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
  • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
  • C10M171/008—Lubricant compositions compatible with refrigerants
• • 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
  • C10M2207/026—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
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
  • C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
  • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
  • C10M2209/1045—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
  • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
  • C10M2209/1055—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
  • C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
• • 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
  • 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
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/04—Molecular weight; Molecular weight distribution
• • 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
  • C10N2020/09—Characteristics associated with water
  • C10N2020/097—Refrigerants
  • C10N2020/101—Containing Hydrofluorocarbons
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/30—Refrigerators lubricants or compressors lubricants

Definitions

• the present invention relates to a lubricating composition, intended for refrigerant systems comprising a gas compression circuit, and more particularly for compressors of automotive air conditioning systems, which operate in the presence of hydrofluorocarbon refrigerants, in particular based on 1, 1, 1,2-tetrafluoroethane (RI 34a) and / or 2,3,3,3-tetrafluoropropene (HFO-1234yf).
• RI 34a 1, 1, 1, 1,2-tetrafluoroethane
• HFO-1234yf 2,3,3,3-tetrafluoropropene
• Such an air conditioning device is based on a thermodynamic cycle comprising the vaporization of the refrigerant at low pressure (in which the fluid absorbs heat); compressing the vaporized fluid to high pressure, condensing the vaporized fluid into a liquid at high pressure (in which the fluid rejects heat), and expanding the fluid to complete the cycle.
• chlorinated compounds for example of the chlorofluorocarbons and hydrochlorofluorocarbons type, which have the disadvantage of damaging the ozone layer, have been gradually replaced by non-chlorinated compounds such as hydrofluorocarbons, fluoroethers and fluoroolefins.
• the refrigerant most commonly used at present in automotive air conditioning systems is 1, 1,1,2-tetrafluoroethane, referred to as “R134a”. More recently, a new refrigerant, exhibiting a reduced global warming potential (GWP), 2,3,3,3-tetrafluoropropene, referred to as “HFO-1234yf”, has been developed, and is now recommended in Europe. due to its low GWP and its good energy performance.
• a lubricating oil must be added at the level of the automobile air conditioning device, in particular at the level of the compressor.
• the oil can generally be mineral or synthetic.
• the lubricating oil used in the automotive air conditioning compressor is brought into contact with the refrigerant gas, which imposes constraints on miscibility, compatibility and chemical stability of the refrigerant with the lubricating oil.
• the lubricating oil must be chosen so as not to react with the refrigerant or to negatively impact the properties of the latter.
• the lubricating oil is compatible with the refrigerant used.
• it must be chemically and thermally stable in the presence of the refrigerant.
• the refrigerant fluid exhibits good properties of miscibility with the lubricating oil, in other words that the mixture of the refrigerant fluid with the lubricating oil does not undergo phase separation during its use at the level of the lubricant.
• air conditioning system i.e. over a wide temperature range, preferably from -10 ° C, in particular from -20 ° C, up to 10 ° C, preferably up to 30 ° vs.
• refrigerant fluids based on hydrofluorocarbon compounds such as R134a and / or HFO-1234yf, exhibit miscibility with lubricating oils, usually used in air conditioning systems, which is often imperfect.
• a lubricating oil which exhibits good properties in terms of chemical and thermal stability, compatibility and miscibility with refrigerant fluids based on hydrofluorocarbon compound (s), in particular with R134a and / or HFO-1234yf.
• document EP 2 161 323 in the name of IDEMITSU proposes for example lubricating formulations, compatible with unsaturated fluorinated hydrocarbon refrigerant fluids, such as 1,2,3,3,3-pentafluoropropene, based on polyoxyalkylenes glycols whose two hydroxyl ends are capped (“double end capped” in English terminology), exhibiting a hydroxyl number less than or equal to 5 mgKOH / g.
• polyoxyalkylene glycols are more particularly chosen from polypropylene glycol dimethyl ether, polyethylene-polypropylene glycol dimethyl ether, polyethylene-polypropylene glycol methyl butyl ether and polypropylene glycol diacetate.
• the present invention aims specifically to provide a novel lubricating composition, intended for a heat transfer system by gas compression, in particular for an air conditioning compressor, using a refrigerant based on fluorocarbon compound (s), in particular of the R134a and / or HFO-1234yf type.
• gas compression in particular for an air conditioning compressor
• refrigerant based on fluorocarbon compound (s) in particular of the R134a and / or HFO-1234yf type.
