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
  • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/04—Mixtures of base-materials and additives
  • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/102—Aliphatic fractions
  • C10M2203/1025—Aliphatic fractions used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
  • C10M2205/026—Butene
• • 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
  • C10M2207/287—Partial esters
  • C10M2207/289—Partial esters containing free hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/043—Ammonium or amine salts thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/045—Metal containing thio derivatives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/04—Groups 2 or 12
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/04—Detergent property or dispersant property
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/40—Low content or no content compositions
  • C10N2030/42—Phosphor free or low phosphor content compositions
• • 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
  • C10N2030/40—Low content or no content compositions
  • C10N2030/43—Sulfur free or low sulfur content compositions
• • 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
  • C10N2030/40—Low content or no content compositions
  • C10N2030/45—Ash-less or low ash content
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/54—Fuel economy
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines

Definitions

• the present invention relates to a lubricant composition for a low ash four-stroke engine having good detergency properties, the use of which promotes fuel economy and comprises at least one hydroxyl ester or derivative thereof.
• the lubricant's behavior in reducing friction will have an impact on fuel consumption. It is mainly the quality of lubricating bases, alone or in combination with viscosity index improvers and friction modifying additives, which gives the lubricant its "fuel eco" properties.
• lubricants specifically formulated in compliance with certain specifications, in particular the low ash specifications ACEA-C4 (so-called “low saps”), or ACEA-C1 (known as “low saps”) is preferred. and “fuel eco”) developed by the Association of European Automobile Manufacturers. These specifications impose lubricant limits on sulphated ash (generated by the presence of metals), sulfur and phosphorus, hence the name “low saps” for "Sulfated Ashes, Phosphorus, Sulfur”.
• detergent additives avoiding the formation of deposits on the surface of metal parts by dissolving secondary oxidation and combustion products, and which are key compounds in the formulation of a motor oil, contain metal salts. that generate ashes. These are generally sulphonates, phenates, salicylates of alkali metals such as calcium, magnesium, overbased or not.
• a possible way to obtain lubricants with low ash content, maintaining a good detergency behavior despite a reduced rate of detergent, and having good fuel eco properties, is to favor the use of certain unconventional mineral base oils or synthetic bases. These bases have the advantage of better resistance to temperature and resistance to oxidation compared to conventional bases, which minimizes the formation of deposits. It is thus possible to lower the rate of treatment of the lubricants with detergent and to lower the ash content.
• VI viscosity index
• the sulfur content of unconventional mineral bases is comparatively lower than that of conventional mineral bases because they undergo extensive hydrotreatment, and the synthetic bases are free of sulfur, which facilitates compliance with the sulfur limits imposed by ACEA specifications.
• Unconventional mineral bases means the Group III bases according to the classification of American Petroleum Institute (API), presenting a value high viscosity index VI (typically greater than 130), commonly referred to as “Group III + bases”, or bases derived from GTL processes (Gas to Liquid).
• API American Petroleum Institute
• Group III + bases or bases derived from GTL processes (Gas to Liquid).
• the unconventional mineral bases called Group III + are prepared in order to improve their cold properties, to reduce their volatility and to increase their viscosity index (VI), to reach values greater than 130.
• group III bases means any type of API group III mineral base, while the term group III unconventional base, or group UH base refers to group III bases of VI greater than 130.
• the synthetic bases are, for example, the polyalphaolefms, the esters, and the internal polyolefins (respectively Group IV, V and V according to the API classification).
• the present invention relates to lubricating compositions for a four stroke engine, low saps and fuel eco, comprising an additivation system allowing the use of an enlarged number of lubricating bases, including in particular conventional Group III bases.
• the subject of the present invention is lubricant compositions for a four-stroke engine, containing additives that in themselves provide a minimum of ash, sulfur and phosphorus, totally or partially substituting for conventional additives used in this type of application, and which, in combination with each other, allow said lubricant compositions to retain detergency properties and eco-optimal fuel with a low or very low rate of ash, sulfur, phosphorus.
• lubricant compositions for a four-stroke engine containing additives that in themselves provide a minimum of ash, sulfur and phosphorus, totally or partially substituting for conventional additives used in this type of application, and which, in combination with each other, allow said lubricant compositions to retain detergency properties and eco-optimal fuel with a low or very low rate of ash, sulfur, phosphorus.
