JPH08209163A - Hydrocarbon refrigerant composition - Google Patents

Abstract

PURPOSE: To obtain a refrigerant compsn. exhibiting a good compatibility, a high stability, and a good lubricity by mixing a hydrocarbon refrigerant with a lubricant comprising a specific fluorinated arom. compd. CONSTITUTION: This refrigerant compsn. contains as the essential components a 1-5C hydrocarbon refrigerant and a lubricant comprising a fluorinated arom. compd. represented by R(XRf)n (wherein X is 0 or S; R is a 6-60C n-valent arom. group; (n) is 1-4; and Rf is an optionally partially substd. 1-25C fluorocarbon group having a ratio of the number of fluorine atoms to the number of carbon atoms of 0.2-3 and optionally having ether linkages in the main chain provided when (n) is 2 or higher, it may comprise a plurality of XRf groups). An another lubricant to be mixed with the fluorinated arom. compd is pref. a hydrocarbon lubricant. The wt. ratio of the total refrigerant to the total lubricant is usually (99:1) to (1:99).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a lubricating oil for hydrocarbon refrigerants.

[0002]

2. Description of the Related Art Conventionally, the refrigerant used in refrigerators for car air conditioners and refrigerators has been mainly CFC-12 (dichlorodifluoromethane). For room air conditioners, HCFC-22 (chlorodifluoromethane)
However, CFC-11 (fluorotrichloromethane) has been mainly used for turbo refrigerators. But,
Chlorofluorocarbon (CFC) -based refrigerants such as CFC-12 and CFC-11 and hydrochlorofluorocarbon (HCFC) -based refrigerants such as HCFC-22 are
It is said to cause ozone layer depletion, and it is desired to develop a refrigerant that can substitute for these.

Since ozone layer depletion is believed to be due to the action of chlorine atoms contained in chlorofluorocarbons and hydrochlorofluorocarbons, HFC (hydrofluorocarbon) type refrigerants containing no chlorine atom are now candidates as alternative refrigerants. ing. For example, CFC-12
As an alternative refrigerant of HFC-134a (1, 1, 1,
2-Tetrafluoroethane) and the like are candidates for a mixed refrigerant containing HFC-32 (difluoromethane) as an alternative refrigerant for HCFC-22. However, HFC-134
Although HFC-based refrigerants such as a and HFC-32 have no ozone depleting ability at all, they have a long life in the atmosphere, so there is concern about their effect on global warming.

As an alternative refrigerant of CFC-11 (bp = 23.8 ° C.), HCFC having a relatively small ozone depletion ability
-123 (1,1-dichloro-2,2,2-trifluoroethane, bp = 27.5 ° C) and HCFC-141b
(1,1-dichloro-1-fluoroethane, bp = 32
C) is a candidate. However, the ozone layer depleting ability of these HCFC-based refrigerants is small compared to CFC-based refrigerants, and the problem is that they are not absent.

Under the above circumstances, there is a demand for a next-generation refrigerant that has no ozone depleting ability and has a minimal effect on global warming. In recent years, various hydrocarbon-based refrigerants have been studied as refrigerant candidates satisfying these points. On the other hand, the lubricating oil used in the refrigeration system needs to have sufficient compatibility with the refrigerant. If you use an incompatible lubricant,
A number of serious problems arise, including: For example, if the lubricating oil is replaced by the refrigerant in the compressor, the lubricity becomes insufficient, or the lubricating oil adheres to the inner wall of the heat exchanger, resulting in a poor heat exchange rate. Further, the lubricating oil for the refrigeration system needs to be practically excellent not only in good compatibility with the refrigerant but also in stability, low hygroscopicity and lubricity.

[0006]

As a lubricating oil for a refrigerator using a hydrocarbon-based refrigerant, which has no ozone layer depleting ability and is expected to be a refrigerant having a small effect on global warming, Excellent compatibility with hydrocarbon refrigerants, and
It is necessary to find one that has excellent stability, low hygroscopicity, and lubricity.

[0007]

The inventors of the present invention have made extensive studies on various lubricating oils. As a result, when chlorofluorocarbons are used as the refrigerant, hydrocarbon lubricants such as mineral oil and alkylbenzene that have been conventionally used are not excellent in compatibility with hydrocarbon refrigerants, stability, and low hygroscopicity. However, it was found that the lubricity was insufficient when using a hydrocarbon refrigerant.

This is because the conventional CFC type refrigerant and HCFC
In a refrigerant composition consisting of a chlorine atom-containing refrigerant and a mineral oil such as a system refrigerant, and a refrigerant composition consisting of a chlorine atom-containing refrigerant and an alkylbenzene, good lubricity is exhibited due to the modification effect of the metal surface by the chlorine atom in the refrigerant. However, it has been shown that in the case of a hydrocarbon-based refrigerant, the effect of modifying the metal surface by such a refrigerant cannot be expected. Therefore, the lubricating oil used in combination with the hydrocarbon-based refrigerant must itself exhibit good lubricating properties.

Therefore, the present inventors investigated the suitability of various lubricating oils as lubricating oils for hydrocarbon refrigerants. First, it was found that although perfluoropolyether is excellent in stability and low hygroscopicity, it cannot be used because its compatibility with a hydrocarbon refrigerant is insufficient. Furthermore, polyalkylene glycol has insufficient lubricity and stability under the conditions of use of lubricating oil, and its high hygroscopicity causes corrosion of metals and reduction of volume resistivity (closed refrigeration such as refrigerators). This is not a practically excellent lubricating oil for refrigeration systems.

Further, since the polyol ester contains an ester group, it has a high hygroscopic property and is easily hydrolyzed, so that there is a problem in durability. On the other hand, the present inventors have found that the fluorine-containing aromatic compound represented by the general formula [I] has good compatibility with various hydrocarbon-based refrigerants and the hydrocarbon-based refrigerant and the general formula [I]. ], The refrigerant composition comprising the compound of [1] shows high stability and good lubricity,
The present invention has been completed.

That is, according to the present invention, a lubricating oil comprising a fluorine-containing aromatic compound represented by the general formula [I] and a hydrocarbon refrigerant having 1 to 5 carbon atoms in the molecule are essential refrigerants. A composition. R (XRf) _n ... [I] [wherein X is an O or S atom. R has 6 to 6 carbon atoms
It represents 0 n-valent aromatic groups. n represents an integer of 1 to 4. Rf represents a fluorocarbon group or a partial substitution product thereof, the number of carbon atoms in Rf is in the range of 1 to 25, and the ratio of the number of fluorine atoms / the number of carbon atoms in Rf is 0. It is 2 or more and 3 or less. Further, Rf may contain an ether bond in a part of the main chain. When n is 2 or more, the compound represented by the general formula [I] may be composed of plural kinds of XRf groups. The contents of the present invention will be described in more detail below.

As the lubricating oil represented by the general formula [I] in the present invention, for example, a fluorine-containing aromatic compound [I] disclosed in JP-A-5-86382 or Japanese Patent Application No. 6-189716. The fluorinated aromatic compound (A) disclosed in the publication can be used. That is, it is as follows. In general formula [I], R has 6 to 60 carbon atoms.
Represents an n-valent aromatic group. The number of carbon atoms in R is 6 to 60, preferably 6 to 50, and more preferably 6 to 40 because it has a viscosity range suitable as a refrigerating machine oil.

The aromatic nucleus contained in the aromatic group R in the general formula [I] may or may not have a substituent. When it has a substituent, the substituent has a carbon number of 0 to 5 because it has a suitable viscosity range as a refrigerating machine oil.
A monovalent substituent containing no 0 aromatic nucleus is preferred, and one selected from the following (A) to (E) is particularly preferred from the viewpoint of the stability of the compound.

