WO2001002517A1 - Composition a base d'huile pour machine frigorifique - Google Patents

Composition a base d'huile pour machine frigorifique Download PDF

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Publication number
WO2001002517A1
WO2001002517A1 PCT/JP1999/004498 JP9904498W WO0102517A1 WO 2001002517 A1 WO2001002517 A1 WO 2001002517A1 JP 9904498 W JP9904498 W JP 9904498W WO 0102517 A1 WO0102517 A1 WO 0102517A1
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Prior art keywords
group
oil composition
trans
phosphate
refrigerating machine
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PCT/JP1999/004498
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English (en)
Japanese (ja)
Inventor
Yuji Shimomura
Satoshi Suda
Hiroyuki Hirano
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Nippon Mitsubishi Oil Corporation
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Priority to AU53032/99A priority Critical patent/AU5303299A/en
Publication of WO2001002517A1 publication Critical patent/WO2001002517A1/fr

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    • 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
    • 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
    • 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
    • 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
    • C10M105/36—Esters of polycarboxylic acids
    • 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
    • C09K2205/10—Components
    • C09K2205/106—Carbon dioxide
    • 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
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • 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
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/042—Epoxides
    • 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/124—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms containing hydroxy groups; Ethers thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • 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

  • the present invention relates to a refrigerator oil composition, and more particularly to a refrigerator oil composition containing an alicyclic dicarboxylic acid ester compound.
  • HFC refrigerants can also be subject to regulation from the perspective of global warming, and the use of natural refrigerants such as carbon dioxide, ammonia, and hydrocarbons is being considered.
  • Refrigeration oil requires many performances such as lubricity, refrigerant compatibility, heat and hydrolysis stability, electrical insulation, and low moisture absorption.
  • a compound is selected.
  • refrigeration oils for HFCs include oxygen-containing compounds such as esters, ethers, and carbonates that are compatible with refrigerants, or alkylbenzenes that have poor refrigerant compatibility but have excellent lubricity and thermal and hydrolytic stability. Etc. are used.
  • An ester-based refrigerating machine oil is obtained by a reaction between an aliphatic polyhydric alcohol and a fatty acid as disclosed in Japanese Patent Application Laid-Open No. Hei 3-556062, Japanese Patent Application Laid-Open No. Hei 3-12891.
  • Polyol esters are known, and such ester refrigerator oils have a low viscosity.
  • One of the effective measures is to select a fatty acid having a small carbon number in the alkyl group of the fatty acid used as a raw material.
  • the alkyl group of the fatty acid becomes small, a problem occurs in that the heat and hydrolysis stability of the obtained ester is reduced.
  • Japanese Patent Application Laid-Open No. H09-221216 is an Esder refrigeration oil excellent in heat and hydrolysis stability.
  • An alicyclic polycarboxylic acid ester as disclosed in 90 is known, but in the case of an ester having such a structure, there is a problem in that lubricity is reduced due to a decrease in viscosity.
  • the present invention has been made in view of the above-mentioned problems of the related art, and when used together with HFC refrigerant and natural refrigerants such as carbon dioxide and hydrocarbon, lubricity, refrigerant compatibility, heat and water It is an object of the present invention to provide a refrigerating machine oil composition which is excellent in decomposition stability, electrical insulation properties, etc., and which enables high efficiency of a refrigerating system.
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a refrigerating machine oil composition excellent in various performances can be obtained by using a base oil containing a specific ester oil. .
  • the refrigerating machine oil composition of the present invention has an alicyclic ring and two ester groups represented by the following general formula (1), and two of the ester groups are adjacent to each other on the alicyclic ring.
  • Trans-type alicyclic dicarboxylic acid ester compound which is bonded to a carbon atom and is trans-form with respect to two orientations of the ester group
  • R 1 represents a hydrocarbon group having 0 to 3 carbon atoms, R 1 for each ester group They may be the same or different.
  • the refrigerator oil composition of the present invention preferably further contains an epoxy compound and / or a phosphorus compound.