• compositions according to the invention are four-cycle lubricant compositions comprising: a) one or more base oils selected from group I oils;
• At least one compound (b) selected from the group of heavy PAOs with a kinematic viscosity at 100 ° C of between 75 and 3000 is optionally mixed with one or more compounds selected from the group of polymeric compounds of polyisubutene type ( PIB), or a mixture thereof, and c) at least one ester of formula R (OH) 1n (COOR '(OH) p ) n in which m is an integer from 0 to 8, preferably from 1 to 4 n is an integer from 1 to 8, preferably from 1 to 4 and p is an integer from 0 to 8, preferably from 1 to 4 and wherein the sum p + m is strictly greater than zero, R and R are independently of one another a linear or branched, saturated or unsaturated hydrocarbon group, optionally substituted by one or more aromatic groups, and having 1 to 30 carbon atoms, and its borate derivatives; said composition having a sulphated ash content of
• the ester (c) contains at least one free OH hydroxyl group belonging to the R group, said OH group being located in the alpha, beta or gamma position with respect to the carbon of the CO function of a function ester on which the group R is attached, and / or contains at least one free OH hydroxyl group belonging to the group R 'said OH group being located in the beta, gamma or delta position with respect to the COO group oxygen of a function ester on which the group R 'is attached.
• the R 'group of the ester (c) represents a C 1 to C 0 preferably C 2 to C 6 group .
• p is strictly greater than zero and the group R of the ester (c) represents a C 8 to C 25 , preferably C 1 to C 18, group .
• the group R of the ester (c) represents a C 8 to C 25 , preferably C 1 to C 18, group .
• at least one ester (c) will be chosen from the monoesters or diesters of glycerol, preferably chosen from glycerol monoleate, glycerol stearate or isostearate and their borate derivatives.
• n is an integer between 1 and 4 and the group R of the ester (c) represents a C 1 to C 5 , preferably C 1 to C 3, group .
• At least one ester (c) is chosen from citrates, tartrates, malates, lactates, mandelates, glycolates, hydroxypropionates, hydroxyglutarates or their borate derivatives.
• composition according to the invention leads to a minimum fuel economy measured on a Ml I lFE test of at least 2.5% and satisfying the specifications ACEA-Cl defined by the Association of European Automobile Manufacturers.
• the composition has a kinematic viscosity at 100 ° C., measured by the ASTM D445 standard of between 5.6 and 16.3 Cst, preferably between 9.3 and 12.5 Cst.
• the composition has a grade 5W30 according to the classification SAEJ300.
• the composition has a VI viscosity index greater than or equal to 130, preferably greater than 150, preferably greater than 160.
• the base oil or the mixture of base (a) represents at least 70% by weight of said composition.
• the base oil or the base oil mixture (a) comprises:
• the composition comprises a compound (b) chosen from the group of heavy PAOs, and a compound (b) chosen from the group of polymeric compounds of the PIB type.
• the composition comprises from 0.1 to 6%, preferably from 2 to 4% of at least one compound (b) and from 0.1 to 2.5%, preferably from 0.5 to 1.5%. % of at least one compound (c).
• the composition comprises at least one anti-wear compound of the Zinc dithiophosphate type, in optional combination with an amine phosphate.
• the composition comprises at least one anti-wear compound of the type of Zinc dithiophosphates in an amount of less than or equal to 1%, preferably less than or equal to 0.5%.
• composition is free of amine phosphate additive. In a preferred embodiment the composition is free of Molybdenum friction modifier additive.
• the composition comprises at least one antioxidant compound, preferably without ash, preferably of phenolic or amine type. In a preferred embodiment the composition comprises from 0.01 to 5% of one or more antioxidant additives.
• the composition has a BN, determined according to ASTM D-2896 less than or equal to 8 milligrams of potassium hydroxide per gram of lubricant, preferably less than or equal to 6.5 milligrams of potash per gram of lubricant
• the composition comprises between 0 and 3%, preferably between 0 and 2.5%, of an improvement polymer of VI chosen from among the polymeric esters, the copolymer olefins (OCP), the homopolymers or copolymers of styrene, butadiene or isoprene, polymethacrylates (PMA).
