EP3921398A1 - Lubricant composition - Google Patents

Lubricant composition

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Publication number
EP3921398A1
EP3921398A1 EP20702016.5A EP20702016A EP3921398A1 EP 3921398 A1 EP3921398 A1 EP 3921398A1 EP 20702016 A EP20702016 A EP 20702016A EP 3921398 A1 EP3921398 A1 EP 3921398A1
Authority
EP
European Patent Office
Prior art keywords
tocopherol
antioxidant
composition
supplement
amine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20702016.5A
Other languages
German (de)
French (fr)
Inventor
Pascal Xanthopoulos
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Polybridge
Original Assignee
Polybridge
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Polybridge filed Critical Polybridge
Publication of EP3921398A1 publication Critical patent/EP3921398A1/en
Withdrawn legal-status Critical Current

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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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
    • 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
    • C10M129/04—Hydroxy compounds
    • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/12—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring with condensed rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/50—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring monocarboxylic
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/17—Fisher Tropsch reaction products
    • C10M2205/173—Fisher Tropsch reaction products 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
    • 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
    • C10M2207/025—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with condensed rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/284—Esters of aromatic monocarboxylic acids
    • 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
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; 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
    • C10N2030/02—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
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C10N2040/25—Internal-combustion engines

Definitions

  • the present invention relates to the field of lubricants. It relates more particularly to a lubricating composition for a heat engine.
  • Lubricants are commonly used in heat engines. In order to improve their hold over time, they generally include an antioxidant additive.
  • the composition of the usual antioxidant additive is a mixture of phenolic antioxidant, and amine antioxidant.
  • An object of the present invention is to provide a lubricating composition having good thermal stability against oxidative degradation.
  • Another object of the present invention is to provide a lubricating composition whose impact on the environment is reduced.
  • the object of the present invention is to respond at least in part to the aforementioned objects by providing a lubricating composition with an improved antioxidant additive.
  • a lubricating composition comprising a base oil and an antioxidant additive, said antioxidant additive comprising a phenolic antioxidant, an antioxidant of amine type, and a tocopherol supplement comprising at least one element from the list consisting of: beta -tocopherol, delta-tocopherol and gamma-tocopherol.
  • the composition according to the invention exhibits better thermal stability against oxidation degradation, compared with the compositions of the state of the art, while allowing a reduction in the proportion of antioxidant of amine type. , which is an advantage due to the toxicity of this product.
  • the present invention also relates to a use of a lubricating composition according to the invention, in a heat engine.
  • the heat engine benefits from a composition which has improved durability over time compared to the compositions of the state of the art thanks to better thermal stability against oxidation degradation, while allowing reduction in the proportion of amine-type antioxidant, which is an advantage because of the toxicological risk that this product may represent.
  • FIG. 1 is a graph showing a second aspect of the results of the series of comparative tests shown in FIG. 1.
  • the lubricating composition according to the invention comprises a base oil and an antioxidant additive.
  • the lubricating composition may have an antioxidant additive content by weight of between 0.5 and 1.5%.
  • the base oil is preferably an oil from Group III, but can also be an oil from Group I, Group II, Group III +, Group IV or even Group V.
  • the antioxidant additive includes a phenolic antioxidant, an amine-type antioxidant, and a tocopherol supplement.
  • the antioxidant additive may have a tocopherol supplement by weight content of between 5 and 30%, preferably between 5 and 20%.
  • the phenolic antioxidant can be any phenolic compound, that is, a compound which has a free OH group attached to a phenyl ring, capable of being an antioxidant.
  • the term "phenolic antioxidant” also includes compounds where the OH group is attached to a phenyl ring, wherein the phenyl ring is part of a fused ring structure, for example, the phenyl ring is part of a ring structure. a benzothiophene ring, a naphthalene ring, an indole ring, a benzofuran ring or the like.
  • Preferred phenolic antioxidants are hindered phenols (e.g., with at least one of the two ortho positions of the OH phenolic group substituted, e.g., by an alkyl group such as methyl, ethyl, propyl, cyclopropyl, isopropyl, butyl, isobutyl or tert-butyl) and dimeric phenols.
  • the phenolic antioxidant can therefore consist of a hindered phenol or of a mixture of several hindered phenols, chosen from 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-dimethylphenol. , 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2 , 6-dicyclopentyl-4-methylphenol, 2- ( ⁇ -methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di -tert-butyl-4-methoxymethylphenol, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methyl-undec-1'-yl) -phenol,
  • the amine antioxidant can be an aliphatic or aromatic amine.
  • Aromatic amine is a compound that has an amine group, whether it is a free amine group (eg, NH2), or a substituted amine group (eg, NR 1 R 2 , where R 1 and R 2 are independently hydrogen , alkyl, arylalkyl, heteroarylalkyl, cycloalkylalkyl, hcierocyclocycloalkyle, hcierocyclocycloalkyle, arylcycloalkyl, arylcycloalkyl, heteroarylcycloalkyl, arylhcierocycloalkyle, hcieroarylhcierocycloalkyle, hcieroarylhcierocycloalkyle, cycloalkyl, arylcycloalkyl, heteroarylcycloalkyl, heteroarylcycloalkyl, heterocycloalkyl, arylhcierocycloalkyle, alkenyl, arylalkenyl, cycloalken
  • the amine antioxidant can be an aromatic amine, wherein the amine group is bonded to two aromatic rings, such as two monocyclic aromatic rings (e.g., as described here) that are the same or different, two polycyclic aromatic rings (e.g. example, as described herein) which are the same or different, or a monocyclic aromatic ring (eg, as described here) and a polycyclic aromatic ring (eg, as described here).
  • the amine antioxidant can be a diphenylamine.
  • the amine antioxidant can further be an aromatic amine having the amine group attached to a monocyclic aromatic ring (eg, a phenyl ring) and a polycyclic aromatic ring (eg, a naphthalene ring).
  • the amine antioxidant can be selected from the group consisting of dinonyl diphenylamine, butylated, octylated diphenylamine, dioctyl diphenylamine, ⁇ , ⁇ '-diisopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine , N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-di (naphth-2-yl) -p-phenylenedi
  • N-allyldiphenylamine 4-isopropoxydiphenylamine, di (4-methoxyphenyl) amine, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'- tetramethyl-4,4'-dia minodiphenylmethane, 1,2-di [(2-methylphenyl) amino] -ethane, 1,2-di (phenylamino) propane, (o-tolyl) biguanide, di [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, phenyl-1-naphthylamine p-amine, p'-dioctyldiphenyl, mixture of tert-butyl-diphenyl,
  • the tocopherol supplement comprises at least one of beta-tocopherol, delta-tocopherol and gamma-tocopherol.
  • the sum of the contents by weight of beta-tocopherol, gamma-tocopherol and delta-tocopherol in the tocopherol supplement can be greater than 50%, preferably greater than 70%.
