WO2017065134A1 - Huile pour machine frigorifique, composition pour machines frigorifiques et machines frigorifiques - Google Patents

Huile pour machine frigorifique, composition pour machines frigorifiques et machines frigorifiques Download PDF

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Publication number
WO2017065134A1
WO2017065134A1 PCT/JP2016/080108 JP2016080108W WO2017065134A1 WO 2017065134 A1 WO2017065134 A1 WO 2017065134A1 JP 2016080108 W JP2016080108 W JP 2016080108W WO 2017065134 A1 WO2017065134 A1 WO 2017065134A1
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WIPO (PCT)
Prior art keywords
acid
refrigerating machine
machine oil
refrigerator
refrigerant
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PCT/JP2016/080108
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English (en)
Japanese (ja)
Inventor
正人 金子
Original Assignee
出光興産株式会社
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Application filed by 出光興産株式会社 filed Critical 出光興産株式会社
Priority to KR1020187010319A priority Critical patent/KR20180070578A/ko
Priority to CN201680060090.0A priority patent/CN108138066A/zh
Publication of WO2017065134A1 publication Critical patent/WO2017065134A1/fr

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/38—Esters of polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B9/00—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point
    • F25B9/002—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B1/00—Compression machines, plants or systems with non-reversible cycle

Definitions

  • the present invention relates to a refrigerating machine oil, a refrigerating machine composition, and a refrigerating machine using the refrigerating machine oil or the refrigerating machine composition.
  • chlorine-containing fluorocarbon refrigerants such as chlorofluorocarbon (CFC) and hydrochlorofluorocarbon (HCFC) have been used for refrigerators such as air conditioners and air conditioners.
  • CFC chlorofluorocarbon
  • HCFC hydrochlorofluorocarbon
  • these refrigerants are subject to regulation from the viewpoint of environmental problems such as ozone depletion, and as a substitute for these refrigerants, there is little risk of environmental problems, and the global warming potential has little impact on global warming
  • a chlorine-free compound such as a fluorinated hydrocarbon compound, a natural refrigerant such as carbon dioxide (carbon dioxide), ammonia, or hydrocarbon gas is used.
  • fluorinated hydrocarbon compound examples include difluoromethane (R32), 1,1,1,2-tetrafluoroethane (R134a), pentafluoroethane (R125), 1,1,1-trifluoroethane (R143a), and the like.
  • saturated fluorinated hydrocarbon compounds 1,3,3,3-tetrafluoropropene (R1234ze), unsaturated fluorinated hydrocarbon compounds such as 2,3,3,3-tetrafluoropropene (R1234yf), and these Use of a mixture or the like is under consideration.
  • the refrigerator has a sealed refrigeration cycle composed of devices such as a compressor, a condenser, an expansion mechanism (expansion valve, etc.), an evaporator, etc., and a mixture of refrigerant and refrigerator oil is contained in the refrigeration cycle. Is circulated while lubricating a sliding portion such as a bearing provided in the compressor. In this refrigeration cycle, since the temperature is usually high in the compressor and low in the evaporator, the composition for the refrigerator is required to have stability that can be used stably over a wide temperature range.
  • a composition containing a synthetic hydrocarbon oil such as mineral oil or alkylbenzene as a refrigerator oil has been used.
  • the composition containing these refrigerating machine oils has low compatibility with alternative CFC refrigerants typified by saturated hydrofluorocarbons, and it has been difficult to sufficiently exhibit the performance as a refrigerating machine composition. Therefore, the use of a composition containing refrigerating machine oil such as polyalkylene glycol, polyol ester, and polyvinyl ether as a composition for a refrigerating machine used together with an alternative chlorofluorocarbon refrigerant such as saturated hydrofluorocarbon has been studied (for example, Patent Document 1). reference). Also in these refrigerating machine oils, polyol esters have been widely studied, and for example, esters of fatty acids having 14 to 22 carbon atoms and polyhydric alcohols have been proposed (see, for example, Patent Document 2).
  • refrigerators are sometimes used for heat pump applications in cold districts and air conditioning applications in low-temperature warehouses, and the usage conditions such as temperature changes are severe, making them more freezer compositions than ever. Is required to have high performance such as stability.
  • the composition for a refrigerator solidifies in a low-temperature environment and precipitates wax, it significantly affects the life and efficiency of the refrigerator.