  • an epoxy compound at least one compound selected from the group consisting of a phenylglycidyl ether type epoxy compound, a glycidyl ester type epoxy compound, an alicyclic epoxy compound and an epoxidized fatty acid monoester is preferable. Type epoxy compounds and / or alicyclic epoxy compounds are more preferred.
  • the fluid composition for a refrigerator according to the present invention contains the refrigerator oil composition of the present invention and a non-chlorine-containing chlorofluorocarbon.
  • the trans-type alicyclic dicarboxylic acid ester compound according to the present invention refers to an alicyclic ring and two ester groups represented by the following general formula (1), and two of the ester groups are alicyclic. It is bonded to adjacent carbon atoms on the ring and is trans-form with respect to the two orientations of the ester group.
  • R 1 represents a hydrocarbon group having 0 to 3 carbon atoms, R 1 for each ester group may be the same or different.
  • the alicyclic ring referred to here includes a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cycloheptene ring, and the like, and a cyclohexane ring and a cyclohexene ring are preferable. .
  • a cyclohexane ring is more preferable because of a small increase in viscosity when used under long-term or severe conditions, and a cyclohexene ring is preferably used when a long-term or severe condition is used.
  • the trans-type alicyclic dicarboxylic acid ester compound needs to have two ester groups represented by the above formula (1) together with the alicyclic ring.
  • a single ester group is not preferred because of insufficient refrigerant compatibility and thermal / hydrolytic stability. Further, when the number of ester groups is 3 or more, it is not preferable from the viewpoint of low-temperature fluidity.
  • the two ester groups represented by the above formula (1) may be bonded to carbon atoms adjacent to each other on the alicyclic ring, and may be trans-form with respect to the orientation of the two ester groups. is necessary.
  • thermal and hydrolytic stability is insufficient, and when it is a cis-isomer, lubricity tends to decrease.
  • ⁇ Trans-form is necessary from the viewpoint of compatibility between hydrolysis stability and lubricity.
  • R 1 in the above formula (1) represents a hydrocarbon group having 1 to 30 carbon atoms, preferably 2 to 24 carbon atoms, and more preferably 3 to 18 carbon atoms.
  • an alkyl group, a cycloalkyl group or an alkylcycloalkyl group is preferred from the viewpoint of thermal and hydrolytic stability.
  • the alkyl group may be linear or branched.
  • Examples of the alkyl group having 3 to 18 carbon atoms include, for example, a linear or branched propyl group, a linear or branched butyl group, a linear or branched pentyl group , Linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear Or a branched decyl group, a linear or branched pendecyl group, a linear or branched dodecyl group, a linear or branched tridecyl group, a linear or branched Tetradecyl group, linear or branched pendecyl group, linear or branched hexadecyl group, linear or branched heptadecyl group, linear or branched Ok And a sil group.
  • the linear alkyl group is preferably one having 5 or more carbon atoms from the viewpoint of heat and hydrolysis stability, and preferably 18 or less from the viewpoint of refrigerant compatibility.
  • the branched alkyl group preferably has 3 or more carbon atoms from the viewpoint of heat and hydrolysis stability, and has 18 or less carbon atoms from the viewpoint of refrigerant compatibility.
  • Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and the like, and a cyclohexyl group is preferred from the viewpoint of heat and hydrolysis stability.
  • the alkylcycloalkyl group is a cycloalkyl group having an alkyl group bonded thereto, and is preferably a cyclohexyl group having an alkyl group bonded thereto from the viewpoint of thermal and hydrolytic stability.
  • the alkylcycloalkyl group preferably has a total carbon number of 6 or more from the viewpoint of heat and hydrolysis stability, and preferably has a total carbon number of 10 or less from the viewpoint of refrigerant compatibility and low-temperature fluidity. .
  • one or more hydrocarbon groups may be bonded to carbon atoms on the alicyclic ring.