• a lubricating composition meeting the aforementioned requirements for lubricants for refrigeration systems, by using, as base oil, a mixture of at least two specific polyalkylene glycols.
• the present invention relates, according to a first of its aspects, to a lubricating composition, intended for a refrigerant system comprising a gas compression circuit, in particular for a compressor of an automobile air conditioning system, comprising:
• PAG A at least a first polyalkylene glycol, denoted PAG A, exhibiting a hydroxyl number strictly greater than 50 mgKOH / g and a kinematic viscosity measured at 100 ° C according to the ASTM D445 standard, ranging from 5 to 10 mm 2 / s;
• polyalkylene glycols A and B being present in a PAG (s) A / PAG (s) B mass ratio of between 60/40 and 99/1.
• the invention also relates, according to another of its aspects, to the use of a lubricating composition, as defined above, in a refrigerant system comprising a gas compression circuit, in particular in a compressor of an air conditioning system.
• a refrigerant system comprising a gas compression circuit, in particular in a compressor of an air conditioning system.
• automotive in association with a refrigerant based on hydrofluorocarbon compounds, in particular with a refrigerant based on RI 34a and / or HFO-1234yf.
• a lubricating composition according to the invention may further comprise one or more additives, in particular chosen from antiwear and extreme pressure additives, antioxidants, lubricating agents, acid scavengers and anti-foaming agents.
• a lubricating composition according to the invention further comprises at least one phenolic antioxidant additive.
• a lubricating composition according to the invention further comprises at least one antiwear additive of amine phosphate type.
• the hydroxyl number represents the amount of potassium hydroxide in mg corresponding to the number of hydroxyl groups present in 1 g of material.
• the hydroxyl number is representative of the functionalization or not of the hydroxyl ends of the polyalkylene glycol used.
• the polyalkylene glycols of PAG A type used according to the invention exhibiting a hydroxyl number strictly greater than 50 mgKOH / g, are typically polyalkylene glycols having a single capped hydroxyl end, more generally designated under the name "single end capped" in Anglo-Saxon terminology.
• the polyalkylene glycols A according to the invention have at least one free hydroxyl end.
• polyalkylene glycols of the “single end capped” type as the majority base oil in a lubricating formulation intended for a refrigerant system was by no means obvious.
• the polyalkylene glycols exhibiting the two capped ends in other words not exhibiting a free hydroxyl function (“double end capped” in English terminology) are usually preferred to “single end capped” polyalkylene glycols, because of their thermal stability.
• a lubricating composition according to the invention comprising a base oil formed mainly from the mixture of the two polyalkylene glycols A and B as defined above, has excellent miscibility with a coolant based on transfer compounds.
• hydrofluorocarbon heaters in particular with a refrigerant based on R134a and / or HFO-1234yf over a wide temperature range.
• a lubricating composition according to the invention advantageously exhibits excellent properties in terms of thermal and chemical stability, in the presence of a refrigerant based on hydrofluorocarbon compounds, in particular based on R134a and / or HFO-1234yf.
• a lubricating formula according to the invention exhibiting good thermal stability and good miscibility with refrigerants based on R134a and / or HFO-1234yf, makes it possible to proceed with the replacement of the refrigerant fluids used up to now in automotive air conditioning systems, such as 1, 1- difluoroethane, without impacting the lubrication of compressor parts and the efficiency of the refrigerant system.
• the lubricating formulation according to the invention in which the first polyalkylene glycols, PAG A, constitute the oil of majority basis, proves particularly advantageous in terms of cost price.
• the lubricating composition according to the invention exhibits satisfactory tribological properties and particularly suitable for its use for lubricating a compressor of an automobile air conditioning system.
• the lubricating composition according to the invention exhibits good lubricating power, a low pour point, good fluidity at low temperature.
• kinematic viscosity measured at 40 ° C (KV40), according to the ASTM D445 (ISO 3104) standard, of between 30 and 60 mm 2 / s, in particular between 30 and 55 mm 2 / s and more particularly between 40 and 50 mm 2 / s.
• the invention also relates, according to another of its aspects, to a heat transfer composition, for a refrigerant system comprising a gas compression circuit, in particular for an automotive air conditioning system, comprising:
• a refrigerating fluid based on orocarbon hydrofluoric compounds in particular based on 1, 1,1,2-tetrafluoroethane (R134a) and / or 2,3,3,3-tetrafluoropropene (HFO-1234yf).
