or additive concentrates.
  • the nature and the proportions of the different base oils and additives in the lubricating compositions according to the present invention will preferably be adjusted so as to that said lubricating compositions are of grade 20 or 30 according to the SAE classification, with a kinematic viscosity at 100 ° C of between 5.6 and 9.3 or between 9.3 and 12.5 Cst, and their viscosity index high, which may be greater than or equal to 160 for oils of grade 20, and greater than or equal to 175 for oils of grade 30.
  • these lubricating compositions are multigrade oils, for example 5W or 0W, for example of grade 5W30, or 0W30 according to the SAE classification.
  • the present invention also relates to the use of an oil according to the invention as a friction modifying additive in lubricating compositions.
  • friction modifier exploits the property that fatty acid esters, such as those present in the oils according to the invention, to form, on the surface of the friction parts, films to maintain a regime. hydrodynamic under heavy load.
  • oils according to the invention are typically incorporated at contents of less than 10% or even less than 5%, typically between 1 and 2%.
  • the present invention also relates to the use of an oil according to the invention as a lubricating base, alone or mixed with oils of natural origin, animal or vegetable, mineral or synthetic.
  • the present invention relates to the use of an oil according to the invention as a lubricating base for motor, hydraulic, transmissions, and industrial lubricants.
  • oil according to the invention as a lubricating base is particularly suitable for outdoor and leisure applications, such as agricultural, construction, recreational vehicles, where a biodegradable character is desired, but the oils according to the invention.
  • the present invention can be used in multiple applications, including industrial lubricants.
  • the oils according to the invention can serve as a single lubricating base for engine, hydraulic and vehicle transmissions, in particular for formulating lubricants that can be used interchangeably in the engine, in the hydraulics and the transmission of the same vehicle.
  • This type of single lubricant is particularly applicable to public works vehicles or agricultural vehicles.
  • oils are typically obtained by transesterification of polyols with methyl esters of short-chain, synthetic fatty acids, comprising between 7 and 12 carbon atoms, followed by transesterification with methyl esters of long-chain natural fatty acids, comprising between 14 and 22 carbon atoms, in the presence of basic transesterification catalysts.
  • These catalysts may for example be chosen from homogeneous catalysts such as sodium methoxide, potassium hydroxide, sodium hydroxide, or heterogeneous such as manganese oxide or zinc oxide.
  • a further step of esterification in the presence of acetic anhydride can be added so as to neutralize the remaining hydroxyl functions and obtain a better tetraester yield, which improves the physical characteristics of the oils obtained, in particular the viscosity and the pour point. .
  • the polyols used to obtain the compounds according to the invention are tetra-alcohols.
  • the tetraalcohols used for the preparation of the oils according to the invention correspond to the formula (III) below or R1, R2, R3, R4 are aliphatic chains comprising from 1 to 10 carbon atoms, preferably 1 to 4 atoms of carbon.
  • oils according to the present invention have the particularity of containing tetraesters of polyols esterified by both unsaturated long fatty acids and saturated short fatty acids.
  • long refers to fatty acids comprising between 14 and 22 carbon atoms. Saturated long acids are solid at room temperature and therefore unsuitable for use in the synthesis of lubricants. Thus unsaturated long acids are used here.
  • oils according to the invention an oxidation resistance adapted to the intended uses, in particular in engine lubricants, monounsaturated long acids will be preferred. Palmitoleic, oleic, eicosenoic and erucic acids, in particular oleic acid, will be preferred.
  • oils can be derived from natural resources.
  • unsaturated long fatty acids of natural origin are therefore preferably used. They are present, in the form of their methyl esters, in the oils of plant or animal origin such as palm oil, sunflower oil, rapeseed oil, olive oil, peanut oil ..., which can be refined, enriched, genetically modified, ... so as to increase their fatty acid content of interest.
  • sunflower oil enriched with methyl oleate, or rapeseed oil it will be advantageous to use sunflower oil enriched with methyl oleate, or rapeseed oil.
  • These natural raw materials are mixtures, which generally also contain, more or less important quantities of methyl esters of polyunsaturated fatty acids (linoleic, linolenic for example), as well as some saturated (myristic, palmitic, stearic, behenic for example ).
  • short is used here to mean fatty acids comprising between 7 and 12 carbon atoms. These saturated acids have the advantage of enhancing the oxidation resistance of the oils according to the invention without adverse effect on their lubricating properties.
  • caproic heptanoic
  • caprylic pelargonic and capric acids.
  • the fatty acids having 7 and 8 carbon atoms are particularly preferred.