  • a hydrocarbon group an alkyl group is preferable, and a methyl group is particularly preferable.
  • the trans type alicyclic dicarboxylic acid ester compound referred to in the present invention has the above-mentioned structure.
  • Such an ester compound is obtained by subjecting a predetermined acid component and an alcohol component to esterification by heating in a conventional manner, preferably under an atmosphere of an inert gas such as nitrogen, under an atmosphere of an esterification catalyst or under no catalyst. Prepared.
  • the acid component of the trans-type alicyclic dicarboxylic acid ester compound is trans-cycloalkanedicarboxylic acid, trans-cycloalkenedicarboxylic acid, or an acid anhydride thereof, and the two ester groups are an alicyclic ring. Bonded to adjacent carbon atoms above, which may be one or more mixtures of two or more. It is possible to use it.
  • trans-1,2-cyclohexanedicarboxylic acid, trans-4-cyclohexene-1,2-dicarboxylic acid, trans-1-cyclohexene-1,1,2-dicarboxylic acid, t rans-3-methyl-1,2-cyclohexanedicarboxylic acid, trans-4-methyl-1,2-cyclohexanedicarboxylic acid, trans-3-methyl-4-cyclohexene-1,2- Dicarboxylic acids, trans-4-methyl-14-cyclohexene-1,2, dicarboxylic acids and their anhydrides are disclosed.
  • trans-1,2-cyclohexanedicarboxylic acid, trans-3-methyl 1,2-cyclohexanedicarboxylic acid, trans-4-methyl-1,2-cyclohexanedicarboxylic acid and their acid anhydrides are preferred, and on the other hand, the total amount when used under long-term or severe conditions is high.
  • trans-4-cyclohexene-1,2-dicarboxylic acid From the viewpoint of suppressing the increase in the acid value, trans-4-cyclohexene-1,2-dicarboxylic acid, trans-1-cyclohexene-1,2-dicarboxylic acid, trans-4-methyl-1- 1,2-cyclohexanedicarboxylic acid, trans-3-methyl-4-cyclohexene-1,2-dicarboxylic acid, trans-4-methyl-14-cyclohexene1-1,2-dicarboxylic acid and the like Are preferred.
  • trans-4-cyclohexene-1,2-dicarboxylic acid can be obtained by reacting butadiene and maleic anhydride at 100 ° C. in a benzene solvent.
  • the alcohol component of the trans-type alicyclic dicarboxylic acid ester compound includes a linear alcohol having 3 to 18 carbon atoms, a branched alcohol having 3 to 18 carbon atoms, or a cycloalkyl having 5 to 10 carbon atoms. Alcohol.
  • linear or branched propanol including n-propanol, 1-methylethanol, etc.
  • linear or branched butanol n-butanol, 1-methyl Propanol, 2-methylpropanol, etc.
  • linear or branched pentanol including n-pentanol, 1-methylbutanol, 2-methylbutanol, 3-methylbutanol, etc.
  • straight chain Linear or branched hexanol including n-hexanol, 1-methylpentanol, 2-methylpentanol, 3-methylpentanol, etc.
  • linear or branched heptanol n-hepanol Phenol, 1-methylhexanol, 2-methylhexanol, 3-methylhexanol, 4-methylhexanol, 5-methylhexanol, 2,4-dimethylpentanol, etc.
  • linear or Branched octanol including n-prop
  • the alcohol component is used, for example, in an amount of 1.0 to 1.5 equivalents, preferably 1.05 to 1.2 equivalents, per equivalent of the acid.
  • esterification catalyst examples include Lewis acids, alkali metal salts, and sulfonic acids.
  • Specific examples of the Lewis acid include aluminum derivatives, tin derivatives, and titanium derivatives.
  • Sodium alkoxides, potassium alkoxides and the like are exemplified, and sulfonic acids include paratoluenesulfonic acid, methanesulfonic acid, sulfuric acid and the like.
  • the amount used is, for example, about 0.1 to 1% by mass based on the total amount of the raw material acid component and alcohol component.