• R134a 1, 1,1,2-tetrafluoroethane
• HFO-1234yf 2,3,3,3-tetrafluoropropene
• the refrigerant under consideration according to the invention may consist of R134a, HFO-1234yf or a mixture of R134a and HFO-1234yf.
• heat transfer compound respectively "heat transfer fluid”, also called “refrigerant fluid” or “refrigerant” is meant a compound, respectively a fluid, capable of absorbing heat in s' evaporating at low temperature and low pressure, and rejecting heat by condensing at high temperature and high pressure, in a gas compression circuit.
• a heat transfer fluid can include one, two, three or more heat transfer compounds.
• the refrigerant comprises only R134a as heat transfer compound.
• the refrigerant comprises only HFO-1234yf as a heat transfer compound.
• the invention is a mixture of RI 34a and HFO-1234yf.
• the invention also relates to the use of a heat transfer composition as defined above in a refrigerant system comprising a gas compression circuit, in particular for an automobile air conditioning system.
• refrigerant system comprising a gas compression circuit, in particular an automobile air conditioning system, comprising a heat transfer composition as defined above.
• the invention also relates to a kit intended to be implemented for a refrigerant system comprising a gas compression circuit, comprising:
• a refrigerating fluid based on hydrofluorocarbon compounds in particular based on 1,1,1,2-tetrafluoroethane (R134a) and / or 2,3,3,3-tetrafluoropropene (HFO-1234yf).
• R134a 1,1,1,2-tetrafluoroethane
• HFO-1234yf 2,3,3,3-tetrafluoropropene
• the kit may be more particularly intended for an automobile air conditioning installation.
• a lubricating composition according to the invention intended for a refrigerant system, in particular for an automobile air conditioning system, comprises a base oil formed mainly from a mixture of at least two distinct polyalkylene glycols, denoted PAG A and PAG B, in particular as defined below.
• PAG A and PAG B in particular as defined below.
• PAG A denotes the polyalkylene glycol (s) used in a lubricating composition according to the invention, meeting the criteria defined above for the first polyalkylene glycol according to the invention.
• PAG A is meant in particular a single PAG A or a mixture of two or more PAG A.
• the PAG A according to the invention exhibits an hydroxyl number strictly greater than 50 mgKOH / g, in particular ranging from 52 to 75 mgKOH / g and more particularly from 55 to 70 mgKOH / g.
• the hydroxyl number can be measured according to ASTM El 899-08.
• the PAG A according to the invention is more particularly a polyalkylene glycol exhibiting only one of its hydroxyl ends capped by a group ("single end capped" in English terminology). In other words, it has at least one free hydroxyl end.
• PAG A according to the invention is thus distinguished from polyalkylene glycols, called “double end capped", having the two capped hydroxyl ends.
• the hydroxyl group may for example be capped with an alkyl group containing from 1 to 10 carbon atoms, in particular from 1 to 5 carbon atoms, optionally comprising one or more heteroatoms, such as nitrogen atoms, or alternatively with a fluoroalkyl group optionally containing heteroatoms such as nitrogen.
• the terminal hydroxyl group can also be capped by forming an ester with a carboxylic acid.
• the carboxylic acid can also be fluorinated.
• the terminal group of a PAG A according to the invention is chosen from alkyl groups having between 1 and 5 carbon atoms, preferably between 1 and 4 carbon atoms, such as a methyl or butyl group.
• the PAG A used according to the invention has a kinematic viscosity measured at 100 ° C. (KV100), measured according to the ASTM D445 standard, ranging from 5 to 10 mm 2 / s.
• KV100 kinematic viscosity measured at 100 ° C. according to the ASTM D445 standard, of between 6 and 9 mm 2 / s.
• the PAG A according to the invention can be formed from oxyalkylene units each containing 1 to 8 carbon atoms, preferably 2 to 4 carbon atoms. It can be a homopolymer or a copolymer of 2, 3 or more than 3 groups selected from oxyethylene, oxypropylene, oxybutylene, oxypentylene groups and combinations thereof.
• the PAG A comprises at least oxypropylene units.
• PO oxypropylene
• PAG A is a copolymer of propylene oxide and ethylene oxide.