• OCP copolymer olefins
• PMA polymethacrylates
• the invention relates to a process for the manufacture of a composition according to the invention by diluting an additive package comprising at least one compound (b) and at least one compound (c), in an oil base or a mixture of base oils (a), and optionally adding a VI improving polymer.
• the additive package is diluted to represent
• the invention relates to a package of additives for four-stroke engine lubricant having a sulphated ash content of less than or equal to 0.5%, measured according to ASTM D874 standard, a phosphorus level of less than or equal to 500 ppm. according to ASTM D5185, and a sulfur content of less than 0.2% measured according to ASTM D5185, characterized in that it comprises:
• the additive package comprises: from 0.5 to 30% by weight, preferably from 10 to 25% by weight, of at least one compound (b), heavy PAO optionally mixed with a (PIB) ;
• the invention relates to the use of a composition according to the invention as a lubricant for a four-stroke engine.
• the invention relates to the use of at least one ester of formula R (OH) m (COOR '(OH) p ) n in which m is an integer of 0 to 8, preferably 1 at 4, n is an integer from 1 to 8, preferably from 1 to 4 and p is an integer from 0 to 8, preferably from 1 to 4 and where the sum p + m is strictly greater than zero, R and R 'represent, independently of each other, a linear or branched, saturated or unsaturated hydrocarbon group optionally substituted with one or more aromatic groups, and comprising from 1 to 30 carbon atoms, and its borate derivatives, as modifying agent method for the preparation of a four-stroke lubricant composition having a sulfated ash content of less than or equal to 0.5% measured according to ASTM D874, a phosphorus level of less than or equal to 500 ppm measured according to ASTM D5185, and a sulfur level less than or equal to 0.2% measured according to the ASTM standard D5
• the lubricating composition for a four-stroke engine according to the invention has a sulphated ash content of less than or equal to 0.5% measured according to ASTM D874 standard, a phosphorus level of less than or equal to 500 ppm measured according to ASTM D5185, and a sulfur less than 0.2% measured according to ASTM D5185.
• compositions according to the present invention are of ACEA C4 type, preferentially ACEA-Cl, according to the specifications established by the European Association of Automobile Manufacturers for gasoline and diesel engine oils for light vehicles.
• compositions according to the present invention have a sulphated ash content less than or equal to 0.30%, preferably less than or equal to 0.25%, and a phosphorus content of less than or equal to 300 ppm, preferentially less than or equal to 200 ppm.
• Lubricating compositions according to the present invention comprise one or more base oils, generally representing at least 50% by weight of the lubricating compositions, generally greater than 70% and up to 90% or more.
• the base oil (s) used in the compositions according to the present invention may be oils of mineral or synthetic origin of groups I to V according to the classes defined in the API classification (or their equivalents according to the ATIEL classification) as summarized herein. below, alone or mixed.
• oils may be oils of vegetable, animal or mineral origin.
• the mineral base oils according to the invention include all types of bases obtained by atmospheric and vacuum distillation of crude oil, followed by refining operations such as solvent extraction, desalphating, solvent dewaxing, hydrotreatment, hydrocracking and hydroisomerization, hydrofinishing.
• the base oils of the compositions according to the present invention may also be synthetic oils, such as certain esters of carboxylic acids and alcohols, or polyalphaolefins.
• the polyoaplphalefins used as base oils, and which are distinguished from the heavy polyalphaolefins (b) also present in the compositions according to the present invention are for example obtained from monomers having from 4 to 32 carbon atoms (for example octene, decene ), and a viscosity at 100 ° C of between 1.5 and 15 Cst. Their weight average molecular weight is typically between 250 and 3000. Mixtures of synthetic and mineral oils may also be employed.
• compositions according to the present invention have a kinematic viscosity at 100 ° C. of between 5.6 and 16.3 Cst, measured by the ASTM D445 standard (grade SAE 20, 30 and 40), preferably between 9.3 and 12.5 Cst (grade 30).
• the compositions according to the present invention are grade 5W30 according to the SAEJ300 classification.
• the compositions according to the present invention also preferably have a VI viscosity index greater than 130, preferably greater than 150, preferably greater than 160.
• group III mineral oils for example, group III mineral oils, and sulfur-free, preferably group IV, synthetic bases, or a mixture thereof.