  • the movable portion of the compressor becomes poorly lubricated, causing seizure or the like, leading to a significant decrease in the lifetime of the refrigerator.
  • the heat exchange efficiency is significantly reduced in the evaporator.
  • Patent Document 1 does not discuss these problems at all, and the ester described in Patent Document 2 solidifies in a low-temperature environment and precipitates wax, resulting in severe temperature changes. I can not cope.
  • the present invention has been made in view of the above-described problems, and uses a refrigerating machine oil, a composition for a refrigerating machine, and a composition for a refrigerating machine oil or a refrigerating machine having excellent lubrication performance and stability against temperature change.
  • An object is to provide a refrigerator.
  • this invention provides the refrigerating machine using the refrigerating machine oil which has the following structures, the composition for refrigerating machines, and this refrigerating machine oil or a composition for refrigerating machines.
  • a refrigerating machine composition comprising the refrigerating machine oil described in 1 above and a refrigerant.
  • a refrigerating machine comprising at least a compressor, a condenser, an expansion mechanism, and an evaporator, and using the refrigerating machine oil described in 1 or the refrigerating machine composition described in 2 above.
  • the present invention it is possible to provide a refrigerating machine oil, a refrigerating machine composition excellent in lubrication performance and stability against temperature change, and a refrigerating machine using the refrigerating machine oil or the refrigerating machine composition.
  • the refrigerating machine oil of the present embodiment includes a polyol ester having a molecular weight ⁇ total carbon number / carbonyl carbon number of 10,000 or less.
  • the polyol ester is an ester of a polyol and a fatty acid, and means an ester in which all the hydroxyl groups of the polyol are esterified.
  • the molecular weight is the molecular weight of the polyol ester
  • the total carbon number is the number of all carbons constituting the polyol ester
  • the carbonyl carbon number is the number of carbons constituting the carbonyl group contained in the polyol ester.
  • the lower limit of molecular weight ⁇ total carbon number / carbonyl carbon number is not particularly limited, but is preferably 2000 or more, more preferably 3000 or more, and still more preferably 3800 or more in consideration of lubrication performance and stability against temperature change. That is, the molecular weight ⁇ total carbon number / carbonyl carbon number is preferably 2000 to 10,000, more preferably 3000 to 10,000, and still more preferably 3800 to 10,000.
  • the total carbon number / carbonyl carbon number is not particularly limited as long as the molecular weight ⁇ total carbon number / carbonyl carbon number is within the above range, but is preferably 6 to 12 from the viewpoint of lubrication performance and stability against temperature change. 5 to 10.5 is more preferable.
  • the molecular weight of the polyol ester is not particularly limited as long as the molecular weight ⁇ the total number of carbons / the number of carbonyl carbons is within the above range, but is preferably 200 to 1500, and preferably 250 to 1200 from the viewpoint of lubrication performance and stability against temperature change. Is more preferable, 350 to 1100 is still more preferable, and 400 to 1100 is particularly preferable.
  • the total number of carbon atoms in the polyol ester is not particularly limited as long as the molecular weight ⁇ the total number of carbons / the number of carbonyl carbons is within the above range, but is preferably 15 to 60 from the viewpoint of lubrication performance and stability against temperature changes.
  • the number of carbonyl carbons is not particularly limited as long as the molecular weight ⁇ the total number of carbons / the number of carbonyl carbons is within the above range, but 2 to 6 is preferable from the viewpoint of lubrication performance and stability against temperature change. 6 is more preferable, and 4 to 6 is still more preferable.
  • the polyol ester is an ester of a polyol and a fatty acid, and the number of hydroxyl groups of the polyol used here is not particularly limited, but is preferably 2 to 20 from the viewpoint of lubricating performance and stability against temperature change. ⁇ 10 are more preferred, and 4 to 8 are even more preferred.
  • the carbon number of the polyol is not particularly limited, but is preferably 2 to 20, more preferably 4 to 15, and still more preferably 5 to 10 from the viewpoints of lubrication performance and stability against temperature changes.
  • polyol examples include ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, and 1,5-pentanediol.