(A) Saturated hydrocarbon residue or unsaturated hydrocarbon residue (b) Saturated hydrocarbon residue or unsaturated hydrocarbon residue partially or wholly substituted with a halogen atom (c) Ester group, Substituent having at least one of an alkoxy group, an ether group, a carbonyl group, and a hydroxyl group (d) Specific examples of the monovalent substituent group substituted on the aromatic nucleus contained in the halogen atom R are as follows. There are things.

[0015]

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[0016]

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[0017]

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[0018]

[Chemical 4]

The aromatic group represented by R in the formula [I] can have one or more substituted or unsubstituted aromatic nuclei. When the number of aromatic nuclei in R is 2 or more, these aromatic nuclei may be directly bonded to each other, or may be linked by a linking group having 0 to 50 carbon atoms and not containing an aromatic nuclei. This linking group usually has a valency of 2 to
4 are used, and those selected from the following (e) to (ki) are preferable from the viewpoint of the stability of the compound.

(E) Saturated hydrocarbon residue or unsaturated hydrocarbon residue (f) Saturated hydrocarbon residue or unsaturated hydrocarbon residue partially or wholly substituted with a halogen atom (ki) Linking group having at least one group —O—, —C (═O) —, —SO ₂ —, —S—, —C
(= O) O -, - C (= O) O- (CH 2) m -OC (=
O)-[wherein, m represents a positive integer such that the total number of carbon atoms in the aromatic group R is 60 or less. ] Specific examples of the linking group connecting two or more aromatic nuclei contained in R include the following.

[0021]

Embedded image

[0022]

[Chemical 6]

[0023]

[Chemical 7]

[0024]

Embedded image [A is a single bond, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. B is a single bond or an oxygen atom (-O
-) Is shown. D is a single bond, an oxygen atom (-O-),-
Either R'or -OR '. R'is 1 to 2 carbon atoms
It is 0 alkyl groups. ]

[0025]

[Chemical 9] [A is a single bond, a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms. ]

[0026]

[Chemical 10]

[0027]

[Chemical 11]

[0028]

[Chemical 12]

As the aromatic group R having the above-mentioned substituent and / or linking group or the aromatic group R having neither substituent nor linking group, inexpensive raw materials can be used and excellent stability is exhibited. Therefore, it is a divalent to tetravalent one having a carbon number of 6 to 33 and X in the general formula [I].
It is preferable that the Rf group is directly bonded to the aromatic nucleus in R, and it is further preferable that X is O. In addition, the aromatic group R
Is preferably a substituted or unsubstituted benzene ring in view of easy availability of raw materials, but when the aromatic group R has two benzene rings, these benzene rings are directly bonded to each other or carbon Those linked by a divalent linking group of several 0 to 20 are more preferable, and as the linking group, any of the following (H) to (H) is further preferable.

(H) Unsubstituted saturated or unsaturated hydrocarbon group (K) Saturated or unsaturated hydrocarbon group partially or wholly substituted with a fluorine atom Aromatic group R in the general formula [I] However, in the case of containing only one aromatic nucleus, the carbon number of R is 6 to 6 because of easy availability of raw materials.
60, preferably 6 to 50, more preferably 6 to
36, and the valence of this aromatic nucleus is n = 1 to 4,
Preferably n = 1 to 2, more preferably 1. X in the general formula [I] is an O or S atom, but an O atom is preferable from the viewpoint of easy availability of raw materials. The XRf group in the general formula [I] may or may not be directly bonded to the aromatic nucleus in R, but from the viewpoint of the stability of the compound,
It is preferably bound directly to the aromatic nucleus.

Among the aromatic groups R in the general formula [I] containing only one aromatic nucleus and the XRf group directly bonded to the aromatic nucleus, the availability of raw materials and the stability of the compound are high. From the viewpoint of the above, those in which the aromatic nucleus is substituted with an alkyl group having 1 to 30 carbon atoms are particularly preferable, and more preferably X is an O atom. The value of n in the general formula [I] depends on the valence of R, and for reasons such as ease of synthesis and taking an appropriate viscosity range,
Usually, it is an integer of 1 to 4, preferably 1 to 3, and more preferably 1 to 2. Further, in the general formula [I], n is 2
When the above is satisfied, the compound of the general formula [I] has a plurality of X
It may be composed of Rf. Specific examples of R as described above include the following.

[0032]

[Chemical 13]

[0033]

Embedded image

[0034]

[Chemical 15]

[0035]

Embedded image

[0036]

[Chemical 17]

[0037]

Embedded image

In the general formula [I], Rf represents a fluorocarbon group or a partial substitution product thereof, and the number of carbon atoms in Rf is in the range of 1 to 25. The fluorocarbon group means a structure in which some or all of hydrogen atoms of various hydrocarbon groups are substituted with fluorine atoms.
Examples thereof include a fluoroalkyl group having a saturated structure, a fluoroalkenyl group having an unsaturated structure, a fluoroaryl group having an aromatic nucleus, a fluoroalkylaryl group, a fluoroaralkyl group and the like, but particularly a fluoroalkyl group and a fluoroalkyl group. The alkenyl group is easy to synthesize and useful. Further, Rf may include an ether bond in the main chain of the fluorocarbon group. When Rf contains an ether bond, the number of ether bonds is preferably in the range of 1 to 7, particularly preferably in the range of 1 to 3. Further, as Rf, the fluorocarbon group or an ether derivative thereof may be substituted with another substituent. When Rf contains a substituent other than a fluorine atom and an ether bond, the number of the substituent is usually in the range of 1 to 4, preferably 1 to 2, and particularly preferably 1.

The substituent of Rf is not particularly limited as long as it is stable under the conditions of use of the refrigerator, and examples thereof include the following. A halogen atom other than a fluorine atom. That is, a chlorine atom, a bromine atom and an iodine atom are preferable, but a chlorine atom is particularly preferable. An active hydrogen group selected from a hydroxyl group, an amino group and a thiol group. (However, a structure in which an active hydrogen group is bonded to a carbon atom to which a halogen atom is bonded is not taken.) Thioalkoxy group, alkyl-substituted amino group, and acyl group, acyloxy group, carboalkoxy group, nitrile group, amide group, imide Substituents having 10 or less, preferably 6 or less, and particularly preferably 3 or less carbon atoms selected from organic acid derivatives such as groups. The substituent may contain a fluorine atom.

[Number of the above-mentioned substituents in Rf] /
The ratio of [total number of fluorine atoms and hydrogen atoms in Rf] is 1.
It is 5 or less, preferably 1.0 or less. Among the above substituted fluorocarbon groups, an ether bond-containing fluorinated hydrocarbon group and a chlorine atom-containing fluorinated hydrocarbon group are particularly preferred because they are easy to synthesize and exhibit good stability. The ratio of the number of fluorine atoms / the number of carbon atoms in Rf does not have a particularly critical range and a wide range can be used, but is usually 0.2 or more and 3 or less, preferably 0.6 or more 3 The following are used, more preferably 1 or more and 3 or less, and particularly preferably 1.5 or more and 3 or less. If this ratio is too low, the pour point of the compound of general formula [I] becomes high, which is not preferable.

The carbon number of Rf is usually 1 to 25.
A range of 1, preferably 1 to 10, particularly preferably 1 to 3 is used. If the number of carbon atoms in Rf is more than 25, it becomes difficult to obtain or synthesize the raw materials, and the synthesis and purification become complicated, and the viscosity becomes too high, which is not preferable. The structure of Rf is not particularly limited as long as it satisfies the above requirements.
The following general formula [VI] shows a typical example of the structure, but the structure is not limited to this structure.