• It is preferably a copolymer of propylene oxide and ethylene oxide, exhibiting a weight ratio of oxypropylene (OP) units / oxyethylene (EO) units greater than or equal to 1: 1, in particular between 2: 1 and 10: 1.
• OP oxypropylene
• EO oxyethylene
• the PAG A used according to the invention can be prepared by polymerization or copolymerization of alkylene oxides comprising from 1 to 8 carbon atoms, in particular from 2 to 4 carbon atoms.
• the synthesis of a PAG A according to the invention more particularly uses an initiator of monovalent alcohol type having from 1 to 10 carbon atoms, in particular methanol or butanol, in order to obtain a polyoxyalkylene glycol having an ether group at one of its ends and a free hydroxyl end.
• a person skilled in the art is able to adjust the operating conditions for the synthesis of polyalkylene glycol, in order to obtain the desired "single end capped" PAG, in particular having an hydroxyl number as defined above.
• a PAG A according to the invention has a molecular mass by weight ranging from 300 to 2000 g / mol, in particular between 800 and 1500 g / mol.
• the molecular mass by weight can be measured by Gel Permeation Chromatography (GPC).
• the flash point of PAG A is preferably greater than or equal to 160 ° C, in particular greater than or equal to 190 ° C.
• the flash point can be measured by ISO 2592.
• the PAG A used to form a lubricating composition according to the invention has a water content of less than or equal to 700 ppm by weight.
• PAG A satisfying the above criteria and can be implemented in a lubricating composition according to the invention may be commercially available, for example the oils sold under the references Konlube ® RF 240 YF, Konlube ® RF 232 and YF Géolube ® PAG A 01930.
• the oil marketed under the Konlube ® RF 232 YF reference is particularly suitable.
• the polyalkylene glycol (s) A can be used in an amount of 60% to 99% by mass, relative to the total mass of the lubricating composition, in particular from 70 to 99% by mass and more preferably from 80 to 98% by weight, even more preferably from 85 to 95% by weight.
• the polyalkylene glycol (s) A according to the invention preferably represent more than 70% by mass, in particular more than 75% by mass, of the total mass of the base oils present in the lubricating composition according to the invention.
• polyalkylene glycol (s) A under the name “PAG B” is meant one or more polyalkylene glycols used in a lubricating composition according to the invention, meeting the criteria defined above for the second polyalkylene glycol according to invention.
• the PAG B used according to the invention differs from a PAG A as described above, in particular in that it has a higher kinematic viscosity KV100 than that of a PAG A.
• PAG B has a kinematic viscosity measured at 100 ° C. (KV100), according to the ASTM D445 standard, greater than or equal to 100 mm 2 / s and less than or equal to 500 mm 2 / s.
• the kinematic viscosity KV100 of a PAG B implemented according to the invention is between 120 and 300 mm 2 / s, and more particularly between 140 and 200 mm 2 / s, or even between 150 and 190 mm 2 / s.
• the PAG B used according to the invention is more particularly obtained by polymerization or copolymerization of alkylene oxides comprising from 1 to 8 carbon atoms, in particular from 2 to 4 carbon atoms.
• the PAG B comprises 50% or less than 50% by weight of oxypropylene units.
• it is a copolymer of propylene oxide and of ethylene oxide, in particular formed of at least 50% by weight of oxyethylene units, and more particularly having a ratio by weight of oxypropylene units (PO ) / oxy ethylene (EO) units ranging from 2: 8 to 1: 1, especially from 4: 6 to 1: 1.
• PO oxypropylene units
• EO oxyethylene
• the PAG B can have a single (“single end capped” in English terminology) or two (“double end capped” in English terminology) capped hydroxyl ends.
• the hydroxyl group can be capped with an alkyl group containing from 1 to 10 carbon atoms, optionally comprising one or more heteroatoms, such as nitrogen atoms, a fluoroalkyl group containing heteroatoms, such as nitrogen .
• the PAG B is a “double end capped” polyalkylene glycol.
• the same extremal group or a combination of two distinct groups can be used.
• PAG B can be synthesized according to methods known to those skilled in the art. Preferably, it can be obtained by polymerization from an initiator of the diol or other type. Preferably, a PAG B according to the invention has a molecular mass by weight M w greater than or equal to 4000 g / mol, in particular greater than or equal to 5000 g / mol and more particularly between 5000 and 15000 g / mol.
• the flash point of PAG B is preferably greater than or equal to 200 ° C.