  • Neopentyl glycol 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl-2-propyl-1,3-propanediol, 2 Diols such as 1,2-diethyl-1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol; Also trimethylolethane, trimethylolpropane, trimethylolbutane, ditrimethylol Lopan), tritrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, polyglycerin (glycerin 2-20 mer), 1,3,5-pent
  • neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, ditrimethylol propane, tritrimethylol propane, pentaerythritol, dipentaerythritol and tripentaerythritol are preferred, neopentyl glycol, trimethylol Propane, pentaerythritol, and dipentaerythritol are more preferable, and pentaerythritol and dipentaerythritol are still more preferable.
  • the number of carbonyl groups in the fatty acid is not particularly limited, but from the viewpoint of lubrication performance and stability against temperature change, the carbonyl group is preferably 1 to 4 fatty acids, more preferably 1 to 2 fatty acids. More preferred are individual fatty acids, ie aliphatic monocarboxylic acids.
  • the carbon number is not particularly limited, but is preferably 1 to 24, more preferably 4 to 12, and still more preferably 6 to 10 from the viewpoint of lubrication performance and stability against temperature change.
  • the fatty acid may be either linear or branched, and is preferably a linear fatty acid from the viewpoint of lubrication performance, and is preferably a branched fatty acid from the viewpoint of stability against temperature changes. Moreover, either saturated fatty acid or unsaturated fatty acid may be sufficient.
  • fatty acids examples include butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, Examples thereof include linear or branched compounds such as nonadecanoic acid, icosanoic acid and oleic acid, or so-called neoacids in which the ⁇ carbon atom is quaternary. These fatty acids can be used alone or in combination of two or more.
  • butyric acid n-butanoic acid
  • isobutyric acid isobutanoic acid
  • valeric acid n-pentanoic acid
  • caproic acid n-hexanoic acid
  • enanthic acid n-heptanoic acid
  • capryl Acid n-octanoic acid
  • pelargonic acid n-nonanoic acid
  • capric acid n-decanoic acid
  • oleic acid cis-9-octadecenoic acid
  • isopentanoic acid 3-methylbutanoic acid
  • 2-methylbutanoic acid 2-ethylbutanoic acid
  • 2-methylpentanoic acid 2-ethylpentanoic acid
  • 2-methylhexanoic acid 2-ethylhexanoic acid
  • 3,5,5-trimethylhexanoic acid 3,5,5-trimethylhexanoic acid
  • Valeric acid (n-pentanoic acid ), Caproic acid (n-hexanoic acid), enanthic acid (n-heptanoic acid), caprylic acid (n-octanoic acid), pelargonic acid (n-nonanoic acid), capric acid (n Decanoic acid), oleic acid (cis-9-octadecenoic acid), 2-methylpentanoic acid, 2-ethylpentanoic acid, 2-methylhexanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid More preferred are 2-methylpentanoic acid, 2-ethylpentanoic acid, 2-methylhexanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid.
  • preferred polyol esters include neopentyl glycol, butyric acid (n-butanoic acid), isobutyric acid (isobutanoic acid), valeric acid (n-pentanoic acid), caproic acid (n-hexanoic acid), enanthic acid ( n-heptanoic acid), caprylic acid (n-octanoic acid), pelargonic acid (n-nonanoic acid), capric acid (n-decanoic acid), oleic acid (cis-9-octadecenoic acid), isopentanoic acid (3-methylbutane) Acid), 2-methylbutanoic acid, 2-ethylbutanoic acid, 2-methylpentanoic acid, 2-ethylpentanoic acid, 2-methylhexanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid At least one diester; trimethylol
  • the polyol ester can be synthesized by an esterification reaction of the above polyol and a fatty acid.
  • the polyol ester is preferably an ester synthesized by an esterification reaction between a polyol having 2 to 20 hydroxyl groups and a fatty acid having 1 to 24 carbon atoms, and a polyol having 2 to 10 hydroxyl groups and an alcohol having 4 to 12 carbon atoms.
  • Esters with fatty acids are more preferred, and esters with polyols having 4 to 8 hydroxyl groups and fatty acids having 6 to 10 carbon atoms are more preferred.
  • the esterification reaction may be performed according to a known method, and it is preferable to perform the esterification reaction in an inert gas atmosphere from the viewpoint of suppressing coloring and obtaining a good appearance. From the same viewpoint, a hydrogenation reaction may be performed after the esterification reaction.
  • the kinematic viscosity of the polyol ester is not particularly limited, from the viewpoint of lubricating performance, preferably 3 ⁇ 200mm 2 / s, more preferably 10 ⁇ 200mm 2 / s, more preferably 20 ⁇ 150mm 2 / s.