• compositions according to the present invention may contain at least 70% base oil, typically at least 60% by weight of one or more Group III base oils and at least 10% by weight of one or more several Group IV base oils.
• PAO polyalphaolefins
• PIB polyisobutenes
• the compounds (b) of the "heavy" polyvalphaolefin (PAO) or “polyvalphaolefin” type "of viscosity" used in the composition according to the invention are chosen from PAOs with a kinematic viscosity at 100 ° C. measured according to ASTM.
• D445 between 75 and 3000 is, preferably between 150 and 1500, preferably between 300 and 1200 cSt.
• Mn is preferably greater than 2500, typically between 3000 and 20000, preferably between 3000 and 10000, preferably between 3000 and 7000.
• Weight-average molecular weight Mw is typically in the range of about 4000 to about 50000, and their MwMn polydispersity index is in the range of from 1.1 to 5 and higher.
• polyalphaolefms are for example obtained from monomers such as octene, decene, dodecene, tetradecene, hexadecene, etc., alone or mixed with other olefins.
• compositions according to the invention can be used alone or as a mixture in the compositions according to the invention.
• the compounds (b) of the polvisobutene type (PIB) used in the composition according to the invention are oil-soluble liquid polymeric compounds.
• Their molecular weight in weight Mw is typically greater than 800, typically between 800 and 8000, usually between 1500 and 7000.
• Their kinematic viscosity at 100 0 C is preferably between 1000 and 6000 is (ASTM D445).
• the PIBs according to the present invention have a weight-average molecular weight of between 2000 and 5000 and a kinematic viscosity at 100 ° C. of between 3000 and 4500 Cst.
• composition may comprise at least one compound chosen from the group of heavy PAOs described above, optionally mixed with at least one compound chosen from the group of the PIB-type polymeric compounds described above.
• the composition also comprises at least one ester of formula R (OH) m (COOR '(OH) p ) n in which m is an integer from 0 to 8, preferably from 1 to 4, n is an integer of 1 at 8, preferably from 1 to 4 and p is an integer from 0 to 8, preferably from 1 to 4 and where the sum p + m is strictly greater than zero, R and R 'independently represent one of the other a linear or branched hydrocarbon group, saturated or unsaturated, optionally substituted with one or more aromatic groups, and having 1 to 30 carbon atoms, and its borate derivatives.
• the ester (c) at least one free OH hydroxyl group belonging to the R group, said OH group being located in the alpha, beta or gamma position with respect to the carbon of the CO function of an ester function on which the R group is attached, and / or contains at least one free OH hydroxyl group belonging to the R 'group, said OH group being located in the beta, gamma or delta position with respect to the oxygen of the COO group of an ester function on which the group R 'is attached.
• R ' representss a C 1 -C 10 , preferably C 2 -C 6, group .
• R is C 8 to C 25 , preferably C 12 to C 18 .
• p is strictly greater than zero when the R group of the ester (c) represents a C 8 -C 25 , preferably C 12 -C 18, group .
• n is an integer between 1 and 4 when the group R of the ester (c) represents a C 1 -C 5 , preferably C 1 -C 3 group .
• the hydroxylated esters (c) may be chosen from monoesters or diesters obtained from glycerol such as glycerol monoleate, glycerol stearate or isostearate and their borate derivatives.
• the hydroxylated esters (c) may also be chosen from citrates, tartrates, malates, lactates, mandelates, glycolates, hydroxypropionates, hydroxyglutarates or their borate derivatives.
• compositions according to the invention may comprise, for example, from 0.1 to
• esters of formula R (OH) n , (COOR '(OH) p ) n according to the invention are prepared according to methods known to those skilled in the art, in particular by reaction of a carboxylic acid of formula R (OH) 1n (COOH) n with an alcohol of formula R '(OH) P> the substituents R, R', and the indices m, n being as defined above. 4) Other additives
• compositions according to the invention may further contain any type of additive suitable for use as a four-stroke engine oil.
• additives may be introduced in isolation and / or included in packages of additives used in the formulations of commercial lubricants for four-stroke engines, with performance levels as defined by F ACEA (Association of European Automobile Manufacturers) and / or FAPI (American Petroleum Institute) well known to those skilled in the art.