  • the tocopherol supplement comprises delta-tocopherol, preferably the content by weight of the tocopherol supplement in delta-tocopherol is greater than 50%.
  • the antioxidant additive may have a ratio of the amine antioxidant to phenolic antioxidant content by weight of between 0.6 and 1.2.
  • the ratio of the weight contents of the amine antioxidant to the phenolic antioxidant is less than 0.9, preferably less than 0.8. This is because the amine-type antioxidant can represent a toxicological risk, which is why it is advantageous to reduce its share in the antioxidant additive. This reduction is possible by the presence of the supplement tocopherol, which allows good antioxidant performance to be obtained while reducing the proportion of the amine-type antioxidant.
  • the base oil is a Group III oil, that is to say it has a sulfur content of less than 0.03% by weight and an index of viscosity greater than 120.
  • the lubricating composition according to the invention may also comprise one or more additional products chosen from the group consisting of an antiwear agent, a detergent, a metal deactivation additive, a phosphite, a lactone, a dispersant, a diluent, a emulsifier, defoamer, corrosion / rust inhibitor, extreme pressure agent, pour point depressant, viscosity index improver and friction modifier.
  • an antiwear agent a detergent, a metal deactivation additive, a phosphite, a lactone, a dispersant, a diluent, a emulsifier, defoamer, corrosion / rust inhibitor, extreme pressure agent, pour point depressant, viscosity index improver and friction modifier.
  • a composition according to the invention was tested using a group III HC6 oil, to compare its performance with comparative compositions.
  • a thermal aging test at 150 ° C. for 216 hours was carried out according to the CEC (“Coordinating European Council”) L-109-14 procedure.
  • the antioxidants tested are AO 1135, AO 5057, alpha-tocopherol, and a tocopherol supplement under the reference VB T70.
  • AO 1135 is a phenolic antioxidant with the composition: benzopropanoic acid, 3,5-bis (1,1-dimethyl-1,1-dimethylethyl) -4-hydroxy-, branched C7-9 alkyl esters.
  • AO 5057 is an amine antioxidant of composition: benzenamine, N-phenyl-, reaction products with 2,4,4-trimethylpentene.
  • VB T70 is a blend of antioxidants and sunflower oil, made up of:
  • Composition F is a composition of Composition F:
  • the graph in Figure 1 and Table 1 show the evolution of the viscosity of the oil during its thermal aging, measured according to the ASTM D445 / D446 protocols.
  • the unit on the ordinate is mm 2 / s.
  • the unit of time on the abscissa is the duration of thermal aging at 150 ° C., expressed in hours. This test is particularly relevant for evaluating the performance of a lubricating composition and its resistance over time.
  • the graph in Figure 2 and Table 2 show the evolution of oxidation, measured according to the DIN 51453 protocol.
  • the unit on the ordinate is A / cm.
  • the unit of time on the abscissa is the duration of thermal aging at 150 ° C, expressed in hours.
  • composition A which does not contain an antioxidant additive.
  • Composition D which is the benchmark antioxidant formulation used on a large scale in the lubricants market, is the state of the art composition that achieves the best performance in terms of viscosity (Fig. 1).
  • Composition F produced according to the invention, is similar to composition D with part of the antioxidants replaced by a mixture of alpha, beta, gamma and delta type tocopherols.
  • composition F is better in terms of viscosity (fig. 1) and oxidation (fig. 2) than those of composition D.
  • the comparison of compositions D and F makes it possible to conclude that an improvement in performance obtained by the presence of tocopherols.
  • Composition E is also similar to composition D, but this time with the presence of exclusively alpha-type tocopherols.
  • composition E shown in FIGS. 1 and 2 are worse than composition F, and even worse than composition D.
  • the performance improvement effect observed previously is therefore not present with exclusively alpha type tocopherols, which shows the importance beta, gamma and delta type tocopherols.
  • Composition B includes only one phenolic antioxidant
  • Composition C is similar to Composition B with part of the phenolic antioxidant replaced by the mixture of alpha, beta, gamma and delta tocopherols.
  • composition C shown in FIGS. 1 and 2 are worse than composition B.
  • the performance enhancing effect observed previously with tocopherols is therefore not present in the absence of an amine-type antioxidant.
  • compositions according to the invention it is possible to reduce the amount of antioxidant of amine type compared to the state of the art by adding a little tocopherol of beta, gamma or delta type, which is a benefit due to the toxicity of amine-type antioxidants.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

The present invention relates to a lubricant composition comprising a base oil and an antioxidant additive, said antioxidant additive comprising a phenolic antioxidant, an amine antioxidant and a tocopherol supplement having at least one member of the list consisting of: beta-tocopherol, delta-tocopherol and gamma-tocopherol. The present invention also relates to a use of a lubricant composition according to the invention in a heat engine.

Description

    Composition lubrifianteLubricating composition
  • La présente invention se situe dans le domaine des lubrifiants. Elle concerne plus particulièrement une composition lubrifiante pour moteur thermique.The present invention relates to the field of lubricants. It relates more particularly to a lubricating composition for a heat engine.
  • Les lubrifiants sont couramment utilisés dans les moteurs thermiques. Afin d’améliorer leur tenue dans le temps, ils comportent généralement un additif antioxydant. La composition de l’additif antioxydant habituelle est un mélange d’antioxydant phénolique, et d’antioxydant de type amine.Lubricants are commonly used in heat engines. In order to improve their hold over time, they generally include an antioxidant additive. The composition of the usual antioxidant additive is a mixture of phenolic antioxidant, and amine antioxidant.
  • Le besoin d’améliorer la résistance des compositions lubrifiantes contre une dégradation à la chaleur existe depuis l’apparition des moteurs thermiques. Or les compositions des packages antioxydants destinés à la formulation de lubrifiants et leurs performances n’ont que très peu évolué depuis plus de 20 ans.The need to improve the resistance of lubricating compositions against heat degradation has existed since the advent of heat engines. However, the compositions of antioxidant packages intended for the formulation of lubricants and their performance have changed very little for more than 20 years.
  • Le document WO2014134506 divulgue des compositions lubrifiantes comportant des antioxydants. Cependant les résultats obtenus en termes de tenue dans le temps ne sont pas satisfaisants. Par ailleurs, ce document propose comme antioxydant une combinaison de phénol et d’amine, et propose en alternative une liste de produits, toutefois sans donner d’effet technique associé à chaque produit proposé, ni d’indication à l’homme du métier sur les avantages de l’un ou l’autre produit.Document WO2014134506 discloses lubricating compositions comprising antioxidants. However, the results obtained in terms of resistance over time are not satisfactory. Furthermore, this document proposes a combination of phenol and amine as an antioxidant, and proposes as an alternative a list of products, however without giving any technical effect associated with each product proposed, nor any indication to those skilled in the art on the benefits of either product.