  • the kinematic viscosity at 100 ° C. is not particularly limited, but is preferably 1 to 50 mm 2 / s, more preferably 3 to 25 mm 2 / s, and still more preferably 4 to 20 mm 2 / s from the viewpoint of lubrication performance.
  • kinematic viscosity are measured using a glass capillary viscometer in accordance with JIS K2283: 2000.
  • the viscosity index (VI) is not particularly limited, but is preferably 40 or more, more preferably 60 or more, and still more preferably 80 or more from the viewpoint of lubrication performance.
  • the upper limit of the viscosity index is not particularly limited, but is usually about 200 or less.
  • the viscosity index (VI) is measured according to JIS K2283: 2000.
  • the acid value of the polyol ester is preferably 0.1 mgKOH / g or less, more preferably 0.06 mgKOH / g or less, and still more preferably 0.04 mgKOH / g or less, from the viewpoint of stability against temperature change.
  • the acid value is measured by an indicator titration method in accordance with “Lubricating oil neutralization test method” defined in JIS K 2501: 2003.
  • the hydroxyl value of the polyol ester is preferably 10 mgKOH / g or less, more preferably 5 mgKOH / g or less, and still more preferably 3 mgKOH / g or less, from the viewpoint of stability against temperature change.
  • the hydroxyl value is measured by a neutralization titration method according to JIS K0070: 1992.
  • the volume resistivity of the polyol ester is preferably 1 ⁇ 10 10 ⁇ ⁇ m or more, and more preferably 1 ⁇ 10 11 ⁇ ⁇ m or more.
  • the volume resistivity is measured at room temperature of 25 ° C. according to JIS C 2101 24 (volume resistivity test).
  • the water content of the polyol ester is preferably less than 200 mass ppm, more preferably 100 mass ppm or less. By reducing the water content, hydrolysis of the refrigerating machine oil is less likely to occur, stability is improved, and good lubricating performance over a long period of time is obtained.
  • the refrigerating machine oil may be dehydrated with a dehydrating agent such as a molecular sieve in order to reduce the water content.
  • the water content is measured by Karl Fischer titration according to JIS K 2275: 1996.
  • the refrigerating machine oil of the present embodiment is one other than the above polyol ester, for example, a polyol ester other than the above, polyoxyalkylene glycol, polyvinyl ether, poly (oxy) alkylene glycol or the like thereof, as long as the effects of the present invention are not impaired.
  • examples thereof include copolymers of monoether and polyvinyl ether, polycarbonates, ⁇ -olefin oligomer hydrides, mineral oil, alicyclic hydrocarbon compounds, alkylated aromatic hydrocarbon compounds, and the like.
  • Those other than the above polyol esters may be used singly or in combination of two or more.
  • the content of the polyol ester is preferably 70% by mass or more, more preferably 90% by mass or more, still more preferably 99% by mass or more, and 100% by mass, that is, the refrigerating machine oil is composed only of the polyol ester. Particularly preferred.
  • the refrigerating machine oil of this embodiment may contain things other than the polyol ester as described above, the preferable range of its kinematic viscosity, viscosity index, acid value, hydroxyl value, volume resistivity, and water content is It is the same as the preferable range of said polyol ester.
  • composition for refrigerators of this embodiment contains the refrigerator oil which concerns on said this embodiment, and a refrigerant
  • refrigerant As the refrigerant, a refrigerant having a low global warming potential that has little fear of environmental problems and little influence on global warming is preferable.
  • refrigerant include a fluorinated hydrocarbon refrigerant, an oxygen-containing refrigerant containing oxygen atoms in the molecule, and a natural refrigerant.
  • fluorinated hydrocarbon refrigerant examples include unsaturated fluorinated hydrocarbon compounds and saturated fluorinated hydrocarbon compounds, and it is preferable to use at least one selected from these.
  • the saturated fluorinated hydrocarbon compound is preferably an alkane fluoride having 1 to 4 carbon atoms, more preferably an alkane fluoride having 1 to 3 carbon atoms, and an alkane (methane or ethane) fluoride having 1 to 2 carbon atoms. Is more preferable.
