RU2454453C2 - Refrigerator oil and refrigerator hydraulic fluid composition - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to refrigerator hydraulic fluid composition, characterised by that it contains refrigerator oil which contains an ester of at least one polyatomic alcohol selected from pentaerythritol and dipentaerythritol, and a fatty acid containing 50-100 mol % C₅-C₉ fatty acid, at least 30 mol % C₅-C₉ branched fatty acid and not more than 40 mol % C₅ or lower fatty acid with a straight chain, where content of the ester is at least 80 wt % per total weight of the refrigerator oil, and fluoropropene coolant and/or trifluoroiodomethane coolant. The invention also relates to refrigerator oil which is characterised by that it contains said ester and fluoropropene coolant and/or trifluoroiodomethane coolant.

EFFECT: refrigerator oil and refrigerator hydraulic fluid composition which can attain a high level of compatibility with both the coolant and thermal and chemical stability in refrigerators.

7 cl, 3 tbl, 6 ex

Description

FIELD OF THE INVENTION

The present invention relates to oil for refrigerating machines and to the composition of the working fluid for refrigerating machines.

State of the art

In light of the ozone depletion problem that has become important in recent years, restrictions on CFCs (chlorofluorocarbons) and HCFCs (hydrochlorofluorocarbons) used as refrigerants in conventional chillers have become more stringent, and HFCs (hydrofluorocarbons) come in for applications as replacements for refrigerants.

Hydrocarbon oils, such as mineral oils or alkylbenzenes, are preferred for use as refrigeration oils when CFC or HCFCs are refrigerants, but since replacing refrigerants may cause the refrigerant oil used to exhibit unpredictable behavior in terms of its compatibility with the refrigerant, lubricity, viscosity in the dissolved state along with the refrigerant and thermal / chemical stability, it is necessary to develop various oils for cold weather nyh machines for different refrigerants. Examples of chiller oils that are designed for HFC refrigerants include polyalkylene glycols (see Patent Document 1), esters (see Patent Document 2), carbonic esters (see Patent Document 3) and polyvinyl ethers (see Patent Document four).

HFC-134a is an HFC refrigerant that is routinely used as a refrigerant for automotive air conditioners, and although it has zero ozone depletion potential (ODP), its high global warming potential (GWP) leads to its limitation in Europe. For this reason, there is an urgent task to develop refrigerants that can be used as substitutes for HFC-134a.

In light of these assumptions, it is proposed to use fluoropropene refrigerants that have very low ODP and GWP as substitutes for HFC-134a, are non-combustible and are comparable or superior to HFC-134a in terms of their thermodynamic properties, as measures for refrigerant performance. It is also proposed to use mixtures of fluoropropene refrigerants with saturated hydrofluorocarbons, saturated hydrocarbons having from 3 to 5 carbon atoms in a molecule, dimethyl ether, carbon dioxide, bis (trifluoromethyl) sulfide or trifluoroiodomethane (see patent document 5).

Oils for refrigeration machines that use mineral oils, alkylbenzenes, polyα-olefins, polyalkylene glycols, monoesters, diesters, polyol esters, phthalic esters, alkyl ethers, ketones, carbonic esters, polyvinyl ethers are also proposed. and the like, as refrigerant oils that can be used with fluoropropene refrigerants or mixtures of fluoropropene refrigerants and saturated hydrocarbon saturated hydrocarbon and having from 3 to 5 carbon atoms in the molecule, dimethyl ether, carbon dioxide, bis (trifluoromethyl) sulfide or trifluoroiodomethane (see Patent Document 5 and Patent Documents 6 and 7).

[Patent Document 1] Publication of Unexamined Japanese Patent HEI No. 02-242888.

[Patent Document 2] Publication of Japanese Unexamined Patent HEI No. 03-200895.

[Patent Document 3] Publication of Unexamined Japanese Patent HEI No. 03-217495.

[Patent Document 4] Publication of Japanese Unexamined Patent HEI No. 06-128578.

[Patent document 5] Publication of the application for an International patent, pamphlet No. WO 2006/094303.

[Patent Document 6] Japanese Patent Application Laid-Open No. 2006-512426.

[Patent document 7] Publication of the application for an International patent, pamphlet No. WO 2005/103190.

Problems to be Solved by the Invention

In a refrigeration system using fluoropropene refrigerant and / or trifluoroiodomethane refrigerant, as described in Patent Documents 5, 6 and 7, the refrigeration oil used may be alkyl benzene, such as mineral oil or hydrocarbon used in CFC or HCFC, or polyalkylene glycols , polyol esters or polyvinyl ethers that are used in HFC. Based on the studies of the inventors of the present invention, however, it is not possible to achieve a high level of refrigerant compatibility and thermal / chemical stability by simply applying conventional refrigerant oils used for refrigerants such as CFC and HCFC in the systems mentioned above.

Brief Description of the Drawings

For this reason, the aim of the present invention, which is achieved in the light of these circumstances, is to provide oil for the refrigeration machine and a composition of the working fluid for the refrigeration machine, which can achieve a high level of both compatibility with the refrigerant and thermal / chemical stability in refrigeration systems using fluoropropene refrigerants and / or trifluoroiodomethane refrigerants.

Problem Solving Tools

As a result of careful research aimed at achieving the goal formulated above, the authors of the present invention found that by using an ester of a specific polyhydric alcohol with a specific fatty acid composition, it is possible to obtain oil for refrigeration machines having sufficient thermal and chemical stability in the presence of fluoropropene refrigerant and / or trifluoroiodomethane refrigerant, while also having sufficient compatibility with the refrigerants, and the present of Bretenoux completed based on these data.

Specifically, the present invention provides a composition of a working fluid for a refrigeration machine, characterized in that it contains an ester of a polyhydric alcohol and a fatty acid with a content of C ₅ -C ₉ fatty acid of 50-100 mol%, with a content of C ₅ -C ₉ branched fatty acid, at least 30 mol%. and with a C ₅ or lower straight chain fatty acid content of not more than 40 mol%, together with a fluoropropene refrigerant and / or trifluoroiodomethane refrigerant.

In addition, the present invention provides oil for refrigeration machines, characterized in that it contains an ester of polyhydric alcohol and a fatty acid with a content of C ₅ -C ₉ fatty acid of 50-100 mol%, with a content of C ₅ -C ₉ branched fatty acid at least 30 mol%. and with a C ₅ or lower straight chain fatty acid content of not more than 40 mol%, and the fact that it is used together with a fluoropropene refrigerant and / or trifluoroiodomethane refrigerant.

The polyhydric alcohol, as an ester component in the oil for refrigerating machines and in the composition of the working fluid for the refrigerating machine in accordance with the present invention, is preferably pentaerythritol and / or dipentaerythritol.

The working fluid composition for a refrigerating machine in accordance with the present invention is also a working fluid composition for a refrigerating machine according to claim 1 or 2, characterized in that it contains at least one component selected from 1,3,3,3 -tetrafluoropropene and 2,3,3,3-tetrafluoropropene, as a fluoropropene refrigerant.