  • Un objet de la présente invention est de proposer une composition lubrifiante ayant une bonne stabilité thermique contre une dégradation à l’oxydation.An object of the present invention is to provide a lubricating composition having good thermal stability against oxidative degradation.
  • Un autre objet de la présente invention est de proposer une composition lubrifiante dont l’impact sur l’environnement est réduit.Another object of the present invention is to provide a lubricating composition whose impact on the environment is reduced.
  • La présente invention a pour objet de répondre au moins en partie aux objets précités en proposant une composition lubrifiante avec un additif antioxydant amélioré. A cet effet, elle propose une composition lubrifiante comportant une huile de base et un additif antioxydant, ledit additif antioxydant comportant un antioxydant phénolique, un antioxydant de type amine, et un complément tocophérol comportant au moins un élément de la liste constituée de : le bêta-tocophérol, le delta-tocophérol et le gamma-tocophérol.The object of the present invention is to respond at least in part to the aforementioned objects by providing a lubricating composition with an improved antioxidant additive. To this end, it provides a lubricating composition comprising a base oil and an antioxidant additive, said antioxidant additive comprising a phenolic antioxidant, an antioxidant of amine type, and a tocopherol supplement comprising at least one element from the list consisting of: beta -tocopherol, delta-tocopherol and gamma-tocopherol.
  • Grâce à ces dispositions, la composition selon l’invention présente une meilleure stabilité thermique contre une dégradation à l’oxydation, par rapport aux compositions de l’état de la technique, tout en permettant une réduction de la part d’antioxydant de type amine, ce qui est un avantage en raison de la toxicité de ce produit.Thanks to these arrangements, the composition according to the invention exhibits better thermal stability against oxidation degradation, compared with the compositions of the state of the art, while allowing a reduction in the proportion of antioxidant of amine type. , which is an advantage due to the toxicity of this product.
  • Selon d’autres caractéristiques :According to other characteristics:
    • la somme des teneurs en poids du bêta-tocophérol, du delta-tocophérol et du gamma-tocophérol dans le complément tocophérol peut être supérieure à 50%, de préférence supérieure à 70%, améliorant la stabilité thermique contre une dégradation à l’oxydation de la composition lubrifiante,the sum of the contents by weight of beta-tocopherol, delta-tocopherol and gamma-tocopherol in the tocopherol supplement may be greater than 50%, preferably greater than 70%, improving thermal stability against oxidative degradation of the lubricating composition,
    • le complément tocophérol peut être constitué d’un mélange de plusieurs types de tocophérols, à raison de 0 à 20% de alpha-tocophérol, 0 à 5% de bêta-tocophérol, 50 à 65% de gamma-tocophérol et 20 à 35% de delta-tocophérol, ce qui est un produit présentant de bons résultats,the tocopherol supplement can consist of a mixture of several types of tocopherols, at a rate of 0 to 20% alpha-tocopherol, 0 to 5% beta-tocopherol, 50 to 65% gamma-tocopherol and 20 to 35% delta-tocopherol, which is a product with good results,
    • le complément tocophérol peut comporter du delta-tocophérol, ce qui permet une tenue dans le temps améliorée de la composition lubrifiante,the tocopherol supplement may contain delta-tocopherol, which allows improved resistance over time of the lubricating composition,
    • le complément tocophérol peut avoir une teneur en poids en delta-tocophérol supérieure à 50 %, ce qui améliore encore la stabilité thermique contre une dégradation à l’oxydation de la composition lubrifiante,the tocopherol supplement may have a delta-tocopherol content by weight greater than 50%, which further improves the thermal stability against oxidative degradation of the lubricating composition,
    • la teneur en poids en additif antioxydant peut être comprise entre 0,5 et 1,5 %, ce qui est un mode de réalisation efficace de l’invention,the content by weight of antioxidant additive can be between 0.5 and 1.5%, which is an effective embodiment of the invention,
    • l’additif antioxydant peut avoir une teneur en poids en complément tocophérol comprise entre 5 et 30 %, ce qui est un mode de réalisation efficace de l’invention,the antioxidant additive may have a content by weight of tocopherol supplement of between 5 and 30%, which is an effective embodiment of the invention,
    • l’additif antioxydant peut présenter un rapport des teneurs en poids de l’antioxydant de type amine à l’antioxydant phénolique inférieur à 0,9, de préférence inférieur à 0,8, ce qui permet d’améliorer le profil toxicologique de la composition lubrifiante,the antioxidant additive may exhibit a ratio of the weight contents of the amine-type antioxidant to the phenolic antioxidant of less than 0.9, preferably less than 0.8, which makes it possible to improve the toxicological profile of the composition lubricating,
    • l’huile de base peut avoir une teneur en poids en soufre inférieure à 0,03 % et un indice de viscosité supérieur à 120, ce qui est un mode de réalisation efficace de l’invention.The base oil can have a sulfur content of less than 0.03% by weight and a viscosity index greater than 120, which is an effective embodiment of the invention.
  • La présente invention concerne également une utilisation d’une composition lubrifiante selon l’invention, dans un moteur thermique.The present invention also relates to a use of a lubricating composition according to the invention, in a heat engine.
  • Grâce à ces dispositions, le moteur thermique bénéficie d’une composition qui présente une tenue dans le temps améliorée par rapport aux compositions de l’état de la technique grâce à une meilleure stabilité thermique contre une dégradation à l’oxydation, tout en permettant une réduction de la part d’antioxydant de type amine, ce qui est un avantage en raison du risque toxicologique que peut représenter ce produit.Thanks to these arrangements, the heat engine benefits from a composition which has improved durability over time compared to the compositions of the state of the art thanks to better thermal stability against oxidation degradation, while allowing reduction in the proportion of amine-type antioxidant, which is an advantage because of the toxicological risk that this product may represent.
  • La présente invention sera mieux comprise à la lecture de la description détaillée qui fait suite, en référence aux figures annexées dans lesquelles :The present invention will be better understood on reading the detailed description which follows, with reference to the appended figures in which:
  • est un graphique montrant les résultats d’une série de tests comparatifs d’une composition selon l’invention, is a graph showing the results of a series of comparative tests of a composition according to the invention,
  • est un graphique montrant un deuxième aspect des résultats de la série de tests comparatifs présentés à la fig. 1. is a graph showing a second aspect of the results of the series of comparative tests shown in FIG. 1.
  • La composition lubrifiante selon l’invention comporte une huile de base et un additif antioxydant. La composition lubrifiante peut avoir une teneur en poids en additif antioxydant comprise entre 0,5 et 1,5 %.The lubricating composition according to the invention comprises a base oil and an antioxidant additive. The lubricating composition may have an antioxidant additive content by weight of between 0.5 and 1.5%.
  • L’huile de base est de préférence une huile du Groupe III, mais peut également être une huile du Groupe I, Groupe II, Groupe III+, Groupe IV ou encore Groupe V.The base oil is preferably an oil from Group III, but can also be an oil from Group I, Group II, Group III +, Group IV or even Group V.
