WO1993006196A1 - Compositions et procede utilises dans la refrigeration - Google Patents

Compositions et procede utilises dans la refrigeration Download PDF

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Publication number
WO1993006196A1
WO1993006196A1 PCT/US1992/008240 US9208240W WO9306196A1 WO 1993006196 A1 WO1993006196 A1 WO 1993006196A1 US 9208240 W US9208240 W US 9208240W WO 9306196 A1 WO9306196 A1 WO 9306196A1
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Prior art keywords
volume
refrigerant
hfc
tetrafluoroethane
lubricant
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PCT/US1992/008240
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English (en)
Inventor
Walter Mahler
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E.I. Du Pont De Nemours And Company
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Publication of WO1993006196A1 publication Critical patent/WO1993006196A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
    • C10M107/34—Polyoxyalkylenes
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22—All components of a mixture being fluoro 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
    • 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
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/02—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only
    • C10M2211/022—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only aliphatic
    • 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
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/06—Perfluorinated 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
    • 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
    • C10M2223/041—Triaryl phosphates
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • 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
    • 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
    • C10N2040/32—Wires, ropes or cables lubricants
    • 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
    • C10N2040/34—Lubricating-sealants
    • 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
    • C10N2040/36—Release agents or mold release agents
    • 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
    • C10N2040/38—Conveyors or chain belts
    • 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
    • C10N2040/40—Generators or electric motors in oil or gas winning field
    • 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
    • C10N2040/42—Flashing oils or marking oils
    • 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
    • C10N2040/44—Super vacuum or supercritical use
    • 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
    • C10N2040/50—Medical uses