The working fluid composition for the refrigeration machine of the present invention also preferably contains at least one fluoropropene refrigerant (hereinafter referred to as “refrigerant (A)”) and at least one component selected from saturated hydrofluorocarbons, hydrocarbons having from 3 up to 5 carbon atoms in the molecule, dimethyl ether, carbon dioxide, and refrigerants based on bis (trifluoromethyl) sulfide and trifluoroiodomethane (hereinafter referred to as "refrigerant (B)").

In a mixture of refrigerants containing refrigerant (A) and refrigerant (B), the fluoropropene refrigerant is preferably at least one refrigerant selected from 1,2,3,3,3-pentafluoropropene, 1, 3, 3, 3- tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1,2,3,3-tetrafluoropropene and 3,3,3-trifluoropropene, saturated hydrofluorocarbon is preferably at least one hydrofluorocarbon selected from difluoromethane, pentafluoroethane, 1 , 1,2,2-tetrafluoroethane, 1,1,1,2-tetrafluoroethane, 1,1-difluoroethane, fluoroethane, 1,1,1,2,3,3,3-heptafluoropropane, 1,1,1,2 , 3,3-hexafluorop ropan, 1,1,1,3,3,3-hexafluoropropane, 1,1,1,3,3-pentafluoropropane and 1,1,1,3,3-pentafluorobutane, and a hydrocarbon having from 3 to 5 carbon atoms in the refrigerant molecule, preferably represents at least one hydrocarbon selected from propane, n-butane, isobutane, 2-methylbutane and n-pentane.

Effect of the invention

As mentioned above, the present invention can provide chiller oil and chiller fluid composition and chiller fluid composition that can achieve a high level of both refrigerant compatibility and thermal / chemical stability in refrigeration systems using fluoropropene refrigerants and / or trifluoroiodomethane refrigerants.

BEST MODE FOR CARRYING OUT THE INVENTION

Now, preferred embodiments of the present invention will be described in detail.

The oil for the refrigeration machine of the present invention is characterized in that it contains a polyhydric alcohol and fatty acid ester with a C ₅ -C ₉ fatty acid content of 50-100 mol%, with a C ₅ -C ₉ branched fatty acid content of at least , 30 mol% and with a C ₅ or lower straight chain fatty acid content of not more than 40 mol%, and the fact that it is used together with a fluoropropene refrigerant and / or trifluoroiodomethane refrigerant.

The composition of the working fluid for the refrigeration machine in accordance with the present invention is characterized in that it contains an ester of polyhydric alcohol and a fatty acid with a content of C ₅ -C ₉ fatty acid of 50-100 mol%, with a content of C ₅ -C ₉ branched fatty acid, at least 30 mol%. and with a C ₅ or lower straight chain fatty acid content of not more than 40 mol%, together with a fluoropropene refrigerant and / or trifluoroiodomethane refrigerant. This includes a mode where the composition of the working fluid for the refrigeration machine of the present invention contains oil for the refrigeration machine in accordance with the present invention and a fluoropropene refrigerant and / or trifluoroiodomethane refrigerant.

The oil for the refrigeration machine and the composition of the working fluid for the refrigeration machine in accordance with the present invention contain an ester of polyhydric alcohol and a fatty acid with a content of C ₅ -C ₉ fatty acid of 50-100 mol%, with a content of C ₅ -C ₉ branched fatty acid at least 30 mol%. and with a content of C ₅ or lower fatty acid with a direct chain of not more than 40 mol%. (hereinafter referred to as the "polyol ester of the present invention").

The proportion of C ₅ -C ₉ fatty acid in the polyol ester fatty acid of the present invention (hereinafter referred to as the “constituent fatty acid”) is 50-100 mol%, as mentioned above, but preferably 60-100 mol%, more preferably 70-100 mol%, even more preferably 90-100 mol%, and most preferably 100 mol%. If the content of C ₅ -C ₉ fatty acid is less than 50 mol%, thermal / chemical stability and / or compatibility with the refrigerant in the presence of fluoropropene refrigerant and / or trifluorodiomethane refrigerant Ghent will be insufficient.

The content of C ₅ -C ₉ branched fatty acid for the fatty acid component is at least 30 mol%, as mentioned above, and preferably at least 40 mol%. If the content of C ₅ -C _{9 is} branched fatty acid less than 30 mol%, thermal / chemical stability and / or compatibility with the refrigerant in the presence of fluoropropene refrigerant and / or trifluoroiodomethane refrigerant will be insufficient.

The content of straight chain C ₅ or lower fatty acid for the fatty acid component is not more than 40 mol%, as mentioned above, and preferably is not more than 30 mol%. If the content of straight chain C ₅ or lower fatty acid is greater less than 40 mol%, thermal / chemical stability and / or compatibility with the refrigerant in the presence of fluoropropene refrigerant and / or trifluoroiodomethane refrigerant will be insufficient.

Insofar as the above conditions for the content of C ₅ -C ₉ fatty acid, C ₅ -C ₉ branched fatty acid and C ₅ or lower straight chain fatty acid for the constituent fatty acid are met, the constituent fatty acid may contain only branched fatty acids or it may be a mixture of straight chain and branched chain fatty acids.

C ₅ -C ₉ fatty acids can be straight or branched chain, and pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid and nonanoic acid can be considered specific straight-chain C ₅ -C ₉ fatty acids.

As specific C ₅ -C ₉ branched fatty acids, branched pentanoic acid, branched hexanoic acid, branched heptanoic acid, branched octanoic acid and branched nonanoic acid may be mentioned. More specifically, fatty acids branched at the α and / or β position are preferred, with 2-methylbutanoic acid, 2-methylpentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-methylheptanoic acid, 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid are particularly preferred and mixtures of 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid are most preferred.

As examples of fatty acids other than C ₅ -C ₉ fatty acids that should be included in the fatty acid component, there can be mentioned C ₁₀ -C ₂₄ fatty acid and a straight chain C ₁₀ -C ₂₄ branched fatty acid. More specifically, decanoic acid having a straight chain or branched chain, undecanoic acid having a straight chain or branched chain, dodecanoic acid having a straight chain or branched chain, tridecanoic acid having a straight chain or branched tetradecanoic acid having a straight chain or branched chain pentadecanoic acid having a straight chain or branched chain hexadecanoic acid having a straight chain or branched heptadecanoic acid having a straight chain or branched chain octadecanoic acid having a straight chain or branched chain nonadecanoic acid having a straight chain or branched chain eicosanoic acid having a straight chain or branched chain genecosanoic acid having a straight chain or branched chain dock a chain or branched chain tricosanoic acid and tetracosanoic acid having a straight chain or branched chain.

The polyol comprising the polyol ester of the present invention is preferably a polyol with 2-6 hydroxyl groups.