  • oils were prepared by first transesterifying pentaerythritol (PET) with saturated C8-C10 fatty acid methyl esters (VHA) and then transesterifying the resulting product with methyl esters of fatty acids in a second step.
  • PET pentaerythritol
  • VHA saturated C8-C10 fatty acid methyl esters
  • EMTO long unsaturated
  • PET 9-1, PET 12-1, PET 25-3, PET 28-2, PET 29-1 are oils according to the invention.
  • Pentaerythritol of formula C (CH 2 OH) 4, was used as the tetraalcohol at 98% purity, marketed by Aldrich (CAS No. 115-77-5, F.G .: 136).
  • Saturated short fatty acid methyl esters a mixture of caprate and methyl caprylate marketed by Oléon (EMHV), containing 55% by weight of caprylic esters and 40% by weight of capric ester, and of molar mass is used average 169 g / mol
  • the free hydroxyl functions have the particularity of forming intermolecular hydrogen bonds, which increases the viscosity of the medium.
  • the final product may be esterified with an acid or even an acetic anhydride at the end of the reaction.
  • the crude reaction mixture is washed 3 times with salt water and then 3 times with demineralized water. Centrifugation may be necessary during the 1st washing to increase the rate of sedimentation.
  • the organic phase is dried at 100 ° C. under a vacuum of 10 mbar in order to eliminate the residual water.
  • Table 2 below groups together the different experimental conditions in which we performed for these two (possibly three) successive stages.
  • Table 2 Conditions for Synthesis of PET Esters Table 2 PET 9-1 PET 12-1 PET 15-3 PET 25-3 PET28-2 PET 29-1 1st step: transesterification of PET by EMHV PET Trans C8C10 9 PET Trans C8C10 12 PET Trans C8C10 15 M PET (g) 138.7 160.1 45 n PET / n EMHV (molar ratios) 1 / 2.4 1 / 2.4 1 / 3.7 1 / 3.7 1 / 2.9 1 / 4.9 % Catalyst MeONa (masses MeONa, compared to the mass of introduced EMHV) 1.4% (m / m EMHV) 1.4% (m / m EMHV) 1.4% (m / m EMHV) 1.4% (m / m EMHV) 1.4% (m / m EMHV) 1.4% (m / m EMHV) 1.4% (
  • NF ISO 5508 gives mass percentages of the different EMAGs present in the samples. From this mass composition, and knowing the molar masses of the different EMAGs, it is possible to calculate the molar percentages, respectively n1, of short-chain fatty acid methyl esters and n2 of long-chain fatty acid methyl esters, relative to the total number of moles. of EMAG present in the sample.
  • n 2 / n 1 The ratio between the number of moles of long fatty acids and the number of moles of short fatty acids, characteristic of the oils according to the invention, n 2 / n 1, is then calculated.
  • a "short" fatty acid methyl ester will be of the formula RCOO CH3, with R olefinic or paraffinic chain comprising from 6 to 11 carbon atoms (also referred to as C8-C10)
  • the method used is a Gas Chromatography (GPC) method, which incorporates the characteristics of the IUPAC method 2.323 used for the determination of Triglycerides.
  • the injector is on-column type and FID detection.
  • the reference used here is a mixture: MGLA referenced by the EEC, covering compounds of 24 to 56 carbon atoms.
  • the sylilation is carried out under the following conditions: 10 mg of the sample are mixed with 200 ⁇ l of a BSTFA (bis trimethylsilyltrifluoroacetamide) / TMSCl (chlorotrimethylsilyl) mixture (80/20 by volume). The whole is placed in an oven at 65 ° C for 1 hour and vortexed from time to time. The sample is then diluted in isooctane to obtain a concentration of 1 mg / ml.
  • BSTFA bis trimethylsilyltrifluoroacetamide
  • TMSCl chlorotrimethylsilyl
  • the GC analysis conditions are as follows:
  • Partial esters which here include both the esters having one or more non-esterified OH functions, the tetraesters having three short chains and one long chain (3C81C18 in the examples), the tetraesters having four short chains (4C8 in the examples ). These three types of compounds can not be separated from each other because of their too close carbon numbers.
  • Partial esters (for all the products according to the invention, partial esters include tetraesters with 3 short chains and a long chain, as well as tetraesters with four short chains and esters having one or more nonesterified OH functions),
  • Tetraesters (other than those included in partial esters).
