JPH0649473A - Refrigerant composition - Google Patents

Abstract

PURPOSE:To provide a refrigerant composition composed of a fluorine-containing aromatic compound and a specific fluorinated alkane refrigerant, exhibiting excellent compatibility of the above compound with the above refrigerant, having excellent lubrication characteristics and useful for refrigeration system. CONSTITUTION:The composition is produced by compounding (A) a lubricating oil composed of a compound of the formula R(XRf)n (X is O or S; R is 6-60C n-valent aromatic group; n is 1-4; Rf is fluorocarbon group or its partial substitution product; the number of C atoms in Rf is 1-25; the number ratio of F/C in Rf is >=0.6; when n>=2, XRf groups may be same or different) with (B) a fluorinated alkane refrigerant containing 0.01-100-wt.% (especially preferably 0.01-50wt.%) of a chlorine containing fluorinated alkane refrigerant. The weight ratio of (the total refrigerant)/(the total lubricating oil) is 99/1 to 1/99 (preferably 90/10 to 20/80).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a refrigerant composition comprising a fluoroalkane-based refrigerant containing a chlorine-containing fluoroalkane-based refrigerant and a lubricating oil.

[0002]

2. Description of the Related Art Conventionally, dichlorodifluoromethane (CFC-12) has been mainly used as a refrigerant for a car air conditioner and a refrigerator. Further, mineral oil is widely used as a lubricating oil.

[0003]

However, in recent years C
It was found that chlorine-containing refrigerants represented by FC-12 are the main cause of ozone depletion in the stratosphere, and particularly CFC-12, CFC-11 (trichlorofluoromethane) and CFC-114 (which have large ozone depletion capacity (ODP)). Dichlorotetrafluoroethane), CFC
Regarding chlorine-containing refrigerants (specified CFCs) such as -115 (chloropentafluoroethane), regulations on the amount used and the amount produced have already been established by international treaties. Therefore, there is a demand for the development of a refrigerant that has a small ozone depletion capacity and can substitute a specific CFC such as CFC-12.

As such an alternative refrigerant, HFC-32 (difluoromethane) and HFC-13, which are fluorinated alkanes containing no chlorine in the molecular structure having almost no ozone depletion ability, are used.
CFC-12 shows the effect on the stratospheric ozone layer by diluting fluorinated alkane containing chlorine in the molecular structure with ozone depletion ability with 4a (1,1,1,2-tetrafluoroethane) etc.
A mixed refrigerant system which is much smaller than the above has been proposed.

For example, Japanese Patent Laid-Open No. 3-168261-168
No. 293, HFC-32, HFC-23 (trifluoromethane), HFC-134a, HFC-134 (1,1,2,2-tetrafluoroethane), HFC-143a (1,1,1-tri). Fluoroethane), H
Fluorinated alkane refrigerants such as FC-152a (1,1-difluoroethane) and HFC-125 (pentafluoroethane) and HCF
C-22 (chlorodifluoromethane), HCFC-142b (1-chloro
-1,1-difluoroethane), HCFC-141b (1,1-dichloro-1-fluoroethaneethane) HCFC-124a (1-chloro-1,1,2,2-tetrafluoroethane), HCFC-124 (2 -Chloro-1,1,1,2-tetrafluoroethane),
HCFC-123a (1,2-dichlorotrifluoroethane), HCFC-
A mixed system of a chlorine-containing fluoroalkane-based refrigerant such as 123 (2,2-dichloro-1,1,1-trifluoroethane) is disclosed.

Further, in Japanese Laid-Open Patent Publication No. 1-121392, CFC-12 is referred to as HFC-32, HCFC-124,
HCFC-124a, HFC-125, HCFC-14
A mixed refrigerant diluted with at least one of 2b has been proposed. Conventionally, in a refrigeration system using CFC-12, mineral oil is used as a lubricating oil for a compressor. Since CFC-12 contains chlorine atoms, it has high lipophilicity and is compatible with mineral oil in a wide temperature range. Therefore, the refrigerant and the lubricating oil are not separated even in the refrigeration system in which the refrigerant repeatedly evaporates and condenses.