[0042]

[Chemical 19]

However, A ₁ , A ₂ and A ₃ are a fluorine atom or a fluorinated alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and particularly preferably fluorine or --CF ₃ . B
₁ , B ₂ and B ₃ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and particularly preferably a hydrogen atom or —CH ₃ . Z is a hydrogen atom or a fluorine atom. n ₁ is an integer of 0 to 25, preferably 1 to 20, n
₂ is an integer from 0 to 10, n ₃ is an integer from 0 to 10 and n ₄ is 0
Is an integer of ~ 7. However, (n ₁ + n ₃ ) is never zero.

In the general formula [VI], n ₁ , n ₂ , n ₃
When is an integer of 2 or more, each may have the same or different structure. In the general formula [VI], each unit of (CA ₁ A ₂ ), (CB ₁ B ₂ ), and (CA ₃ B ₃ ) may have a plurality of structures or may be randomly arranged. Further, each may be linked by a double bond, or may form an alicyclic or aromatic cyclic structure.

The following units are not connected to each other, and the following units are not located at the end of the general formula [VI] or next to Z.

Embedded image Further, as Rf, a part of the fluorine atom or hydrogen atom of the structure of the general formula [VI], preferably 1 in the range of 1 to 4, is a halogen atom other than the above-mentioned fluorine atom, an active hydrogen group and It may have a structure substituted with at least one substituent selected from substituents having 10 or less carbon atoms.

Rf in the general formula [I] has 1 carbon atom from the viewpoint of easy availability of raw materials and stability of the compound.
To three fluoroalkyl group, -CF = CFCF _3, -
_{CF 2 CFClH, -CF = CFCl,} -CF 2 CFCl
_{2, -CF 2 CHFO (C 3} F 6 O) m 'CF 2 CF 2 CF 3
[However, m 'is an integer of 0 to 6] Particularly preferably, -CHF _{2 Among, -CF 2 CHF 2, -CF 2} CHFC
_{F 3, -CF = CFCF 3,} -CF 2 CHClF, -CF
₂ CFCl ₂ is more preferred. Examples of Rf in the compound represented by the general formula [I] used in the present invention are shown below. Examples of Rf shown here are those in the compound of the general formula [I] obtained by various synthetic methods. However, the present invention is not limited to this.

[0047]

[Chemical 21]

[0048]

[Chemical formula 22]

[0049]

[Chemical formula 23]

[0050]

[Chemical formula 24]

[0051]

[Chemical 25]

The fluorine-containing aromatic compound represented by the general formula [I] used in the present invention can be synthesized by various methods. In the following, an example of synthesis in the case of n = 1 in the general formula [I] is illustrated, but in the case of n = 2, 3, 4, the synthesis can be performed by the same method. 1) Reaction of Phenols or Thiophenols with Fluorine-Containing Olefins Many reaction examples are known for the synthesis of fluorine-containing aromatic compounds by the reaction of phenols or thiophenols with fluorine-containing olefins.

As a typical reaction example, a case of perfluoroolefin is shown, and the following ionic reactions (1 ') and (2') can be mentioned.

[Chemical formula 26]

The reaction examples of phenols and fluorinated olefins are shown below. For example, Advance in F
luorine Chemistry, 4, 50 (19
65) shows reaction examples similar to the formulas (1 ') and (2') by ionic reaction of various fluorine-containing olefins with phenols or alcohols or thiophenols as shown below. There is.

CF ₂ = CF ₂ , CF ₂ = CFCl, CF ₂ =
CFBr, CF ₂ = CFH, CF ₂ = CHCl, CF ₂ =
CCl ₂ , CHF = CCl ₂ , CF ₃ CF = CF ₂ , CCl
F ₂ CF = CF ₂ , CF ₃ CCl = CF ₂ , CF ₃ CF = C
Cl ₂ , CF ₃ CCl = CClF, CF ₃ CH = CH ₂ , C
F ₃ CH = CHCl, CF ₃ CCl = CHCl, CF ₃ C
Cl = CCl ₂ , CF ₃ CF ₂ CCF = CF ₂ , CF ₃ CF
_{= CFCF 3, (CF 3)} 2 C = CF 2, CF 2 = CF-C
F = CF ₂ ,

[0056]

[Chemical 27] CF ₃ CCl = CClCF ₃ , CCl ₂ FCClFCF =
_{CClF, CF 3 - (CF 2} ) 4 -CF = CF 2.

In addition, Journal of Ameri
can Chemical Society, 73, 5
831 describes a reaction represented by the following formula (3 ′).

[Chemical 28] [Wherein R ₂ = H, an alkyl group; X ¹ , X ² = F, C
l, H]

142nd, Meeting, Ameri
can Chemical Society, Atla
Nic City, N.N. J. , Sept, 1962
Abs, P19U describes a reaction represented by the following formula (4 ′).

[Chemical 29]

Journal of American
Chemical Society, 82, 5116
(1960) describes reactions such as formulas (5 ′) to (7 ′).

Embedded image

[0060]

[Chemical 31] [X ³ = Cl, F]

The reactions of the following formulas (8 ') and (9') are described in the Journal of Japan Society, 1975, 311.

Embedded image ^{[Y 1 = H, -OMe,} -NO 2; X 4 = F, CF 3]

[Chemical 33]

Further, an oligomer of hexafluoropropene (HFP) represented by the general formula (10 ') and tetrafluoroethylene (TF) represented by the general formula (11').
E) oligomers, or unsaturated bond-containing oligomers derived from various fluorinated olefins typified by chlorotrifluoroethylene oligomers,
It can be used as a raw material for a synthetic reaction such as the formulas (1 ′) and (2 ′). _{C3m F6m} ... (10 ') [m: integer of 2 or more, preferably 2 to 6] _{C2m' F4m '} ... (11') [m ': integer of 2 or more , Preferably an integer of 2 to 10]

As an example of the reaction of such an oligomer,
Bull. Chem. Soc. Japan, 49, 50
2 (1976), the formulas (12 ′) to (1
There is a reaction like 3 ').

Embedded image

The reaction of the formula (14 ') is described in the Journal of the Chemical Society of Japan, 1978, 253.

Embedded image

"Oligomer" (Kodansha Scientific) Okawara, Saegusa, Higashimura, (1976), P288-
291 is a reaction of a number of TFE pentamers (C ₁₀ F ₂₀ ) or HFP trimers (C ₉ F ₁₈ ) represented by the reactions of the formulas (15 ′) to (19 ′) with phenols. Are shown in large numbers.

Embedded image

[0066]

Embedded image

Also, Journal of Fluor
ine Chemistry, 54, 162 (199
In 1), an addition reaction of phenols and perfluorovinyl ethers represented by formulas (20 ′) and (21 ′) is reported.

[Chemical 38]

In addition, Izvest. Akad. Nauk
S. S. S. R. Otdel, Khim, Nauk,
1952, 261-7, the addition reaction of thiophenol and chlorotrifluoroethylene or tetrafluoroethylene as shown in the reaction formula of (22 ') is reported.

[Chemical Formula 39]

Bull. Soc. Chim. F
r. , 1972, (8), 3202-5 have (23 ')
An addition reaction of thiophenol and chlorotrifluoroethylene as shown in the formula has been reported.

[Chemical 40]

2) Reaction of Phenols or Thiophenols with Saturated Fluorocarbons There are many possible reaction methods for the reaction of fluorine-containing aromatic compounds by the reaction of phenols or thiophenols with saturated fluorocarbons. As a typical reaction method, for example, the reactions of the formulas (24 ′) to (25 ′) can be mentioned.