• F ACEA Association of European Automobile Manufacturers
• FAPI American Petroleum Institute
• compositions according to the invention may contain, in particular and without limitation, anti-wear and extreme pressure additives, friction modifiers, antioxidants, overbased or non-overbased detergents, viscosity index improvers, point improvers. flow, dispersants, anti-foam, thickeners ...
• the anti-wear and extreme pressure additives protect the friction surfaces by forming a protective film adsorbed on these surfaces.
• the most commonly used is Zinc di thiophosphate or DTPZn. This category also contains various phosphorus, sulfur, nitrogen, chlorine and boron compounds.
• anti-wear additives there is a wide variety of anti-wear additives, but the most used category in motor oils is that of phospho-sulfur-containing additives such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates or DTPZn.
• the preferred compounds have the formula Zn ((SP (S) (ORl) (OR2)) 2, where R1 and R2 are alkyl groups, preferably containing from 1 to 18 carbon atoms.
• amine phosphates are also commonly used anti-wear additives.
• the phosphorus provided by these additives acts as poison catalytic systems of automobiles, and they also bring ash.
• additives not providing phosphorus such as, for example, polysulfides, including sulfur olefins.
• Lubricant compositions are also usually encountered with anti-wear and extreme pressure additives of the nitrogen and sulfur type, such as, for example, metal dithiocarbamates, in particular ash-forming dithiocarbamate, which are also ash generators.
• nitrogen and sulfur type such as, for example, metal dithiocarbamates, in particular ash-forming dithiocarbamate, which are also ash generators.
• Glycerol esters are also anti-wear additives. Mention may be made, for example, mono-, di- and trioleate monopalmitates and monomyristates.
• the anti-wear and extreme pressure additives are present in the compositions for engine lubricants at contents of between 0.01 and 6%, preferably between 0.01 and 4%.
• the presence of hydroxylated esters or of polyalcohol esters (c) makes it possible to limit the amount of sulfur, phospho-sulfur, nitrogen-containing and sulfur-containing additives, of phosphates, so as to reach low levels.
• sulfated ash, sulfur and phosphorus for example compatible with the ACEA-C and ACEA-C2 specifications, while maintaining performance compatible with use as a four-stroke engine oil.
• the lubricating compositions according to the present invention may contain DTPZN 5 and / or other antiwear and extreme pressure additives, in amounts compatible with an overall sulfated ash content of less than 0.5%, measured according to ASTM D874, a phosphorus level below 500 ppm measured according to ASTM D5185, and a sulfur content of less than 0.2% measured according to ASTM D 5185.
• They may contain a level of DTPZn less than or equal to 1% by weight, preferably less than or equal to 0.5%. They can also be free (0% by weight) of additives providing phosphorus, for example amine phosphates.
• the friction modifiers encountered in the four-stroke lubricant compositions may be compounds providing metallic elements or ash-free compounds. Solid compounds such as molybdenum sulfide, graphite or PTFE are also found.
• the metal compounds are, for example, transition metal complexes such as Mo, Sb, Sn, Fe, Cu and Zn, the ligands of which may be hydrocarbon compounds containing oxygen, nitrogen, sulfur or phosphorus.
• the molybdenum-containing compounds can be particularly effective, such as, for example, dithiocarbamates, molybdenum dithiophosphates.
• the ashless friction modifiers can be, for example, fatty alcohols, fatty acids, esters, fatty amines.
• Friction modifying additives are generally present at levels of between 0.01 and 5%, preferably 0.01 and 1.5%, in engine lubricants.
• the presence of hydroxylated esters or of polyalcohol esters (c) makes it possible to limit the amount of friction modifiers that bring in sulfated ash, phosphorus and sulfur, so as to attain a low ash content.
• sulfates, sulfur and phosphorus for example compatible with the specification ACEA-Cl and ACEA-C4, while maintaining performance compatible with use as four-stroke engine oil, including fuel eco or fuel-saving properties, so as to fall within the specification ACEA-Cl.
• compositions according to the present invention may be free of ash delivery friction modifiers, for example molybdenum friction modifiers.
• the lubricating compositions according to the present invention may, however, contain all types of friction-modifying additives, in amounts compatible with an overall level of sulfated ash of less than or equal to 0.5%, measured according to ASTM D874, a lower phosphorus level. or equal to 500 ppm measured according to ASTM D5185, and a sulfur level of less than or equal to 0.2% measured according to ASTM D 5185.