As specific examples of dihydric alcohols (diols), mention may be made of ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 2-methyl-l, 3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl-2-propyl-1,3-propanediol, 2,2-diethyl-1, 3-propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecandiol, 1,12-dodecandiol and the like. As specific examples of trihydric and higher alcohols, polyhydric alcohols can be mentioned, such as trimethylol ethane, trimethylol propane, trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, di- (pentaerythritol), tri- (pentaerythritol) polyglycerol (2-3 measures of glycerol), 1,3,5-pentantriol, sorbitol, sorbitan, condensation products of sorbitol glycerol, adonitol, arbitol, xylitol, mannitol and the like, saccharides such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose and cellobiosis, and their partially esterified forms. Among them, esters of hindered alcohols are preferred, such as neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri (trimethylol propane), pentaerythritol, di (pentaerythritol), tri (pentaerythritol, more preferred, are pentaerythritol) trimethylol ethane, trimethylol propane, trimethylol butane, pentaerythritol and di (pentaerythritol), and neopentyl glycol, trimethylol propane, pentaerythritol and di (pentaerythritol) are even more preferred due to converging hydrolytic stability, while pentaerythritol or mixed esters of pentaerythritol and di- (pentaerythritol) are most particularly preferred because of excellent compatibility with the refrigerant and hydrolytic stability.

As more specific examples, the polyol ester of the present invention is preferably an ester of one or more fatty acids selected from 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-methylheptanoic acid, 2-ethylhexanoic acid and 3,5,5 -trimethylhexanoic acid as branched fatty acids with one or more polyhydric alcohols selected from neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylolbutane, pentaerythritol and di (pentaerythritol), more preferably a branched fatty acid ester such as 2-ethylhexanoic acid and / or 3,5,5-trimethylhexanoic acid with one or more polyols selected from neopentyl glycol, trimethylolpropane, pentaerythritol and di (pentaerythritol), and most preferably a mixed fatty acid ester including 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid, with pentaerythritol and / or di (pentaerythritol). There are no particular restrictions on the mixing ratio for 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid, but the molar ratio between 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid is preferably 5-95: 95-5 more preferably 10-90: 90-10, and most preferably 30-70: 70-30.

As more specific examples, the polyol ester of the present invention is preferably a mixed fatty acid ester, including one or more fatty acids selected from hexanoic acid, heptanoic acid and octanoic acid, as straight chain fatty acids and one or more fatty acids selected from 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-methylheptanoic acid, 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid, as branched fatty acids t, with one or more polyhydric alcohols selected from neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, pentaerythritol and di (pentaerythritol), more preferably a mixed fatty acid ester including one or more fatty acids selected from hexanoic acid, heptanoic acid as straight chain fatty acids and one or more fatty acids selected from 2-methylhexanoic acid, 2-ethyl pentanoic acid, 2-methylheptanoic acid, 2-ethylhexanoic acid and 3,5,5-trimethy hexanoic acid, as branched fatty acids, with one or more polyhydric alcohols selected from pentaerythritol and di (pentaerythritol), and even more preferably, a mixed fatty acid ester, including heptanoic acid as a straight chain fatty acid, and 3, 5,5-trimethylhexanoic acid as a branched fatty acid, with one or more polyols selected from pentaerythritol and di (pentaerythritol). The mixing ratio of the straight chain fatty acid and the branched fatty acid is preferably such that the proportion of branched fatty acids is 30-100 mol%, more preferably 35-95 mol%, and most preferably 40-95 mol%. in relation to fatty acids in general.

The polyol ester according to the present invention may be a partial ester with a portion of the hydroxyl groups of a polyhydric alcohol remaining as hydroxy groups without esterification, a full ester with all esterified hydroxyl groups, or a mixture of a partial ester and a full ester, but the amount of hydroxyl is preferred is not more than 10 mg KOH / g, even more preferably not more than 5 mg KOH / g, and most preferably not more than 3 mg KOH / g.

Chiller oil and chiller fluid composition of the present invention may comprise, as the polyol ester of the present invention, a single polyol ester with a single structure or a mixture of two or more polyol esters with different structures.

The polyol ester of the present invention may be an ester of one fatty acid and one polyhydric alcohol, an ester of two or more fatty acids and one polyhydric alcohol, an ester of one fatty acid and two or more polyhydric alcohols, or an ester of two or more fatty acids and two or more polyols. Among them, particularly excellent low temperature characteristics and compatibility with refrigerants are demonstrated by polyol esters using mixed fatty acids and especially polyol esters containing two or more fatty acids in an ester molecule.

There is no restriction on the content of the polyol ester of the present invention in the oil for the chillers of the present invention, but for better performance, including lubricity, refrigerant compatibility, thermal / chemical stability and electrical insulation properties, the content is preferably at at least 50 wt.%, more preferably at least 70 wt.%, even more preferably at least 80 wt.%, and most preferably at least 90 wt.%, p regarding the total mass of oil for refrigerators.

The oil for chillers of the present invention may consist entirely of the polyol ester of the present invention or it may further comprise a base oil other than the polyol ester and various additives. The composition of the working fluid for refrigerators of the present invention may also further comprise a base oil, other than the polyol ester of the present invention, and various additives. In the explanation that follows, the content of base oils other than the polyol esters of the present invention and additives is given with respect to the total weight of oil for refrigeration machines, and the content of these components in the fluid composition for refrigeration machines is preferably selected so that it was in the preferred ranges defined below in relation to the total amount of oil for refrigeration machines.

As base oils other than the polyol ester of the present invention, hydrocarbon-based oils can be used including mineral oils, olefin polymers, alkyl diphenylalkanes, alkylnaphthalenes, alkylbenzenes and the like, ester base oils other than the polyol esters of the present the invention (monoesters, polyol esters containing only straight chain fatty acids as constituent fatty acids, alkyl aromatic esters and alicyclic esters carboxylic acids), and oxygen-containing synthetic oils such as polyglycols, polyvinyl ethers, ketones, polyphenyl ethers, silicones, polysiloxanes and perfluoroethers. Among the above oxygen-containing synthetic oils, esters other than the polyol esters of the present invention and polyglycols and polyvinyl ethers are preferably used.

If necessary, the refrigeration oil of the present invention can be used in a form that further comprises various additives. In the explanation that follows, the content of additives is given in relation to the total weight of oil for refrigeration machines, and the content of these components in the fluid composition for refrigeration machines is preferably selected to be in the preferred range defined below with respect to the total amount of oil for refrigerators.

To further improve the properties of preventing wear and the ability to carry the load of oil for refrigeration machines and the composition of the working fluid for refrigeration machines in accordance with the present invention, one or more phosphorus compounds selected from the group consisting of phosphoric esters, complex acid esters of phosphoric acid, esters of thiophosphoric acid, amine salts of acid esters of phosphoric acid, chlorinated esters of phosphoric acid and complex x esters of phosphorous acid. These phosphorus compounds are esters of phosphoric acid or phosphorous acid with alkanols or polyether alcohols or their derivatives.