Definitions

  • This invention relates to lubricants used with refrigerants in compression refrigeration and air- conditioning systems. More particularly, it relates to lubricants for use with saturated hydrocarbons having
  • this invention relates to lubricants for use with tetrafluoroethanes, e.g. 1,1,1,2-tetrafluoroethane
  • CFC-12 dichlorodifluoromethane
  • Refrigeration systems that use CFC-12 as the refrigerant generally use mineral oils to lubricate the compressor. (See for example the discussion in Chapter 32 of the 1980 ASHRAE Systems Handbook) .
  • CFC-12 is
  • refrigerants which are not com- pletely miscible with an oil in the full range of mixture compositions and operating temperatures may become miscible or immiscible as the temperature is raised or lowered from room temperature.
  • the areas of immiscibility may assume a variety of shapes, i.e. parabolic or non-parabolic.
  • the curve of miscibility temperature vs. percent oil in the mixture may have its open or concave portion facing the low or high temperatures.
  • the closed or convex portion of the parabolic curve identifies, respectively, the maximum or minimum temperature above or below which the refrigerant and the lubricating oil are completely miscible. These temperatures are referred to as the maximum or minimum "consolute temperatures.”
  • Beside parabolas these curves can assume skewed parabolic shapes or curves of varying slope wherein immiscibility occurs above or below the curve.
  • One of the objects of this invention is to provide a combination of lubricating oil and tetra- fluoroethane, e.g. HFC-134a and HFC-134, where the area of miscibility encompasses the full range of temperature and composition encountered in compression refriger ⁇ ation, i.e. complete miscibility occurs for all compo ⁇ sitions in the range of -10*C to at least 20*C, preferably from -45 ' C to at least 50*C.
  • Another object is to provide a process for using such compositions in compression refrigeration.
  • Prior Art U.S. Patent No. 4.248.726. issued February 5, 1981, and U.S. Patent No. 4.278.064. issued May 12, 1981, both to Nippon Oil Company et al, relate to the use of a polyglycol oil such as polyoxypropylene glycoi (or an alkyl ether thereof) having a viscosity index of at least 150 and a glycidyl ether type epoxy compound as a high viscosity refrigeration oil composition for halogen-containing refrigerants.
  • These polyglycol/- glycidyl ether compositions are disclosed for use with Freon ⁇ ll, 12, 13, 22, 113, 114, 500 and 502; and as being "particularly effective" with Freon*12 or 22.
  • the "Ucon" LB-525" has been found to be immiscible at above about +5 ⁇ C with HFC-134a... Practically this means that such lubricants are not miscible with HFC-134a over most of the temperature range used in automotive air conditioning.
  • the miscible range should be from -40*C to at least +50 ⁇ C or higher, above 90"C, if possible”.
  • the present invention is based on the discovery that the use of at least about 10% by volume of HFC-134, preferably at least 20%, most preferably at least 50%, in a blend with HFC-134a or HFC-125 will expand the'miscibility range of the latter tetrafluoro ⁇ ethane, HFC-134a, or pentafluoroethane, HFC-125, with both the monofunctional and the difunctional poly ⁇ alkylene glycols of the polyoxyethylene-polyoxypropylene type.
  • Polyalkylene glycols of this type are defined as glycols that are either monofunctional or at least difunctional with respect to hydroxyl groups and contain 25-75% ethylene oxide units and 75-25% propylene oxide units.
  • Other mils may derive from butylene oxide or hydroxylated esters, hydroxylated olefins and the like which are poly erizable with ethylene oxide and/or propylene oxide.
  • a sufficient amount to lubricate usually 10-20% by volume for automotive use, and in some situations as high as 50% by volume of at least one mono- or di-functional, preferably a random, polyalkylene glycoi (PAG) , also referred to as polyoxyalkylene glycoi, based on a significant amount of ethylene oxide, in a random copolymer, preferably at least 25% ethylene oxide, and most preferably, 50% ethylene oxide and 50% propylene, will be completely miscible with a refrigerant blend of the tetrafluoroethanes, usually 80-90% by volume of the tetrafluoroethanes, the blend containing at least about 10% by volume of HFC-134 with the remainder of HFC-134a.
  • PAG polyalkylene glycoi
  • This blend may also be blended with other refrigerants operating in the range of temperatures from -40*C to at least 50*C. It should also be understood that 100% HFC-134 is miscible with the aforementioned glycols of the 50-50 polyoxy- ethylene-polyoxyproplene type.
  • HFC-134a Basically, the use of 10% by volume of HFC-134 in a blend with 90% by volume of HFC-134a will expand the miscibility range of HFC-134a with the polyoxy- alkylene glycoi (based on at least 25% ethylene oxide) by 20*C, i.e. +10*C at the upper end of the range and -10*C at the lower end.
  • the weight ratio of refrigerant (HFC-134 or HFC-134 blended with HFC-134a) to the PAG lubricant in the mixtures used for refrigeration may be anywhere from 99/1 to 1/99, preferably 99/1 to 70/30.
  • the viscosities of the polyalkylene glycols may be anywhere from 50 to 3000 SUS at 100*F but for most commercial uses, from 100 to 1200 SUS at about 100 ⁇ F.
  • the process of manufacturing the mono- functional PAGs may involve initiation with methanol, ethanol, propanol or butanol.
  • butanol is the preferred initiator; and the process of manufacture is described in the Encyclopedia of Polymer Science and Engineering, Volume 6, pps. 225-273; "Ethylene Oxide Polymers and Copolymers” by Clinton and Matlock, 2nd edition, 1986, John Wiley & Sons.
  • the process of manufacturing the di-functional PAGs may involve initiation with a glycoi having anywhere from two to six carbon atoms between -OH groups.
  • Diethylene glycoi is the preferred initiator; and the process of manufacture is Engineering, Volume 6; "Ethylene Oxide Polymers and Copolymers” by Clinton and Matlock, 2nd edition, 1986, John Wiley & Sons. It has been known that the use of an appropriate amount of an "extreme pressure additive* improves the lubricity and load-bearing characteristics of the butanol-initiated monofunctional random poly ⁇ alkylene glycoi having 50% oxyethylene units as set forth in the U.S. Application Serial No.
  • EP additives for use in this invention are included among those disclosed in Table D of U.S. Patent 4,755,316.
  • the preferred ones are the organic phosphates and include Lubrizol*1097, a zinc (dialkyl dithio) phosphate manufactured by the Lubrizol Corporation; and SYN-O-AD* 8478, a 70%/30% blend of tri (2,4, 6-tri-t-butyl phenyl) phosphate/- triphenyl phosphate manufactured by the Stauffer Chemical Company.
  • EP additives may also be used in conjunction with some of the anti-wear additives, oxidation and thermal stability improvers, corrosion inhibitors, viscosity index improvers, detergents and anti-foaming agents disclosed in Table D of U.S. Patent 4,755,316. These additives may also be partially or fully fluorinated.