• Antioxidants delay the degradation of oils in service, which can result in the formation of deposits, the presence of sludge, or an increase in the viscosity of the oil. They act as free radical inhibitors or destroyers of hydroperoxides.
• antioxidants commonly used are the antioxidants of the phenolic type, amines. Some of these additives, for example phospho-sulfur, can be ash generators.
• Phenolic anoxidants 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 hydroxyl groups are in the o or p position of each other, or the phenol is substituted by an alkyl group having at least 6 carbon atoms.
• Amino compounds are another class of antioxidants that can be used, possibly in combination with phenolics.
• Typical examples are aromatic amines, of the formula R 8 R 10 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 a group alkyl or aryl, or a group of formula R 11 S (O) x R 12 , where R 11 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.
• antioxidants are that of 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.
• the lubricating compositions according to the present invention may contain all types of antioxidant additives known to those skilled in the art, in amounts compatible with an overall level of sulphated ash of less than or equal to 0.5%, measured according to the ASTM D874 standard. phosphorus level less than or equal to 500 ppm measured according to ASTM D5185, and a sulfur content of less than or equal to 0.2% measured according to the ASTM D 5185 standard. Ashless antioxidants will be preferred.
• Detergents reduce the formation of deposits on the surface of metal parts by dissolving secondary oxidation and combustion products.
• the detergents used in the lubricant compositions according to the present invention are well known to those skilled in the art.
• the detergents commonly used in the formulation of lubricating compositions are typically anionic compounds having a long lipophilic hydrocarbon chain and a hydrophilic head.
• the associated cation is typically a metal cation of an alkali or alkaline earth metal.
• the detergents are preferably chosen from alkali metal or alkaline earth metal salts of carboxylic acids, sulphonates, salicylates and naphthenates, as well as the salts of phenates.
• the alkaline and alkaline earth metals are preferably calcium, magnesium, sodium or barium.
• metal salts may contain the metal in an approximately stoichiometric amount or in excess (in an amount greater than the stoichiometric amount). In the latter case, we are dealing with so-called overbased detergents.
• the excess metal providing the overbased detergent character is in the form of oil insoluble metal salts, for example carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate.
• the metals of these insoluble salts may be the same as those of the oil-soluble detergents or may be different. They are preferably selected from calcium, magnesium, sodium or barium.
• the overbased detergents are thus in the form of micelles composed of insoluble metal salts maintained in suspension in the lubricating composition by the detergents in the form of oil-soluble metal salts.
• These micelles may contain one or more types of insoluble metal salts, stabilized by one or more detergent types.
• Overbased detergents with a single type of detergent soluble metal salt will generally be named after the nature of the hydrophobic chain of the latter detergent.
• the overbased detergents will be said to be of mixed type if the micelles comprise several types of detergents, different from each other by the nature of their hydrophobic chain.
• the lubricant compositions according to the present invention may contain any type of detergent known to those skilled in the art, neutral or overbased or highly overbased.
• the more or less overbased character of the detergents is characterized by the BN (base number), measured according to the ASTM D2896 standard, and expressed in mg of KOH per gram.
• Neutral overbased detergents have a BN ranging from about 0 to about 80.
• Overbased detergents on the other hand, have BN values typically of the order of 150 or more, or even 250 or 450 or more.
• the BN of the lubricant composition containing detergents is measured by ASTM D2896 and expressed as mg KOH per gram of lubricant.
• the lubricant compositions according to the present invention can contain any type of detergents known to those skilled in the art, neutral or overbased, or strongly overbased, in amounts compatible with an overall sulfated ash level of less than or equal to 0, 5% measurement according to ASTM standard
• the amounts of overbased detergents included in the lubricating compositions according to the invention are adjusted so that the BN of said compositions, measured according to the ASTM D2896 standard, is less than or equal to
• the viscosity improving polymers make it possible to guarantee a good cold behavior and a minimum viscosity at high temperature, in particular to formulate multi-grade oils.
• the introduction of these compounds into the lubricating compositions allows them to achieve viscosity index (VI) values giving them good fuel eco properties or fuel economy.
• the lubricant compositions according to the invention preferably have VI values, measured according to ASTM D2270, greater than or equal to 130, preferably greater than 150, and preferably greater than 160.