As specific examples of phosphoric acid esters there may be mentioned tributyl phosphate, tripentilfosfat, trigeksilfosfat, trigeptilfosfat, trioctyl phosphate, trinonilfosfat, tridetsilfosfat, triundetsilfosfat, tridodetsilfosfat, tritridetsilfosfat, tritetradetsilfosfat, tripentadetsilfosfat, trigeksadetsilfosfat, trigeptadetsilfosfat, trioktadetsilfosfat, trioleilfosfat, triphenyl phosphate, tricresyl phosphate, triksilenilfosfat, krezildifenilfosfat and xylenyl diphenyl phosphate.

As acidic phosphoric acid esters there may be mentioned fosfatmonobutilovaya acid fosfatmonopentilovaya acid fosfatmonogeksilovaya acid fosfatmonogeptilovaya acid fosfatmonooktilovaya acid fosfatmonononilovaya acid fosfatmonodetsilovaya acid fosfatmonoundetsilovaya acid fosfatmonododetsilovaya acid fosfatmonotridetsilovaya acid fosfatmonotetradetsilovaya acid fosfatmonopentadetsilovaya acid fosfatmonogeksadetsilovaya acid fosfatmonogeptadetsilovaya acid phosphate monooctadecium lovaya acid fosfatmonooleilovaya acid fosfatdibutilovaya acid fosfatdipentilovaya acid fosfatdigeksilovaya acid fosfatdigeptilovaya acid fosfatdioktilovaya acid fosfatdinonilovaya acid fosfatdidetsilovaya acid fosfatdiundetsilovaya acid fosfatdidodetsilovaya acid fosfatditridetsilovaya acid fosfatditetradetsilovaya acid fosfatdipentadetsilovaya acid fosfatdigeksadetsilovaya acid fosfatdigeptadetsilovaya acid fosfatdioktadetsilovaya acid and phosphatidioleilic acid.

As thiophosphoric acid esters may be mentioned tributilfosfortionat, tripentilfosfortionat, trigeksilfosfortionat, trigeptilfosfortionat, trioktilfosfortionat, trinonilfosfortionat, tridetsilfosfortionat, triundetsilfosfortionat, tridodetsilfosfortionat, tritridetsilfosfortionat, tritetradetsilfosfortionat, tripentadetsilfosfortionat, trigeksadetsilfosfortionat, trigeptadetsilfosfortionat, trioktadetsilfosfortionat, trioleilfosfortionat, triphenyl phosphorothionate, trikrezilfosfortionat, triksilenilfosfortionat, cresyldiphenyl phosphorothionate and xylenyl diphenyl phosphorothionate.

As amine salts of acidic phosphoric acid esters, amine salts such as methylamine salt, ethylamine salt, propylamine salt, butylamine salt, pentylamine salt, hexylamine salt, heptylamine salt, octylamine salt, dimethylamine salt, diethylamine salt can be mentioned dibutylamine salt, dipentylamine salt, dihexylamine salt, diheptylamine salt, dioctylamine salt, trimethylamine salt, triethylamine salt, tripropylamine salt, tributylamines ith salt, tryptylamine salt, trihexylamine salt, triheptylamine salt and trioctylamine salt of the above acidic phosphoric acid esters.

As chlorinated phosphoric acid esters, tris (dichloropropyl) phosphate, tris (chloroethyl) phosphate, tris (chlorophenyl) phosphate and polyoxyalkylene bis [di (chloroalkyl)] phosphate may be mentioned. As esters of phosphorous acid can be mentioned dibutyl phosphite, dipentilfosfit, digeksilfosfit, digeptilfosfit, dioktilfosfit, dinonilfosfit, didetsilfosfit, diundetsilfosfit, didodetsilfosfit, dioleilfosfit, diphenyl phosphite, dikrezilfosfit, tributyl phosphite, tripentilfosfit, trigeksilfosfit, trigeptilfosfit, trioktilfosfit, trinonilfosfit, tridecyl, triundetsilfosfit, tridodetsilfosfit , trioleylphosphite, triphenylphosphite and tricresylphosphite. Mixtures of the above compounds may also be used.

When the refrigeration oil and refrigerant fluid composition of the present invention contain such phosphorus compounds, the content of the phosphorus compound is not particularly limited, but is preferably 0.01-5.0% by weight, and more preferably 0.02- 3.0% wt., With respect to the total weight of oil for refrigeration machines (to the total weight of the base oil and all additives). One type of phosphorus compounds alone may be used, or two or more types may be used in combination.

Chiller oil and chiller fluid composition of the present invention may also contain added terpene compounds to further improve thermal and chemical stability. A "terpene compound" in accordance with the present invention is a compound obtained by polymerization of isoprene or a derivative thereof, and 2-8 measures of isoprene are preferably used. As terpene compounds, specifically monoterpenes can be mentioned, such as geraniol, nerol, linalool, citral (including geranial), citronellol, menthol, limonene, terpinerol, carvone, ionon, foughen, camphor and borneol, sesquiterpenes such as farnesene, farnesol, nerolidol, juvenile hormone, humulene, karyofillen, elemen, cadinol, cadinene and tutin, diterpenes such as geranylgeraniol, phytol, abietic acid, pimaradiene, dapnetoxin, taxol, abietic acid and pimenerephene such as such as squalene, limonin, camelliagenin, hopan and lanosterol, and tetraterpenes such as carotenoids.

Among these terpene compounds, monoterpenes, sesquiterpenes and diterpenes are preferred, while sesquiterpenes are more preferred and α-farnesene (3,7,11-trimethyldodec-1,3,6,10-tetraene) and / or β-farnesene (7, 11-dimethyl-3-methylidendodec-1,6,10-triene) are particularly preferred. In accordance with the present invention, a particular type of terpene compound may be used alone or two or more of them may be used in combination.

There are no restrictions on the content of terpene compounds in the oil for refrigerators of the present invention, but 0.001-10% by weight, more preferably 0.01-5% by weight, and even more preferably 0.05- are preferred 3% wt. in relation to the total mass of oil for refrigerators. A content of the terpene compound less than 0.001% by weight will tend to insufficiently improve the effect on thermal and chemical stability, while a content greater than 10% by weight will tend to lack lubricity. The content of terpene compounds in the composition of the working fluid for refrigeration machines in accordance with the present invention is preferably selected so that it falls into the above preferred range relative to the total weight of oil for refrigeration machines.

To further improve the thermal and chemical stability of refrigeration oil and refrigerant fluid composition in accordance with the present invention, they may contain one or more epoxy compounds selected from phenoxy glycidyl ether epoxy compounds, alkyl glycidyl ether epoxy compounds, glycidyl complex epoxy compounds ether, allyloxyran compounds, alkyloxyran compounds, alicyclic epoxy compounds, epoxy monoesters Rowan fatty acids and epoxidized vegetable oils.