  • the reaction temperature is usually 150 ° C to 30 ° C.
  • the reaction is completed at 0 ° C. and a reaction time of 3 to 30 hours.However, in order to obtain the trans-type alicyclic dicarboxylic acid ester compound of the present invention, under a high temperature condition of 200 ° C. to 300 ° C. It is preferred to carry out the reaction.
  • the tran S-type alicyclic dicarboxylic acid ester compound can also be obtained by heating the cis-type alicyclic dicarboxylic acid ester compound at 250 ° C. to 300 ° C. in the presence of sodium acetate. it can.
  • the ester compound is purified by a conventional purification method, for example, adsorption purification treatment such as liquid-liquid extraction, vacuum distillation, and activated carbon treatment. can do.
  • adsorption purification treatment such as liquid-liquid extraction, vacuum distillation, and activated carbon treatment. can do.
  • the content of the trans-type alicyclic dicarboxylic acid ester compound in the refrigerator oil composition of the present invention is not particularly limited, it is possible to further bring out the various excellent properties of the trans-type alicyclic dicarboxylic acid ester compound. Therefore, the content is preferably at least 5% by mass, more preferably at least 10% by mass, even more preferably at least 30% by mass, more preferably at least 50% by mass, based on the total amount of the refrigerator oil composition. It is most preferable to contain the above.
  • the trans-type alicyclic dicarboxylic acid ester compound is mainly used as a base oil.
  • the base oil of the refrigerator oil composition of the present invention only the trans-type alicyclic dicarboxylic acid ester compound may be used, but in addition to this, esters other than the trans-type alicyclic dicarboxylic acid ester compound defined in the present invention, such as polyol ester ⁇ complex ester, may be used.
  • Oxygen-containing synthetic oils such as polyglycols, polyvinyl ethers, ketones, polyesters, silicones, polysiloxanes and perfluoroethers may be used in combination.
  • the amount of the synthetic oil containing oxygen is not particularly limited. However, from the viewpoint of improving the thermal efficiency and at the same time achieving high lubricating properties of the refrigerating machine oil and the stability of heat and hydrolysis, 100 parts by weight of the trans-type alicyclic dicarboxylic acid ester compound is not used.
  • the amount of the oxygen-containing synthetic oil is preferably at most 150 parts by weight, more preferably at most 100 parts by weight.
  • a trans-type alicyclic dicarboxylic acid ester compound and a hydrocarbon-based oil for example, a mineral oil, an olefin polymer, a naphthalene compound, an alkylbenzene, or a mixture of two or more of these) ) May be used in combination.
  • the refrigerating machine oil composition of the present invention contains a trans type alicyclic dicarboxylic acid ester compound and, if necessary, a synthetic oil containing oxygen, and is mainly used as a base oil.
  • the refrigerating machine oil composition of the present invention can be suitably used in a state in which no additives are added, but may be used in a form in which various additives are blended as necessary.
  • a phosphate ester an acid phosphate, an amine salt of an acid phosphate, a chlorinated phosphate and a phosphite are used.
  • phosphate esters include tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate, trindecyl phosphate, and trimethyl phosphate.
  • Examples of the acid phosphate include monobutyl acid phosphate, monopentyl acid phosphate, monohexyl acid phosphate, monoheptyl acid phosphate, monooctyl acid phosphate, monononyl acid phosphate, and monodecyl acid phosphate.
  • Examples of the amine salt of the acidic phosphate include methylamine, ethylamine, propylamine, and the like of the acidic phosphate. Butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, getylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, tripropylamine. And salts with amines such as amine, trihexylamine, triheptylamine and trioctylamine.
  • chlorinated phosphoric acid ester examples include tris-dichloro propyl phosphate, tris-chloro-ethyl phosphate, tris-chloro phenyl phosphate, polyoxyalkylene bis [di (chloroalkyl)] phosphate, and the like.
  • phosphites include dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, octyl phosphite, dinonyl phosphite, didecyl phosphite, and didecyl phosphite.