Embedded image [Here, X represents an O or S atom. The X ^5, X ⁶ is a halogen _{atom, -OSO 2 Me, -OCOCF 3,} -OSO 2
CF _3, -OSO ₂ CCl _3, represents the easily eliminated substituents as anion such as -OSO ₂ Cl. Ar 'represents a monovalent aromatic group. Rf ′ is the same as Rf in the general formula, and Rf
It represents a compound that can have an anion structure of f′X ⁻ . ]

Actual. Chem. , 1987, 1
In 51, reactions such as formulas (26 ′) to (27 ′) are described.

Embedded image [Where R ³ = H, 4-Cl, 4-Br, 2-MeO
C (= O), 4- NO 2, 2-NO 2, 4-CF 3,; X 7
= F, Cl, Br; R 4 = -SO 2 Me, -COCF 3,
_{-SO 2 CCl 3, -SO 2 C} 6 H 4 Me-p, -SO 2 C
l]

"Chemistry of Organ"
ic Fluorine Compounds ”Ha
1st Press, 2nd Edition, P
279 includes alkylation of alcohols, phenols and thiols with oxygen or sulfur atoms (Alkyr
ation at Oxygen or Sulfu
Many methods for synthesizing a fluorine-containing ether compound or a fluorine-containing thioether compound by r) have been shown.

Journal of Organic C
chemistry, 50, 4047 (1985) describes the reaction of formula (28 ').

[Chemical 43] [Z ¹ = H, Me, OMe, Cl; X = O, S]

Industrial and Engi
neering Chemistry, 39, 412
(1947) describes the reactions of formulas (29 ') to (30').

[Chemical 44]

Tetrahedron Letter
s, 22, 323 (1981) describes the reaction of formula (31 ').

Embedded image

Pure and Applied Ch
In many studies, 59, 1015 (1987), various reactions of various fluorinated halides represented by the general formula (32 ') with phenoxides are shown. CZ ₂ Z ₃ Z ₄ CFZ ₃ Z ₄ (32 ′) [where Z ₂ = Cl, Br, I, and Z ₃ = Z ₄ = F,
Cl, Br, CF ₃ and H. ]

As an example thereof, equations (33 ') to (3
4 ') reaction is mentioned.

Embedded image

Journal of Organic
Chemistry, 25, 2009 (1960) describes the reaction of formula (35 ').

[Chemical 47] [Here, Z ⁵ , Z ⁶ = H, Me, MeO, NO ₂ , C
In addition to H ₃ , Cl], the method of forming various ether bonds or thioether bonds can be utilized to synthesize the fluorine-containing aromatic compound of the general formula [I].

As an example, for example, equations (36 ')-
An ether-forming reaction by a reaction between a hydroxyl group and an epoxy group such as (37 ′) can be mentioned.

Embedded image [Here, Ar 'represents a monovalent aromatic group, and Rf "represents a fluorocarbon group having 1 to 16 carbon atoms.] Further, various methods can be applied to a precursor substance of the compound represented by the general formula [I]. You can also use the method of introducing fluorine atoms with
Alternatively, the reaction products synthesized by various methods shown so far are further converted by various reactions to obtain the desired general formula [I].
You may induce | guide | derive to the compound shown by.

As an example thereof, there is a method described in Actual. Che
m. , 1987, 151 describe the reaction of formula (38 ').

[Chemical 49] [Here, R ³ is the same as R ^{3 in the} formula (27 ′). The fluorinated compound such as fluorinated olefin and saturated fluorocarbon used in the above reaction can be synthesized by various known methods.

As an example, "Advances i
n Fluorine Chemistry ”But
terworth, vol. 3, a synthetic method by halogen exchange shown in P181, "Chemistry"
of Organic Fluorine Compo
unds “Halted Press”, or JP-A-50-117705, JP-B-43-11885, and JP-B-47-22563.
Examples thereof include a method for synthesizing a fluoroolefin oligomer described in JP-A No. 2003-154, but the method is not limited to these methods.

The fluorine-containing aromatic compound represented by the general formula [I] can be synthesized by various methods, and the reactions shown so far are some of the specific examples. Therefore, the synthetic method of the compound of the general formula [I] is not limited to these methods.

When the compound represented by the general formula [I] of the present invention is used alone as a lubricating oil for a refrigerator using a refrigerant containing a hydrocarbon, its viscosity is usually 40. Those having a kinematic viscosity in the range of 2 to 500 centistokes (hereinafter abbreviated as “cSt”) at 0 ° C., preferably in the range of 3 to 300 cSt, more preferably in the range of 5 to 170 cSt, particularly preferably 1
Those in the range of 0 to 150 cSt are used.

Alternatively, the kinematic viscosity at 100 ° C. is usually
The range of 0.5 to 100 cSt, preferably 1 to 50 cSt, particularly preferably 2 to 30 cSt is used. If the viscosity is too low, sufficient lubricity cannot be obtained in the compressor part, and if the viscosity is too high, the rotating torque of the compressor part becomes high, which is not preferable. Also,
When the compound represented by the general formula [I] is used as a mixture of a plurality of types, or when it is used as a mixture with another type of lubricating oil, the compound represented by the general formula [I] itself is used. The viscosity is not particularly limited, and the viscosity of the mixed system may be in the same range as when the compound represented by the above general formula [I] is used alone.

Specific examples of the above-mentioned compound of the general formula [I] are as follows:
As disclosed in Japanese Patent Application Laid-Open No. 5-86382, for example, the following formulas can be given.

Embedded image

[0086]

[Chemical 51]

[0087]

Embedded image

[0087]

Embedded image

[0088]

[Chemical 54]

[0089]

[Chemical 55]

[0090]

[Chemical 56]

Further, among the compounds represented by the general formula [I], the present inventors have particularly shown the following general formula [II],
The compounds [III] and [V] have 1) low so-called “bioconcentration”, which is a measure of the degree of concentration in living organisms, and 2) low hygroscopicity and good electrical insulation. , 3) It has excellent compatibility with hydrocarbon-based oils such as alkylbenzene and mineral oil, so when mixed with hydrocarbon-based oils, properties such as low temperature fluidity, low hygroscopicity, and electrical insulation properties are greatly improved. In addition, it has been found that it is particularly practically excellent because it has the features that it can be manufactured at low cost.

That is, according to one aspect of the present invention, there is provided a refrigerant composition in which a fluorine-containing aromatic compound is represented by the general formula [II].

[Chemical 57]

However, R ¹ and R ² in the general formula [II] represent an alkyl group having 1 to 19 carbon atoms or a hydrogen atom, and the total number of carbon atoms of R ¹ and R ² is 4 to 19, The range is preferably 5 to 16, and particularly preferably 5 to 12. R ¹
When the total number of carbon atoms of R ² and R ² is 3 or less, high bioconcentration is exhibited. On the other hand, when the total number of carbon atoms of R ¹ and R ² is 20 or more, it becomes difficult to obtain the raw material, which is not preferable. Also,
From the viewpoint of stability, it is preferred that both R ¹ and R ² are alkyl groups rather than R ¹ and R ² being hydrogen atoms. Rf is a fluorocarbon group, like the general formula [I].
Alternatively, it represents a partial substitution product thereof, and its definition is also the same.

According to another aspect of the present invention,
There is provided a refrigerant composition in which a fluorinated aromatic compound is represented by the general formula [III].