Specific examples of epoxy compounds with phenyl glycidyl ether include phenyl glycidyl ethers and alkyl phenyl glycidyl ethers. Alkylphenylglycidyl ether is one which has 1-3 C ₁ -C ₁₃ alkyl groups, among which preferred examples with 1 C ₄ -C ₁₀ alkyl group include n-butylphenylglycidyl ether, iso-butylphenylglycidyl ether, sec. -butylphenylglycidyl ether, tert-butylphenylglycidyl ether, pentylphenylglycidyl ether, hexylphenylglycidyl ether, heptylphenylglycidyl ether, octylphenylglycidyl ether, nonylphenylglycidyl ether ir and decylphenyl glycidyl ether.

Specific examples of the epoxy compounds with simple alkyl glycidyl ether include simple detsilglitsidilovy ether, undetsilglitsidilovy ether, dodetsilglitsidilovy ether, tridetsilglitsidilovy ether, tetradetsilglitsidilovy ether, 2-ethylhexyl glycidyl ether, diglycidyl ether of neopentyl glycol, simple trimethylolpropane ether, pentaeritritoltetraglitsidilovy ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, monogly polyalkylene glycol licidyl ether and polyalkylene glycol diglycidyl ether.

As specific examples of the type of epoxy compound with glycidyl ester, phenyl glycidyl esters, alkyl glycidyl esters and alkenyl glycidyl esters can be mentioned, among which preferred examples include glycidyl-2,2-dimethyl octanoate, glycidyl benzoate, glycidyl acrylate and glycidyl acrylate.

Specific examples of allyloxyran compounds include 1,2-epoxystyrene and alkyl-1,2-epoxystyrenes.

Specific examples of alkyloxyran compounds include 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane, 1 , 2-epoxyundecane, 1,2-epoxydecodane, 1,2-epoxytridecane, 1,2-epoxytetradecane, 1,2-epoxypentadecane, 1,2-epoxyhexadecane, 1,2-epoxyheptadecane, 1,1,2-epoxyoctadecane, 2 -epoxinonadecane and 1,2-epoxyeycosan.

Specific examples of alicyclic epoxy compounds include 1,2-epoxycyclohexane, 1,2-epoxycyclopentane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, exo-2,3-epoxyinorborn bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (7-oxabicyclo [4.1.0] hept-3-yl) -spiro (1,3-dioxan-5,3 '- [7] oxabicyclo [ 4.1.0] heptane, 4- (1'-methylepoxyethyl) -1,2-epoxy-2-methylcyclohexane and 4-epoxyethyl-1,2-epoxycyclohexane.

Specific examples of epoxidized fatty acid monoesters include epoxidized C ₁₂ -C ₂₀ fatty acid esters and C ₁ -C ₈ alcohols or phenols or alkyl phenols. Most preferably, butyl, hexyl, benzyl, cyclohexyl, methoxyethyl, octyl, phenyl and butylphenyl esters of epoxy stearic acid are used.

Specific examples of epoxidized vegetable oils include epoxy compounds of vegetable oils such as soybean oil, linseed oil and cottonseed oil.

Preferred among these epoxy compounds are phenyl glycidyl ether epoxy compounds, glycidyl ether epoxy compounds, alicyclic epoxy compounds and epoxidized fatty acid monoesters. More preferred among them are epoxy compounds with phenyl glycidyl ether and epoxy compounds with glycidyl ether, with compounds with phenyl glycidyl ether, butyl phenyl glycidyl ether, alkyl glycidyl ether or mixtures thereof are particularly preferred.

When the refrigeration oil and refrigerant fluid composition of the present invention contain such epoxy compounds, the content of the epoxy compound is not particularly limited, but is preferably 0.1-5.0% by weight, and more preferably 0.2- 2.0% wt. in relation to the total mass of oil for refrigerators. A single type of epoxy compound may be used alone or two or more types may be used in combination.

To further improve the performance of chiller oil and chiller fluid composition in accordance with the present invention, the universally known chiller oil additives may be included in them when necessary. Examples of such additives include phenol-based antioxidants, such as di-tert-butyl-p-cresol and bisphenol A, amine-based antioxidants, such as phenyl-α-naphthylamine and N, N-di (2-naphthyl) p-phenylenediamine, anti-wear agents such as zinc dithiophosphate, extreme pressure agents such as chlorinated paraffins and sulfur compounds, lubricating agents such as fatty acids, silicone-based agents and other types of anti-foaming agents, agents metal deactivating agents such as benzotriazoles, viscosity index improvers, dew point suppressants, dispersants for detergents, and the like. A single type of additive may be used alone or two or more of them may be used in combination. There are no restrictions on the content of such additives, but it is preferable that they have no more than 10% wt., And more preferably not more than 5% wt. in relation to the total mass of oil for refrigerators.

The kinematic viscosity of the oil for chillers of the present invention is not specifically limited, but preferably, the kinematic viscosity at 40 ° C is 3-1000 mm ² / s, more preferably 4-500 mm ² / s, and most preferably 5-400 mm ² / s The kinematic viscosity at 100 ° C is preferably 1-100 mm ² / s, and more preferably 2-50 mm ² / s.

The specific volume resistivity of oil for chillers in accordance with the present invention is also not particularly limited, but is preferably 1.0 × 10 ¹² Ω · cm or more, more preferably 1.0 × 10 ¹³ Ω · cm or more, and most preferably 1.0 × 10 ¹⁴ Ω · cm or more. High electrical insulating properties are usually required for use in a sealed type of refrigeration equipment. In accordance with the present invention, the specific volume resistivity is a value measured in accordance with JIS C 2101, "Testing methods of electrical insulating oils", at 25 ° C.

The moisture content in the oil for chillers of the present invention is not particularly limited, but is preferably not more than 200 ppm, more preferably not more than 100 ppm, and most preferably not more than 50 ppm . in relation to the total mass of oil for refrigerators. A lower moisture content is desirable from the point of view of influencing the thermal / chemical stability and the electrical insulating properties of the oil for chillers, especially for use in pressurized chillers.

The acid number of oil for chillers of the present invention is also not specifically limited, but to prevent corrosion of metals used in chillers or pipes, and to prevent decomposition of ester oil in chillers in fluoropropene refrigerant in accordance with the present invention it is preferably not more than 0.1 mg KOH / g, and more preferably not more than 0.05 mg KOH / g. According to the present invention, an acid number is a value measured based on JIS K2501, "Petroleum products and lubricants - Determination of neutralization number".

The ash content in the oil for refrigerators of the present invention is not particularly limited, but to increase the thermal and chemical stability of the oil for refrigerators for the fluoropropene refrigerant in accordance with the present invention and to inhibit the generation of sludge, it is preferably not more than 100 m. d., and more preferably not more than 50 ppm. In accordance with the present invention, the ash content is a value measured based on JIS K2272, "Crude oil and petroleum products - Determination of ash and sulfates ash".

The chiller oil of the present invention is used together with a fluoropropene refrigerant and / or trifluorodiomethane refrigerant, and the working fluid composition for the chillers of the present invention contains a fluoropropene refrigerant and / or trifluorodiomethane refrigerant. The refrigerant used for the present invention may consist of either fluoropropene refrigerant or trifluorodiomethane refrigerant per se, or it may be a mixture of refrigerants containing fluoropropene refrigerant and trifluorodiomethane refrigerant.