  • the amount of the phosphorus compound is not particularly limited. However, the content is usually based on the total amount of the refrigerator oil composition (based on the total weight of the base oil and all the blended additives). It is desirable to add a phosphorus compound in such an amount that the amount becomes 0.01 to 5.0% by mass, more preferably 0.02 to 3.0% by mass.
  • At least one epoxy compound selected from the group consisting of
  • phenylglycidyl ether type epoxy compound examples include phenylglycidyl ether and alkylphenylglycidyl ether.
  • the alkylphenyl glycidyl ether referred to herein includes those having 1 to 3 alkyl groups having 1 to 13 carbon atoms, among which those having one alkyl group having 4 to 10 carbon atoms, for example, n- Butylphenyl glycidyl ether, i-butyl phenyl glycidyl ether, sec-butyl phenyl glycidyl ether, tert-butyl phenyl glycidyl ether, pentyl phenyl glycidyl ether, hexyl phenyl glycidyl ether, heptyl phenyl glycidyl ether —Ter, octylphenyl glycidyl ether
  • alkyl glycidyl ether type epoxy compound examples include decyl glycidyl ether, pendecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, and 2-ethyl.
  • Xyl glycidyl ether neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, polyalkylene glycol Examples include monoglycidyl ether and polyalkylene glycol diglycidyl ether. Monkey
  • glycidyl ester type epoxy compound examples include a compound represented by the following general formula (2).
  • R represents a hydrocarbon group having 1 to 18 carbon atoms.
  • R represents a hydrocarbon group having 1 to 18 carbon atoms
  • examples of such a hydrocarbon group include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and a carbon atom.
  • a cycloalkyl group having 5 to 7 carbon atoms, an alkylcycloalkyl group having 6 to 18 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkyl aryl group having 7 to 18 carbon atoms, and having 7 to 18 carbon atoms Aryl alkyl group and the like.
  • an alkylphenyl group having a C5 to C15 alkyl group, a C2 to C15 alkenyl group, a phenyl group and a C1 to C4 alkyl group is preferable.
  • glycidyl ester type epoxy compounds are, for example, glycidyl 2,2-dimethyloctanoate, glycidyl benzoate, glycidyl tert-butyl benzoate, glycidyl acrylate, Glycidyl methacrylate can be exemplified.
  • aryloxysilane compounds include 1,2-epoxystyrene and alkyl-1,2-epoxystyrene.
  • alkyloxysilane compound specifically, 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxy Octane, 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxypandecane, 1,2-epoxidedodecane, 1,2-epoxytridecane, 1,2-epoxytetradecane, 1, 2—Epoxy pen Evening decane, 1,2-epoxyhexadecane, 1,2-epoxyheptane, 1,1,2-epoxyoctadecane, 2-epoxynonadecane, 1,2-epoxyicosane, and the like can be given as examples.
  • Examples of alicyclic epoxy compounds include compounds in which carbon atoms constituting an epoxy group directly constitute an alicyclic ring, such as compounds represented by the following general formula (3).
  • alicyclic epoxy compound examples include, for example, 1,2-epoxycyclohexane, 1,2-epoxycyclopentane, 3,4-epoxycyclohexylmethyl-1,3,4-epoxycyclohexanecarboxy. Rate, bis (3,4-epoxycyclohexylmethyl) adipate, exo-1,2,3-epoxynorbornane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (7-oxabicyclo [4 1.
  • epoxidized fatty acid monoester examples include esters of epoxidized fatty acids having 12 to 20 carbon atoms and alcohols or phenols having 1 to 8 carbon atoms, and alkylphenols. Particularly, butyl, hexyl, benzyl, cyclohexyl, methoxethyl, octyl, phenyl and butylphenyl esters of epoxystearic acid are preferably used.
  • epoxidized vegetable oils include epoxy compounds of vegetable oils such as soybean oil, linseed oil, and cottonseed oil.