• PAG B satisfying the aforementioned criteria and which can be used in a lubricating composition according to the invention, can be commercially available.
• These include for example the oils sold under the references SYNALOX ® 40D700, Breox ® 50A1000, Breox ® 60W1000, Emkarox ® VG 1050W.
• the oil marketed under the reference Synalox ® 40D700 is particularly suitable.
• the polyalkylene glycol (s) B can be used in an amount of 1% to 30% by mass, relative to the total mass of the lubricating composition, in particular from 1 to 15% by mass and more preferably from 3 to 10% en masse.
• Polyalkylenes A and B exhibit excellent properties of miscibility with each other.
• the polyalkylene glycols A and B are used in a lubricating composition according to the invention in a PAG A / PAG B mass ratio ranging from 60/10 to 99/1, in particular from 70/30 to 98/2 and more preferably from 85/15 to 95/5.
• the lubricating composition according to the invention may optionally comprise one or more additional base oils, in minor amounts compared to PAG A and B.
• the mixture of polyalkylene glycols A and B represents more than 95% by mass, in particular more than 98% by mass, of the total mass of the base oils of a lubricating composition.
• a lubricating composition according to the invention is free from base oil other than said polyalkylene glycols A and B according to the invention.
• the mixture of said polyalkylene glycols A and B represents more than 70% by mass, in particular more than 80% by mass, in particular more than 90% and in particular more than 95% by mass, of the total mass of the lubricating composition according to the invention.
• a lubricating composition used according to the invention may comprise, in addition to said polyalkylene glycols A and B according to the invention, one or more additives.
• the additives can be chosen in particular from antiwear and extreme pressure additives, lubricating agents, antioxidants, acid scavengers and anti-foaming agents.
• a lubricating composition according to the invention comprises at least one anti-wear or extreme pressure additive.
• phosphorus-based agents such as phosphates, phosphoric acids, phosphites, acid phosphites and their amine salts.
• phosphate esters such as tricresyl phosphate, trithiophenyl phosphate, tris (nonylphenyl) phosphite, dioleylhydrogen phosphite, phosphite of 2 -ethylhexyldiphenyl, etc.
• the extreme pressure additives can also be metal salts of carboxylic acids, in particular metal salts of carboxylic acids having from 3 to 60 carbon atoms, in particular from 3 to 30 carbon atoms and more particularly from 12 to 30 atoms. of carbon. They can also be metal salts of dimers and trimers of aliphatic acids, and dicarboxylic acids having 3 to 30 carbon atoms.
• the metal salt can more particularly be an alkali metal or alkaline earth metal salt, in particular an alkali metal salt.
• extreme pressure additives can also be envisaged, such as extreme pressure additives based on sulfur, such as, for example, sulphurous fats, sulphurous aliphatic acids, sulphurous esters, sulphurous olefins, dihydrocarvyl polysulphides, thiocarbamates, thioterpenes and dialkyl thiodipropionates.
• the antiwear / extreme pressure additive is a phosphate additive.
• the lubricating composition according to the invention comprises at least one antiwear / extreme pressure additive chosen from amine phosphates.
• the amine phosphates can more particularly be C10 to C18 alkyl amine phosphates of the formula:
• R 1 is C1-C8 alkyl and R 2 is C10-C18 alkyl.
• Such amine phosphates are for example marketed under the reference VANLUB 672 ® by Vanderbilt or Irgalube ® 349 by BASF Corporation.
• an anti-wear additive of amine phosphate type makes it possible, compared to other anti-wear / extreme-pressure phosphorus additives such as phosphate esters, to significantly improve the thermal stability of the lubricating composition in the presence of the coolant used at a temperature of the order of 175 ° C.
• the anti-wear and extreme pressure additive (s), preferably of amine phosphate type can be used in an amount of 0.001 to 3% by mass, relative to the total mass of the composition, preferably from 0.005 to 1% by weight and more particularly from 0.05 to 0.5% by weight.
• Antioxidant additives preferably of amine phosphate type
• the lubricating composition according to the invention comprises at least one antioxidant additive.
• Antioxidant additives can be, for example, phenolic antioxidant additives or amine-based antioxidant additives, such as phenyl-a-napthylamine or N, N-diphenyl-p-phenylenediamine.
• the lubricating composition comprises at least one phenolic antioxidant additive.