Embedded image

However, in the general formula [III], R ³ , R ⁴ and R
Each of ⁵ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. n'represents an integer of 1 to 3. When n ′ is 2 or 3, the compound represented by the general formula [III] may be composed of plural kinds of R ³ R ⁴ R ⁵ C-groups. Further, in the general formula [III], the total number of carbon atoms of all R ³ R ⁴ R ⁵ C-groups bonded to the aromatic nucleus is 4 to 25.
Range. In addition, when the total number of carbon atoms of all R ³ R ⁴ R ⁵ C-groups is 26 or more, it becomes very difficult to obtain raw materials, which is not preferable. Rf represents a fluorocarbon group or a partial substitution product thereof, like the general formula [I], and the definition is the same.

The alkyl groups R ¹ , R ² , R ³ , R ⁴ and R ⁵
The compound may contain the same substituents and linking groups as those contained in R in the general formula [I], examples of which include unsaturated hydrocarbon residues and halogen atoms such as chlorine and fluorine. , Hydroxyl group, thiol group, alkoxy group, nitrile group,
Nitro group, ether group, thioether group, ester group,
Carbonyl group, sulfonyl group, sulfinyl group, carboxyl group, carboxylate group, amino group, thiocarbamate group, amide group, imide group, pyridine group, pyrimidine group, piperidine group, triazine group, phosphine group, benzimidazole group, phosphorus Examples include various oxygen-containing, nitrogen-containing, phosphorus-containing, and sulfur-containing polar groups such as acid ester groups, triazole groups, tetrazole groups, thiazole groups, and thiadiazole groups. Of these, fluorine atoms and ether groups are particularly preferable because they exhibit high stability. The number of the above-mentioned substituents and linking groups is usually 5 or less, preferably 3 or less, and particularly preferably 1 or less.

Specific examples of R ¹ , R ² , R ³ , R ⁴ and R ⁵ are shown below using the general formula [II] or the general formula [III].

Embedded image

[0098]

Embedded image

[0099]

[Chemical formula 61]

In the general formula [II] or [III], Rf represents a fluorocarbon group or a partial substitution product thereof as in the general formula [I], and the definition is the same. Rf
As may fluoroalkyl group is in the range of 1 to 25 carbon atoms, even fluoroalkenyl group, specific examples _{thereof, -C 6 F 11, -C 6} F 12 H, -C 9 F 17, −
C ₉ F ₁₈ H, and the like. The carbon number of Rf is preferably in the range of 1-10, more preferably 1-3. Further, Rf may be a fluoroalkyl group having a carbon number of 2 to 25 and containing 1 to 7 ether groups in the main chain. Further, Rf may be a structure of general formula [VI] substituted with 1 to 4 chlorine atoms.

More preferably, Rf has 1 to 10 carbon atoms.
3 fluoroalkyl group, -CF = CFCF _3, -CF ₂
CFClH, -CF = CFCl, and

Embedded image Can be used.

Specific examples of the fluoroalkyl group having 1 to 3 carbon atoms include -CF ₂ H, -CF ₃ and -CF ₂ C.
_{F 2 H, -CF 2 CF 3} , may be mentioned -CH ₂ CF ₃ and the like. The fluorine-containing aromatic compound represented by the general formula [II] or the general formula [III] is characterized by exhibiting particularly high stability among the structures represented by the general formula [I].
For example, a nonylphenyl ether type or dodecylphenyl ether type fluorine-containing aromatic compound represented by the following general formula [VII] or general formula [VIII] as described in JP-A-5-86382 is While heating in air causes oxidation and thermal decomposition, the general formula [I
I] or the fluorine-containing aromatic compound represented by the general formula [III] does not decompose even if it is heated in air at 175 ° C. for a long time.

[0103]

[Chemical formula 63]

Further, the more stable the substance is in the environment, the higher the probability that the chemical substance will come into contact with the living body. Therefore, the chemical substance released into the environment will enter the living body in the water, soil, or atmosphere. It can be taken up and concentrated and can become an environmental pollutant. From the standpoint of environmental hygiene, the present inventors examined the correlation between the structure of various fluorine-containing aromatic compounds represented by the general formula [I] and bioconcentration.
As a result, it was confirmed that the fluorine-containing aromatic compounds represented by the general formula [II] and the general formula [III] showed low bioconcentration in the bioconcentration test.

Among the general formulas [III], those having the structure of the general formula [IV] are particularly preferable from the viewpoint of easy availability of raw materials.

[Chemical 64] [R ⁶ , R ⁷ , R ⁸ and Rf are each represented by the general formula [II
I]] are the same as R ³ , R ⁴ , R ⁵ and Rf.
However, the number of total carbon atoms of R ⁶ R ⁷ R ⁸ C- group is 5 to 2
The range is 5. ]

In the general formula [IV], R ⁶ , R ⁷ and R ⁸ are alkyl groups having 1 to 20 carbon atoms, and the R ⁶ R ⁷ R ⁸ C-group has 5 to 25 carbon atoms, particularly It is preferably in the range of 7 to 15. R ⁶ R ⁷ R ⁸ carbon atoms in the C- group has a proper viscosity as a lubricating oil in the case of 5 to 25, also preferred to indicate the value lower bioaccumulation.

According to another aspect of the present invention, there is provided a refrigerant composition in which the fluorine-containing aromatic compound is represented by the general formula [V].

Embedded image [However, R ⁹ and R ¹⁰ each represent a hydrocarbon group having 1 to 6 carbon atoms. Also, R ^11, R ^12, R ^13, R ¹⁴ are each hydrogen atom or an alkyl group, an aryl group, a hydrocarbon group having 1 to 10 carbon carbon atoms selected from an aralkyl group, R ^11, R ^12, R The total number of carbon atoms in ¹³ and R ¹⁴ is in the range of 1 to 36. Further, Rf represents a fluorocarbon group containing a fluorine atom, or a partial substitution product thereof, the number of carbon atoms in Rf is in the range of 1 to 25, and the number of fluorine atoms in Rf / the number of carbon atoms is The ratio is 0.
It is 2 or more and 3 or less. ]

R ⁹ and R ¹⁰ in the general formula [V] are hydrocarbon groups having 1 to 6 carbon atoms, preferably alkyl groups having 1 to 6 carbon atoms, and particularly preferably carbon atoms. Is an alkyl group having a number of 1 to 4. When R ⁹ and R ¹⁰ have a carbon number of 7 or more, it is difficult to obtain the raw materials. Furthermore, in the general formula [V], even if R ⁹ and R ¹⁰ are the same,
It may be different, but in terms of availability of raw materials,
It is desirable that either one of R ⁹ and R ¹⁰ is a methyl group. Further, R ⁹ and R ¹⁰ may be connected to each other to form a 5- to 8-membered ring structure.

R ¹¹ , R ¹² , R ¹³ and R ^{14 in the} general formula [V]
Are each a hydrogen atom or the number of carbon atoms selected from an alkyl group, an aryl group and an aralkyl group, which is 1 to 10
Hydrocarbon group, preferably having 2 to 10 hydrogen atoms or carbon atoms, and more preferably 2 carbon atoms.
-8, particularly preferably an alkyl group having 3 to 6 carbon atoms. Furthermore, the total number of carbon atoms in R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ is in the range of 1 to 36, preferably 4 to 24, and more preferably 6 to 18.
When the total number of carbon atoms in R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ is 37 or more, the compatibility with the fluoroalkane-based refrigerant or the fluorine-containing ether-based refrigerant is decreased, and the raw materials are Becomes difficult to obtain.