• polymeric esters olefins copolymers (OCP), homopolymers or copolymers of styrene, butadiene or isoprene, polymethacrylates (PMA).
• OCP olefins copolymers
• PMA polymethacrylates
• the lubricant compositions according to the present invention may contain from about 0.0 to 10% by weight of VI improvers.
• compositions according to the invention contain at most 3% by weight of VI-improving polymers generating deposition, for example chosen from among the polymeric Esters, the Olefins Copolymers (OCP), the homopolymers or copolymers of styrene, butadiene or isoprene, polymethacrylates (PMA), preferably at most 2.5% by weight, or are free.
• VI-improving polymers generating deposition for example chosen from among the polymeric Esters, the Olefins Copolymers (OCP), the homopolymers or copolymers of styrene, butadiene or isoprene, polymethacrylates (PMA), preferably at most 2.5% by weight, or are free.
• VI-improving polymers generating deposition for example chosen from among the polymeric Esters, the Olefins Copolymers (OCP), the homopolymers or copolymers of styrene, butadiene or isoprene
• Pour point depressant additives improve the cold behavior of oils by slowing the formation of paraffin crystals. They are, for example, alkyl polymethacrylates, polyacrylates, polyarylamides, polyalkylsphenols, polyalkylnaphthalenes, alkylated polystyrene, etc.
• Dispersants such as succinimides, PIB (polyisobutene) succinimides, Mannich bases ensure the maintenance in suspension and evacuation of insoluble solid contaminants formed by the secondary oxidation products that are formed when the engine oil is in use.
• PIB polyisobutene
• Mannich bases ensure the maintenance in suspension and evacuation of insoluble solid contaminants formed by the secondary oxidation products that are formed when the engine oil is in use.
• the hydroxylated ester (s) (c) can be introduced as individual compounds. Some or all of the additives may be part of a concentrate or package of additives that will be diluted in the base oil or base oil mixture (a).
• VI improving polymers can, in particular, be added independently of the package
• the subject of the present invention is also such preparation processes, in particular a process where the additive package is diluted so as to represent from 10 to 30%, preferably from 15 to 20% by weight of the lubricating composition, and the VI improving polymer represents from 0 to 3% of the lubricating composition.
• the present invention also relates to packets of additives for four-stroke engine lubricant having a sulphated ash content of less than or equal to 0.5% measured according to ASTM D874, a phosphorus level is less than or equal to 500 ppm measured according to ASTM D5185, and a sulfur level is less than or equal to 0.2% measured according to the ASTM D5185 standard, which comprise: at least one compound (b), heavy PAO optionally mixed with a (PIB) at least one ester hydroxylated (c) optionally, anti-wear and extreme pressure additives, friction modifiers, detergents, antioxidants, overbased and non-overbased detergents, pour point depressants, dispersants, anti-foam additives, thickeners , viscosity index improving polymers
• the additive packets according to the present invention comprise: from 0.5 to 30% by weight, preferably from 10 to 25% by weight, of at least one compound (b), heavy PAO optionally mixed with a (PIB) from 0.5 to 15% by weight, preferably from 2.75 to 8.75% by weight of at least one hydroxyl ester (c).
• a compound b
• heavy PAO optionally mixed with a (PIB) from 0.5 to 15% by weight, preferably from 2.75 to 8.75% by weight of at least one hydroxyl ester (c).
• PIB hydroxyl ester
• Another object of the present invention relates to the use of lubricant compositions as described above as lubricant for four-stroke engine, diesel or gasoline, preferably for light-duty engine.
• the present invention relates to the use of hydroxylated esters (c) described above as friction modifiers making it possible to formulate lubricant compositions for a four-stroke engine having a sulphated ash content of less than or equal to 0.5%, measured according to ASTM D874, a phosphorus level less than or equal to 500 ppm measured according to ASTM D5185, and a sulfur content of less than or equal to 0.2% measured according to ASTM D5185.
• Example 1 Improvement of detergency properties thanks to heavy PIB (b ') and PAO (b)
• compositions are described in Table 1.
• Composition A is a reference composition of grade 5W30 comprising an OCP type enhancer polymer.
• compositions B, C and D a portion of OCP enhancer of VI with PIB or heavy PAO was substituted for reference A.