• the phenolic antioxidants can be more particularly chosen from 2,6-di-tert-butylphenol (as sold under the reference Irganox® 140 by Ciba-Geigy Corporation), 2,2'-methylene-bis- (4,6 -di-tert-butylphenol), 1,6-hexamethylene-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) (as marketed under the reference Irganox ® L109 by Ciba-Geigy Corporation), esters C10 -Ci4 isoalkyl and acid
• the phenolic antioxidants are chosen from esters of C7 to C9 alkyl and 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, for example commercially available under the reference Irganox® L135 from Ciba- Geigy Corporation.
• a lubricating composition according to the invention may comprise the said antioxidant additive (s), preferably of the phenolic type, in an amount of 0.01 to 5% by weight, relative to the total weight of said composition, preferably from 0.05 to 3. % by mass and more particularly from 0.1 to 1% by mass.
• a lubricating composition according to the invention thus comprises, in addition to said polyalkylene glycols A and B, in particular as described above:
• At least one phenolic antioxidant in particular of the C7 to C9 alkyl ester type and of 3, 5 -di -tert-buty 1 -4 -hy droxy hy drocinnami c.
• the inventors have observed that the combined presence of at least one antiwear / extreme pressure additive of amine phosphate type and of at least one phenolic antioxidant, in addition to the combination of polyalkylene glycols A and B according to the invention makes it possible to optimize the thermal stability of the lubricating composition according to the invention.
• Such a composition advantageously exhibits a stable viscosity and an absence of chemical degradation (oxidation) at high temperatures of the order of 175 ° C.
• the lubricating composition according to the invention comprises, or even consists of:
• the lubricating composition according to the invention comprises, or even consists of:
• the sum of the constituents being equal to 100%, and the percentages being expressed relative to the total mass of the lubricating composition.
• Other additives may optionally be present in the lubricating composition according to the invention.
• lubricity additives or lubricity additives such as for example chosen from saturated and unsaturated aliphatic monocarboxylic acids such as stearic acid and oleic acid, polymerized aliphatic acids such as acids dimers and hydrogenated dimer acids, hydroxyaliphatic acids such as ricinoleic acid and 12-hydroxy stearic acid, saturated and unsaturated aliphatic monohydric alcohols such as lauryl alcohol and oleyl alcohol; saturated and unsaturated aliphatic monoamines such as stearylamine and oleylamine; saturated and unsaturated aliphatic monocarboxylic acid amides such as lauric acid amide and oleic acid amide, and polyhydric alcohol partial esters such as glycerin and sorbitol, and saturated aliphatic monocarboxylic acids or unsaturated.
• saturated and unsaturated aliphatic monocarboxylic acids such as stearic acid and oleic acid
• the lubricity additive (s) or lubricity additives may be present in an amount of 0.01 to 10% by mass, in particular from 0.1 to 5% by mass relative to the total mass of said composition.
• a lubricating composition according to the invention may also comprise one or more “acid scavenger” compounds, such as, for example, chosen from glycidyl and phenyl ethers, alkyl and glycidyl ethers, alkylene glycol glycidyl ether, phenyl and glycidyl esters, alkenyl and glycidyl esters, cyclohexene oxide, Ga-olefinoxide and epoxy compounds such as epoxidized soybean oil.
• “acid scavenger” compounds such as, for example, chosen from glycidyl and phenyl ethers, alkyl and glycidyl ethers, alkylene glycol glycidyl ether, phenyl and glycidyl esters, alkenyl and glycidyl esters, cyclohexene oxide, Ga-olefinoxide and epoxy compounds such as epoxid
• the “acid scavenger” additives can be chosen from phenyl and glycidyl ethers, alkyl and glycidyl ethers, alkylene glycol and glycidyl ethers, glycidyl-2,2-dimethyloctanoate. , glycidyl benzoate, glycidyl-tert-butyl benzoate, glycidyl acrylate, glycidyl methacrylate, cyclohexene oxide, and Ga-olefinoxide.
• Each of the alkyl groups of the alkyl glycidyl ether and the alkylene group of an alkylene glycol glycidyl ether may be branched, and present typically from 3 to 30 carbon atoms, preferably from 4 to 24 and more particularly from 6 to 16 carbon atoms.
• Ga-olefmoxide it may have more particularly from 4 to 50 carbon atoms, in particular from 4 to 24 and more particularly from 6 to 16 carbon atoms.
