WO2008041492A1 - Lubrifiant pour machine frigorigène à compression et appareil frigorigène utilisant celui-ci - Google Patents
Lubrifiant pour machine frigorigène à compression et appareil frigorigène utilisant celui-ci Download PDFInfo
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- WO2008041492A1 WO2008041492A1 PCT/JP2007/068279 JP2007068279W WO2008041492A1 WO 2008041492 A1 WO2008041492 A1 WO 2008041492A1 JP 2007068279 W JP2007068279 W JP 2007068279W WO 2008041492 A1 WO2008041492 A1 WO 2008041492A1
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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
- 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
- C10M107/22—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M107/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol, aldehyde, ketonic, ether, ketal or acetal radical
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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
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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
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol, aldehyde, ketonic, ether, ketal or acetal radical
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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- 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
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
- C10M2209/043—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical used as base material
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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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/14—Containing carbon-to-nitrogen double bounds, e.g. guanidines, hydrazones, semicarbazones
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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
- 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
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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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/02—Unspecified siloxanes; Silicones
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/011—Cloud point
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/09—Characteristics associated with water
- C10N2020/097—Refrigerants
- C10N2020/106—Containing Carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/66—Hydrolytic stability
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
Definitions
- the present invention relates to a lubricating oil for a compression type refrigerator, and more particularly relates to a lubricating oil for a compression type refrigerator using a natural refrigerant and a refrigeration apparatus using the same.
- CFC black opening fluorocarbon
- HCFC noise rotaloro fluorocarbon
- a compression refrigerator is composed of at least a compressor, a condenser, an expansion mechanism (such as an expansion valve), and a vaporizer.
- the mixture of refrigeration oil and refrigerant, which is oil, circulates in this sealed system.
- the force depends on the type of equipment. Generally, the temperature inside the compressor is high and the temperature inside the cooler is low, so the refrigerant and lubricating oil range from low to high! /, Temperature range It is necessary to circulate in this system without phase separation within it.
- the temperature range where the refrigerant and lubricating oil are compatible without phase separation is preferably in the range of 20 ° C or lower to 0 ° C or higher, especially on the high temperature side is 10 ° C or higher. preferable. If phase separation occurs during the operation of the refrigerator, the life and efficiency of the equipment will be significantly affected.
- phase separation of refrigerant and lubricating oil occurs in the compressor part, the moving part will be poorly lubricated, causing seizure, etc., which will significantly shorten the life of the device, while phase separation will occur in the evaporator, Due to the presence of lubricating oil with high viscosity, the efficiency of heat exchange is reduced.
- the lubricating oil for the compression type refrigerator is used for the purpose of lubricating the movable part of the refrigerator, the lubricating performance is naturally important.
- Lubricating oil viscosity (kinematic viscosity) at 100 ° C is preferably 1 to 50 mm 2 / s, especially 5 to 20 mm 2 / s! / ⁇ .
- the pour point is ⁇ 20 ° C., preferably ⁇ 30 ° C. or less, more preferably ⁇ 40 ° C. or less, and the viscosity index is at least 80 or more, preferably 100 or more, more preferably 120 or more.
- refrigerating machine oil is required to have various properties such as lubricity and hydrolysis stability in addition to refrigerant compatibility and low temperature fluidity.
- the conventional PAG refrigerating machine oil is compatible in a composition having a low ratio of carbon dioxide refrigerant, the compatible region is not necessarily sufficient. Therefore, there is a method to lower the viscosity of PAG in order to obtain sufficient refrigerant compatibility for such refrigeration oil. In that case, when lubricity and stability become insufficient, Vicious cycles are likely to occur.
- Patent Document 1 Japanese Patent Laid-Open No. 10-46169
- the present invention has been accomplished under such circumstances, and is compatible with a natural refrigerant, particularly in a carbon dioxide atmosphere, has a high viscosity index, and is excellent in stability.
- An object of the present invention is to provide a lubricating oil for a compression type refrigerator that does not deteriorate and deteriorate due to hydrolysis, and a refrigeration apparatus using the lubricating oil.
- the present inventors mainly comprise an ether compound having a specific structure and a dehydrating agent. It has been found that the above-mentioned problems can be solved by lubricating oil.
- the present invention provides:
- Lubricating oil for a compression type refrigerator comprising
- a lubricating oil for a compression refrigeration machine characterized by comprising a base and
- Consisting of a compressed refrigerant circulation system for a natural refrigerant comprising at least a compressor, a condenser, an expansion mechanism, and an evaporator, and the natural refrigerant and the lubricating oil for the compression type refrigerator described in 1 or 2 above Refrigeration apparatus characterized by using
- the lubricating oil of the present invention is excellent in compatibility with a natural refrigerant as a refrigerant, has excellent lubrication performance and stability, and does not deteriorate due to hydrolysis. Used as lubricating oil for type refrigerators.
- the lubricating oil of the present invention can be used as a lubricating oil for a compression refrigeration machine for a mixed refrigerant of a natural refrigerant such as a carbon dioxide refrigerant.
- lubricating oils for compression refrigerators for example, ester compounds, polycarbonate compounds, mineral oils, alkylbenzenes, polyalphaolefins and the like.
- FIG. 1 is a longitudinal sectional view of an essential part of an example of a compression refrigerator in a refrigeration apparatus of the present invention.
- the lubricating oil for a compression refrigerator of the present invention (hereinafter sometimes simply referred to as a lubricating oil) has two modes, that is,
- a lubricating oil II characterized in that it contains at least one force s of a compound, an alkylene glycol residue or a polyoxyalkylene glycol residue
- examples of the lubricating oil satisfying the lubricating oil I or II include those containing the following polybutyl ether compounds 1 to 4.
- Polybule ether compound 1 has the general formula (I)
- R 1 , R 2 and R 3 each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different from each other.