The hydrocarbon groups R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R
¹³ and R ¹⁴ may contain a substituent, and examples thereof include a halogen atom such as fluorine and chlorine, a hydroxyl group, a thiol group, an alkoxy group, a nitrile group, a nitro group, an ether group, an ester group and a carbonyl group. Group, carboxyl group, sulfonyl group, sulfinyl group, amino group, amide group, phosphine group, phosphite group, triazole group, tetrazole group, thiazole group, various oxygen-containing nitrogen, phosphorus-containing atom, such as thiadiazole group, Mention may be made of polar groups of sulfur-containing atoms. Among these, particularly in the case of a fluorine atom and an ether group, high stability is exhibited, which is desirable.

Specific examples of R ⁹ and R ¹⁰ include the following.

[Chemical formula 66]

Specific examples of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ include the following.

Embedded image

Further, specific examples of the compound of the general formula [V] are shown below, and the examples of the compounds shown here are some of the compounds of the formula [V] obtained by various synthetic methods. However, it is not limited to this.

[Chemical 68]

[0114]

[Chemical 69]

[0115]

Embedded image

[0116]

Embedded image

[0117]

Embedded image

[0118]

Embedded image

[0119]

[Chemical 74]

[0120]

[Chemical 75]

[0121]

[Chemical 76]

[0122]

Embedded image

[0123]

Embedded image

[0124]

Embedded image

[0125]

Embedded image

[0126]

[Chemical 81]

[0127]

[Chemical formula 82]

[0128]

[Chemical 83]

As the lubricating oil used in the present invention, the compound of the general formula [I] can be used alone or in combination of two or more kinds. Furthermore, if necessary, naphthene-based mineral oil, paraffin-based mineral oil, alkylbenzene, alkylnaphthalene, hydrocarbon-based lubricating oil such as poly-α-olefin, further, polyalkylene glycol, ether-based lubricating oil such as polyphenyl ether, Fluorine-based lubricating oil such as polychlorotrifluoroethylene, ester-based lubricating oil such as polyol ester and mixed ester,
It can also be used as a mixture with various lubricating oils having a structure other than the general formula [I], such as carbonate-based lubricating oils such as polycarbonate. Of these, hydrocarbon-based lubricating oils have excellent stability, electrical insulation properties, and low hygroscopicity, and therefore, are represented by the general formula [I]
It is preferable as a lubricating oil to be used by mixing with the above compound. Among hydrocarbon-based lubricating oils, alkyl-substituted aromatic compounds such as alkylbenzene and alkylnaphthalene are preferable because they have particularly excellent compatibility with the compound of the general formula [I], and the mixed oil has low hygroscopicity. It is a highly practical lubricating oil because of its excellent stability, electrical insulation, and lubricating characteristics.

When the compound of the general formula [I] is mixed with a lubricating oil having another structure as described above, the weight ratio of the compound of the general formula [I] to the whole mixed lubricating oil is It is usually in the range of 0.1% by weight to 99.9% by weight, preferably in the range of 1% by weight to 99% by weight, particularly preferably
5 wt% to 95 wt%, more preferably 10
It is in the range of wt% to 90 wt%.

In the refrigerant composition of the present invention, the weight ratio of total amount of refrigerant / total amount of lubricating oil in the refrigeration system is usually 99.
/ 1 to 1/99, preferably 95/5 to 5/95
The range is more preferably 90/10 to 10/90. In addition, the refrigerant composition of the present invention may optionally contain load-bearing additives (oiliness agent, extreme pressure agent, antiwear agent), metal deactivators such as benzotriazole, rust inhibitors, detergent dispersants, and hinders. Additives such as antioxidants such as dephenol, antifoaming agents, viscosity index improvers, pour point depressants, and epoxy type additives such as alkyl glycidyl ethers and alkyl glycidyl esters can be added.

Specific examples of load-bearing additives include phosphorus-based additives, sulfur-based additives such as diphenyldisulfide, chlorine-based additives such as chlorotrifluoroethylene polymer, and 3,
Fluorine-based additives such as 3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanol, and long-chain alkyl groups such as oleyl alcohol and polar groups Examples thereof include additives (oil-based agents), organometallic additives such as sulfurized oxymolybdenium phosphorodithioate, and benzotriazole derivatives such as alkyl-substituted benzotriazole. Further, these load-bearing additives may be added alone, depending on the application, and, for example, a combination of a phosphorus-based additive and oleyl alcohol, a chlorotrifluoroethylene polymer and oleyl alcohol, and the like. A plurality of types may be combined and added like the combination of.

The hydrocarbon type refrigerant used in the present invention has 1 to 5, preferably 3 to 4 carbon atoms in the molecule. When the number of carbon atoms in the molecule is larger than 5, the boiling point becomes too high, which is not preferable for use as a refrigerant. Examples of the hydrocarbon-based refrigerant used in the present invention include methane, ethane, propane, n-butane, n-pentane, cyclopropane, 2-methylpropane, 2-methylbutane, ethylene and propylene.

The hydrocarbon-based refrigerant used in the present invention may be of one type or a mixture of a plurality of types. Further, it can be used as a mixture with other types of refrigerants such as hydrofluoroalkane-based refrigerants, chlorine-containing fluoroalkane-based refrigerants, and hydrofluoroether-based refrigerants. Further, when the hydrocarbon-based refrigerant used in the present invention is mixed with other types of refrigerants as described above, the ratio of the hydrocarbon-based refrigerant in the present invention is relative to the weight of the mixed refrigerant as a whole. It is usually in the range of 1% to 99%, preferably in the range of 5% to 95%, and more preferably in the range of 10%.
It is in the range of 90%.

[0135]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to Examples, but the scope of the present invention is not limited to the Examples. (Reference Reaction Example 1) 1,300 g of 2,2-bis (4-hydroxyphenyl) -4-methylpentane and 106 g of potassium hydroxide were dissolved in 2020 g of dimethyl sulfoxide, and this solution was placed in a 5 liter autoclave, and then in an autoclave. Was replaced with nitrogen, then heated to 60 ° C. and stirred. Furthermore, tetrafluoroethylene was injected under pressure to carry out the reaction. During the reaction, the pressure of tetrafluoroethylene is 3
The pressure was kept at ˜4 kg / cm ² (gauge pressure). The reaction is completed in about 1 hour and 40 minutes, and after removing the reaction solution,
Dimethyl sulfoxide was distilled off with a rotary evaporator. Next, the obtained oil was washed with distilled water and then distilled under reduced pressure to obtain 2040 g of oil [SH1].
(Yield 90%) It was confirmed that the structure of oil [SH1] was as shown below by infrared absorption spectrum analysis (FIG. 1) and mass spectrometry. Mass spectrometry: m / e = 470 (m ⁺ ) Kinematic viscosity (at 40 ° C.) = 109.3 cSt

[0136]

[Chemical 84]

(Reference Reaction Example 2) Instead of 2,2-bis (4-hydroxyphenyl) -4-methylpentane, p-
Reference Reaction Example 1 using tert-octylphenol
Oil [SH2] was obtained in the same manner as described in. Oil [SH
The structure of [2] was confirmed to be as shown below by infrared absorption spectrum analysis (FIG. 2) and mass spectrometry. Mass spectrometry: m / e = 306 (m ⁺ ) Kinematic viscosity (at 40 ° C.) = 6.1 cSt

[0138]

Embedded image

(Reference Reaction Example 3) 6.2 g of potassium hydroxide
Was dissolved in 200 ml of methanol. To this, 2,2-
200 ml of a methanol solution containing 12.7 g of bis (4-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A) was gradually added, and the mixture was stirred at room temperature for about 1 hour. After the reaction, the methanol was dried up to obtain 18.9 g of potassium alkoxide of bisphenol A. 18.9 g of this potassium alkoxide was obtained. 18.9 g of this potassium alkoxide and bisphenol A
56.0 g was dissolved in 200 ml of dimethyl sulfoxide and put in a 500 ml capacity micro bomb.