  • a preferred blend of additives is MLX-788, a proprietary mixture of Union Carbide Corporation containing a phosphate and two amine-containing compounds.
  • HFC-134 and the blends of tetrafluoroethanes HFC-134a and HFC-134 have physical characteristics which allow substitution for CFC-12 with only a minimum of equipment changes in compression refrigeration.
  • bends could be further blended with other refrigerants, including CFC-12(CCI2F2) , HCFC-22(CHC1F2), HFC-152a(CH3CHF2) , HCFC-124(CHCIFCF3) , HCFC-124a(CHF2CClF2) , HFC-125(CHF2CF3) , HCFC- 142b(CH3CClF2) , HFC-32(CH2F2) , HFC-143a(CH3CF3) , HFC- 143(CHF2CH2F) 1 and FC-218 CF 3 CF2CF3) ; and for purposes of the present invention these latter blends are not excluded. However, only those blends of the tetra ⁇ fluoroethanes with other refrigerants which are miscible with the lubricants of this invention in the range of -45*C to about +20'C are included.
  • HFC-134a may be prepared by any of the methods disclosed in the prior art; e.g., U.S. 2,745,886; 2,887,427; 4,129,603; 4,158,675; 4,311,863; 4,792,643 and British 1,578,933 and 2,030,981.
  • HFC-134 may be prepared by the method disclosed by Wilford, Forster and Stone in Journal of The Chemical Society, 1965, 6519-6523.
  • the most preferred mono-hydroxyl polyalkylene glycoi for use in this invention is based on the random polymerization of propylene oxide and ethylene oxide initiated with butanol.
  • the viscosity can range from about 100 to 1200 SUS viscosity at 100°F, preferably 400 to 1200 SUS
  • the most preferred PAG is the "Ucon* 50 HB500, 500 representing the SUS viscosity at 100 ⁇ F and "H" representing "hydrophylic", that is manufactured by the Union Carbide Corporation. The process for its manufacture is described in the 1986 edition of the Encyclopedia of Polymer Science and engineering.
  • the preferred 50HB500 oil has a pour point below -40°c, is completely miscible with the 10% blend of HFC-134 with HFC-134a from -50 ⁇ C to condenser temperatures above 50"C, and meets all the other requirements for automotive air conditioning, i.e. viscosity index, stability, lubricity, and miscibility with the blend of HFC-134 and HFC-134a down to below -20"C. Furthermore, the use of an extreme pressure oil additive such as those mentioned previously should improve the load-carrying capability significantly.
  • the lubricants used in the compositions of this invention, and in the invented method for providing lubrication in compression refrigeration and air-conditioning equipment have the following characteristics:
  • Greter than 10 preferably at least 70 and higher Pour Point -10"C, preferably -10 ⁇ C to about -45 * C and
  • Solubility or miscibility ran ⁇ e 100% from 100*C to (a) less than -40*C to about 20*C for 1-99 weight percent of the blend of HFC-134 and HFC-134a in mixture with the lubricant of 100 ⁇ F viscosities of 50 SUS to 3000 SUS (b) less than -10 ⁇ C for the preferred 500 SUS mixtures.
  • Four-ball wear test with a specific set of steel balls. Scar wear and coefficient of friction equal to or slightly higher than that for the oils currently used with CFC-12 in automotive air-conditioning, i.e., 0.37 mm scar wear and 0.07 friction coefficient when saturated with CFC-12 at atmospheric pressure.
  • "Falex" (load failure) test with a specific type of steel for the V-block and pin. The fail load equal to or greater than that for the CC/refrigerant oil combinations, i.e., 1300 lbs. when saturated with CFC-12 at atmospheric pressure.
  • the refrigerant/lubricant solubilities were determined by completely immersing the tube in a bath at each test temperature for a minimum of 15 minutes and providing agitation to facilitate mixing and equilibration. The accuracy of determining the temperatures when the refrigerant/lubricant blend became either miscible or immiscible was about + 2°C. The refrigerant/lubricant blends were called immiscible when the blend acquired and retained "schlieren" lines; or formed floe; or became cloudy; or formed two liquid layers. These solubility tests were run from about 93 ⁇ C to at least -50*C. Tests were not run above 93 ⁇ C for safety and practical reasons. 2. Viscosity and Viscosity Index a.
  • Viscosity is a property that defines a fluid's resistance to shearing force. It is expressed in terms of absolute viscosity, kinematic viscosity or Saybolt Universal Seconds viscosity (SUS) , depending on the method by which it is determined. Conversion from SUS to mm 2 /s (centistokes) can be readily made from tables contained in.ASTM D-445, but it is necessary to know the density to convert kinematic viscosity to absolute viscosity. Refrigeration oils are sold in viscosity grades, and ASTM has proposed a system of standardized viscosity grades from industry-wide usage (D-2422) . b. Viscosity Index is a measure of the amount of change experienced by an oil with changes in temperature.
  • Viscosity decreases as the temperature increases; and increases as the temperature decreases.
  • A,B constants for each oil
  • the slope of the viscosity-temperatures lines is different for different oils.
  • the viscosity- ⁇ g temperature relationship of an oil is described by an empirical number called "the viscosity index* (VI) as referred to in ASTM D-2270.
  • VI the viscosity index*
  • An oil with a high viscosity index (HVI) shows less change in viscosity over a given temperature range than an oil with a low viscosity index (LVI) . 0 3.
  • Table I summarizes the solubility data for various blends of HFC-134 and HFC-134a as refrigerant 0 with 20 volume per cent 50HB660, a monofunctional poly- oxyalkylene glycoi, as the lubricant. It will be noted that as little as 20% HFC-134 expands the solubility range from -50*C to 31*C to a range of -100*C to 54*C. 5 Table II summarizes the solubility data for various blends of HFC-134 and HFC-134a (compared to 100% HFC-134a) as the refrigerant with 20 volume percent 50HB500, a monofunctional polyoxyalkylene glycoi, as the lubricant.
  • Both 50HB660 and 50HB500 are monofunctional polyoxyalkylene glycols prepared from 50 weight per cent ethylene oxide and 50 weight per cent propylene oxide using butanol as the end capping agent.
  • the "660" glycoi has an SUS viscosity at 100°F of 660; and the "500” glycoi, an SUS viscosity of 500.
  • refrigerant amounting to about 80% by volume of a blend of HFC-134 and HFC-134a together with 20% by volume of lubricant were used for the solubility studies.
  • This refrigerant-lubricant composition corresponds to the ratio generally employed in air-conditioning engines and is usually the least soluble mixture.
  • These air-free mixtures were contained in sealed "Pyrex" glass tubes of 3mm inside diameter and 15 cm length. Compatibility was determined by cooling or heating the tubes while fully immersed and observing phase separation which was signalled by the optically clear mixture turning cloudy.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