- R b is a divalent having 2 to 4 carbon atoms.
- a hydrocarbon group is a hydrogen atom, an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, an aromatic group optionally having a substituent having 1 to 20 carbon atoms, an acyl having 2 to 20 carbon atoms Group or acid having 2 to 50 carbon atoms
- Element-containing hydrocarbon group R 4 represents a hydrocarbon group having 1 to 10 carbon atoms, and R a , R b , and R 4 may be the same or different when there are a plurality of them m is an average of 1 to 50, k is !! to 50, p is a number from 0 to 50, k and p are
- the hydrocarbon group with ⁇ ! ⁇ 8 specifically includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group , tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl alkyl groups, cyclopentyl group, cyclohexyl group, various methylcyclohexyl groups, various ethylcyclohexyl groups, various types It represents a cycloalkyl group such as dimethylcyclohexyl group, a phenyl group, various methylphenyl groups, various ethenylphenyl groups, an aryl group of various dimethylphenyl groups, a benzyl group, various phenylethyl groups, or an arylalkyl group of various methylbenzy
- R 2 and R 3 a hydrogen atom is particularly preferable.
- the divalent hydrocarbon group having 2 to 4 carbon atoms represented by R b is specifically a divalent alkylene group such as a methylene group, an ethylene group, a propylene group, a trimethylene group or various butylene groups. There is.
- m represents the number of repeats of R b O, and the average value thereof is;! To 50, preferably 2 to 20, more preferably 2 to 10, particularly preferably 2 to 5. The number of ranges.
- R b O When R b O is plural, plural R b O may be the same or different.
- kttl ⁇ 50 preferably (ma;! ⁇ 10, more preferably (ma;! ⁇ 2, more preferably (ma 1, pi m 0 ⁇ 50, preferably 2 ⁇ 25, more preferably 5 ⁇
- a number of 15 and k and p are preferably an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms among them, preferably an alkyl group having 1 to 10 carbon atoms or 5 to 5 carbon atoms; 10 cycloalkyl groups, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups Groups, various hexyl groups, Various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, cyclopentyl groups, cyclohexyl groups, various
- the aromatic group optionally having a substituent having 1 to 20 carbon atoms is specifically a phenyl group, various tolyl groups, various ethylphenyl groups, various xylyl groups, various trimethylenophenyl groups.
- aryl groups such as various butylphenyl groups and various naphthyl groups, benzyl groups, various phenylethyl groups, various methylbenzyl groups, various phenylpropyl groups, and arylalkyl groups such as various phenylbutyl groups.
- examples of the acyl group having 2 to 20 carbon atoms include acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, bivaloyl group, benzoyl group, and toluoyl group.
- oxygen-containing hydrocarbon group having 2 to 50 carbon atoms include: methoxymethyl group, methoxyethyl group, methoxypropyl group, 1,1 bismethoxypropyl group, 1,2 bismethoxypropyl group, ethoxypropyl Preferred examples include a group, (2-methoxyethoxy) propyl group, (1-methyl-2-methoxy) propyl group and the like.
- the hydrocarbon group represented by R 4 ;! -10 is specifically a methino group, an ethyl group, an n propyl group, an isopropyl group, an n butynole group.
- Cycloyl group such as xyl group, various pro-propyl cyclohexyl groups, various dimethyl cyclohexyl groups, phenyl group, various methyl phenyl groups, various ethenyl phenyl groups, various dimethyl phenyl groups, various propyl phenyl groups, various trimethyl
- ⁇ , R a , R b and m and I ⁇ to R 4 may be the same or different for each structural unit.
- the polybutyl ether compound 1 is, for example, represented by the general formula (VI) [0022] [Chemical 2]
- R a , R b, m and I ⁇ to R 4 are as described above.
- Specific examples of the alkylene glycol compound and the polyoxyalkylene glycol compound include ethylene glycol, ethylene glycol monomethyl ether, diethylene glycolone, diethyleneglycol monomethinoethylenoate, triethyleneglycolanol, triethyleneglycolenomonomonomethylol.
- Anoleylene glycols such as etherenole, propylene glycolenole, propyleneglycolenomonoethyleneenore, dipropyleneglycolenole, dipropyleneglycolenomonomonochinenoreatenore, tripropyleneglycolenole, tripropyleneglycolenomonomonoethylenotenole, and poly Examples thereof include oxyalkylene glycol and monoether compounds thereof.
- examples of the butyl ether compound represented by the general formula (VII) include, for example, Vininoremethinoreethenore, Vininoreethinoreethenore, Vininole npropinorethenore, Vinyletenole, such as Noleyatenore, Vininole n Butinoleethenole, Vininole Isobutinole Iter, Vinyl-sec butyl ether, Vinyl-tert butyl ether, Vininole n Pentinoleate nore, Vininole n Hexinoleatenore, etc.
- butyl ether monomers can be produced by a known method.
- Polybule ether compound 2 has the general formula ( ⁇ )
- R d and R f are alkylene groups having 2 to 4 carbon atoms, a and e are 0 to 50 in average, c is an integer of!
- R e is a hydrogen atom, 1 to carbon atoms;
- R 5 , R 6 and R 7 each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different, and R 8 has 1 carbon atom
- R 9 is a hydrogen atom; carbon number;!
- n is an average value of 0 to
- R 5 to R 9 may be the same for each structural unit or different for each structural unit. 8 when ⁇ there are a plurality, the plurality of R 8 ⁇ may be the same or different.
- n in the structural unit A represents an integer of 1 or more.
- the alkyl group of 10 for example, a methyl group, E Ji Le group, n- propyl group, an isopropyl group, n- Buchinore group, an isobutyl group, various pentyl groups, the various Xyl group, various heptyl groups, various octyl groups, various nonyl groups, various decinole alkyl groups, cyclopentyl group, cyclohexyl group, various methyl cyclohexyl groups, various ethyl cyclohexyl groups, various propyl cyclohexyl groups
- the acyl group having 2 to 10 carbon atoms include acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, bivaloyl group, benzoyl group, and toluoyl. Examples include groups.