However, HFC-32 and HFC-134a
Since various fluorinated alkane-based refrigerants represented by No. 1 do not contain chlorine atoms, they hardly show compatibility with mineral oil.
HC with fluorinated alkanes such as C-32 and HFC-134a
When mineral oil is used as a lubricating oil in a mixed refrigerant diluted with chlorine-containing fluoroalkane such as FC-22, the compatibility of the refrigerant and the lubricating oil is poor, and the lubricating oil is replaced by the refrigerant in the compressor, resulting in insufficient lubrication. However, a number of serious problems occur, such as that the lubricating oil adheres to the inner wall of the heat exchanger and the heat exchange rate deteriorates.

Lubricating oils for refrigerators are in the range of at least 0 ° C to 50 ° C, preferably -20 ° C to 70 ° C.
It is necessary to exhibit compatibility with the mixed refrigerant in the above range, more preferably in the range of -40 ° C or lower to 90 ° C or higher, or in a wider range. Various polyalkylene glycol-based compounds and polyester-based compounds have been proposed as lubricating oils that exhibit good compatibility with fluorinated alkane-based refrigerants such as HFC-134a. For example, polyalkylene glycols having two or more hydroxyl groups (especially polyoxypropylene glycol) disclosed in US Pat. No. 4,755,316 are said to have a wide range of compatibility. . The polyester compounds disclosed in JP-A-3-128991, JP-A-3-179091, etc. are also said to have excellent compatibility with HFC-134a.

However, polyalkylene glycol and polyester oils have high hygroscopicity, and have a problem in durability such that they are apt to undergo oxidative decomposition or hydrolysis. In particular, it is known that if a chlorine-containing refrigerant such as CFC-12 coexists even in a small amount, the decomposition of oil is significantly promoted and therefore it cannot be used. Therefore, it is not possible to use polyalkylene glycol or polyester oil as a lubricating oil in a mixed refrigerant obtained by diluting a chlorine-containing fluoroalkane such as HCFC-22 with a fluoroalkane such as HFC-32 or HFC-134a. Have difficulty.

As an alternative refrigerant for CFC-12 and other specific CFCs, in addition to the mixed refrigerant system shown above, it is known to use fluorinated alkanes containing no chlorine atoms, for example, HFC-134a alone. . However, HFC-
As a refrigerating machine oil for 134a, a refrigerant composition using a polar oil such as polyalkylene glycol or polyester-based oil has not only problems in hygroscopicity, durability, lubrication characteristics, etc., but also HFC-134a and these When replacing a refrigerator using a refrigerant composition composed of polar oil with an existing refrigerant composition composed of CFC-12 and mineral oil, it is said that chlorine-containing compounds such as CFC-12 remain in the refrigerator even in a small amount. Polyalkylene glycol and polyester oils are easily decomposed. Therefore, in order to avoid such troubles, it takes a lot of time to wash the refrigerator, and it is very difficult to replace the refrigerant composition of the existing refrigerator with the refrigerant composition of HFC-134a and polar oil.

[0011]

Under such circumstances, the present inventors have found that a fluoroalkane-based refrigerant such as HFC-134a or HFC-32 and a chlorine-containing fluoroalkane-based refrigerant such as CFC-12. The inventors have earnestly studied to develop a lubricating oil for a refrigerator, which has good compatibility with any of the refrigerants in a wide temperature range and has stable and good lubricating characteristics even in the coexistence of a chlorine-based refrigerant such as CFC-12.

As a result, the fluorine-containing aromatic compound having the structure represented by the formula [I] was obtained in a wide temperature range from a low temperature region to a high temperature region, such as a fluorinated alkane such as HFC-134a or HFC-32 and CFC-. It was found that the compatibility with chlorine-containing fluoroalkanes such as 12 and the like is good, and that they are very stable even in the coexistence of chlorine-based refrigerants such as CFC-12 and that they exhibit good lubricating characteristics, and completed the present invention. .