  • epoxy compounds phenylglycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds, alicyclic epoxy compounds, and epoxidized fatty acid monoesters are preferable because they can further improve the thermal and hydrolytic stability. Glycidyl ester type epoxy compounds and alicyclic epoxy compounds are more preferred.
  • the blending amount is not particularly limited, but usually the content is based on the total amount of the refrigerator oil composition (based on the total amount of the base oil and all the blended additives). It is desirable to mix the epoxy compound in such an amount that the amount becomes 0.1 to 5.0% by mass, more preferably 0.2 to 2.0% by mass.
  • refrigerating machine oil additives for example, phenols such as di-tert-butyl-p-cresol, bisphenol A, etc., if necessary.
  • Antioxidants phenyl-naphthylamine, N, N-di (2-naphthyl) -p-phenylenediamine, etc., antioxidants of zinc, anti-wear agents such as zinc dithiophosphate, chlorinated balafins , Extreme pressure agents such as sulfur compounds, oily agents such as fatty acids, silicone-based defoamers, metal deactivators such as benzotriazole, viscosity index improvers, pour point depressants, additives such as cleaning dispersants May be used alone or in combination of several kinds.
  • the total amount of these additives is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total amount of the refrigerating machine oil composition (based on the total amount of the base oil and all the blended additives). It is.
  • the kinematic viscosity of the refrigerator oil composition of the present invention is not particularly limited, but the kinematic viscosity at 40 ° C. is preferably 3 to: L 00 mm 2 / s, and more preferably 4 to 50 mm 2 / s. most Preferably, it can be 5 to 40 mm 2 / s. Further, the kinematic viscosity at 100 ° C. can be preferably 1 to 20 mm 2 / s, more preferably 2 to 10 mm 2 / s.
  • a feature of the refrigerating machine oil of the present invention that the lubricating property and the heat-hydrolysis stability are good even when the viscosity is reduced is that the kinematic viscosity at 40 ° C. is preferably 5 to 35 mm 2 Zs, more preferably 5 to 35 mm 2 Zs. 2 5 mm 2 / s, even more preferably 5
  • the volume resistivity of the refrigerating machine oil composition of the present invention is not particularly limited, preferably 1. 0 ⁇ 1 0 ⁇ 1 ⁇ ⁇ ⁇ m or more, more preferably 1. 0 X 10 12 ⁇ ⁇ cm or more, and most Preferably, it can be 1.0 X 10 13 ⁇ ⁇ cm or more.
  • the volume resistivity means a value at 25 ° C. measured in accordance with JISC2101 “Electric insulating oil test method”.
  • the water content of the refrigerator oil composition of the present invention is not particularly limited, but is preferably 200 ppm or less, more preferably 100 ppm or less, and most preferably 50 ppm or less based on the total amount of the refrigerator oil composition. Can be. In particular, when used for hermetic refrigerators, it is required that the water content be low from the viewpoint of the thermal and hydrolytic stability of the oil and the effect on the electrical insulation.
  • the total acid value of the refrigerator oil composition of the present invention is not particularly limited, but is preferably 0.1 mgCOH / g or less, more preferably, in order to prevent corrosion of metal used in the refrigerator or piping. It can be less than 0.05mgKOHZg.
  • the total acid value refers to the value of the total acid value measured in accordance with JIS K2501 “Petroleum products and lubricating oil-neutralization value test method”.
  • the ash content of the refrigerating machine oil composition of the present invention is not particularly limited, but is preferably 100 ppm to enhance the thermal and hydrolytic stability of the refrigerating machine oil composition of the present invention and suppress the generation of sludge and the like. Or less, more preferably 50 ppm or less.
  • ash refers to JISK 2272 “ash of crude oil and petroleum products. And ash content measured in accordance with the “Test Methods for Sulfate Ash Content”.