- hydrocarbon groups having 1 to 10 carbon atoms having 2 to 6 bonding parts for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, Residues obtained by removing the hydroxyl groups of polyhydric alcohols such as neopentinoleglycolanol, trimethylololeane, trimethylolpropane, glycerin, ditrimethylolpropane, diglycerin, pentaerythritol, dipentaerythritol, sorbitol, etc.
- the power to raise S for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, Residues obtained by removing the hydroxyl groups of polyhydric alcohols such as neopentinoleglycolanol, trimethylololeane, trimethylolpropane, glycerin, ditrimethylol
- Examples of the alkylene group having 2 to 4 carbon atoms represented by R d include an ethylene group, a propylene group, a trimethylene group, and various butylene groups.
- the hydrocarbon group having 1 to 8 carbon atoms includes, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Isobutyl group, various Pentyl group, various hexyl groups, various heptyl groups, various octyl groups and other alkyl groups, cyclopentyl group, cyclohexyl group, various methyl cyclohexyl groups, various ethyl cyclohexyl groups, various dimethyl cyclohexyl groups and other cyclo groups
- Examples include alkyl groups, phenyl groups, various methylphenyl groups, various ethylphenyl groups, arylenoic groups such as various dimethylphenyl groups, and arylalkyl groups such as benzyl group, various phenyl groups, and various methylbenzy
- Each of R 6 and R 7 is particularly preferably a hydrogen atom.
- divalent hydrocarbon group having 1 to 10 carbon atoms in R 8 include a methylene group, an ethylene group, a phenylethylene group, a 1,2-propylene group, and a 2-phenyl group.
- Bivalent such as 2-ru 1, 2-propylene group, 1,3-propylene group, various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, various octylene groups, various nonylene groups, various decylene groups, etc.
- An alicyclic group having two bonding sites to an alicyclic hydrocarbon such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, and propylcyclohexane;
- Divalent aromatic hydrocarbon groups such as dilene groups, various methylphenylene groups, various ethenylphenols, various dimethylphenylene groups, and various naphthylene groups: toluene, xylene, ethylbenzene, etc.
- Alkyl aromatic groups having a monovalent binding site on each of the alkyl group and aromatic part of the alkyl aromatic hydrocarbon; a bonding site on the alkyl group of a polyalkyl aromatic hydrocarbon such as xylene or jetylbenzene And alkyl aromatic groups.
- aliphatic groups having 2 to 4 carbon atoms are particularly preferred.
- divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms in R 8 include methoxymethylene group, methoxyethylene group, methoxymethylethylene group, 1, 1 bismethoxymethyl.
- Preferred examples include an ethylene group, 1,2-bismethoxymethylethylene group, ethoxymethylethylene group, (2-methoxyethoxy) methylethylene group, (1-methyl-2-methoxy) methylethylene group, and the like.
- the hydrocarbon group having 1 to 20 carbon atoms of R 9 specifically includes methyl group, ethyl group, n propyl group, isopropyl group, n butyl group, isobutyl group, sec butyl group.
- Group tert butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various groups Such as alkyl groups such as octyl group, various nonyl groups, various decyl groups, cyclopentyl group, cyclohexyl group, various methyl cyclohexyl groups, various ethyl cyclohexyl groups, various propyl cyclohexyl groups, various dimethyl cyclohexyl groups, etc.
- alkyl groups such as octyl group, various nonyl groups, various decyl groups, cyclopentyl group, cyclohexyl group, various methyl cyclohexyl groups, various ethyl cyclohexyl groups, various propyl cyclohexyl groups, various dimethyl cyclohexyl groups, etc.
- Cycloalkyl groups phenyl groups, various methylphenyl groups, various ethenylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, various naphthyl groups, benzyl groups, Examples include arylalkyl groups such as various phenyl groups, various methyl benzyl groups, various phenyl propyl groups, and various phenyl butyl groups.
- R 5 to R 7 are both hydrogen atoms, n is an average value of 0 to 4 , any one is 1 or more, and R 8 is a hydrocarbon group having 2 to 4 carbon atoms. Some are preferred.
- Polybule ether compound 3 has the general formula (IV)
- R d , R f , A, a, b, d and e are the same as those in the general formula (II), and is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms; 1 to 10; an alkoxy group having 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms having 2 to 6 bonding parts.
- OR d and / or OR f and A may be random or block.
- n in the structural unit A represents an integer of 1 or more.
- Examples of the alkylene group having 2 to 4 carbon atoms represented by R f include an ethylene group, a propylene group, a trimethylene group, and various butylene groups.
- the alkyl group having 1 to 10 carbon atoms, the carbon number 2 to 2; the 10 acyl group and the 2 to 6 carbon atoms having 1 to 6 carbon atoms as the hydrocarbon group in the general formula (II) Description Examples thereof include the same groups as those exemplified in.
- 1 to the number of carbon atoms of; the alkoxy groups of 10, may include the same groups as exemplified in the description of R e in the general formula ([pi).
- R 5 to R 7 are both hydrogen atoms, n is an average value of 0 to 4 , any one is 1 or more, and R 8 is a hydrocarbon group having 2 to 4 carbon atoms. Some are preferred.
- the polybutyl ether compound 4 comprises (a) the structural unit represented by the general formula (III), and (b) the general formula (V).
- R 1Q to R 13 each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, their these are Yogu also R 1Q even different from one another identical ⁇ R 13 may be the same or different for each structural unit.
- examples of the hydrocarbon group having 1 to 20 carbon atoms out of R 1Q to R 13 include the same groups as those exemplified in the description of R 9 in the general formula (III).