• Said compound (s) "acid scavengers” may be present in an amount of 0.005 to 5% by weight, in particular from 0.05 to 3% by weight, relative to the total weight of said lubricating composition.
• a lubricating composition according to the invention can also comprise one or more anti-foam additives, such as, for example, a silicone oil, or a fluorinated silicone oil.
• one or more anti-foam additives such as, for example, a silicone oil, or a fluorinated silicone oil.
• additives known to those skilled in the art may also be present in a lubricating composition according to the invention, for example copper deactivators such as N- [N, N-dialkyl aminomethyl triazole.
• a lubricating composition according to the invention has a kinematic viscosity, measured at 40 ° C (KV40), according to the standard ASTM D445 (ISO 3104) of between 30 and 60 mm 2 / s, in particular between 35 and 60 mm 2 / s and more particularly between 40 and 50 mm 2 / s.
• KV40 kinematic viscosity
• the kinematic viscosity, measured at 100 ° C (KV100), according to standard ASTM D445 (ISO 3104), of a lubricating composition according to the invention can advantageously be between 5 and 10 mm 2 / s, in particular between 8 and 10 mm 2 / s.
• a lubricating composition according to the invention has an hydroxyl number strictly greater than 40 mg KOH / g, in particular between 45 and 70 mgKOH / g.
• It preferably has an acid number, measured according to the ISO 6618 standard, of between 0.02 mgKOH / g and 0.2 mgKOH / g, preferably less than 0.1 mgKOH / g.
• the water content of the lubricating composition according to the invention is strictly less than 700 ppm by weight.
• a lubricating composition according to the invention proves to be particularly suitable for its use in combination with a refrigerating fluid, in a refrigerating system, in particular in an automobile air conditioning system.
• the invention thus relates, according to another of its aspects, to a heat transfer composition, for a refrigerant system comprising a gas compression circuit, in particular for an automotive air conditioning system, comprising:
• a refrigerating fluid based on orocarbon hydrofluoric compounds in particular based on 1, 1,1,2-tetrafluoroethane (R134a) and / or 2,3,3,3-tetrafluoropropene (HFO-1234yf).
• R134a 1, 1,1,2-tetrafluoroethane
• HFO-1234yf 2,3,3,3-tetrafluoropropene
• the proportion of lubricating composition to be used in combination with the coolant depends on the type of installation concerned. Indeed, the total amount of lubricating oil in the installation depends mainly on the nature of the compressor, while the total amount of refrigerant in the installation mainly depends on the exchangers and the piping.
• the proportion of coolant relative to the lubricating composition is between 99/1 and 1/99, in particular between 95/5 and 5/95.
• the refrigerant fluid is more particularly based on heat transfer compounds chosen from saturated or unsaturated hydrofluorocarbon compounds, and mixtures thereof.
• the refrigerant can be binary (consisting of two heat transfer compounds) or ternary (consisting of three heat transfer compounds) or quaternary (consisting of four heat transfer compounds.
• Hydrofluorocarbon compounds generally correspond to the following formula (A):
• p represents an integer between 2 and 6
• r represents an integer between 1 and 12
• s represents an integer between 0 and 11.
• the unsaturated hydrofluorocarbon compounds can be more particularly chosen from isomers of pentafluoropropene, in particular 3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene and 2, 3,3,3-tetrafluoropropene.
• the refrigerant fluid comprises, or even is formed, 2,3,3,3-tetrafluoropropene (HFO-1234yf).
• the saturated hydrofluorocarbon compounds can be more particularly chosen from fluorinated alkane compounds comprising from 1 to 4 carbon atoms, preferably methane or ethane, such as trifluoromethane, difluoromethane, 1, 1-difluoroethane, 1,1,1-trifluoroethane, 1, 1,2-trifluoroethane, 1,1, 1,2-tetrafluoroethane, 1, 1,2,2-tetrafluoroethane and 1, 1,1,2,2, -pentafluoroethane.
• fluorinated alkane compounds comprising from 1 to 4 carbon atoms, preferably methane or ethane, such as trifluoromethane, difluoromethane, 1, 1-difluoroethane, 1,1,1-trifluoroethane, 1, 1,2-trifluoroethane, 1,1, 1,2-tetrafluoroethane, 1, 1,2,2-tetrafluoroethane and 1, 1,1,2,2,
• the refrigerant fluid comprises, or even is formed, 1,1, 1,2-tetrafluoroethane (RI 34a).