  • Refrigerants used in refrigerators using the refrigerator composition of the present invention include HFC refrigerants, fluorine-containing ether-based refrigerants such as perfluoroethers, non-fluorine-containing ether-based refrigerants such as dimethyl ether, and carbon dioxide and hydrocarbons. Although they are natural refrigerants, they may be used alone or as a mixture of two or more.
  • HFC refrigerant examples include hydrofluorcarbon having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms.
  • hydrofluorcarbon having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms.
  • difluoromethane HFC-32
  • trifluoromethane HFC-23
  • penduorofluorethane HFC-125
  • 1,1,2,2-tetrafluorofluoroethane HFC-134
  • 1,1,1,2-tetrafluroethane HFC-134a
  • HF C-143a 1,1,1-difluoroethane
  • HFC-152a 1,1-difluoroethane
  • HFC or a mixture of two or more thereof.
  • examples of natural refrigerants include carbon dioxide and hydrocarbons.
  • a gaseous refrigerant at 25 ° C. and 1 atm is preferably used as the hydrocarbon refrigerant.
  • it is an alkane, cycloalkane, alkane or a mixture thereof having 1 to 5, preferably 1 to 4 carbon atoms.
  • Specific examples include methane, ethylene, ethane, propylene, propane, cyclopropane, butane, isobutane, cyclobutane, methylcyclopropane, and a mixture of two or more of these.
  • propane, butane, isobutane or a mixture thereof is preferred.
  • the refrigerating machine oil composition according to the present invention is usually present in a refrigerating machine in the form of a refrigerating machine fluid composition mixed with the above-described refrigerant.
  • the mixing ratio of the refrigerating machine oil composition and the refrigerant in the fluid composition is not particularly limited, but the refrigerating machine oil composition is preferably 1 to 500 parts by weight, more preferably 2 to 400 parts by weight, per 100 parts by weight of the refrigerant. Parts by weight.
  • the refrigerating machine oil composition of the present invention can be used as a lubricating oil for a refrigerant compressor of any refrigerating machine due to its excellent electrical properties and low moisture absorption.
  • Refrigerators used are, specifically, room air conditioners, package air conditioners, refrigerators, automotive air conditioners, dehumidifiers, freezers, freezer and refrigerated warehouses, vending machines, showcases, cooling equipment for chemical plants, etc. Is mentioned.
  • the refrigerator oil composition of the present invention is particularly preferably used for a refrigerator having a hermetic compressor.
  • the refrigerating machine oil composition of the present invention can be used for any type of compressor such as a reciprocating type, a rotary type, and a centrifugal type. [Example]
  • Tables 1 to 3 show the properties (kinematic viscosity at 40 ° C and 100 ° C, total acid value) of each sample oil obtained.
  • Motoda ⁇ trans- 12-Diisoheptyl 2-cyclohexanedicarboxylate Base oil 2: trans- 12 2-cyclohexanedicarboxylate di (2-ethylhexyl)
  • Base oil 3 trans- 12-cyclohexanedicarboxylic acid di (3,5,5-trimethylhexyl)
  • Base oil 4 trans-12-cyclohexanedicarboxylate di (2,6-dimethyl 4-heptyl) base oil 5 tran s-1, diisodecyl 2-cyclohexanedicarboxylate Base oil 6 tran s- 4-cyclohexene-1,2-dicarboxylate diisobutyl base oil 7-trans-4-dicyclohexene-1,2-dicarboxylate diheptyl
  • tran s-4 cyclohexene-1,2, -dicarboxylic acid di
  • tran s-4 cyclohexene-1,1,2-dicarboxylic acid di (3,5, 5-trimethylhexyl)
  • Base oil 10 0 trans-4—cyclohexene 1-diisobutyl carboxylate 2 1-ethylhexyl rubonate 2-ethylhexyl
  • Base oil 1 1 ci sl, diisoheptyl 2-cyclohexanedicarboxylate
  • Base oil 1 2 diisoheptyl trans-1,3-cyclohexanedicarboxylate (additive)
  • a friction tester using a vane (SKH-51) for the upper test piece and a disk (FC250 HRC40) for the lower test piece was installed inside the closed container. 600 ml of sample oil was introduced into the friction test site, the system was evacuated to vacuum, and R-134a was introduced and heated. After adjusting the system temperature to 100 ° C and the refrigerant pressure to 1.5 MPa, the load was increased stepwise to 100 kgf at a load step of 10 kgf (step time 2 minutes). The wear width of the vane and the wear depth of the disk after the test for 60 minutes were measured for each sample oil. Tables 1 to 3 show the obtained results.