After degassing the system, the pressure was returned to normal pressure with an inert gas N ₂ . The reaction vessel was heated to 60 ° C. in an oil bath and tetrafluoroethylene was introduced to start the reaction. Tetrafluoroethylene was supplied so that the system internal pressure (gauge pressure) was kept at ² to 3 kg / cm ^2, and the reaction was carried out for about 5 hours. After the reaction, pour the container into a large amount of water and add 1 to the separated reaction product.
500 ml of 1,2-trichloro-1,2,2-trifluoroethane (hereinafter abbreviated as R-113) was added.
The R-113 layer was washed twice with distilled water, dried, and the solvent was removed to remove colorless oil ([SH3] 9%).
113 g (containing 0.1 wt%) was obtained.

After simple distillation (bp = 0.20 mmHg,
160 ° C) Separation treatment is performed using a silica gel column,
The oil [SH3] was isolated. Infrared absorption spectrum analysis, mass spectrometry [m / e = 428 (M ⁺ ), 413 (M ⁺
From -CH _3)], the oil [SH3] was confirmed to be a compound having a structure shown below. [Kinematic viscosity (at 40 ° C.) = 26 cSt]

[0142]

[Chemical 86]

(Reference Reaction Example 4) 10 g of bisphenol A
Was dissolved in 10 ml of tetrahydrofuran, 15 g of triethylamine was added thereto, and the mixture was placed in a four-necked flask equipped with a reflux cooling stirrer. To this, 180 g of hexafluoropropene trimer C ₉ H ₁₈ (manufactured by US PCR) was added, and the mixture was reacted at 60 ° C. for 6 hours. After the reaction, tetrahydrofuran, excess hexafluoropropene trimer and triethylamine were removed by an evaporator.

50 ml of R-113 was added to the reaction mixture to form a solution, which was washed with dilute hydrochloric acid and water. R-113
After the phase was purified by a silica gel column, the solvent was removed by an evaporator to remove oil [SH4].
7 g was obtained (yield 97%). Infrared absorption spectrum analysis,
From the results of mass spectrometry, it was confirmed that [SH4] was a compound having the structure shown below.

[0145]

[Chemical 87]

(Reference Reaction Example 5) Sodium hydroxide 7.1
g in 20.7 g of water, then 4.0 g of bisphenol A
And 13.8 g of dimethyl sulfoxide were added, and 100 ml was added.
It was charged in a micro-cylinder with a capacity. This micro-bomb was cooled to −78 ° C., the pressure inside the bomb was reduced, and 7.8 g of chlorodifluoromethane (R22) was introduced. 1 at 70 ° C
After reacting for 0 hour, the reaction solution was poured into a large amount of water, and 100 ml of R-113 was added to the separated reaction product. The lower layer R-113 phase was washed twice with distilled water, purified by a silica gel column, and the solvent was removed to remove oil [SH
5] was obtained (yield 18%).

Mass spectrometry [m / e 328 (M ⁺ ), 31
3 (M ⁺ -CH3)] and the results of infrared absorption spectrum analysis, it was confirmed that the oil [SH5] was a compound having the structure shown below.

Embedded image

Reference Reaction Example 6 Except for using Compound [GH6] in place of bisphenol A and hexafluoropropene in place of the hexafluoropropene trimer, the same procedure as in Reference Reaction Example 4 was conducted. Oil [SH6] was obtained (yield 70%). As a result of gas chromatography analysis and mass spectrometry, the ratio of saturated groups and unsaturated groups,
That _{-CF 2 CHFCF 3 / -CF = CF} -CF 3 4
It was 6/54.

[0149]

[Chemical 89]

Reference Reaction Example 7 17 g of potassium alkoxide of bisphenol A synthesized by the same method as in Reference Reaction Example 3 was dissolved in 100 ml of dimethyl sulfoxide to prepare 1,1-difluoro-1,2,2,2-tetrachloroethane. After adding 65 g, the mixture was heated to 60 ° C. and reacted for about 18 hours.

After the reaction, the solution was poured into a large amount of water, and 100 ml of R-113 was added to the separated reaction product. The phase-separated R-113 phase was washed twice with distilled water and the solvent was removed to give a solid 2 containing [GH7] as a main component.
3 g were obtained. Of this, 11 g was added to a solution prepared by suspending 9 g of lithium aluminum hydride in 200 ml of tetrahydrofuran, and reacted at room temperature for 5 hours and further at 65 ° C. for 5 days. After the reaction, tetrahydrofuran was distilled off, and 100 ml of toluene was added to give a solution. After washing this with distilled water,
The toluene phase was purified by silica gel to obtain 3.5 g of a colorless transparent oil (yield 50%).

From the results of infrared absorption spectrum analysis and mass spectrometry, it was confirmed that [SH7] was a compound having the structure shown below. Mass ^{spectrometry: m / e = 356M +,} 341 (M + -CH
3)

[Chemical 90]

Reference Reaction Example 8 Oil [SH8] was obtained in exactly the same manner as Reference Reaction Example 3 except that the compound [GH8] shown below was used in place of bisphenol A (yield 90%). It was confirmed by infrared absorption spectrum analysis and mass spectrometry [m / e 498 (M ⁺ )] that this compound had the structure shown below. The kinematic viscosity of this compound at 40 ° C. was 112 cSt.

[0154]

Embedded image

[0155]

Embedded image

Reference Reaction Example 9 Oil [SH9] was obtained in exactly the same manner as Reference Reaction Example 3 except that the compound [GH9] shown below was used in place of bisphenol A (yield 88%). It was confirmed by infrared absorption spectrum analysis and mass spectrometry [m / e 498 (M ⁺ )] that this compound had the structure shown below. The kinematic viscosity of this compound at 40 ° C. was 250 cSt.

[0157]

Embedded image

[0158]

Embedded image

(Reference Reaction Example 10) 4,4 '-(1-Methylethylidene) bis [2- (1,1-dimethylethyl)]
Phenol] 800 g and potassium hydroxide 53 g were dissolved in 1 liter of dimethyl sulfoxide, the solution was placed in a 5 liter autoclave, and then the inside of the autoclave was replaced with nitrogen, followed by heating to 60 ° C. and stirring. Furthermore, tetrafluoroethylene was injected under pressure to carry out the reaction. During the reaction, the pressure of tetrafluoroethylene is 3 to 4 kg / cm ^2.
(Gauge pressure). Reaction takes about 2 hours 10
Finished in minutes. After removing the reaction solution and distilling off dimethyl sulfoxide with a rotary evaporator, 1,
1.5 L of 1,2-trichloro-1,2,2-trifluoroethane (hereinafter abbreviated as R-113) was added,
It was washed 3 times with 1.5 L of distilled water. After distilling off R-113 with an evaporator, the compound [SH1
0] was obtained. (Yield 85%)

The structure of the compound [SH10] was determined by infrared absorption spectrum analysis (FIG. 3) and mass spectrometry (m / e = 540).
(M ⁺ )) confirmed the following.

Embedded image

(Reference Reaction Example 11) 4,4 '-(1-Methylethylidene) bis [2- (1,1-dimethylethyl)]
1110 g of compound [SH11] was obtained in the same manner as in Reference Reaction Example 1 except that 4,4 ′-(1-methylethylidene) bis [2- (1-methylpropyl) phenol] was used instead of [phenol]. It was (88% yield)

The structure of the compound [SH11] was determined by infrared absorption spectrum analysis (FIG. 4) and mass spectrometry (m / e = 540).
(M ⁺ )) confirmed the following.