  • L’additif antioxydant comprend un antioxydant phénolique, un antioxydant de type amine, et un complément tocophérol.The antioxidant additive includes a phenolic antioxidant, an amine-type antioxidant, and a tocopherol supplement.
  • L’additif antioxydant peut avoir une teneur en poids en complément tocophérol comprise entre 5 et 30 %, de préférence entre 5 et 20 %.The antioxidant additive may have a tocopherol supplement by weight content of between 5 and 30%, preferably between 5 and 20%.
  • L’antioxydant phénolique peut être n’importe quel composé phénolique, c'est-à-dire un composé qui a un groupe OH libre attaché à un noyau phényle, apte à être un antioxydant. Tel qu'utilisé ici, le terme « antioxydant phénolique » comprend également les composés où le groupe OH est fixé à un noyau phényle, dans lequel le noyau phényle fait partie d'une structure cyclique fusionnée, par exemple, le noyau phényle fait partie d'un noyau benzothiophène, d'un noyau naphtalène, d'un noyau indolique, d'un noyau benzofuranne ou similaire. Les antioxydants phénoliques préférés sont les phénols encombrés (par exemple, avec au moins l'une des deux positions ortho du groupe phénolique OH substitué, par exemple, par un groupe alkyle tel qu'un groupe méthyle, éthyle, propyle, cyclopropyle, isopropyle, butyle, isobutyle ou tert-butyle) et les phénols dimères.The phenolic antioxidant can be any phenolic compound, that is, a compound which has a free OH group attached to a phenyl ring, capable of being an antioxidant. As used herein, the term "phenolic antioxidant" also includes compounds where the OH group is attached to a phenyl ring, wherein the phenyl ring is part of a fused ring structure, for example, the phenyl ring is part of a ring structure. a benzothiophene ring, a naphthalene ring, an indole ring, a benzofuran ring or the like. Preferred phenolic antioxidants are hindered phenols (e.g., with at least one of the two ortho positions of the OH phenolic group substituted, e.g., by an alkyl group such as methyl, ethyl, propyl, cyclopropyl, isopropyl, butyl, isobutyl or tert-butyl) and dimeric phenols.
  • L’antioxydant phénolique peut donc être constitué d’un phénol encombré ou d’un mélange de plusieurs phénols encombrés, choisis parmi le 2,6-di-tert-butyl-4-méthylphénol, le 2-butyl-4,6-diméthylphénol, le 2,6-di-tert-butyl-4-éthylphénol, le 2,6-di-tert-butyl-4-n-butylphénol, le 2,6-di-tert-butyl-4-isobutylphénol, le 2,6-dicyclopentyl-4-méthylphénol, le 2-(α-méthylcyclohexyl)-4,6-diméthylphénol, le 2,6-dioctadécyl-4-méthylphénol, le 2,4,6-tricyclohexylphénol, le 2,6-di-tert-butyl-4-méthoxyméthylphénol, le 2,6-dinonyl-4-méthylphénol, le 2,4-diméthyl-6-(1'-méthyl-undec-1'-yl)-phénol, le 2,4-diméthyl-6-(1'-méthylheptadec-1'-yl)-phénol, le 2,4-diméthyl-6-(1'-méthyltridec-1’-yl)-phénol, le 2,4-diotylthiométhyl-6-tert-butylphénol, le 2,4-diotylthiométhyl-6-méthylphénol, le 2,4-diotylthiométhyl-6-éthylphénol, et le 2,6-didodécylthiométhyl-4-nonylphénol.The phenolic antioxidant can therefore consist of a hindered phenol or of a mixture of several hindered phenols, chosen from 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-dimethylphenol. , 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2 , 6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di -tert-butyl-4-methoxymethylphenol, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methyl-undec-1'-yl) -phenol, 2,4- dimethyl-6- (1'-methylheptadec-1'-yl) -phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) -phenol, 2,4-diotylthiomethyl-6- tert-butylphenol, 2,4-diotylthiomethyl-6-methylphenol, 2,4-diotylthiomethyl-6-ethylphenol, and 2,6-didodecylthiomethyl-4-nonylphenol.
  • L’antioxydant de type amine peut être une amine aliphatique ou aromatique.The amine antioxidant can be an aliphatic or aromatic amine.
  • L’amine aromatique est un composé qui a un groupe amine, que ce soit un groupe amine libre (par exemple, NH2), ou un groupe amine substitué (par exemple, NR1R2, où R1 et R2 sont indépendamment hydrogène, alkyle, arylalkyle, hétéroarylalkyle, cycloalkylalkyle, hétérocyclocycloalkyle, hétérocyclocycloalkyle, arylcycloalkyle, arylcycloalkyle, hétéroarylcycloalkyle, arylhétérocycloalkyle, hétéroarylhétérocycloalkyle, hétéroarylhétérocycloalkyle, cycloalkyle, arylcycloalkyle, hétéroarylcycloalkyle, hétéroarylcycloalkyle, hétérocycloalkyle, arylhétérocycloalkyle, alcényle, arylalcényle, cycloalcényle, arylcycloalcène, hétéroarylcycloalcényle, hétérocycloalcényle, hétérocycloalcényle, arylhétérocycloalcényle, hétéroarylhétérocycloalcényle, hétéroarylhétéroalcényle, alcynyle, arylalcynyle, aryle, cycloalkylaryle, hétérocycloalkylaryle, cycloalcénylaryle, hétérocycloalcényle, hétéroaryle, cycloalkylhétéroaryle, hétéroalkylhétéroaryle, cycloalcénylhétéroaryle ou hétérocycloalcénylhétéroaryle), directement attaché à un noyau aromatique, tel qu'un cycle aromatique monocyclique (par exemple un cycle phényle, ou un cycle hétéroaromatique monocyclique tel qu'un cycle thiophène, un cycle pyridine, un cycle pyrimidine, un cycle furanne, un cycle pyrazine, un cycle pyridazine, un cycle triazine), ou un cycle aromatique polycyclique (par exemple un cycle aromatique bicyclique tel qu'un cycle naphtalène, ou un cycle hétéroaromatique bicyclique tel qu'un cycle indole, un cycle benzofuranne, un cycle benzoimidazole ou un cycle benzothiophène, etc. ou un cycle aromatique tricyclique tel qu'un carbazole).Aromatic amine is a compound that has an amine group, whether it is a free amine group (eg, NH2), or a substituted amine group (eg, NR 1 R 2 , where R 1 and R 2 are independently hydrogen , alkyl, arylalkyl, heteroarylalkyl, cycloalkylalkyl, hétérocyclocycloalkyle, hétérocyclocycloalkyle, arylcycloalkyl, arylcycloalkyl, heteroarylcycloalkyl, arylhétérocycloalkyle, hétéroarylhétérocycloalkyle, hétéroarylhétérocycloalkyle, cycloalkyl, arylcycloalkyl, heteroarylcycloalkyl, heteroarylcycloalkyl, heterocycloalkyl, arylhétérocycloalkyle, alkenyl, arylalkenyl, cycloalkenyl, arylcycloalcène, heteroarylcycloalkenyl, heterocycloalkenyl, heterocycloalkenyl , arylheterocycloalkenyl, heteroarylheterocycloalkenyl, heteroarylheteroalkenyl, alkynyl, arylalkynyl, aryl, cycloalkylaryl, heterocycloalkylaryl, cycloalkenylaryl, heterocycloalkenyl, cycletoaryylheteroaryylheteroaryylheteroaryylheteroaryylheteroaryylheteroaryylheteroaryylheteroaryylheteroaryyl le), directly attached to an aromatic ring, such as a monocyclic aromatic ring (for example a phenyl ring, or a monocyclic heteroaromatic ring such as a thiophene ring, a pyridine ring, a pyrimidine ring, a furan ring, a ring pyrazine, a pyridazine ring, a triazine ring), or a polycyclic aromatic ring (for example a bicyclic aromatic ring such as a naphthalene ring, or a bicyclic heteroaromatic ring such as an indole ring, a benzofuran ring, a benzoimidazole ring or a benzothiophene ring, etc. or a tricyclic aromatic ring such as a carbazole).