That is, the present invention is a refrigerant composition comprising a fluoroalkane-based refrigerant and a fluorine-containing aromatic compound represented by the general formula [I], wherein the fluoroalkane-based refrigerant contains chlorine-containing fluorine. Alkane-based refrigerant at least 0.0
A refrigerant composition comprising 1 to 100% by weight. 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 0.6. That is all. When n is 2 or more, the compound represented by the general formula [I] may be composed of plural kinds of XRf groups. ] Is provided.

The present invention will be described in more detail below. R in the general formula [I] used in the present invention has 6 to 60 carbon atoms.
Preferably 6 to 40, more preferably 6 to 30
Represents n-valent aromatic groups. Further, in consideration of availability of raw materials and easiness of synthesis, it is particularly preferable that R has 6 to 20 carbon atoms. n represents an integer of 1 to 4.

The aromatic group means a group containing an aromatic ring, and the aromatic group has a carbon number of 50 or less, preferably 20 or less, more preferably 10 or less and other than the aromatic ring. It may contain a substituent or a linking group. However, the ratio of the carbon atoms of the aromatic ring in the aromatic group to the total number of carbon atoms in the aromatic group is 0.1 or more, preferably 0.2.
Or more, more preferably 0.5 or more.

Examples of the substituents and linking groups include saturated hydrocarbon groups such as alkyl groups, alkylene groups and alicyclic hydrocarbon groups, unsaturated hydrocarbon groups such as allyl groups and 2-
Halogenated hydrocarbon group such as chloroethyl group, halogen atom 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,
Examples thereof include various oxygen-containing, nitrogen-containing, phosphorus-containing and sulfur-containing polar groups such as phosphine group, benzimidazole group, phosphite group, triazole group, tetrazole group, thiazole group and thiadiazole group.

Specific examples of R include the following. R2;

[0018]

[Chemical 1]

R3;

[0020]

[Chemical 2]

R4;

[0022]

[Chemical 3]

R5;

[0024]

[Chemical 4]

R6;

[0026]

[Chemical 5]

R7;

[0028]

[Chemical 6]

R8;

[0030]

[Chemical 7]

R9;

[0032]

[Chemical 8]

R10;

[0034]

[Chemical 9]

Examples of various aromatic ring-containing groups that can be used as R in the general formula [I] have been shown above. Among these, in the case of R having a structure in which the aromatic ring is directly linked to -XRf, It is particularly preferable because the compound of the general formula [I] having excellent stability can be easily synthesized. X in the general formula [I] is an O or S atom. When X is 0, 1) it is possible to economically synthesize a fluorine-containing aromatic compound in a high yield using inexpensive synthetic raw materials. 2) Fluorine-containing aromatic ether compounds are preferable because they have extremely high stability.

The value of n in the general formula [I] depends on the valency of R, and is usually 1, 2, 3, for reasons such as easiness of synthesis and taking an appropriate viscosity range. It is an integer selected from 4, preferably an integer selected from 2, 3, 4 and particularly preferably an integer selected from 2. Also,
When n is 2 or more in the general formula [I], the substance of the general formula (I) may be composed of a plurality of Rf.

In the general formula [I], Rf represents a fluorocarbon group or a partial substitution product thereof. The fluorocarbon group means a substituent having a structure in which some or all of the hydrogen atoms of various hydrocarbon groups are replaced 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 fluoroaraalkyl group, and the like, but particularly a fluoroalkyl group and a fluoroalkenyl group. The groups are easy to synthesize and useful.

As Rf, a part of the fluorine atom or hydrogen atom of the fluorocarbon group is a halogen atom such as chlorine atom, bromine atom, iodine atom, hydroxyl group, ether group, amino group, nitrile group or ester group, It may be substituted with various substituents that are stable under the conditions of use of refrigerating machine oil, such as an amide group, an acyl group, and a carbonyl-containing group such as a carboxyl group, or a part of the main chain may have an ete structure.