  • Specific methane or ethane fluorides include trifluoromethane (R23), difluoromethane (R32), 1,1-difluoroethane (R152a), 1,1,1-trifluoroethane (R143a), 1,1, 2-trifluoroethane (R143), 1,1,1,2-tetrafluoroethane (R134a), 1,1,2,2-tetrafluoroethane (R134), 1,1,1,2,2-penta Fluoroethane (R125) and the like can be mentioned, among which difluoromethane and 1,1,1,2,2-pentafluoroethane are preferable.
  • saturated fluorinated hydrocarbon compounds may be used alone or in combination of two or more.
  • a mixed refrigerant obtained by mixing two or more kinds of saturated fluorinated hydrocarbon compounds having 1 to 3 carbon atoms, or two or more kinds of saturated fluorinated hydrocarbon compounds having 1 to 2 carbon atoms are mixed.
  • a mixed refrigerant etc. are mentioned.
  • Specific mixed refrigerants include a mixture of R32 and R125 (R410A), a mixture of R125, R143a and R134a (R404A), a mixture of R32, R125 and R134a (R407A, R407C, R407E, etc.), R125 and R143a. (R507A) and the like.
  • Unsaturated fluorohydrocarbon compounds having a carbon-carbon double bond such as linear or branched chain olefins having 2 to 6 carbon atoms and fluorinated products of cyclic olefins having 4 to 6 carbon atoms Is mentioned.
  • ethylene with 1 to 3 fluorine atoms introduced propene with 1 to 5 fluorine atoms introduced, butene with 1 to 7 fluorine atoms introduced, 1 to 9 fluorine atoms introduced Pentene, hexene introduced with 1 to 11 fluorine atoms, cyclobutene introduced with 1 to 5 fluorine atoms, cyclopentene introduced with 1 to 7 fluorine atoms, 1 to 9 fluorine atoms And cyclohexene in which is introduced.
  • ethylene fluoride and propene fluoride are preferred, and ethylene fluoride is preferably 1,1,2-trifluoroethylene (R1123), and propene fluoride.
  • ethylene fluoride is preferably 1,1,2-trifluoroethylene (R1123), and propene fluoride.
  • propene into which 3 to 5 fluorine atoms are introduced is more preferable, and propene into which 4 fluorine atoms are introduced is more preferable.
  • More specific examples of the propene fluoride include 1,3,3,3-tetrafluoropropene (R1234ze) and 2,3,3,3-tetrafluoropropene (R1234yf).
  • These unsaturated fluorinated hydrocarbon compounds may be used alone or in combination of two or more, and refrigerants other than unsaturated fluorinated hydrocarbon compounds, for example, the above saturated fluorinated hydrocarbons It may be used in combination with a refrigerant.
  • a mixed refrigerant of a saturated fluorinated hydrocarbon compound and an unsaturated fluorinated hydrocarbon compound can be given as an example in the case of using in combination with a refrigerant other than the unsaturated fluorinated hydrocarbon compound.
  • Specific examples of the mixed refrigerant include a mixed refrigerant of R32, R1234ze, and R152a (AC5, the mixing ratio is 13.23: 76.20: 9.96).
  • oxygen-containing refrigerant containing an oxygen atom in the molecule examples include a fluorinated ether compound, a fluorinated alcohol compound, and a fluorinated alcohol compound.
  • oxygen-containing refrigerant can be represented by the following general formula (1).
  • R represents Cl, Br, I, or H
  • p is an integer of 1 to 6
  • q is 1 to 2
  • r is 1 to 14
  • s is an integer of 0 to 13.
  • fluorinated ether compound for example, in the above general formula (1), R is H, p is 2 to 6, q is 1 to 2, r is 1 to 14, and s is 0 to 13.
  • a fluorinated ether compound for example, a fluoride of a linear aliphatic ether having 2 to 6 carbon atoms, having 1 to 2 ether bonds, and an alkyl group being linear or branched is preferable. And a cyclic aliphatic ether fluoride having 3 to 6 carbon atoms and having 1 to 2 ether bonds.
  • fluorinated dimethyl ether introduced with 1 to 6 fluorine atoms
  • fluorinated methyl ethyl ether introduced with 1 to 8 fluorine atoms
  • fluorinated with 1 to 8 fluorine atoms Dimethoxymethane
  • fluorinated methyl propyl ethers with 1 to 10 fluorine atoms introduced
  • 1 fluorinated methyl butyl ethers with 1 to 12 fluorine atoms introduced
  • oxetane fluoride with 1-6 fluorine atoms introduced
  • 1,3-dioxolane fluoride with 1-6 fluorine atoms introduced
  • fluorinated tetrahydrofuran may be used individually by 1 type, and may be used in combination of 2 or more type.