  • L’antioxydant de type amine peut être une amine aromatique, dans lequel le groupe amine est lié à deux cycles aromatiques, tels que deux cycles aromatiques monocycliques (par exemple, comme décrit ici) qui sont identiques ou différents, deux cycles aromatiques polycycliques (par exemple, comme décrit ici) qui sont identiques ou différents, ou un cycle aromatique monocyclique (par exemple, comme décrit ici) et un cycle aromatique polycyclique (par exemple, comme décrit ici). L’antioxydant de type amine peut être une diphénylamine. L’antioxydant de type amine peut encore être une amine aromatique ayant le groupe amine attaché à un cycle aromatique monocyclique (par exemple, un cycle phényle) et un cycle aromatique polycyclique (par exemple, un cycle naphtalène). L’antioxydant de type amine peut être choisi dans le groupe constitué de dinonyl diphenylamine, butylated, octylated diphenylamine, dioctyl diphenylamine, Ν,Ν'-diisopropyl-p-phénylènediamine, N,N'-di-sec-butyl-p-phénylènediamine, N,N'-bis(1,4-dimethylpentyl)-p-phénylènediamine, N,N'-bis(1-éthyl-3-méthylpentyl)-p-phénylènediamine, N,N'-bis(1-méthylheptyl)-p-phénylènediamine, N,N'-dicyclohexyl-p-phénylènediamine, N,N'-diphényl-p-phénylènediamine, N,N'-di(naphth-2-yl)-p-phénylènediamine, N-isopropyl-N'-phényl-p-phénylènediamine, N-(1,3-diméthylbutyl)-N'-phényl-p-phénylènediamine, N-(1-méthylheptyl)-N'-phényl-p-phénylènediamine, N-cyclohexyl-N'-phényl-N'-phényl-p-phénylènediamine, 4-(p-toluènesulfonamido)-diphénylamine, N,N'-diméthyl-N,N'-di-sec-butyl-p-phénylènediamine, diphénylamine, diphényl amine styrène (CAS n° 68442-68-2), N-allyldiphénylamine, 4-isopropoxydiphénylamine, di(4-méthoxyphényl)amine, 2,4'-diaminodiphénylméthane, 4,4'-diaminodiphénylméthane, N,N,N',N'-tétraméthyl-4,4'-diaminodiphénylméthane, 1,2-di[(2-méthylphényl)amino]-éthane, 1,2-di(phénylamino)propane, (o-tolyl)biguanide, di[4-(1’,3'-diméthylbutyl)phényl]amine, N-phényl-1-naphthylamine tert-octylée, phényl-1- naphtylamine amine p,p'-dioctyldiphényl, mélange de tert-butyl-diphénylamines tert-butylées/tert-octylées mono- et di-alkylées, mélange de nonyldiphénylamines mono- et di-alkylées, mélange de dodécyldiphénylamines mono- et di-alkylées, mélange de isopropyl/isohexyl-diphénylamines mono- et di-alkylées, mélanges de tert-butyldiphénylamines mono- et di-alkylées, 2,3-dihydro-3,3-diméthyl-4H-1,4-benzothiazine, phénothiazine, mélange de tert-butyl/tert-octyl-phénothiazines mono- et di-alkylées, mélanges de tert-octylphénothiazines mono- et di-alkylées, N-allylphénothiazine et Ν,Ν,Ν',Ν'-tetraphényl-1,4-diaminobut-2-ène.The amine antioxidant can be an aromatic amine, wherein the amine group is bonded to two aromatic rings, such as two monocyclic aromatic rings (e.g., as described here) that are the same or different, two polycyclic aromatic rings (e.g. example, as described herein) which are the same or different, or a monocyclic aromatic ring (eg, as described here) and a polycyclic aromatic ring (eg, as described here). The amine antioxidant can be a diphenylamine. The amine antioxidant can further be an aromatic amine having the amine group attached to a monocyclic aromatic ring (eg, a phenyl ring) and a polycyclic aromatic ring (eg, a naphthalene ring). The amine antioxidant can be selected from the group consisting of dinonyl diphenylamine, butylated, octylated diphenylamine, dioctyl diphenylamine, Ν, Ν'-diisopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine , N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-di (naphth-2-yl) -p-phenylenediamine, N-isopropyl-N '-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N' -phenyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfonamido) -diphenylamine, N, N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, diphenyl amine styrene ( CAS No. 68442-68-2), N-allyldiphenylamine, 4-isopropoxydiphenylamine, di (4-methoxyphenyl) amine, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'- tetramethyl-4,4'-dia minodiphenylmethane, 1,2-di [(2-methylphenyl) amino] -ethane, 1,2-di (phenylamino) propane, (o-tolyl) biguanide, di [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, phenyl-1-naphthylamine p-amine, p'-dioctyldiphenyl, mixture of tert-butyl-diphenylamines tert-butyl / tert-octyl mono- and di-alkyl, mixture of nonyldiphenylamines mono- and di-alkylated, mixture of mono- and di-alkylated dodecyldiphenylamines, mixture of mono- and di-alkylated isopropyl / isohexyl-diphenylamines, mixtures of mono- and di-alkylated tert-butyldiphenylamines, 2,3-dihydro-3 , 3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixture of mono- and di-alkylated tert-butyl / tert-octyl-phenothiazines, mixtures of mono- and di-alkylated tert-octylphenothiazines, N-allylphenothiazine and Ν , Ν, Ν ', Ν'-tetraphenyl-1,4-diaminobut-2-ene.