Among the above-mentioned fluorocarbon group substituents, a fluorochloroalkyl group is particularly preferable because it is easy to synthesize and exhibits good lubricating characteristics. The ratio of the number of fluorine atoms / the number of carbon atoms in Rf is usually 0.6 or more,
It is preferably 1 or more, and particularly preferably 1.5 or more. If the ratio of the number of fluorine atoms / the number of carbon atoms in Rf is too low, the compatibility with the fluoroalkane becomes low and the stability tends to decrease, which is not preferable.

The carbon number of Rf is usually in the range of 1 to 25, preferably in the range of 1 to 10, and particularly preferably in the range of 1 to 3. If the number of carbon atoms in Rf exceeds 25, it will be difficult to obtain or synthesize raw materials,
In addition, the synthesis and purification are complicated and the viscosity becomes too high, which is not preferable.

The substance represented by the general formula [I] used in the present invention can be synthesized by various methods. In the following, in the general formula [I], an example of synthesis in the case of n = 1 will be illustrated, but in the case of n = 2, 3 and 4, synthesis is performed by the same method. (1) Reaction of phenols or thiophenols with fluorinated 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. A typical reaction example will be shown by taking the case of perfluoroolefin as an example.

[0043]

[Chemical 10]

The reaction examples of phenols and fluorine-containing olefins are shown below. For example, Advance in Fluorine Chem
istry, 4 , 50 (1965) includes various fluorine-containing olefins as described below and phenols, or ionic reactions of alcohols or thiophenols [2],
An example of reaction similar to the formula [3] is shown.

CF ₂ = CF ₂ , CF ₂ = CFCl, CF
_{2 = CFBr, CF 2 = CFH} , CF 2 = CHCl, C
F ₂ = CCl ₂ , CHF = CCl ₂ , CF ₃ CF = CF
₂ , CClF ₂ CF = CF ₂ , CF ₃ CCl = CF ₂ ,
CF ₃ CF = CCl ₂ , CF ₃ CCl = CClF, CF
₃ CH = CH ₂ , CF ₃ CH = CHCl, CF ₃ CCl
_{= CHCl, CF 3 CCl = CCl} 2, CF 3 CF 2 C
CF = CF ₂ , CF ₃ CF = CFCF ₃ , (CF ₃ ) _{2
C = CF 2, CF 2 =} CF-CF = CF 2, R11:

[0046]

[Chemical 11]

CF ₃ CCl = CClCF ₃ , CCl ₂ F
_{CClFCF = CClF, CF 3 - (} CF 2) 4 -CF
= CF _2. Journal of American Chemical Society, 73 , 5831
(1951) Reaction formula of formula [4];

[0048]

[Chemical 12]

142nd, Meeting, American Chemical Societ
y, Atlantic City, NJ, Sept, 1962Abs, P19U Reaction formula [5];

[0050]

[Chemical 13]

Journal of American Chemical Society,
82, 5116 (1960) formula [6], the reaction formula (7);

[0052]

[Chemical 14]

Reaction formula of the formula [8]: [X ³ = -Cl, F] Journal of Japanese Society of Society, 1975, 311

[0054]

[Chemical 15]

Expression

[9] reaction formula;

[0056]

[Chemical 16]

Reaction formula of the formula [10]:

[0058]

[Chemical 17]

Further, an oligomer of hexafluoropropene (HFP) represented by the general formula [11] and tetrafluoroethylene (TFE) represented by the general formula [12].
Or an unsaturated bond-containing oligomer derived from various fluorine-containing olefins typified by chlorotrifluoroethylene oligomers [2],
It can be used as a raw material for a synthetic reaction such as the formula [3].

C _3m F _6m [11] [m: integer of 2 or more, preferably 2 to 6] C _{2m '} F _4m' [12] [m ': integer of 2 or more, preferably 2 to 10 Integer] Examples of the reaction of such an oligomer include the following examples.