  • Table 3 Retention time of chromatographable species in GPC analysis in samples Chromatographable species Retention time (min) Short methyl esters (C7H15COOCH3)) 0.8 Short methyl esters (C10H21COOCH3) 2.2 pentaerythritol 5.0 Long methyl esters (C15H31COOCH3) 8.0 Long methyl esters (C18H37COOCH3) From 9.5 to 10.5 Partial Esters From 10.7 to 27.7 Tetraester 2C182C8 28 to 29.9 Tetraester 3C181C8 From 30.3 to 31.7 Tetraester 4C18 From 32.9 to 35.6
  • compositions and physicochemical characteristics of the oils prepared are summarized in Table 4 below.
  • PET oils 9-1, PET 12-1, PET 25-3, PET 28-2, PET 29-1 are oils according to the invention.
  • PET oil 15-3 is outside the invention.
  • Table 4 Characteristics and Properties of PET Esters Sample PET 9-1 PET 12-1 PET 15-3 outside the invention PET 25-3 PET 28-2 PET 29-1 Acid number (mg KOH / g) 0.38 3.32 1.30 0.74 0.48 0.20 Iodine number (g I 2 / 100g) nd nd 57.1 34.0 43.0 21.0 Hydroxyl number (mg KOH / g) 37.0 3.3 9.4 8.9 3.1 7.8 Composition in EMAG ( mol %), according to NF ISO 5509/5508 n1 C8C10 "short” 35.0 38.0 49.4 61.4 50.1 70.4 n2 C18 "long” 65.0 62.0 47.1 38.6 49.9 29.6 n2 / n1 1.86 1.63 0.95 0.63 0.99 0.42 Ester composition (% by mass) GPC Tetraesters (total
  • PET samples 9-1 and PET 12-1 which have undergone a neutralization step of residual hydroxyl functions with acetic acid or acetic anhydride, have a viscosity compatible with use as lubricating oils. However, they are a little too viscous for a motor application: their viscosity at 100 ° C is between 8 and 9 cSt, then that the base oil mixtures in the 5W30 formulas are set around 4 to 5 cst. Their viscosity is, on the other hand, well adapted to the application of industrial lubricants.
  • the cold properties are good for the oils according to the invention whereas for the PET 15-3 oil, these properties are so bad that they could not be measured.
  • PET sample 15-3 has a viscosity of 2.7cSt at 100 ° C, becoming too low compared to engine or industry applications.
  • Samples PET 25-3, PET 28-2 and PET 29-1 are oils according to the invention. Their viscosity at 100 ° C approaches the target by 6 cSt and is suitable for engine application.
  • oils can be expected to have low volatility, as in the case of rapeseed oil.
  • the stability tests are carried out in a test tube in a climatic chamber. Most samples are clear and stable at room temperature and at 60 ° C. A tendency to deposit formation is observed after prolonged storage at 0 ° C, probably resulting from the presence of compounds or impurities having a high pour point. This point could be improved by better purification of the product.
  • thermo-oxidative properties of the PET esters described in Example 1 were evaluated in a screening formula consisting of 91.9% of said oils and 8.1% by weight of a conventional performance additive package for motor oils. sold by Lubrizol under the reference 7819H.
  • these screening formulas were also prepared from two widely available vegetable oils, oleic sunflower oil 85% oleic acid and rapeseed oil.
  • the ICOT test (Iron Catalysed Oxidation Test) is described in ASTM D4871-06 (or ASTM D4871) and consists in bringing the lubricant to a temperature between 50 and 375 ° C. in the presence of air, oxygen, nitrogen or other gas at a flow rate of 1.3 to 131 / h, with or without an iron catalyst.
  • the relative viscosity variation at 40 ° C, RKV40 (%) obtained after ICOT test is then measured.
  • Table 5 Increase in KV 40 (RKV40%) after ICOT oxidation test RKV40% PET 9-1 5000+ PET 12-1 5000+ PET 25-3 2400 PET 29-1 950 Refined rapeseed 5000+ Oleic sunflower 85% 5000+
  • the oils 25-3 and 29-1 according to the invention have a significantly improved oxidation resistance, resulting in a lower increase in viscosity at 40 ° C after ICOT test.
  • MCT Micro Coking Test
  • the MCT test evaluates the thermal stability of a lubricant in a thin layer, subjected to temperature conditions similar to those encountered in the hottest parts of the engine (230 to 280 ° C). The deposits and varnish are measured by a videocotator. The result is expressed as a score out of 10, called merit.
  • the mixed esters 9-1 and 12-1 exhibit a very poor performance compared to the mineral bases (33 Ns) and synthetic (PAO8, Priolube 3985). Their behavior is similar to that of vegetable oils, with a significant formation of deposits.