- the polybutyl ether compound 4 is, for example, represented by the general formula (VIII)
- Examples of the butyl ether monomer represented by the general formula (VIII) include butyl methyl ethere, vinyleno ethinore etherenore, vinylinole n propino ree enore, vinylinole isopropino reeenore, vinino butino ree enore, vinore isobutinole.
- butyl ether monomers can be produced by known methods.
- examples of the hydrocarbon monomer having an olefinic double bond represented by the general formula (IX) include, for example, ethylene, propylene, various butenes, various pentenes, various hexenes, various heptenes, various otatense, diene.
- examples include isobutylene, triisobutylene, styrene, and various alkyl-substituted styrenes.
- the burether compounds 1 to 4 include radical polymerization, cation polymerization, radiation polymerization, and the like of the corresponding burether compound and a hydrocarbon monomer having an olefinic double bond that is optionally used.
- a butyl ether monomer can be polymerized using the method shown below to obtain a polymer having a desired viscosity.
- Bronsted acids include hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydrofluoric acid, nitric acid, sulfuric acid, trichloroacetic acid, trifluoroacetic acid and the like.
- Lewis acids examples include boron trifluoride, aluminum trichloride, aluminum tribromide, tin tetrachloride, zinc dichloride, ferric chloride and the like.
- Boron trifluoride is preferred.
- organometallic compound examples include jetyl aluminum chloride, ethyl ether chloride, and jetyl zinc.
- alcohols for example, methanol, ethanol, propanol, iso Carbon number such as propanol, butanol, isobutanol, sec-butanol, tert-butanol, various pentanols, various hexanols, various heptanols, various octanols, etc. Carbon number of 1 to 20 saturated aliphatic alcohols, aryl alcohols, etc.
- unsaturated fatty alcohols ethylene glycol monomethyl ether, diethylene glycol monole monomethylenoatenore, triethyleneglycolenomonomonochinenoatenore, propylene glycol monomonomethinoatenore, dipropylene glycolenolemono
- alkylene glycols such as methylenoatenole and tripropylene glycol monomethyl ether.
- carboxylic acids when using adducts of butyl ethers and carboxylic acids include acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, 2-methylbutyric acid, and bivalin.
- Acid n-power pro-acid, 2, 2-dimethylbutyric acid, 2-methylvaleric acid, 3-methylvaleric acid, 4-methylvaleric acid, enanthic acid, 2-methylcaproic acid, power prillic acid, 2-ethylcaproic acid 2-n-propylvaleric acid, n-nonanoic acid, 3,5,5-trimethylcaproic acid, strong prillic acid and undecanoic acid.
- the bur ether may be the same as that used for polymerization! / May be different! /.
- This adduct of butyl ether and the carboxylic acid is obtained by mixing the two and reacting them at a temperature of about 0 to 100 ° C, and can be separated by distillation and used for the reaction. It can also be used in the reaction without separation.
- the polymerization initiation terminal of the polymer is that hydrogen is bound when water, alcohols, or phenols are used, and hydrogen or one of the alkoxy groups is eliminated from the used acetals when acetals are used. Become.
- the terminal of the polymer thus obtained can be converted into a desired group by a known method.
- residues of saturated hydrocarbons, ethers and alcohols which can include residues of saturated hydrocarbons, ethers, alcohols, ketones, nitriles, amides and the like are preferable.
- the polymerization of the butyl ether monomer represented by the general formula (VIII) can be initiated between 80 ° C and 150 ° C, usually depending on the raw material and the type of initiator. It can be carried out at a temperature in the range of 80-50 ° C.
- the polymerization reaction is completed in about 10 seconds to 10 hours after the start of the reaction.
- a polymer having a low average molecular weight can be obtained by increasing the amount of the Bronsted acids or Lewis acids.
- This polymerization reaction is usually performed in the presence of a solvent.
- the solvent is not particularly limited as long as it dissolves a necessary amount of the reaction raw material and is inert to the reaction.
- hydrocarbons such as hexane, benzene, toluene, and ethyl ether, 1, Ether type solvents such as 2-dimethoxyethane and tetrahydrofuran can be preferably used.
- This polymerization reaction can be stopped by adding an alkali.
- the desired poly (bureurether) compound can be obtained by applying a conventional separation / purification method as necessary.
- the polybule ether compound contained in each of the lubricating oils I and II of the present invention preferably has a carbon / oxygen molar ratio of 4 or less. When this molar ratio exceeds 4, carbon dioxide Compatibility with natural natural refrigerants is reduced.
- the carbon / oxygen molar ratio of the raw material monomer is adjusted.
- a polymer having the molar ratio within the above range can be produced.
- the carbon / oxygen molar ratio can be adjusted by adding water, alcohols, phenols, acetals, and bull ethers and carboxylic acids used as initiators as shown in the above-mentioned polymerization method of the bull ether monomers. It is also possible by combining the product with monomers.
- the carbon / oxygen molar ratio is larger than the monomer to be polymerized! /
- Alcohols, phenols, etc. are used as initiators, a polymer with a larger carbon / oxygen molar ratio than the raw material monomer can be obtained, while By using alcohols with a low carbon / oxygen molar ratio, a polymer with a lower carbon / oxygen molar ratio than the starting monomer can be obtained.
- a polymer having a carbon / oxygen molar ratio larger than the carbon / oxygen molar ratio of the butyl ether monomer is obtained.
- the ratio and the ratio of the obtained mosquito can be adjusted by the ratio of the hydrocarbon monomer having an olefinic double bond to be used and the number of carbon atoms.
- the lubricating oil for a compression-type refrigerator of the present invention preferably contains the polybutyl ether compound in an amount of 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more. Contains 100% by mass.
- butyl ether compound one kind may be used alone, or two or more kinds may be used in combination.