  • fluorinated alcohol compound for example, in the above general formula (1), R is H, p is 1 to 6, q is 1 to 2, r is 1 to 13, and s is 1 to 13
  • examples include alcohol compounds.
  • Preferable examples of such a fluorinated alcohol compound include fluorides of linear or branched aliphatic alcohols having 1 to 6 carbon atoms and having 1 to 2 hydroxyl groups.
  • fluorinated methyl alcohol with 1 to 3 fluorine atoms introduced fluorinated ethyl alcohol with 1 to 5 fluorine atoms introduced, and fluorinated with 1 to 7 fluorine atoms introduced
  • fluorinated butyl alcohols having 1 to 9 fluorine atoms introduced fluorinated pentyl alcohols having 1 to 11 fluorine atoms introduced, and fluorines having 1 to 4 fluorine atoms introduced
  • ethylene glycol, and fluorinated propylene glycol introduced with 1 to 6 fluorine atoms fluorinated alcohol compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • fluorinated ketone compound for example, in the above general formula (1), R is H, p is 2 to 6, q is 1 to 2, r is 1 to 12, and s is 0 to 11 A ketone compound is mentioned.
  • fluorinated ketone compound include fluorides of aliphatic ketones having 3 to 6 carbon atoms and linear or branched alkyl groups.
  • fluorinated acetone into which 1 to 6 fluorine atoms are introduced fluorinated methyl ethyl ketone into which 1 to 8 fluorine atoms are introduced, and fluorinated diethyl ketone into which 1 to 10 fluorine atoms are introduced
  • fluorinated methyl propyl ketones having 1 to 10 fluorine atoms introduced therein A fluorine ketone compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Natural refrigerants include carbon dioxide gas (carbon dioxide), ammonia, and hydrocarbon gases such as propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentaneisobutane, and normal butane.
  • One kind of natural refrigerant may be used alone, two or more kinds may be used in combination, or a refrigerant other than natural refrigerant may be used in combination.
  • a mixed refrigerant with a saturated fluorinated hydrocarbon compound and / or an unsaturated fluorinated hydrocarbon compound can be mentioned.
  • Specific examples of the mixed refrigerant include a mixed refrigerant of carbon dioxide, R134a, and R1234ze (AC6, the mixing ratio is 5.71: 10.56: 83.73).
  • At least one selected from unsaturated fluorinated hydrocarbon compounds, saturated fluorinated hydrocarbon compounds, and natural refrigerants is preferable from the viewpoint of the stability of the refrigerating machine oil.
  • difluoromethane (R32), 2,3,3,3-tetrafluoropropene (R1234yf), and 1,1,2-trifluoroethylene (R1123) are used.
  • R1123 1,1,2-trifluoroethylene
  • a refrigerant in which two or three types are mixed may be used, and as a refrigerant in which two types are mixed, in particular, difluoromethane (R32) and 2,3,3,3-tetrafluoropropene.
  • a mixed refrigerant of (R1234yf) is preferable.
  • a refrigerant consisting only of difluoromethane (R32), a refrigerant consisting only of 2,3,3,3-tetrafluoropropene (R1234yf), 1,1,2-trifluoroethylene is preferred.
  • the content ratio of the refrigeration oil to the refrigerant (refrigeration oil / refrigerant) in the composition for the refrigeration machine is preferably 1/99 to 99/1, more preferably 5/95 to 60/40 by mass ratio. .
  • the refrigerating machine oil and the refrigerating machine composition of the present embodiment may further contain an additive as long as the effects of the present invention are not impaired.
  • additives include antioxidants, acid scavengers, oxygen scavengers, extreme pressure agents, copper deactivators, oiliness agents, rust preventives, and antifoaming agents. At least one agent can be used.
  • the content of each additive is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the refrigerating machine oil.
  • Antioxidants include 2,6-di-tert-butyl-4-methylphenol (DBPC), 2,6-di-tert-butyl-4-ethylphenol, 2,2′-methylenebis (4-methyl- Phenol-based antioxidants such as 6-tert-butylphenol) and amine-based antioxidants such as phenyl- ⁇ -naphthylamine and N, N′-diphenyl-p-phenylenediamine.