Bull. Chem. Soc. Japan, 49, 502 (197
6) Reaction formulas of the formulas [13] and [14];

[0062]

[Chemical 18]

The Chemical Society of Japan, 1978, 253 Reaction formula of formula [15]:

[0064]

[Chemical 19]

"Oligomer" (Kodansha Scientific) Okawara, Saegusa, Higashimura, (1976), P288-291. A number of TFE pentamers (C ₁₀
Many reactions of F ₂₀ ) and HFP trimer (C ₉ F ₁₈ ) with phenols have been shown. Reaction formulas of formulas [16], [17], and [18];

[0066]

[Chemical 20]

Reaction formulas of formulas [19] and [20]:

[0068]

[Chemical 21]

Further, Journal of Fluorine Chemistry 54,
162 (1991) reports addition reactions of phenols and perfluorovinyl ethers such as the formulas [21 ′] and [21 ″]. Reaction formulas of formulas [21 ′] and [21 ″];

[0070]

[Chemical formula 22]

Izvest. Akad. Nauk SSSR, Otde
1, Khim, Nauk, 1952, 261-7 reported an addition reaction of thiophenol and chlorotrifluoroethylene or tetrafluoroethylene as shown in the reaction formula of [21 ′ ″]. The reaction formula of the formula [21 ″ ′];

[0072]

[Chemical formula 23]

Bull, Soc.Chim.Fr., 1972, (8), 3202.
In -5, addition reaction of thiophenol and chlorotrifluoroethylene such as [21 ″ ″] formula is reported.

[0074]

[Chemical formula 24]

(2) Reaction of Phenols or Thiophenols with Saturated Fluorocarbons As a reaction of the fluorine-containing aromatic compound by the reaction of phenols or thiophenols with saturated fluorocarbons, many reaction methods are possible. However, typical reaction methods include, for example, the following reactions.

[0076]

[Chemical 25]

R12

[0078]

[Chemical formula 26]

_{[0079], - OSO 2 CF 3, -OSO} 2 CC
It represents a substituent that is easily desorbed as an anion such as l ₃ or —OSO ₂ Cl. Ar 'represents a monovalent aromatic group. Rf '
Is the same as Rf in the general formula [I] and represents an anion structure of Rf′X ⁻ . ] Actual, Chem., 1987, 151 Reaction formulas of formulas [23] and [24];

[0080]

[Chemical 27]

"Chemistry of Organic Fluorine Compoun
ds "Halsted Press, 2nd Edition, P279 includes Alkylation at Oxygen or Sulfur of alcohols, phenols and thiols at oxygen or sulfur atoms.
Many methods for synthesizing a fluorine-containing ether compound or a fluorine-containing thioether compound have been disclosed. Jornal of Organic Chemistry, 50, 4047 (1985) Reaction formula of formula (25);

[0082]

[Chemical 28]

Industrial and Engineering Chemistry
, 39, 412 (1947) Reaction formulas of formulas [26] and [27];

[0084]

[Chemical 29]

Pure and Applied Chemistry, 59, 1015
(1987) Many reactions of various fluorinated halides represented by the general formula [29] with phenoxide are shown. CZ ² Z ³ Z ⁴ CFZ ³ Z ⁴ [29] [wherein Z ² = Cl, Br, I, and Z ³ = Z ⁴ =
F, Cl, Br, CF ₃ , H]] As an example,
For example, the following reactions can be mentioned.

[0086]

[Chemical 30]

Journal of Organic Chemistry, 25, 20
09 (1960) Reaction formula of formula [32]:

[0088]

[Chemical 31]

In addition to the above, various methods for forming an ether bond or a thioether bond can be used to obtain the compound of the general formula [I]
It is possible to synthesize the fluorinated aromatic compound. An example thereof is an ether-forming reaction by the following reaction between a hydroxyl group and an epoxy group. Reaction formulas of formulas [33] and [34]:

[0090]

[Chemical 32]

[Here, Ar 'represents a monovalent aromatic group, and Rf "represents a fluorocarbon group having 1 to 16 carbon atoms.] Further, a precursor substance of the substance represented by the general formula [I] A method of introducing a fluorine atom by various methods can also be used, or the reaction product synthesized by the various methods described above can be further converted by various reactions to obtain a desired substance represented by the general formula [I]. You may be guided to.