- the kinematic viscosity before mixing with the refrigerant is preferably 1 to 50 mm 2 / s at 100 ° C., particularly preferably 5 to 25 mm 2 / s.
- the viscosity index is preferably 80 or more, more preferably 90 or more, and still more preferably 100. That's it.
- the lubricating oil of the present invention preferably has a carbon / oxygen molar ratio of 4 or less, and if this molar ratio exceeds 4, the compatibility with carbon dioxide decreases.
- the lubricating oil for a compression refrigerator of the present invention contains a dehydrating agent.
- Examples of the dehydrating agent include compounds having a carpositimide group, and also include polycarposimide compounds having one or more carposimide groups in the molecule.
- a carbodiimide compound having an aliphatic hydrocarbon group, particularly an alicyclic hydrocarbon group or an aromatic hydrocarbon group is preferred.
- Specific examples of the compound having a carpositimide group include N, N′-dimethylcarposimidium.
- N'-dihexyl carpositimide N, N'-dioctyl carpoimide, N, N'-diotadecyl carpoimide, N, N'-dicyclohexyl carpositimide, N, N'-diphenol Examples include force-repository imide, N, N, mononaphthenorecanolepositimide, N, N, mono-isopropylenophenol force-repository imide, and the like.
- the amount of dehydrating agent, in The lubricating oil of the present invention usually, 0.00;! ⁇ 5 mass 0/0, preferably 0. 005 ⁇ ;! mass 0/0, more preferably is 0.5 01-0. 5 mass 0/0.
- the amount of the dehydrating agent is within the above range, the stability is particularly good and there is no deterioration due to hydrolysis.
- the lubricating oil for compression type refrigerators of the present invention includes various commonly used additives, for example, load-resistant additives exemplified below, extreme pressure agents, oiliness other than the dehydrating agent of the present invention.
- Lubricant improvers such as agents, antioxidants, metal deactivators, detergent dispersants, viscosity index improvers, antifungal agents, corrosion inhibitors, pour point depressants, antifoaming agents, etc. as appropriate Can be added.
- Examples of the lubricity improver include monosulfides, polysulfides, sulfoxides, sulfones, thiosulfinates, sulfurized fats and oils, thiocarbonates, thiophenes, thiazoles, methanesulfonic acid esters, and the like.
- Organic sulfur compounds of the above fatty acid esters such as higher fatty acids, hydroxyaryl fatty acids, polyhydric alcohol esters, carboxylic acid-containing polyhydric alcohol esters, and acrylate esters; chlorinated hydrocarbons , Organic chlorinated derivatives such as chlorinated carboxylic acid derivatives; organic fluorinated products such as fluorinated aliphatic carboxylic acids, fluorinated ethylene resins, fluorinated alkylpolysiloxanes, fluorinated graphite; higher alcohols, etc.
- Alcohol-based products metal salts of fatty acids, metal salts of naphthenic acid (alkali metal naphthenate, lead naphthenate, iron naphthenate), thiocarbamates, organomolybdenum compounds, organotin compounds, organogermanium compounds, Metal compounds such as boric acid esters can be used.
- metal salts of fatty acids metal salts of naphthenic acid (alkali metal naphthenate, lead naphthenate, iron naphthenate), thiocarbamates, organomolybdenum compounds, organotin compounds, organogermanium compounds, Metal compounds such as boric acid esters can be used.
- antioxidant phenols (2, 6 ditertiary butyl-p cresol), aromatic amines ( ⁇ -naphthylamine) and the like can be used.
- metal deactivators examples include benzotriazole derivatives.
- Antifoaming agents include silicone oil (dimethylpolysiloxane) and polymetatalylates.
- detergent dispersant sulfonates, phenates, succinimides and the like can be used.
- polymetatalylate polyisobutylene, ethylene-propylene copolymer, styrene-hydrogenated copolymer, and the like can be used.
- the amount of these additives is usually about 0.001 to 5% by mass in the lubricating oil for a compression refrigerator of the present invention.
- the lubricating oil of the present invention is suitable for natural refrigerants.
- natural refrigerants include carbon dioxide (carbon dioxide) refrigerant, ammonia refrigerant, and hydrocarbon refrigerant.
- hydrocarbon refrigerants isobutane, normal butane, propane, or a mixture of these can be used.
- the lubricating oil of the present invention is particularly suitably used as a lubricating oil for a carbon dioxide compression refrigerant circulation system because it has excellent compatibility with a carbon dioxide refrigerant and is excellent in lubricating performance.
- a mixed refrigerant of each of the above natural refrigerants, various HFC refrigerants and the above natural refrigerant alone or a mixture thereof, the above natural refrigerant and an HFC refrigerant, a fluorine-containing ether refrigerant, a non-fluorine-containing ether such as dimethyl ether Also used in mixed refrigerants with system refrigerants Let's go out.
- examples of the HFC refrigerant include R134a, R410A, R404A, and R407C.
- the refrigeration apparatus of the present invention requires at least a compressor, a condenser, an expansion mechanism (such as an expansion valve) and an evaporator, or a compressor, a condenser, an expansion mechanism, a dryer, and an evaporator.
- the above-described lubricating oil of the present invention is preferably used as a natural refrigerant such as carbon dioxide and lubricating oil (refrigeration machine oil).
- a desiccant composed of zeolite having a pore diameter of 3.5 A or less.
- zeolite examples include natural zeolite and synthetic zeolite.
- the refrigeration apparatus of the present invention constitutes a circulation system as a refrigeration cycle of the refrigeration apparatus, and is of an internal high pressure type or an internal low pressure type in which a compressor and an electric motor are covered in one cover. It is a hermetic compressor, or an open type compressor, a semi-hermetic type compressor, and a canned motor type compressor, in which the drive unit of the compressor is outside.
- the winding force of the stator of the motor (motor) core wire is coated with enamel having a glass transition temperature of 130 ° C or higher, or the enamel wire is glass transition temperature 50 °. Those fixed with a varnish of C or higher are preferred.