• the refrigerant under consideration according to the invention may also comprise one or more additional heat transfer compounds, for example chosen from hydrocarbons, hydrofluorocarbons, ethers, hydrofluoroethers and fluoro-oolfins.
• the refrigerant fluid is formed at more than 90% by mass, in particular at more than 95% by mass and more particularly at more than 99% by mass, of saturated and / or unsaturated hydrofluorocarbon compounds, in particular such as previously defined.
• the refrigerant fluid is based on 1,1,2-tetrafluoroethane (R134a), 2,3,3,3-tetrafluoropropene (HFO-1234yf) or a mixture of R134a and HFO-1234yf.
• R134a 1,1,2-tetrafluoroethane
• HFO-1234yf 2,3,3,3-tetrafluoropropene
• the refrigerant fluid is based on 1,1,2-tetrafluoroethane (R134a), 2,3,3,3-tetrafluoropropene (HFO-1234yf) or a mixture of R134a and HFO-1234yf.
• the refrigerant fluid considered according to the invention can consist of R134a, HFO-1234yf or a mixture of R134a and HFO-1234yf.
• a lubricating composition according to the invention is more particularly intended to be used, with a refrigerant based on R134a and / or HFO-1234yf, in an installation comprising a vapor compression circuit.
• the vapor compression circuit comprises at least one evaporator, one compressor, one condenser and one expansion valve, as well as fluid transport lines between these elements.
• the evaporator and the condenser include a heat exchanger allowing heat exchange between the heat transfer fluid and another fluid or body.
• the vapor compression circuit operates according to a conventional gas compression cycle.
• the cycle involves changing the state of the heat transfer fluid from a liquid (or two-phase liquid / gas) phase to a gas phase at a relatively low pressure, then compressing the gas phase fluid to a relatively low pressure. high, the change of state (condensation) of the heat transfer fluid from the gas phase to the liquid phase at a relatively high pressure, and the reduction in pressure to restart the cycle.
• the lubricating composition according to the invention is intended for an air conditioning device, and more particularly for an automobile air conditioning device.
• an automobile air conditioning compressor in particular for an oscillating plate compressor or an electric scroll compressor.
• the invention relates to a compressor of an automotive air conditioning system using a lubricating composition according to the invention.
• the compressor can be driven by an electric or thermal motor or by a gas turbine (for example, powered by vehicle exhaust gases), or by gears.
• Example 1 Preparation of a lubricating composition according to the invention
• a lubricating composition in accordance with the invention was prepared by simple mixing, at room temperature, of the following components, in the proportions by weight indicated in Table 1 below.
• the antioxidant is a phenolic compound.
• the antiwear / extreme pressure agent is an amine phosphate.
• polyalkylene glycol used in the context of the present examples are:
• PAG A (1) and PAG A (2) polyalkylene glycols formed from at least 96% by mass of oxypropylene units; whose ends are uncapped, and synthesized from the initiator methanol, for example, under the reference Konlube ® RF 240 YF.
• PAG B random copolymer of ethylene oxide (60% by mass) and propylene oxide (40 mass%), synthesized from a diol-type initiator, for example sold under the reference SYNALOX 40D700 ®.
• compositions and the amounts are indicated in Table 3 below.
• thermal stability tests are performed according to ASHRAE 97-2007: “Sealed Glass Tube Method to Test the Chemical Stability of Materials for use within Refrigerant Systems”.
• the lubricant / refrigerant systems HFO-1234yf (mass ratio 1: 1), and metal coupons (Al, Cu and Fe (steel)) as catalyst materials are introduced into glass tubes.
• the tubes are closed and placed in a stainless steel autoclave at 175 ° C for 336 hours.
• the target pressure at 175 ° C is 35 bar.
• Lubricants are tested as is (“1) Aging without water”), and adding water to reach 2000 ppm of water ("2) Aging with 2000 ppm of water”).
• the viscosity of the lubricant is determined, before and after aging, according to DIN 51562-1 using a Ubbelohde viscometer. The variation in viscosity for each of the lubricating compositions tested is reported in Table 4 below.
• the lubricating composition according to the invention combining a PAG A and a PAG B according to the invention, thus exhibits properties in terms of improved thermal stability, compared to the commercial composition C1 not comprising PAG B.

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

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• 2019
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