Preferred fluoropropene refrigerants are fluoropropenes with 3-5 fluorine atoms, among which one refrigerant or mixtures of two or more refrigerants from 1,2,3,3,3-pentafluoropropene (HFC-1225ye), 1,3,3,3-tetrafluoropropene (HFC-1234ze), 2,3,3,3-tetrafluoropropene (HFC-1234yf), 1,2,3,3-tetrafluoropropene (HFC1234ye) and 3,3,3-trifluoropropene (HFC-1243zf) are preferred. In terms of refrigerant properties, it is preferable to use one or more of them selected from HFC-1225ye, HFC-1234ze and HFC-1234yf.

The refrigerant used for the present invention may also be a mixture of refrigerants containing fluoropropene refrigerant and trifluoroiodomethane refrigerant together with another refrigerant. As other refrigerants, HFC refrigerants, fluorinated ether refrigerants such as perfluoroethers, and natural refrigerants including dimethyl ether, ammonia, hydrocarbons and the like can be mentioned.

As HFC refrigerants, C ₁ -C ₃ , and preferably C ₁ -C ₂ hydrofluorocarbons, may be mentioned. As specific examples, difluoromethane (HFC-32), trifluoromethane (HFC-23), pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2 may be mentioned. -tetrafluoroethane (HFC-134a), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane (HFC-152a), fluoroethane (HFC-161), 1,1,1,2,3,3 3-heptafluoropropane (HFC-227ea), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1, 1,1,3,3-pentafluoropropane (HFC-245fa) and 1,1,1,3,3-pentafluorobutane (HFC-365 mfc), as well as mixtures of two or more of them. These refrigerants may be appropriately selected depending on the purpose of use and the required performance, but HFC-32 alone may be mentioned as preferred examples; HFC-23 by itself; HFC-134a by itself; HFC-125 by itself; HFC-134a / HFC-32 = mixture 60-80% wt./ 40-20% wt .; HFC-32 / HFC-125 = mixture of 40-70% wt. / 60-30% wt .: HFC-125 / HFC-143a = mixture of 40-60% wt. / 60-40% wt .; HFC-134a / HFC-32 / HFC-125 = 60% w / 30% w / 10% w / w mixture; HFC-134a / HFC-32 / HFC-125 = mixture of 40-70% wt. / 15-35% wt. / 5-40% wt. and HFC-125 / HFC-134a / HFC-143a = mixture of 35-55% wt. / 1-15% wt. / 40-60% wt. More specifically, HFC-134a / HFC-32 = a mixture of 70/30% by weight; HFC-32 / HFC-125 = a mixture of 60/40% wt .; HFC-32 / HFC-125 = a mixture of 50/50% wt. (R410A); HFC-32 / HFC-125 = a mixture of 45/55% wt. (R410B); HFC-125 / HFC-143a = a mixture of 50/50% wt. (R507C); HFC-32 / HFC-125 / HFC-134a = a mixture of 30/10/60% wt .; HFC-32 / HFC-125 / HFC-134a = a mixture of 23/25/52% wt. (R407C); HFC-32 / HFC-125 / HFC-134a = a mixture of 25/15/60% wt. (R407E) and HFC-125 / HFC-134a / HFC-143a = 44/4/52 mixture wt. (R404A).

As saturated hydrofluorocarbons among HFC refrigerants, a separate refrigerant or mixtures of two or more refrigerants selected from difluoromethane (HFC-32), pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane (HFC-134), are preferred. 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1-difluoroethane (HFC-152a), fluoroethane (HFC-161), 1,1,1,2,3,3,3-heptafluoropropane (HFC -227ea), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,1,3, 3-pentafluoropropane (HFC-245fa) and 1,1,1,3,3-pentafluorobutane (HFC-365 mfc), and in terms of refrigerant properties, HFC-32, HFC-125, HFC-134a, HF are particularly preferred C-152a and mixtures of HFC-32 and HFC-134a.

As hydrocarbon refrigerants, hydrocarbons having 3 to 5 carbon atoms in a molecule are preferred, and methane, ethylene, ethane, propylene, propane, cyclopropane, n-butane, isobutane, cyclobutane, methylcyclopropane, 2- can be mentioned as specific examples. methylbutane, n-pentane and mixtures of two or more of the compounds indicated above. Among them, preferred are refrigerants which are gases at 25 ° C. under 1 atmosphere, such as propane, n-butane, isobutane, 2-methylbutane, and mixtures thereof.

As specific examples of fluorinated ether-based refrigerants, HFE-134p, HFE-245mc, HFE-236mf, HFE-236me, HFE-338mcf, HFE-365mcf, HFE-245mf, HFE-347mmy, HFE-347mcc, HFE can be mentioned -125, HFE-143m, HFE-134m, HFE-227me and the like, and these refrigerants can be selected appropriately depending on the purpose of use and the required performance.

When the refrigerant used for the present invention is a mixture of refrigerants, the mixture of refrigerants preferably contains at least one component selected from fluoropropene refrigerants (hereinafter referred to as "refrigerant (A)"), and at least one component, selected from saturated hydrofluorocarbons, hydrocarbons having from 3 to 5 carbon atoms in the molecule, dimethyl ether, carbon dioxide, bis (trifluoromethyl) sulfide and trifluorodiomethane refrigerants (hereinafter referred to as “the refrigerant ( ) ").

When the refrigerant used for the present invention is a mixture of refrigerants containing refrigerant (A) and refrigerant (B), the mixture of refrigerants is preferably an azeotropic mixture, but not necessarily an azeotropic mixture, insofar as it has the properties required as a refrigerant and the mixing ratio of both components is preferably 1: 99-99: 1, and more preferably 5: 95-95: 5.

Also, when the refrigerant used for the present invention is a mixture of refrigerants containing refrigerant (A) and refrigerant (B), the mixture of refrigerants may further comprise HFC refrigerant other than fluoropropene refrigerant or saturated hydrofluorocarbon, a fluorinated ether-based refrigerant, such as a perfluoroether ether, or a natural refrigerant such as a hydrocarbon other than a hydrocarbon having from 3 to 5 carbon atoms in the molecule, or ammonia.

The chiller oil of the present invention will typically be used in an air conditioner for cooling air in the form of the aforementioned chiller fluid composition mixed with fluoropropene refrigerant and / or trifluoroiodomethane refrigerant or as a mixture of refrigerants. There are no restrictions on the mixing ratio of refrigeration oil and refrigerant in the composition or on the mixing ratio of refrigeration oil and refrigerant in the working fluid composition for refrigeration in accordance with the present invention, but the oil content for refrigeration machines is preferably 1- 500 parts by weight, and more preferably 2-400 parts by weight. in relation to 100 parts by weight. refrigerant.