- this enamel coating has a single layer of polyesterimide, polyimide, polyamide or polyamideimide! /, Preferably a composite layer! /.
- the enamel coating which has a lower glass transition temperature as the lower layer and a higher glass transition temperature as the upper layer, is excellent in water resistance, softening resistance, and swelling resistance, as well as mechanical strength, rigidity, and insulation. Its practical value is high.
- Lum is preferably made of a crystalline plastic film having a glass transition temperature of 60 ° C or higher.
- this crystalline plastic film is suitable as an oligomer content of 5 mass 0/0 or less.
- Examples of such a crystalline plastic having a glass transition temperature of 60 ° C or higher include polyethylene nitrile, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyether ether ketone, polyethylene naphthalate, polyamide imide, and polyimide. The ability to list it as a suitable one.
- the motor insulating film may be composed of a single layer of the above-mentioned crystalline plastic film, or may be a composite film in which a plastic layer having a high glass transition temperature is coated on a film having a low glass transition temperature. it can.
- the force capable of disposing the vibration isolating rubber material inside the compressor is acrylonitrile monobutadiene rubber (NBR), ethylene-propylene mono Those selected from Gen-based rubber (EPDM, EPM), hydrogenated talylonitrile tributadiene rubber (HNBR), silicone rubber and fluoro rubber (FKM) are preferably used, and the rubber swelling rate is especially 10% by mass.
- NBR acrylonitrile monobutadiene rubber
- EPDM, EPM Gen-based rubber
- HNBR hydrogenated talylonitrile tributadiene rubber
- FKM fluoro rubber
- various organic materials for example, lead wire covering material, binding yarn, enameled wire, insulating film, etc.
- the organic material those having a tensile strength reduction rate of 20% or less are preferably used.
- the swelling rate of the gasket in the compressor is 20% or less.
- FIG. 1 is a longitudinal sectional view of an essential part of an example of a hermetic twin rotary compressor that is a kind of the refrigeration apparatus of the present invention, in which a motor part is arranged in an upper stage in a case 1 that is a hermetic container also serving as an oil reservoir. (Electric motor part), the compressor part is accommodated in the lower stage.
- the motor part is a stator ( Stator) 2 and motor rotor (rotor) 3, and rotating shaft 4 is fitted to motor rotor 3.
- the winding portion 5 of the stator 2 is usually covered with an enameled wire at the core, and an electric insulating film is attached between the core portion and the winding portion of the stator 2.
- the compressor section is composed of two compression chambers, an upper compression chamber 6 and a lower compression chamber 7.
- compressed refrigerant gas is alternately discharged from the upper and lower compression chambers 6, 7 with a phase difference of 180 degrees.
- a cylindrical rotary piston is driven by a crank fitted inside, and rotates eccentrically in contact with one point of the cylinder wall surface.
- the blade is pressed by a spring and reciprocates so that the tip always touches the rotating piston.
- the rotary piston rotates eccentrically, the volume in one of the two spaces divided by the blades decreases, and the refrigerant gas is compressed.
- the valve provided on the bearing flange surface opens and the refrigerant gas is discharged outside.
- the open type compressor includes a car air conditioner
- the semi-hermetic type compressor includes a high-speed multi-cylinder compressor
- the canned motor type compressor includes an ammonia compressor
- a 2 L volume autoclave made of SUS316L was charged with 6 g of nickel diatomaceous earth catalyst (trade name Ni l 3 manufactured by JGC Chemical Co., Ltd.) and 300 g of isooctane. After the atmosphere in the autoclave was replaced with nitrogen, and then replaced with hydrogen, the temperature was raised to 3. OMPaG, maintained at 140 ° C for 30 minutes, and then cooled to room temperature.
- Ni l 3 manufactured by JGC Chemical Co., Ltd.
- the kinematic viscosity of this crude product was 79.97 mm 2 / s at 40 ° C and 9. 380 mm 2 / s at 100 ° C.
- the inside of the autoclave was purged with nitrogen and then purged with hydrogen, and then the temperature was raised to a hydrogen pressure of 3. OMPaG.
- the filtrate was treated with a rotary evaporator under reduced pressure to remove the solvent and light components, and base oil 1 was obtained.
- the yield was 88.5g.
- the average value), the calculated molecular weight is 940.
- the carbon / oxygen molar ratio is 3 ⁇ 64.
- the carbon / oxygen molar ratio is 3.77.
- a 1 L glass separable flask was charged with 60.5 g of toluene, 25.0 g (1.52 ⁇ 10-imol) of triethylene glycol monomethyl ether and 0 g of boron trifluoride jetyl ether complex GI-LS.
- the kinematic viscosity of this crude product was 81.98 mm 2 / s at 40 ° C. and 9 ⁇ 679 mm 2 / s at 100 ° C.
- the catalyst-containing autoclave prepared in Catalyst Preparation Example 1 was opened, and the liquid layer Was removed with decantation, and then 300 g of isooctane and lOOg of the above crude product were added.
- the carbon / oxygen molar ratio is 3.60.
- a 1 L glass separable flask was charged with 60.5 g of isooctane, 51 ⁇ 6 g (2.50 ⁇ 10—imol) of tripropylene glycol monomethyl ether, and 0.296 g of boron trifluoride jetyl ether complex.
- the kinematic viscosity of the crude product was 9 ⁇ 755mm 2 / s at 83. 13mm 2 / s 100 ° C at 40 ° C was then opened entering the catalyst autoclave prepared in Catalyst Preparation Example 1, a liquid layer was removed by decantation, and then 300 g of isooctane and 100 g of the above crude product were added.
- the carbon / oxygen molar ratio is 3.71.