  • the mixed esters according to the invention, 28-2, 25-3 and 29-1 show good performances, and even, in the case of the oil 29-1, performances superior or equivalent to those of the mineral bases. and synthetic synthetics.
  • Example 3 Lubricating compositions for a four-stroke engine
  • the PET ester oils obtained in Example 1 were included at 20% in two formulas of four-stroke lubricant compositions.
  • the mixed ester oils are evaluated by comparison with a commercial ester, Priolube 3970, and well-known vegetable oils, rapeseed oil and 85% oleic sunflower oil.
  • ester-based oils are here used as lubricating bases, in combination with Group IV commercial bases (polyalphaolefins): PAO4 Durasyn (kinematic viscosity of 4 cSt at 100 ° C) PAO6 Durasyn (kinematic viscosity from 6 cSt to 100 ° C), and PAO 8 Durasyn (kinematic viscosity of 8 cSt at 100 ° C).
  • PAO4 Durasyn kinematic viscosity of 4 cSt at 100 ° C
  • PAO6 Durasyn kinematic viscosity from 6 cSt to 100 ° C
  • PAO 8 Durasyn kinematic viscosity of 8 cSt at 100 ° C.
  • the amounts of these commercial bases are adjusted to formulate oils of grade 30 (compositions A to I), and grade 20 (compositions J to P).
  • compositions A to I and J to P respectively are also differentiated by the nature of the additives employed, the table below gives the characteristics of the additives of the two formulas made.
  • Table 7 additive oil formulations for 4-cycle engine Compositions A to I ( Formula G05162A ) ( Formula 1 ) Trade name Type of additive Molecule type IDN3276 Friction modifier (MF) Irganox L57 antioxidant Viscoplex 1-256 pour point depressant (ppd) IDN3269F Package (Infineum) for 4-stroke engine oil SV206 Improving Polymer VI (VII) OCP Compositions J to P (Formula G02300F) (Formula 2) Trade name Type of additive Molecule type XOA3041C Package (Oronite) for 4-stroke engine oil SV261 Improving Polymer VI (VII) OCP PI156S pour point depressant (ppd) Irganox L57 antioxidant
  • compositions and physicochemical properties of the various lubricating compositions obtained, as well as the ICOT and MCT test results are given in Table 8 and Table 9.
  • compositions D, E, F are lubricating compositions according to the invention, as well as compositions K, L, M.
  • compositions A, B, C, as well as the composition J were made with oils based on mixed esters not being oils according to the invention.
  • compositions G, H, as well as the compositions O, P were made with known vegetable oils, rapeseed oil and 85% oleic sunflower oil.
  • compositions 1 and N were carried out with commercial ester Priolube 3970.
  • lubricant compositions according to the invention which are additive according to formula 1 are more resistant to oxidation than those additives according to formula 2.
  • the lubricant compositions according to the invention formulated from oils based on PET esters, show a markedly improved behavior compared to compositions formulated from conventional vegetable bases (85% oleic sunflower and Colza oil).
  • the composition F has a behavior similar to that of the composition I, based on commercial ester.
  • All lubricating compositions made with mixed ester oils are positioned between the vegetable bases (rapeseed oil and oleic sunflower oil) and commercial synthetic ester Priolube 3970.
  • the additive lubricant compositions according to Formula 2 have significantly better performance than those of vegetable bases.
  • the lubricating compositions according to the invention, F and M are equivalent to the compositions prepared with commercial ester Priolube 3970.
  • Grade 30 lubricants (compositions D, E, F), and grade 20 (compositions K, L, M) could be formulated from PET oils 28-2, PET 25-3, PET 29-1 according to the invention.

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EP09775311.5A 2008-12-05 2009-12-07 Huile lubrifiante a base d'esters de polyols Not-in-force EP2373768B1 (fr)

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JP5764298B2 (ja) * 2010-03-31 2015-08-19 出光興産株式会社 難燃性能を有する生分解性潤滑油組成物
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JP6789615B2 (ja) * 2015-03-31 2020-11-25 出光興産株式会社 変速機用潤滑油組成物
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EP2373768A1 (fr) 2011-10-12
CN102300966A (zh) 2011-12-28
US20110306526A1 (en) 2011-12-15
JP5675637B2 (ja) 2015-02-25
FR2939443B1 (fr) 2013-01-18
KR101667692B1 (ko) 2016-10-19
JP2012511077A (ja) 2012-05-17
CN102300966B (zh) 2015-07-29
WO2010064220A1 (fr) 2010-06-10
ES2536419T3 (es) 2015-05-25
FR2939443A1 (fr) 2010-06-11
KR20110111284A (ko) 2011-10-10

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