The chiller oil and chiller fluid composition of the present invention is preferably used in an air conditioner or in a chiller with a hermetic type reciprocating or rotary compressor, or in an open or closed type automobile air conditioner. The oil for refrigerators and the composition of the working fluid for refrigerators in accordance with the present invention can also be suitably used in cooling devices for moisture absorbers, water heaters, freezers, refrigerated storage / refrigerated warehouses, automatic vending machines, display cases, chemical plants, etc. Chiller oil and chiller fluid composition in accordance with the present invention can also be suitably used in centrifugal compressor devices.

Examples

The present invention will now be explained in more detail based on examples and comparative examples, with the understanding that these examples in no way limit the present invention.

[Examples 1-11 and Comparative Examples 1-4]

For Examples 1-11 and Comparative Examples 1-4, chiller oils are prepared using the base oils 1-15 listed below. The properties of the oils obtained for refrigeration machines are shown in tables 1-3.

(Essential oils)

Base oil 1: 2-ethylhexanoic acid ester and neopentyl glycol.

Base oil 2: 2-ethylhexanoic acid ester and trimethylolpropane.

Base Oil 3: 2-ethylhexanoic acid ester and pentaerythritol.

Base Oil 4: An ester of a mixture of fatty acids from 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid (mixing ratio (molar ratio): 50/50) and pentaerythritol.

Base Oil 5: An ester of a mixture of fatty acids from 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid (mixing ratio (molar ratio): 50/50) and dipentaerythritol.

Base oil 6: A mixture of base oil 1 and base oil 3 (mixing ratio (mass ratio): base oil 1 / base oil 3 = 35/65).

Base oil 7: A mixture of base oil 1 and base oil 4 (mixing ratio (mass ratio): base oil 1 / base oil 4 = 25/75).

Base oil 8: A mixture of base oil 4 and base oil 5 (mixing ratio (mass ratio): base oil 4 / base oil 5 = 75/25).

Base Oil 9: An ester of a mixture of fatty acids from n-heptanoic acid and 3,5,5-trimethylhexanoic acid (mixing ratio (molar ratio): 15/85) and pentaerythritol.

Base oil 10: An ester of a mixture of fatty acids from n-heptanoic acid and 3,5,5-trimethylhexanoic acid (mixing ratio (molar ratio): 55/45) with pentaerythritol / dipentaerythritol = molar ratio 50/50.

Base oil 11: An ester of a mixture of fatty acids from n-pentanoic acid, n-heptanoic acid and 3,5,5-trimethylhexanoic acid (mixing ratio (molar ratio): 10/40/50) and pentaerythritol.

Base oil 12: n-heptanoic acid ester and pentaerythritol.

Base oil 13: An ester of a mixture of fatty acids from n-pentanoic acid, n-heptanoic acid and 3,5,5-trimethylhexanoic acid (mixing ratio (molar ratio): 45/10/45) and pentaerythritol.

Base oil 14: Naphthenic mineral oil

Base oil 15: Polypropylene glycol monomethyl ether.

Each refrigeration oil obtained in Examples 1-11 and Comparative Examples 1-4 is tested as follows.

(rating 1 refrigerant compatibility).

Following the procedure shown in the "Refrigerant Compatibility Test Method" as "Refrigerating Machine Oils" of JIS-K-2211, 2 g of oil for refrigeration machines are combined with 18 g of a mixture of refrigerants 2,3,3,3-tetrafluoropropene and trifluorodiomethane (ratio mixing (mass ratio): 2,3,3,3-tetrafluoropropene / trifluoroiodomethane = 70/30), and observe whether refrigerant and refrigerant oil are mutually dissolved at 0 ° C. The results are shown in Tables 1-3. 1-3, “compatible” means that the refrigerant and chiller oil are mutually dissolved, and “delaminate” means that the refrigerant and m layer for refrigerating machines are stratified into two layers.

(Refrigerant compatibility rating 2)

Following the procedure shown in the "Refrigerant Compatibility Test Method" as "Refrigerating Machine Oils" of JIS-K-2211, 2 g of oil for chillers are combined with 18 g of 2,3,3,3-tetrafluoropropene and it is observed whether the refrigerant is mutually dissolved and chiller oil at 0 ° C. The results are shown in tables 1-3. In Tables 1-3, “compatible” means that the refrigerant and chiller oil are mutually dissolved, and “exfoliate” means that the refrigerant and chiller oil are stratified into two layers.

(Grade 1 thermal / chemical stability)

Following the procedure shown in JIS-K-2211, 1 g of oil for chillers is adjusted to a moisture content of not more than 10 ppm. (initial color according to ASTM: L0.5), and 1 g of a mixture of refrigerants from 2,3,3,3-tetrafluoropropene and trifluorodiodomethane (mixing ratio (mass ratio): 2,3,3,3-tetrafluoropropene / trifluorodiomethane = 70 / 30) filled into a glass tube with the catalyst (iron, copper and aluminum wires), and then heated to 150 ° C and stored for one week for research. After the study, ASTM color for chiller oil and the color change of the catalyst are evaluated. ASTM color is evaluated according to ASTM D156. The color change of the catalyst is determined by visual observation of the appearance and assessed as “no change”, “no gloss” or “blackening”. The results are shown in tables 1-3.

(Grade 2 thermal / chemical stability)

Following the procedure shown in JIS-K-2211, 1 g of oil for chillers is adjusted to a moisture content of not more than 10 ppm. (ASTM initial color: L0.5), and 1 g of 2,3,3,3-tetrafluoropropene was filled into a glass tube together with the catalyst (iron, copper and aluminum wires), and then heated to 150 ° C and stored for one week for research. After the study, the color is evaluated by ASTM refrigeration oil composition and catalyst color change. ASTM color is evaluated according to ASTM D156. The color change of the catalyst is determined by visual observation of the appearance, and estimates are made as “no change”, “no gloss” or “blackening”. The results are shown in tables 1-3.

Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Base oil No. one 2 3 four 5 6 Kinematic viscosity at 40 ° C (mm ² / s) 7.3 24.1 45.3 68.3 244 22.3 Kinematic viscosity at 100 ° C (mm ² / s) 2 4.2 6.3 8.3 19.2 4.1 The proportion of C ₅ -C ₉ fatty acids among the constituent fatty acids of the ester (mol%) one hundred one hundred one hundred one hundred one hundred one hundred The proportion of C ₅ -C ₉ branched fatty acids among the constituent fatty acids of the ester (% mol.) one hundred one hundred one hundred one hundred one hundred one hundred Proportion of straight chain C ₅ or lower fatty acids among the constituent ester fatty acids (mol%) 0 0 0 0 0 0 Refrigerant Compatibility 1 Compatible Compatible Compatible Compatible Compatible Compatible Thermal / Chemical Stability 1 ASTM Color (ASTMD156) L0.5 L0.5 L0.5 L0.5 L0.5 L0.5 The appearance of the catalyst Cu
Fe
Al No changes No changes No changes No changes No changes No changes No changes No changes No changes No changes No changes No changes No changes No changes No changes No changes No changes No changes Refrigerant Compatibility 2 Compatible Compatible Compatible Compatible Compatible Compatible Thermal / Chemical Stability 2 ASTM Color (ASTM D156) L0.5 L0.5 L0.5 L0.5 L0.5 L0.5 The appearance of the catalyst Cu
Fe
Al No changes No changes No changes No changes No changes No changes No changes No changes No changes No changes No changes No changes No changes No changes No changes No changes No changes No changes