- the flask was placed in an ice-water bath and the reaction solution was kept at 25 ° C. After completion of the reaction, the reaction solution was transferred to a 1 L separatory funnel, and 10% by mass aqueous sodium hydroxide solution was added until the reaction solution became alkaline.
- reaction solution was transferred to a 1L eggplant-shaped flask, and ion exchange resin was added and stirred to neutral.
- the filtrate was treated with a rotary evaporator under reduced pressure to remove the solvent and light components, and base oil 5 was obtained.
- the yield was 57.3g.
- the kinematic viscosity of the crude product was 8 ⁇ 991mm 2 / s at 67. 23mm 2 / s, 100 ° C at 40 ° C was then opened entering the catalyst autoclave prepared in Catalyst Preparation Example 1, the liquid After removing the layer by decantation, 300 g of isooctane and the above crude lOOg were added.
- the carbon / oxygen molar ratio is 3.662.
- the kinematic viscosity of the crude product was 10. 50 mm 2 / s at 81. 59mm 2 / s, 100 ° C at 40 ° C was then opened entering the catalyst autoclave prepared in Catalyst Preparation Example 1, the liquid After removing the layer with decantation, 300 g of isooctane and 100 g of the above crude product were added.
- the carbon / oxygen molar ratio is 3.660.
- a 1 L glass separable flask was charged with 60.5 g of isooctane, 70.0 g (l.79X10-imol) of polypropylene glycol monomethyl ether (average molecular weight of about 390) and 0.218 g of boron trifluoride jetyl ether complex.
- the carbon / oxygen molar ratio is 3 ⁇ 50.
- a 1 L glass separable flask was charged with 60.5 g of isooctane, 70.0 g (l.59X10-imol) of polypropylene glycol monomethyl ether (average molecular weight of about 440) and 0.189 g of boron trifluoride jetyl ether complex.
- Kinematic viscosity of the crude product was 10.75mm 2 / s at 40 ° C at 75.63mm 2 / s, 100 ° C
- the catalyst-containing autoclave prepared in Catalyst Preparation Example 1 was opened, the liquid layer was removed with decantation, and then 300 g of isooctane and lOOg of the above crude product were added.
- the carbon / oxygen molar ratio is 3 ⁇ 51.
- the carbon / oxygen molar ratio is 3.78.
- the kinematic viscosity of the crude product is then a which was 40 ° C at 138.2mm 2 / s, 100 ° C at 15.61mm 2 / s, a catalyst-containing autoclave prepared in Catalyst Preparation Example 1 was opened and a liquid layer After removal with decantation, 300 g of isooctane and the above crude product lOOg were added.
- the carbon / oxygen molar ratio is 3.558.
- a 1 L glass separable flask was charged with 60.5 g of isooctane, 76.6 g (l.20 ⁇ 10-imol) of polypropylene glycol monomethyl ether (average molecular weight of about 640) and 0.148 g of boron trifluoride jetyl ether complex.
- the kinematic viscosity of this crude product was 152. ImmVs at 40 ° C and 18.36 mm 2 / s at 100 ° C.
- the autoclave containing the catalyst prepared in Catalyst Preparation Example 1 was opened, and the liquid layer was decanted. Then, 300 g of isooctane and lOOg of the above crude product were added.
- a 1-L glass separable flask was charged with 60.5 g of isooctane, polypropylene glycol monomethyl ether (average molecular weight of about 915), 112 ⁇ 9 g (l.23X10-imol), and 0.148 g of boron trifluoride jetyl ether complex.
- the kinematic viscosity of the crude product is then a which was 40 ° C at 121.8mm 2 / s, 100 ° C at 18.54mm 2 / s, a catalyst-containing autoclave prepared in Catalyst Preparation Example 1 was opened and a liquid layer After removal with decantation, 300 g of isooctane and the above crude product lOOg were added.
- the carbon / oxygen molar ratio is 3.31.
- a 1-L glass separable flask was charged with 60.5 g of isooctane, polypropylene glycol monomethyl ether (average molecular weight of about 1250) 149.2 g (l.19 X 10-imol) and 0.148 g of boron trifluoride jetyl ether complex. .
- the kinematic viscosity of the crude product is then a which was 40 ° C at 121.5mm 2 / s, 100 ° C at 20.88mm 2 / s, a catalyst-containing autoclave prepared in Catalyst Preparation Example 1 was opened and a liquid layer After removing with decantation, 300 g of isooctane and 100 g of the crude product were added. After substituting the autoclave with nitrogen and then with hydrogen, a base oil 14 was obtained in the same manner as in Production Example 1. The yield was 96.2g.
- the carbon / oxygen molar ratio is 3.13.
- a 1 L glass separable flask was charged with 60.5 g of tetrahydrofuran, 25.5 g of neopentylglycol glycol (2.45 X 10-imol), and 0.579 g of a three-stained rice cake element jetinoreethenole complex.
- reaction solution was transferred to a 1 L separatory funnel, the lower layer was removed, and after washing 4 times with lOOmL of distilled water, the solvent and light components were removed under reduced pressure using a rotary evaporator to obtain 155.8 g of a crude product. It was.
- R d CHCH
- the sum of in one molecule is 8 (average)
- a l
- c l
- d 2
- the calculated molecular weight is 737.
- the filtrate was treated with a rotary evaporator under reduced pressure to remove the solvent and light components, thereby obtaining 92.3 g of a crude polybule ether having a hydroxyl group at the terminal.
- the average theoretical structural formula of the base oil 16 estimated from the charge and the final product yield is the formula (XI), and the calculated molecular weight is 932.
- the carbon / oxygen molar ratio is 3.557.
- the viscosity index was determined from the obtained kinematic viscosity.
- the lubricant is blended so that each lubricating oil is 10, 20, and 30% by mass, and the temperature is gradually raised from 50 ° C. to 20 ° C., and the temperature at which the oil is separated or clouded is increased. It was measured. In Table 1,! /, “20” indicates that no separation or cloudiness is seen at 20 ° C! /.