  • DBPC 2,6-di-tert-butyl-4-methylphenol
  • 2,6-di-tert-butyl-4-ethylphenol 2,2′-methylenebis (4-methyl- Phenol-based antioxidants such as 6-tert-butylphenol)
  • amine-based antioxidants such as phenyl- ⁇ -naphthylamine and N, N′-diphenyl-p-phenylenediamine.
  • the acid scavenger examples include epoxy compounds such as phenyl glycidyl ether, alkyl glycidyl ether, alkylene glycol glycidyl ether, glycidyl ester, cyclohexene oxide, ⁇ -olefin oxide, and epoxidized soybean oil.
  • oxygen scavenger examples include 4,4′-thiobis (3-methyl-6-tert-butylphenol), diphenyl sulfide, dioctyl diphenyl sulfide, dialkyl diphenylene sulfide, benzothiophene, dibenzothiophene, phenothiazine, benzothiapyran, thiapyran, thianthrene, Examples thereof include sulfur-containing aromatic compounds such as dibenzothiapyran and diphenylene disulfide, aliphatic unsaturated compounds such as various olefins, dienes and trienes, and terpenes having a double bond.
  • Extreme pressure agents include phosphoric acid esters, acidic phosphoric acid esters, phosphite esters, acidic phosphite esters and phosphorus salts such as amine salts thereof, sulfur-based fats and oils, sulfurized fatty acids, sulfurized esters such as sulfurized esters, etc. Examples include extreme pressure agents and fatty acid metal salts having 3 to 60 carbon atoms.
  • Examples of the copper deactivator include N- [N, N′-dialkylaminomethyl] triazole (the alkyl group is an alkyl group having 3 to 12 carbon atoms) and the like.
  • load bearing additives for example, load bearing additives, chlorine scavengers, detergent dispersants, viscosity index improvers, antiwear agents, pour point depressants, and the like can be used as necessary.
  • load bearing additives for example, chlorine scavengers, detergent dispersants, viscosity index improvers, antiwear agents, pour point depressants, and the like can be used as necessary.
  • These additives may be used alone or in combination of two or more.
  • the preferable ranges of the kinematic viscosity, the viscosity index, the acid value, the hydroxyl value, the volume resistivity, and the water content of the composition for a refrigerator of the present embodiment are the same as the preferable ranges of the above refrigerator oil.
  • the refrigerator of this embodiment includes at least a compressor, a condenser, an expansion mechanism, and an evaporator, and uses the above-described refrigerator oil or the composition for a refrigerator.
  • the refrigerator of the present embodiment is a compression refrigerator having a refrigeration cycle including at least a compressor, a condenser, an expansion mechanism, and an evaporator, and further having a refrigeration cycle including a dryer. Also good.
  • the refrigerating machine oil or the refrigerating machine composition is used, for example, for lubricating a sliding portion provided in a compressor or the like.
  • the sliding portion is not particularly limited, but any member constituting the sliding portion preferably contains a metal such as iron, and preferably slides between metal and metal.
  • the refrigeration machine of this embodiment includes a refrigeration system provided in an air conditioner, a refrigerator, a gas heat pump (GHP), an air conditioner, a showcase, a vending machine, etc., a hot water supply system using the exhaust heat, and a heating system such as floor heating It is also used for. That is, the refrigerating machine oil and the refrigerating machine composition of the present embodiment can be widely used in various systems such as the refrigerating system, the hot water supply system, and the heating system.
  • GTP gas heat pump
  • the measuring method of the property of the refrigerator oil adjusted in the Example and the comparative example and the composition for refrigerators is as follows. (1) Measurement of kinematic viscosity at 40 ° C. and kinematic viscosity at 100 ° C. It was measured using a glass capillary viscometer according to JIS K2283: 2000. (2) Viscosity index (VI) The measurement was performed according to JIS K2283: 2000.
  • difluoromethane (R32) a mixed refrigerant of difluoromethane (R32) and 2,3,3,3-tetrafluoropropene (R1234yf) (mixing mass ratio 1: 1), 1,1,2-trifluoro Three types of ethylene (R1123) were used.
  • moisture content of the composition for refrigerators in a glass tube was prepared to 50 mass ppm or less.