  • Le complément tocophérol comporte au moins un élément parmi le bêta-tocophérol, le delta-tocophérol et le gamma-tocophérol.The tocopherol supplement comprises at least one of beta-tocopherol, delta-tocopherol and gamma-tocopherol.
  • La somme des teneurs en poids du bêta-tocophérol, gamma-tocophérol et delta-tocophérol dans le complément tocophérol peut être supérieure à 50%, de préférence supérieure à 70%.The sum of the contents by weight of beta-tocopherol, gamma-tocopherol and delta-tocopherol in the tocopherol supplement can be greater than 50%, preferably greater than 70%.
  • Exemple de composition du complément tocophérol selon l’invention :Example of the composition of the tocopherol supplement according to the invention:
    • 0 à 20 % d’alpha-tocophérol,0 to 20% alpha-tocopherol,
    • 0 à 5 % de bêta-tocophérol,0 to 5% beta-tocopherol,
    • 50 à 65 % de gamma-tocophérol,50 to 65% gamma-tocopherol,
    • 20 à 35% de delta-tocophérol.20 to 35% delta-tocopherol.
  • Dans un mode préféré de réalisation de l’invention, le complément tocophérol comporte du delta-tocophérol, de préférence la teneur en poids du complément tocophérol en delta-tocophérol est supérieure à 50%.In a preferred embodiment of the invention, the tocopherol supplement comprises delta-tocopherol, preferably the content by weight of the tocopherol supplement in delta-tocopherol is greater than 50%.
  • L’additif antioxydant peut présenter un rapport des teneurs en poids de l’antioxydant de type amine à l’antioxydant phénolique compris entre 0,6 et 1,2.The antioxidant additive may have a ratio of the amine antioxidant to phenolic antioxidant content by weight of between 0.6 and 1.2.
  • Dans un mode de réalisation préféré, le rapport des teneurs en poids de l’antioxydant de type amine à l’antioxydant phénolique est inférieur à 0,9, de préférence inférieur à 0,8. En effet l’antioxydant de type amine peut représenter un risque toxicologique, c’est pourquoi il est avantageux d’en réduire la part dans l’additif antioxydant. Cette réduction est possible par la présence du complément tocophérol, qui permet d’obtenir de bonnes performances antioxydantes tout en réduisant la part d’antioxydant de type amine.In a preferred embodiment, the ratio of the weight contents of the amine antioxidant to the phenolic antioxidant is less than 0.9, preferably less than 0.8. This is because the amine-type antioxidant can represent a toxicological risk, which is why it is advantageous to reduce its share in the antioxidant additive. This reduction is possible by the presence of the supplement tocopherol, which allows good antioxidant performance to be obtained while reducing the proportion of the amine-type antioxidant.
  • Dans un mode préféré de réalisation de l’invention, l’huile de base est une huile du Groupe III, c’est-à-dire qu’elle présente une teneur en poids en soufre inférieur à 0,03% et un indice de viscosité supérieur à 120.In a preferred embodiment of the invention, the base oil is a Group III oil, that is to say it has a sulfur content of less than 0.03% by weight and an index of viscosity greater than 120.
  • La composition lubrifiante selon l’invention peut encore comprendre un ou plusieurs produits supplémentaires choisis dans le groupe constitué par un agent anti-usure, un détergent, un additif de désactivation de métaux, un phosphite, une lactone, un dispersant, un diluant, un émulsionnant, un agent antimousse, un inhibiteur de corrosion/rouille, un agent extrême pression, un agent abaisseur de point d'écoulement, un agent améliorant l'indice de viscosité et un agent modificateur de friction.The lubricating composition according to the invention may also comprise one or more additional products chosen from the group consisting of an antiwear agent, a detergent, a metal deactivation additive, a phosphite, a lactone, a dispersant, a diluent, a emulsifier, defoamer, corrosion / rust inhibitor, extreme pressure agent, pour point depressant, viscosity index improver and friction modifier.
  • ExempleExample
  • Une composition selon l’invention a été testée en utilisant une huile de groupe III HC6, pour comparer ses performances avec des compositions comparatives. Un test de vieillissement thermique à 150°C pendant 216 heures a été réalisé selon la procédure CEC (« Coordinating European Council ») L-109-14.A composition according to the invention was tested using a group III HC6 oil, to compare its performance with comparative compositions. A thermal aging test at 150 ° C. for 216 hours was carried out according to the CEC (“Coordinating European Council”) L-109-14 procedure.
  • L’évolution de la viscosité KV100 (mm²/s) selon la norme ASTM D445/446 ainsi que la résistance à l’oxydation (A/cm) selon la norme DIN 51453 ont été mesurées à des intervalles réguliers du vieillissement à 150°C : t=0 heures (initial), t= 72 heures, t=144 heures, t=168 heures, t=216 heures.The evolution of the viscosity KV100 (mm² / s) according to standard ASTM D445 / 446 as well as the resistance to oxidation (A / cm) according to standard DIN 51453 were measured at regular intervals during aging at 150 ° C. : t = 0 hours (initial), t = 72 hours, t = 144 hours, t = 168 hours, t = 216 hours.
  • Les antioxydants testés sont l’AO 1135, l’AO 5057, l’alpha-tocophérol, et un complément tocophérol sous la référence VB T70.The antioxidants tested are AO 1135, AO 5057, alpha-tocopherol, and a tocopherol supplement under the reference VB T70.
  • L’AO 1135 est un antioxydant phénolique de composition : acide benzopropanoïque, 3,5-bis(1,1-diméthyl-1,1-diméthyléthyl)-4-hydroxy-, esters alkyliques ramifiés en C7-9.AO 1135 is a phenolic antioxidant with the composition: benzopropanoic acid, 3,5-bis (1,1-dimethyl-1,1-dimethylethyl) -4-hydroxy-, branched C7-9 alkyl esters.
  • L’AO 5057 est un antioxydant de type amine, de composition : benzenamine,N-phényl-, produits de réaction avec le 2,4,4-triméthylpentène.AO 5057 is an amine antioxidant of composition: benzenamine, N-phenyl-, reaction products with 2,4,4-trimethylpentene.
  • Le VB T70 est un mélange d’antioxydants et d’huile de tournesol, de composition :VB T70 is a blend of antioxidants and sunflower oil, made up of:
    • 30% d’huile de tournesol30% sunflower oil
    • 70% de tocophérols, parmi lesquels se trouvent :
      • 9 à 20 % d’alpha-tocophérol
      • 1 à 4 % de bêta-tocophérol
      • 50 à 65 % de gamma-tocophérol,
      • 20 à 35 % de delta-tocophérol.
      70% of tocopherols, among which are found:
      • 9 to 20% alpha-tocopherol
      • 1 to 4% beta-tocopherol
      • 50 to 65% gamma-tocopherol,
      • 20 to 35% delta-tocopherol.