- Fe, Cu, and A1 are added to the autoclave as catalyst, and 50g of lubricating oil / 10g of refrigerant (carbon dioxide) and 500ppm of water are filled. After holding at 175 ° C for 30 days, oil appearance, catalyst appearance, sludge The presence / absence and acid value (mgKOH / g) were evaluated.
- Table 1 shows 100 of Examples and Comparative Examples.
- C kinematic viscosity indicates an object property value of 10 mm / S before and after the base oil. Examples;! To 9, 15, and 16 of the base oils of the present invention are all compatible with the PAG oil of Comparative Example 1 in all cases.
- base oils of the present invention are particularly suitable for lubricating oils for car air conditioners.
- Table 2 shows the physical properties of base oils having a 100 ° C kinematic viscosity of about 20 mm 2 Zs among the examples and comparative examples.
- Examples 10- The 14 base oils of the present invention are all compatible with the PAG oil of Comparative Example 2 Is good.
- base oils of the present invention are particularly suitable for lubricating oil for showcases, vending machines and water heaters.
- Antifoaming agent Silicone antifoaming agent (D 1)
- the lubricating oil of the present invention is excellent in compatibility with a natural refrigerant as a refrigerant, excellent in lubrication performance and stability, and does not deteriorate due to hydrolysis.
- the refrigeration apparatus of the present invention is a refrigeration system, an air conditioning system, a car air conditioner system, a showcase, a water heater, and a vending machine as a compression type refrigerator It can be effectively used as a compressor type refrigerator such as a refrigerator or a refrigerator.
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Description
Claims
Priority Applications (5)
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CN200780036343.1A CN101522870B (zh) | 2006-09-29 | 2007-09-20 | 压缩型冷冻机用润滑油以及使用其的冷冻装置 |
EP07807643A EP2067844A4 (en) | 2006-09-29 | 2007-09-20 | REFRIGERANT REFRIGERATING MACHINE LUBRICANT AND REFRIGERATING APPARATUS USING THE SAME |
KR1020097006456A KR101420458B1 (ko) | 2006-09-29 | 2007-09-20 | 압축형 냉동기용 윤활유 및 이것을 사용한 냉동 장치 |
JP2008537450A JP5379484B2 (ja) | 2006-09-29 | 2007-09-20 | 圧縮型冷凍機用潤滑油、及びそれを用いた冷凍装置 |
US12/443,606 US8916060B2 (en) | 2006-09-29 | 2007-09-20 | Lubricant for compression refrigerating machine and refrigerating apparatus using the same |
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JP2006-269262 | 2006-09-29 | ||
JP2006269262 | 2006-09-29 |
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PCT/JP2007/068279 WO2008041492A1 (fr) | 2006-09-29 | 2007-09-20 | Lubrifiant pour machine frigorigène à compression et appareil frigorigène utilisant celui-ci |
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US (1) | US8916060B2 (ja) |
EP (1) | EP2067844A4 (ja) |
JP (1) | JP5379484B2 (ja) |
KR (1) | KR101420458B1 (ja) |
CN (1) | CN101522870B (ja) |
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CN112088205A (zh) * | 2018-04-13 | 2020-12-15 | 株式会社Moresco | 润滑油组合物以及使用其的润滑剂 |
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JP5122740B2 (ja) * | 2005-11-15 | 2013-01-16 | 出光興産株式会社 | 冷凍機油組成物 |
US8486871B2 (en) * | 2007-03-08 | 2013-07-16 | Idemitsu Kosan Co., Ltd. | Lubricant for compression type refrigerating machine and refrigeration system using the same |
JP5759696B2 (ja) * | 2010-09-28 | 2015-08-05 | 出光興産株式会社 | 圧縮型冷凍機用潤滑油組成物 |
US8889031B2 (en) * | 2010-11-30 | 2014-11-18 | Jx Nippon Oil & Energy Corporation | Working fluid composition for refrigerator machine and refrigerating machine oil |
JP6271102B1 (ja) * | 2016-05-17 | 2018-01-31 | 三菱電機株式会社 | 冷凍サイクル装置 |
CN111925856B (zh) * | 2020-07-15 | 2023-01-10 | 珠海凌达压缩机有限公司 | 一种冷冻油组合物及其应用和压缩机 |
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- 2007-09-20 JP JP2008537450A patent/JP5379484B2/ja not_active Expired - Fee Related
- 2007-09-20 EP EP07807643A patent/EP2067844A4/en not_active Withdrawn
- 2007-09-20 WO PCT/JP2007/068279 patent/WO2008041492A1/ja active Application Filing
- 2007-09-20 KR KR1020097006456A patent/KR101420458B1/ko not_active IP Right Cessation
- 2007-09-28 TW TW096136393A patent/TWI431110B/zh not_active IP Right Cessation
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112088205A (zh) * | 2018-04-13 | 2020-12-15 | 株式会社Moresco | 润滑油组合物以及使用其的润滑剂 |
US11441093B2 (en) | 2018-04-13 | 2022-09-13 | Moresco Corporation | Lubricating oil composition and lubricating agent using same |
Also Published As
Publication number | Publication date |
---|---|
CN101522870A (zh) | 2009-09-02 |
JP5379484B2 (ja) | 2013-12-25 |
US8916060B2 (en) | 2014-12-23 |
KR20090058001A (ko) | 2009-06-08 |
US20100005830A1 (en) | 2010-01-14 |
KR101420458B1 (ko) | 2014-07-16 |
TW200831663A (en) | 2008-08-01 |
EP2067844A4 (en) | 2011-05-04 |
EP2067844A1 (en) | 2009-06-10 |
TWI431110B (zh) | 2014-03-21 |
JPWO2008041492A1 (ja) | 2010-02-04 |
CN101522870B (zh) | 2014-02-12 |
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