  • the acid value was measured by an indicator titration method in accordance with “Lubricating oil neutralization test method” defined in JIS K 2501: 2003.
  • Falex Wear Test Using a Falex testing machine, AISC1137 / SAE3135 was used as a pin / block.
  • the above-mentioned pin / block is set in a Falex testing machine, and 100 g of the refrigeration oil of each Example and Comparative Example and additive (1 part by mass of tricresyl phosphate (TCP 0.5 parts by mass of 2,6-di-t-butylparacresol (DBPC, as an antioxidant), 1 part by mass of 2-ethylhexyl glycidyl ether (as an acid scavenger) ) And 1,1,2-trifluoroethylene (R1123) was used as a refrigerant at 0.5 MPa.
  • TCP 0.5 parts by mass of 2,6-di-t-butylparacresol
  • R1123 1,1,2-trifluoroethylene
  • the pin wear amount (mg) after 1 hour was measured at a rotational speed of 290 rpm, a room temperature (25 ° C.), and a load of 1334 N.
  • Table 1 shows total carbon number, carbonyl carbon number, total carbon number / carbonyl carbon number, molecular weight ⁇ total carbon number / carbonyl carbon number for refrigerating machine oils 1 to 22. Moreover, (1) kinematic viscosity (40 degreeC, 100 degreeC), (2) viscosity index (VI), and (3) flock point were measured about these refrigerating machine oil. The results are shown in Table 1.
  • Refrigerator oil 1 Diester refrigeration oil of neopentyl glycol and 2-methylpentanoic acid 2: Diester refrigeration oil of neopentyl glycol and 2-ethylpentanoic acid 3: Triester refrigeration of trimethylolpropane and 2-methylpentanoic acid
  • Machine oil 4 Triester refrigerating machine oil of trimethylolpropane and 3,5,5-trimethylhexanoic acid
  • 5 Tetraester refrigerating machine oil of pentaerythritol and n-butanoic acid 6: Tetraester of pentaerythritol and 2-methylbutanoic acid
  • Flock point * 2 A mixed refrigerant (mixing mass ratio 1: 1) of difluoromethane (R32) and 2,3,3,3-tetrafluoropropene (R1234yf) was used as a refrigerant.
  • Flock point * 3 1,1,2-trifluoroethylene (R1123) was used as a refrigerant.
  • refrigeration oils 1 to 17 of Examples 1 to 17 have a flock point of less than ⁇ 35 ° C. or less than ⁇ 40 ° C. in any refrigerant, and solidify in a low temperature environment. It was confirmed that no wax precipitated.
  • the refrigerating machine oils 18 to 21 of Comparative Examples 1 to 4 had a flock point of -35 ° C. using 1,1,2-trifluoroethylene (R1123) as the refrigerant of the refrigerating machine oil 21 (Comparative Example 4).
  • the other flock point was ⁇ 20 ° C. or ⁇ 30 ° C., and it was confirmed that the wax solidifies and precipitates the wax in a low temperature environment.
  • the refrigerating machine oils 1 to 17 of Examples 18 to 34 were generally good although some examples of yellow oil appearance were present, and the results of the Falex abrasion test were also good.
  • the amount of pin wear in the Falex wear test was less than 25 mg, and more excellent results were shown.
  • the refrigerating machine oil and the refrigerating machine composition according to the present embodiment are excellent in stability against temperature change because wax does not precipitate in various refrigerants in a low temperature environment. In addition, it was confirmed that sludge and the like were not generated at high temperatures and that the lubrication performance was excellent.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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  • Lubricants (AREA)

Abstract

La présente invention concerne : une huile pour machine frigorifique présentant d'excellentes performances de lubrification et une excellente stabilité par rapport à un changement de température. Plus particulièrement, l'invention concerne une huile pour machine frigorifique qui contient un ester de polyol dans lequel la valeur obtenue par (masse moléculaire) x (nombre total d'atomes de carbone) / (nombre d'atomes de carbone des carbonyle) est inférieure ou égale à 10 000 ; une composition pour machines frigorifiques ; et une machine frigorifique qui utilise cette huile pour machine frigorifique ou cette composition pour machines frigorifiques.
PCT/JP2016/080108 2015-10-16 2016-10-11 Huile pour machine frigorifique, composition pour machines frigorifiques et machines frigorifiques WO2017065134A1 (fr)

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