  • Compositions comparatives :Comparative compositions:
    • Composition A :
      • huile de base HC6
      Composition A:
      • base oil HC6
    • Composition B :
      • 99% huile de base HC6
      • 1% AO 1135
      Composition B:
      • 99% HC6 base oil
      • 1% AO 1135
    • Composition C :
      • 99% huile de base HC6
      • 0,7% AO 1135
      • 0,3% VB170 (ce qui correspond à environ 0,21% de complément tocophérol, du fait de la présence d’huile de tournesol dans le VB170)
      Composition C:
      • 99% HC6 base oil
      • 0.7% AO 1135
      • 0.3% VB170 (which corresponds to approximately 0.21% tocopherol supplement, due to the presence of sunflower oil in VB170)
    • Composition D (état de la technique) :
      • 99% huile de base HC-6
      • 0,5% AO 1135
      • 0,5% AO 5057
      Composition D (state of the art):
      • 99% HC-6 base oil
      • 0.5% AO 1135
      • 0.5% AO 5057
    • Composition E :
      • 99% huile de base HC-6
      • 0,4% AO 1135
      • 0,4% AO 5057
      • 0,2% alpha-tocophérol
      Composition E:
      • 99% HC-6 base oil
      • 0.4% AO 1135
      • 0.4% AO 5057
      • 0.2% alpha-tocopherol
  • Exemple de composition lubrifiante selon l’invention :Example of a lubricating composition according to the invention:
  • Composition F :Composition F:
    • 98,9% huile de base HC698.9% HC6 base oil
    • 0,45% AO 11350.45% AO 1135
    • 0,45% AO 50570.45% AO 5057
    • 0,2% VB 170 (ce qui correspond à environ 0,14% de complément tocophérol)0.2% VB 170 (corresponding to approximately 0.14% tocopherol supplement)
  • Les résultats des tests sont repris dans les tableaux 1 et 2 ci-dessous, ainsi que sur les figures 1 et 2.The results of the tests are given in Tables 1 and 2 below, as well as in Figures 1 and 2.
    • Tableau 1 : Viscosité KV100 selon les normes ASTM D445/446 (mm²/s)Table 1: Viscosity KV100 according to standards ASTM D445 / 446 (mm² / s)
    • Tableau 2 : Oxydation (A/cm) selon la norme DIN 51543Table 2: Oxidation (A / cm) according to DIN 51543
  • Durée de vieillissement à 150°C (heures)Aging time at 150 ° C (hours) 00 7272 144144 168168 216216
    Composition AComposition A 6,3656.365 8,2588.258 11,5411.54 13,4513.45 19,8719.87
    Composition BComposition B 6,3486.348 7,4757.475 9,9569.956 11,1411.14 14,5714.57
    Composition CComposition C 6,3516.351 7,5037.503 10,0410.04 11,3711.37 15,2115.21
    Composition DComposition D 6,3486.348 6,9626.962 9,3579.357 10,4310.43 13,5913.59
    Composition EComposition E 6,3586.358 7,5317,531 10,4610.46 1212 17,0617.06
    Composition FComposition F 6,3546.354 7,1987.198 8,8678.867 9,5959.595 11,411.4
  • Durée de vieillissement à 150°C (heures)Aging time at 150 ° C (hours) 00 7272 144144 168168 216216
    Composition AComposition A 00 79,379.3 128,6128.6 144,6144.6 173,9173.9
    Composition BComposition B 00 47,147.1 104,6104.6 118,5118.5 144,2144.2
    Composition CComposition C 00 48,248.2 110,6110.6 126,1126.1 156,9156.9
    Composition DComposition D 00 29,529.5 102,4102.4 120,9120.9 157157
    Composition EComposition E 00 50,450.4 119,3119.3 138,2138.2 174,6174.6
    Composition FComposition F 00 36,536.5 8787 99,599.5 123,2123.2
  • Le graphique de la figure 1 et le tableau 1 montrent l’évolution de la viscosité de l’huile lors de son vieillissement thermique, mesurée selon les protocoles ASTM D445/D446. L’unité en ordonnée est le mm2/s. L’unité de temps en abscisse est la durée du vieillissement thermique à 150°C, exprimée en heures. Ce test est particulièrement pertinent pour évaluer les performances d’une composition lubrifiante et sa tenue dans le temps.The graph in Figure 1 and Table 1 show the evolution of the viscosity of the oil during its thermal aging, measured according to the ASTM D445 / D446 protocols. The unit on the ordinate is mm 2 / s. The unit of time on the abscissa is the duration of thermal aging at 150 ° C., expressed in hours. This test is particularly relevant for evaluating the performance of a lubricating composition and its resistance over time.
  • Le graphique de la figure 2 et le tableau 2 montrent l’évolution de l’oxydation, mesurée selon le protocole DIN 51453. L’unité en ordonnée est le A/cm. L’unité de temps en abscisse est la durée du vieillissement thermique à 150°C, exprimée en heures.The graph in Figure 2 and Table 2 show the evolution of oxidation, measured according to the DIN 51453 protocol. The unit on the ordinate is A / cm. The unit of time on the abscissa is the duration of thermal aging at 150 ° C, expressed in hours.
  • Sur les fig. 1 et 2, on voit que les performances sont les plus faibles pour la composition A, qui ne comporte pas d’additif antioxydant.In fig. 1 and 2, we see that the performance is the lowest for composition A, which does not contain an antioxidant additive.
  • La composition D, qui est la formulation antioxydante de référence utilisée à grande échelle sur le marché des lubrifiants, est la composition de l’état de la technique qui obtient les meilleures performances en termes de viscosité (fig. 1). La composition F, réalisée selon l’invention, est similaire à la composition D avec une partie des antioxydants remplacée par un mélange de tocophérols de types alpha, bêta, gamma et delta.Composition D, which is the benchmark antioxidant formulation used on a large scale in the lubricants market, is the state of the art composition that achieves the best performance in terms of viscosity (Fig. 1). Composition F, produced according to the invention, is similar to composition D with part of the antioxidants replaced by a mixture of alpha, beta, gamma and delta type tocopherols.
  • Les résultats de la composition F sont meilleurs en termes de viscosité (fig. 1) et d’oxydation (fig. 2) que ceux de la composition D. La comparaison des compositions D et F permet de conclure à une amélioration des performances obtenue par la présence de tocophérols.The results of composition F are better in terms of viscosity (fig. 1) and oxidation (fig. 2) than those of composition D. The comparison of compositions D and F makes it possible to conclude that an improvement in performance obtained by the presence of tocopherols.
  • La composition E est également similaire à la composition D, mais cette fois avec une présence de tocophérols exclusivement de type alpha.Composition E is also similar to composition D, but this time with the presence of exclusively alpha-type tocopherols.