table 2 Example 7 Example 8 Example 9 Example 10 Example 11 Base oil No. 7 8 9 10 eleven Kinematic viscosity at 40 ° C (mm ² / s) 33.5 83.8 74.2 67.5 44.3 Kinematic viscosity at 100 ° C (mm ² / s) 5.4 9.6 9.2 9.5 6.83 The proportion of C ₅ -C ₉ fatty acids among the constituent fatty acids of the ester (mol%) one hundred one hundred one hundred one hundred one hundred The proportion of C ₅ -C ₉ branched fatty acids among the constituents one hundred one hundred 85 45 60 ester fatty acids (mol%) Proportion of straight chain C ₅ or lower fatty acids among the constituent ester fatty acids (mol%) 0 0 0 0 10 Compatible with
refrigerant 1 Compatible Compatible Compatible Compatible Compatible Thermal
/ chemical stability 1 ASTM Color (ASTM D156) L0.5 L0.5 L1.0 L1.5 L1.5 Catalyst appearance Cu
Fe
Al No changes No changes No changes No change
No change
No change No change
No change
No change No gloss
No change
No change No gloss
No change
No change Refrigerant Compatibility 2 Compatible Compatible Compatible Compatible Compatible Thermal
/ chemical stability 2 ASTM Color (ASTMD156) L0.5 L0.5 L0.5 L0.5 L0.5 Catalyst appearance Cu
Fe
Al No changes No changes No changes No change
No change no change No change no change
No change No gloss
No change no change No gloss
No change
No change

Table 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Base oil No. 12 13 fourteen fifteen Kinematic viscosity at 40 ° C
(mm ² / s) 21.8 33.2 56.1 50.2 Kinematic viscosity at 100 ° C (mm ² / s) 4.7 5.8 5.9 9.9 The proportion of C ₅ -C ₉ fatty acids among the constituent fatty acids of the ester (mol%) one hundred one hundred - - The proportion of C ₅ -C ₉ branched fatty acids among the constituent fatty acids of the ester (% mol.) 0 45 - - Proportion of straight chain C ₅ or lower fatty acids among the constituent ester fatty acids (mol%) 0 45 - - Refrigerant Compatibility 1 Compatible Compatible Are stratified Compatible Thermal / chemical stability 1 ASTM Color (ASTM D156) L4.0 L4.0 D8.0 D8.0 Catalyst appearance Cu
Fe
Al No gloss
Blackening
No change No gloss
Blackening
No change Blackening
Blackening
Blackening Blackening
Blackening
Blackening Refrigerant Compatibility 2 Are stratified Compatible Are stratified Compatible Thermal / chemical stability 2 ASTM color
(ASTM Dl 56) L0.5 L0.5 L0.5 L0.5 Catalyst appearance Cu
Fe
Al No gloss
No gloss
No change No gloss
No gloss
No change No change
No change
No change No change
No change
No change

As can be clearly seen from the results in tables 1-3, refrigeration oils of Examples 1-11, when used together with fluoropropene refrigerant and trifluorodiomethane refrigerant, demonstrate excellent refrigerant compatibility and thermal / chemical stability.

Industrial applicability

The present invention is suitable for use as an oil for refrigerating machines and a working fluid composition for use in refrigerating machines using fluoropropene refrigerant and / or trifluorodiomethane refrigerant.

Claims (7)

1. The composition of the working fluid for the refrigeration machine, characterized in that it contains oil for refrigeration machines containing an ester of at least one polyhydric alcohol selected from pentaerythritol and dipentaerythritol and a fatty acid with a content of C ₅ -C ₉ fatty acid of 50-100 mol .%, with a content of C ₅ -C ₉ branched fatty acid of at least 30 mol.% and with a content of C ₅ or lower fatty acid with a straight chain of not more than 40 mol.%,
where the ester content is at least 80 wt.% calculated on the total weight of oil for refrigeration machines, and
fluoropropene refrigerant and / or trifluoroiodomethane refrigerant. 2. The composition of the working fluid for refrigerators according to claim 1, characterized in that
the content of C ₅ -C ₉ fatty acid is 90-100 mol.%;
the content of C ₅ -C ₉ branched fatty acid is at least 40 mol.%; and
the content of C ₅ or lower straight chain fatty acid is not more than 30 mol%. 3. The composition of the working fluid for refrigerators according to claim 1 or 2, characterized in that it contains at least one component selected from 1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene, as a fluoropropene refrigerant. 4. The composition of the working fluid for refrigerators according to claim 1, characterized in that it contains at least one fluoropropene refrigerant and at least one component selected from among refrigerants based on saturated hydrofluorocarbons, saturated hydrocarbons having from 3 to 5 carbon atoms in the molecule, dimethyl ether, carbon dioxide, bis (trifluoromethyl) sulfide and trifluorodiodomethane. 5. The composition of the working fluid for refrigerators according to claim 4, characterized in that
fluoropropene refrigerant is at least one refrigerant selected from refrigerants based on 1,2,3,3,3-pentafluoropropene, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1 2,3,3-tetrafluoropropene and 3,3,3-trifluoropropene,
saturated hydrofluorocarbon is at least one hydrofluorocarbon selected from difluoromethane, pentafluoroethane, 1,1,2,2-tetrafluoroethane, 1,1,1,2-tetrafluoroethane, 1,1-difluoroethane, fluoroethane, 1,1, 1,2,3,3,3-heptafluoropropane, 1,1,1,2,3,3-hexafluoropropane, 1,1,1,3,3,3-hexafluoropropane, 1,1,1,3,3- pentafluoropropane and 1,1,1,3,3-pentafluorobutane, and
a saturated hydrocarbon based refrigerant having from 3 to 5 carbon atoms in the molecule is at least a hydrocarbon selected from propane, n-butane, isobutane, 2-methylbutane and n-pentane. 6. Oil for refrigerators, characterized in that it contains an ester of at least one polyhydric alcohol selected from pentaerythritol and dipentaerythritol, and a fatty acid with a content of C ₅ -C ₉ fatty acid of 50-100 mol%, with a content of C ₅ —C ₉ branched fatty acids of at least 30 mol% and with a C ₅ or lower straight chain fatty acid content of not more than 40 mol%, where the ester content is at least 80 wt% based on the total mass of oil for refrigerators, and the fact that it is used with fluoride propene refrigerant and / or trifluoroiodomethane refrigerant. 7. Oil for refrigerators according to claim 6, characterized in that the polyhydric alcohol is pentaerythritol and / or dipentaerythritol.