[Chemical 96]

(Reference Reaction Example 12) 4,4 '-(1-Methylethylidene) bis [2- (1,1-dimethylethyl)]
Compound [SH12] was prepared in the same manner as in Reference Reaction Example 1 except that 750 g of 4,4 ′-(1-methylethylidene) bis [2- (1-methylethyl) phenol] was used instead of 800 g of phenol. 1009 g was obtained. (Yield 82%) It was confirmed that the structure of the compound [SH12] was as shown below by infrared absorption spectrum analysis (FIG. 5) and mass spectrometry (m / e = 512 (M ⁺ )).

[0164]

Embedded image

<Compatibility Test> (Example 1) 0.1 g of oil [SH1] and 0.9 g of hydrocarbon refrigerant [CH ₃ CH (CH ₃ ) CH ₃ ] were enclosed in a glass ampoule. After confirming that the composition is completely uniform at room temperature (20 ° C.), it is gradually cooled in a dry ice-ethanol refrigerant, and the temperature at which the refrigerant and the oil become incompatible for the first time is measured by visual judgment, The minimum compatible temperature was determined. Table 1 shows the results. As can be seen from Table 1, the oil used in the present invention shows good compatibility with the hydrocarbon refrigerant.

(Examples 2 to 12) Oil [SH2]
The compatibility of [SH12] with the hydrocarbon refrigerant [CH ₃ CH (CH ₃ ) CH ₃ ] was examined by the same method as in Example 1.
As a result, it was confirmed that the lower limit temperature of compatibility was 0 ° C. or lower in all cases, indicating good compatibility.

(Examples 13 to 15) Oil [SH1] /
Alkylbenzene (weight ratio 90/10) mixed oil, oil [SH1] / alkyldiphenyl ether (weight ratio 90
/ 10) mixed oil, oil [SH1] / mineral oil (weight ratio 90
/ 10) Hydrocarbon refrigerant of mixed oil {CH ₃ CH (C
The lower limit temperature of compatibility with H ₃ ) CH ₃ } was measured by the same method as in Example 1. It was confirmed from the results that the compatibility lower limit temperature was 0 ° C. or lower and that the good compatibility was exhibited. Alkylbenzene is manufactured by Nippon Oil Detergent Co., Ltd.
Alomix 20T was used, as the alkyl diphenyl ether, Moresco High-Lube Neovac Series LB-15 manufactured by Matsumura Oil Research Co., Ltd. was used, and as the mineral oil, SUNISO 1GS manufactured by Nippon San Oil Co., Ltd. was used.

(Comparative Example 1) The lower limit temperature of compatibility with a hydrocarbon refrigerant when perfluoropolyether was used as the lubricating oil was measured by the same method as in Example 1. As a result, they were not compatible at room temperature (20 ° C), and the lower limit temperature of compatibility was room temperature (20 ° C) or higher. Table 1 shows the results.

[0169]

[Table 1]

<Lubricity Test> (Examples 16 to 17) A hydrocarbon-based refrigerant (CH ₃ CH ₂ CH ₂ C) was added to each of the oil [SH1] / [SH2] mixed oil and the oil [SH1] / alkylbenzene mixed oil.
The lubrication characteristics of the oil containing 1 wt% of H ₂ CH ₃ ) were evaluated by measuring the seizure load using a Falex tester. The measurement was performed according to ASTM D3233-73 (method A) except that the initial oil temperature was 25 ° C. The results are shown in Table 2.

(Example 18) Oil [SH1] / alkylbenzene mixed oil was mixed with tricresyl phosphate (0.5%).
Wt%) was added to the oils of Examples 16-17.
Similar to hydrocarbon refrigerants (CH ₃ CH ₂ CH ₂ CH ₂ C
H ₃ ) was contained in an amount of 1 wt%, and the seizure load was measured by a Falex tester. Table 2 shows the results.

(Comparative Examples 2 to 3) The seizure load was measured by a Falex tester using mineral oil and alkylbenzene. The results are shown in Table 2. Hydrocarbon-based lubricating oils such as mineral oil and alkylbenzene show good compatibility with hydrocarbon-based refrigerants, but as shown in Table 2, they have insufficient lubricity, and refrigerator-based lubrication using hydrocarbon-based refrigerants. It turns out to be unsuitable as oil. From Table 2, it can be seen that the refrigerant composition of the present invention has good lubricating properties.

[0173]

[Table 2]

<Bioconcentration Test> (Reference Experimental Example 1) The test method is “about the test method relating to a new chemical substance” (Environmental Safety No. 5, Yakuhin 615, 4).
9 Base Station No. 392, July 13, 1974) <Concentration test of chemical substances in the body of seafood> and "OECD Guideline for Test"
ng of Chemicals "(May 12, 1
981) '305C, Bioaccumula
section: Degree of Bioconcentr
ation in Fish '.

As a concrete test method, first, an exposure test was conducted using test water in which the concentration of oil [SH1] was set to 0.01 mg / L and a normal carp after acclimation, and exposure 2, After 4 weeks, it was collected, fragmented, homogenized, centrifuged, and the concentration ratio of the oil concentrated in the living body was measured by high performance liquid chromatography analysis.
Table 3 shows the results.

(Reference Experimental Examples 2 to 4) In the same manner as in Reference Experimental Example 1, oils [SH2], [SH3] and [SH11] were subjected to bioconcentration test. Table 3 shows the results. From Table 3, among the compounds of the present invention represented by the general formula [I], the compounds represented by the general formulas [II] to [IV] have a particularly low bioconcentration property, and are also represented by the general formula [V]. It can be seen that the compounds represented are even less bioaccumulative.

[0177]

[Table 3]

[0178]

INDUSTRIAL APPLICABILITY According to the present invention, when a lubricating oil comprising a fluorine-containing aromatic compound represented by the general formula [I] and a hydrocarbon type refrigerant are used, there is little influence on ozone layer depletion and global warming, and A refrigerant composition having good compatibility can be obtained.

[Brief description of drawings]

FIG. 1 is a result of infrared absorption spectrum analysis of oil [SH1] obtained in Reference Reaction Example 1.

FIG. 2 is a result of infrared absorption spectrum analysis of the oil [SH2] obtained in Reference Reaction Example 2.

FIG. 3 Oil obtained in Reference Reaction Example 10 [SH10]
2 is a result of infrared absorption spectrum analysis of.

FIG. 4 Oil obtained in Reference Reaction Example 11 [SH11]
2 is a result of infrared absorption spectrum analysis of.

FIG. 5: Oil [SH12] obtained in Reference Reaction Example 12
2 is a result of infrared absorption spectrum analysis of.

Claims (1)

[Claims] 1. A lubricating oil comprising a fluorine-containing aromatic compound represented by the general formula [I] and having 1 to 5 carbon atoms in the molecule.
A refrigerant composition comprising the hydrocarbon-based refrigerant of 1. as an essential component. R (XRf) _n ... [I] [wherein X is an O or S atom. R has 6 to 6 carbon atoms
It represents 0 n-valent aromatic groups. n represents an integer of 1 to 4. Rf represents a fluorocarbon group or a partial substitution product thereof, the number of carbon atoms in Rf is in the range of 1 to 25, and the ratio of the number of fluorine atoms / the number of carbon atoms in Rf is 0. It is 2 or more and 3 or less. Further, Rf may contain an ether bond in a part of the main chain. When n is 2 or more, the compound represented by the general formula [I] may be composed of plural kinds of XRf groups. ]