  • Les performances de la composition E représentées sur les fig. 1 et 2 sont moins bonnes que la composition F, et même moins bonnes que la composition D. L’effet d’amélioration des performances observé précédemment n’est donc pas présent avec des tocophérols exclusivement de type alpha, ce qui montre l’importance des tocophérols de type bêta, gamma et delta.The performance of composition E shown in FIGS. 1 and 2 are worse than composition F, and even worse than composition D. The performance improvement effect observed previously is therefore not present with exclusively alpha type tocopherols, which shows the importance beta, gamma and delta type tocopherols.
  • La composition B ne comprend qu’un antioxydant phénolique, et la composition C est similaire à la composition B avec une partie de l’antioxydant phénolique remplacée par le mélange de tocophérols alpha, bêta, gamma et delta.Composition B includes only one phenolic antioxidant, and Composition C is similar to Composition B with part of the phenolic antioxidant replaced by the mixture of alpha, beta, gamma and delta tocopherols.
  • Les performances de la composition C représentées sur les fig. 1 et 2 sont moins bonnes que la composition B. L’effet d’amélioration des performances observé précédemment grâce aux tocophérols n’est donc pas présent en l’absence d’un antioxydant de type amine. Cela fait apparaitre un effet de régénération de l’antioxydant de type amine par les tocophérols, expliquant que les tocophérols permettent d’améliorer les performances dans la composition F.The performance of composition C shown in FIGS. 1 and 2 are worse than composition B. The performance enhancing effect observed previously with tocopherols is therefore not present in the absence of an amine-type antioxidant. This shows an effect of regeneration of the amine-type antioxidant by tocopherols, explaining that tocopherols improve the performance in composition F.
  • Dès lors, dans les compositions selon l’invention il est possible de réduire la quantité d’antioxydant de type amine par rapport à l’état de la technique en ajoutant un peu de tocophérol de type bêta, gamma ou delta, ce qui est un avantage en raison de la toxicité des antioxydants de type amine. On peut par exemple prévoir un antioxydant avec 50% d’antioxydant phénol, 40% d’antioxydant amine, et 10% de complément tocophérol, ou encore 45% d’antioxydant phénol, 40% d’antioxydant amine, et 15% de complément tocophérol.Therefore, in the compositions according to the invention it is possible to reduce the amount of antioxidant of amine type compared to the state of the art by adding a little tocopherol of beta, gamma or delta type, which is a benefit due to the toxicity of amine-type antioxidants. For example, we can provide an antioxidant with 50% phenol antioxidant, 40% amine antioxidant, and 10% tocopherol supplement, or 45% phenol antioxidant, 40% amine antioxidant, and 15% supplement tocopherol.
  • Bien que la description ci-dessus se base sur des modes de réalisation particuliers, elle n’est nullement limitative de la portée de l’invention, et des modifications peuvent être apportées, notamment par substitution d’équivalents techniques ou par combinaison différente de tout ou partie des caractéristiques développées ci-dessus.Although the above description is based on particular embodiments, it is in no way limiting the scope of the invention, and modifications can be made, in particular by substitution of technical equivalents or by a different combination of any. or part of the characteristics developed above.

Claims (8)

  1. Composition lubrifiante comportant une huile de base et un additif antioxydant, dans laquelle :
    • la teneur en poids en additif antioxydant est comprise entre 0,5 et 1,5 %,
    • ledit additif antioxydant comporte un antioxydant phénolique, un antioxydant de type amine, et un complément tocophérol,
    • l’additif antioxydant a une teneur en poids en complément tocophérol comprise entre 5 et 30 %,
    • le complément tocophérol comporte au moins un élément de la liste constituée de : le bêta-tocophérol, le delta-tocophérol et le gamma-tocophérol,
    • la somme des teneurs en poids du bêta-tocophérol, du delta-tocophérol et du gamma-tocophérol dans le complément tocophérol est supérieure à 50%.
    Lubricating composition comprising a base oil and an antioxidant additive, in which:
    • the antioxidant additive content by weight is between 0.5 and 1.5%,
    • said antioxidant additive comprises a phenolic antioxidant, an amine-type antioxidant, and a tocopherol supplement,
    • the antioxidant additive has a content by weight of additional tocopherol of between 5 and 30%,
    • the tocopherol supplement contains at least one element from the list consisting of: beta-tocopherol, delta-tocopherol and gamma-tocopherol,
    • the sum of the contents by weight of beta-tocopherol, delta-tocopherol and gamma-tocopherol in the tocopherol supplement is greater than 50%.
  2. Composition lubrifiante selon la revendication 1, dans laquelle la somme des teneurs en poids du bêta-tocophérol, du delta-tocophérol et du gamma-tocophérol dans le complément tocophérol est supérieure à 70%.A lubricating composition according to claim 1, in which the sum of the contents by weight of beta-tocopherol, delta-tocopherol and gamma-tocopherol in the tocopherol supplement is greater than 70%.
  3. Composition lubrifiante selon la revendication précédente, dans laquelle le complément tocophérol est constitué d’un mélange de plusieurs types de tocophérols, à raison de 0 à 20% de alpha-tocophérol, 0 à 5% de bêta-tocophérol, 50 à 65% de gamma-tocophérol et 20 à 35% de delta-tocophérol.Lubricating composition according to the preceding claim, in which the tocopherol supplement consists of a mixture of several types of tocopherols, in a proportion of 0 to 20% of alpha-tocopherol, 0 to 5% of beta-tocopherol, 50 to 65% of gamma-tocopherol and 20 to 35% delta-tocopherol.
  4. Composition lubrifiante selon l’une des revendications 1 à 2, dans laquelle le complément tocophérol comporte du delta-tocophérol.A lubricating composition according to one of claims 1 to 2, in which the tocopherol supplement comprises delta-tocopherol.
  5. Composition lubrifiante selon la revendication 4, dans laquelle le complément tocophérol a une teneur en poids en delta-tocophérol supérieure à 50 %.A lubricating composition according to claim 4, wherein the tocopherol supplement has a delta-tocopherol content by weight of greater than 50%.
  6. Composition lubrifiante selon l’une des revendications précédentes, dans laquelle l’additif antioxydant présente un rapport des teneurs en poids de l’antioxydant de type amine à l’antioxydant phénolique inférieur à 0,9, de préférence inférieur à 0,8.A lubricating composition according to one of the preceding claims, wherein the antioxidant additive has a ratio of the weight contents of the amine antioxidant to the phenolic antioxidant of less than 0.9, preferably less than 0.8.
  7. Composition lubrifiante selon l’une des revendications précédentes, dans laquelle l’huile de base a une teneur en poids en soufre inférieure à 0,03 % et un indice de viscosité supérieur à 120.A lubricating composition according to one of the preceding claims, in which the base oil has a sulfur content of less than 0.03% by weight and a viscosity index of more than 120.
  8. Utilisation d’une composition lubrifiante selon l’une des revendications précédentes, dans un moteur thermique.Use of a lubricating composition according to one of the preceding claims, in a heat engine.
EP20702016.5A 2019-02-04 2020-01-29 Lubricant composition Withdrawn EP3921398A1 (en)

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