  • Example 11 Comparative Example 1 Comparative Example 2 units, 8 8 11 12
  • the refrigerating machine oil composition of the present invention when used in combination with an HFC refrigerant and a natural refrigerant such as carbon dioxide or hydroxycarbon, it has lubricity, refrigerant compatibility, and electrical insulation properties. It is possible to achieve high efficiency of the refrigeration system while at the same time.

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Abstract

L'invention concerne une composition à base d'huile pour machine frigorifique, qui renferme un composé d'ester d'acide dicarboxylique alicyclique doté d'une chaîne alicyclique et de deux groupes ester représentés par la formule générale -COOR1 (1), et liés respectivement à des atomes de carbone adjacents sur la chaîne, sachant que le composé ester est trans par rapport à la configuration des deux groupes ester. Dans la formule (1), R1 est un groupe hydrocarbure C¿1-30? et les R?1¿ de chaque groupe ester peuvent être identiques ou différents).
PCT/JP1999/004498 1999-07-05 1999-08-20 Composition a base d'huile pour machine frigorifique WO2001002517A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU53032/99A AU5303299A (en) 1999-07-05 1999-08-20 Refrigerating machine oil composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11/190336 1999-07-05
JP19033699A JP4677067B2 (ja) 1999-07-05 1999-07-05 冷凍機油組成物

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WO2001002517A1 true WO2001002517A1 (fr) 2001-01-11

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002008367A1 (fr) * 2000-07-24 2002-01-31 Nippon Oil Corporation Composition a base d'huile pour machine frigorifique
WO2002008365A1 (fr) * 2000-07-24 2002-01-31 Nippon Oil Corporation Composition a base d'huile pour machine frigorifique

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5522895B2 (ja) * 2007-03-14 2014-06-18 Ｊｘ日鉱日石エネルギー株式会社 冷凍機油および冷凍機用作動流体組成物
JP6773976B2 (ja) * 2017-02-28 2020-10-21 新日本理化株式会社 軸受用潤滑油基油

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08134481A (ja) * 1994-11-11 1996-05-28 Matsushita Electric Ind Co Ltd 冷凍機作動流体用組成物及びそれを用いた冷凍システム
WO1997021792A1 (fr) * 1995-12-12 1997-06-19 New Japan Chemical Co., Ltd. Huile lubrifiante
JPH09221690A (ja) * 1995-12-12 1997-08-26 New Japan Chem Co Ltd 冷凍機用潤滑油

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08134481A (ja) * 1994-11-11 1996-05-28 Matsushita Electric Ind Co Ltd 冷凍機作動流体用組成物及びそれを用いた冷凍システム
WO1997021792A1 (fr) * 1995-12-12 1997-06-19 New Japan Chemical Co., Ltd. Huile lubrifiante
JPH09221690A (ja) * 1995-12-12 1997-08-26 New Japan Chem Co Ltd 冷凍機用潤滑油

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002008367A1 (fr) * 2000-07-24 2002-01-31 Nippon Oil Corporation Composition a base d'huile pour machine frigorifique
WO2002008365A1 (fr) * 2000-07-24 2002-01-31 Nippon Oil Corporation Composition a base d'huile pour machine frigorifique
US6831045B2 (en) 2000-07-24 2004-12-14 Nippon Oil Corporation Refrigerating machine oil composition
US7045490B2 (en) 2000-07-24 2006-05-16 Nippon Oil Corporation Refrigerating machine oil composition

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