• MCT Micro Coking Test
• the ECBT test (EIf Coking Bench Test) is a thermal resistance test on a coking bench. It simulates a high-temperature engine piston that is sprayed with oil from a crankcase. The lubricant arrives on a very hot surface, deteriorates and gives rise to deposits. This test allows an approach of the nature of the deposits formed on the upper parts of the piston
• Table 2 gives the results of the detergency tests obtained for oils A, B, C and D. It is found that at fixed detergent level (fixed TBN), the detergency performances of the oils B, C, D where Partially substituted PIB or heavy PAO to the OCP polymer are better than those of Reference A, which contains only OCP. Table 2: detergency tests.
• composition A is a reference composition with a very low level of ash, sulfur and phosphorus, 5W30, with a VI improving polymer different from that of reference A.
• the mass composition of the oil A' and its properties are Data in Table 2.
• the composition B ' was prepared by adding 1% by weight of triethylcitrate to the composition A'.
• the fuel eco properties of oils A 'and B' were measured by a Cameron Plint Frottement laboratory test. This laboratory test is correlated with Ml I lFE motor tests (CEC standard L54-T-96).
• the test bench consists of a plane cylinder tribometer immersed in the oil to be tested. A variable normal force is applied to the heated plane and the resulting frictional force is measured. Comparison of the results with those obtained for the reference oils of the Ml I lFE engine test (CEC L54-T-96) makes it possible to calculate the fuel economy achieved with the oil tested.
• the results reported in Table 3 below highlight the improvement of fuel eco properties induced by the addition of triethylcitrate.
• Composition E is a reference composition of grade 5W30 comprising an OCP type enhancer polymer, and an additive package comprising dispersants, detergents (Sulfonates and calcium phenates, weakly and strongly overbased), DTPZn, a friction modifier, amino and phenolic antioxidants, an anti foam additive, a pour point depressant.
• an additive package comprising dispersants, detergents (Sulfonates and calcium phenates, weakly and strongly overbased), DTPZn, a friction modifier, amino and phenolic antioxidants, an anti foam additive, a pour point depressant.
• compositions F, G and H a part of the OCP improving polymer of VI has been substituted, relative to reference E, by a heavy PAO with a kinematic viscosity at 100 ° C. of 1000 mm 2 / s, marketed by Exxon Mobil under the name of SpectraSyn Ultra 1000.
• Compositions G and H are compositions according to the invention, in which the VI-improving polymer is partially substituted by this same heavy PAO (compound (b)) and further comprising 1% by weight of a compound (c), respectively triethyl citrate and glycerol monoisostearate.
• the compositions (in mass%) and physicochemical properties of the compositions E, F, G, H are given in table 4.
• compositions E, F, G, H were evaluated by a MlIlFE motor test and a Cameron Plint laboratory test.
• the detergency properties were evaluated by the ECBT test conducted at 280 ° C.
• Cycles that represent a taxi with a strong urban character speed between 750 and 3070 rpm power between 0 and 49 KW oil temperature between 20 and 75 ° C Fuel economy measured by comparison with a reference oil of grade 15W40 (RLl 91).
• Test conditions Cameron Plint fuel eco laboratory Friction This laboratory test is correlated to the Ml 1 IFE engine tests (CEC standard L54-T-96).
• the test bench consists of a plane cylinder tribometer immersed in the oil to be tested. A variable normal force is applied to the heated plane and the resulting frictional force is measured. Comparison of the results with those obtained for the reference oils of the Ml I lFE engine test (CEC L54-T-96) makes it possible to calculate the fuel economy achieved with the oil tested.
• the partial substitution of OCP with heavy PAO in the composition F makes it possible to minimize the formation of deposition, and therefore to improve the detergency properties with respect to the reference E, at a constant detergent treatment rate.
• the addition of hydroxylated esters is without influence and the good performances in detergency are preserved.
• OCP type VI improving polymer with heavy PAO has a positive effect in detergency (one goes from 25.30 to 34.20 in ECBT 280 ° C) but a negative effect on the fuel eco properties (one passes from 1.97 to 1.78 in Cameron Plint test and from 2.57 to 1.90 in Ml 1 IFE engine test).
• the addition of hydroxyl ester in the compositions G and H makes it possible to compensate for the lowering of the fuel eco property and even to improve with respect to the reference.

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