L'invention se rapporte à une combinaison de (a) au moins 10 % en poids de 1,1,2,2-tétrafluoroéthane avec au moins 10 % en poids de 1,1,1,2-tétrafluoroéthane ou de pentafluoroéthane comme réfrigérant, mélangée à (b) un polyalkylène glycol monofonctionnel ou difonctionnel, à base de 25 à 75 % d'oxyde de propylène et de 75 à 25 % d'oxyde d'éthylène ayant une viscosité SAYBOLT à 100 °F comprise entre 100 et 1200. De telles compositions sont destinées à être utilisées dans la réfrigération avec compression.
PCT/US1992/008240 1991-09-26 1992-09-28 Compositions et procede utilises dans la refrigeration WO1993006196A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003057804A1 (fr) * 2001-12-29 2003-07-17 Fuchs Petrolub Ag Agents d'exploitation pour installations frigorifiques et de climatisation au dioxyde de carbone
WO2005028605A1 (fr) * 2003-09-19 2005-03-31 Arkema Solution de nettoyage

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0400894A1 (fr) * 1989-06-02 1990-12-05 Union Carbide Chemicals And Plastics Company, Inc. Compositions de réfrigération et procédé d'utilisation
EP0402009A1 (fr) * 1989-06-02 1990-12-12 Union Carbide Chemicals And Plastics Company, Inc. Compositions pour réfrigération par compression et méthode pour les utiliser
WO1991009090A1 (fr) * 1989-12-19 1991-06-27 E.I. Du Pont De Nemours And Company Compositions et procede utilises en refrigeration

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0400894A1 (fr) * 1989-06-02 1990-12-05 Union Carbide Chemicals And Plastics Company, Inc. Compositions de réfrigération et procédé d'utilisation
EP0402009A1 (fr) * 1989-06-02 1990-12-12 Union Carbide Chemicals And Plastics Company, Inc. Compositions pour réfrigération par compression et méthode pour les utiliser
WO1991009090A1 (fr) * 1989-12-19 1991-06-27 E.I. Du Pont De Nemours And Company Compositions et procede utilises en refrigeration

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003057804A1 (fr) * 2001-12-29 2003-07-17 Fuchs Petrolub Ag Agents d'exploitation pour installations frigorifiques et de climatisation au dioxyde de carbone
US7303693B2 (en) 2001-12-29 2007-12-04 Fuchs Petrolub Ag Operating medium for carbon dioxide-cooling systems and air-conditioning systems
WO2005028605A1 (fr) * 2003-09-19 2005-03-31 Arkema Solution de nettoyage

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