As an example, the following method may be mentioned. Actual. Chem., 1987, 151 Reaction formula of formula (35);

[0093]

[Chemical 33]

[Here, R ³ is the same as R ^{3 in the} formulas [23] and [24]] The fluorine-containing compound such as fluorine-containing olefin and saturated fluorocarbon used in the above reaction can be prepared by various known methods. Can be synthesized with. For example, "Advances in Fluorine Chemistry"
Butterworth, vol.3, P181, Halogen exchange synthesis, "Chemistry of Organic Fluorine Comp
ounds "Halsted Press, or JP-A-50-117705, JP-B-43-11.
Examples thereof include methods for synthesizing fluoroolefin oligomers described in Japanese Patent Publication No. 885, Japanese Patent Publication No. 47-22563, etc., but are not limited thereto.

The fluorine-containing aromatic compound represented by the general formula [I] can be synthesized by various methods, and the reactions shown so far are only some of the specific examples thereof. Therefore, the method for synthesizing the substance of the general formula [I] is not limited to these methods. Further, the refrigerating machine oil used in the present invention has only to have the structure represented by the general formula [I] and is not limited by the manufacturing method.

The general formula [I] used in the present invention is described below.
Examples of Rf- in the substance represented by are shown below, but the examples of Rf shown here are some of the examples of Rf in the substance of the general formula [I] synthesized by various methods. It is not limited to this. ^{_{Z 7 - (CF 2) L1}} - (CH 2) L2 - ·· [36] ^{[Z 7 = F, Cl, I} , H; L 1 = 1~18 integer; L
₂ = 0,1,2] Specific examples of the compound of the formula [36] include the following.

CF _3- , CF ₃ CH _2- , CF ₃ CH _{2
CH 2 -, F- (CF 2} ) 2 -, F- (CF 2) 3 -,
_{F- (CF 2) 6 -,} F- (CF 2) 10 -, F- (CF
_{2) 2 -CH 2 -, F-} (CF 2) 4 -CH 2 -, F-
_{(CF 2) 4 -CH 2 CH} 2 -, F- (CF 2) 8 -C
_{H 2 CH 2 -, I- (} CF 2) 4 -CH 2 CH 2 -, C
_{lCF 2 -, Cl- (CF 2} ) 2 -, Cl- (CF 2)
_{4 -, Cl (CF 2)} 3 -CH 2 -, BrCF 2 CF 2
_{-, BrCF 2 -I-CF 2} -, I- (CF 2) 3 -C
_{H 2 -, H- (CF 2} ) 3 CH 2 -, H- (CF 2) 10
_{-CH 2 -, HCF 2 -,} HCF 2 CH 2 CH 2 -, H
_{CF 2 CH 2 -, I- (} CF 2) 2 -CH 2 CH 2 -, R13;

[0098]

[Chemical 34]

(L ₂ = 1 to 7) [37] Formula [37 '];

[0100]

[Chemical 35]

F- [CF ₂ CF ₂ O] _{L 3} —CF ₂ CH ₂ — (L ₃ = 1 to 11) [38] F- [CF ₂ CF ₂ CF ₂ O] _{L 4} —CF ₂ CF ₂ CH ₂ — _{(L 4 = 1~7) ··· [} 39] CF 3 CHF-, CH 3 CF 2 -, CH 2 FCF 2 -,
_{CF 2 HCF 2 -, CH 2} F-, CHF 2 CH 2 -, C
_{F 3 CCl 2 -, CF 3} CHCl-, CF 3 CFCl
_{-, CFCl 2 CF 2 -,} CHFClCF 2 -, C 6 F
_{5 -, CHCl 2 CF 2 -} , CH 3 CHFCH 2 -, C
_{H 2 FCH (CH 3) -} , CF 3 CHFCF 2 -, CF
_{3 CF 2 CHFCF 2 -, HOCH} 2 CF 2 CF 2 CH
_{2 -, CH 2 ClCF 2 -} , CF 3 CHClCF 2 - -CZ 3 Z 4 CFZ 3 Z 4 [40] [Z ^3, Z ⁴ is Z ³ in the general formula [29], Z ⁴ identical] formula [ 41];

[0102]

[Chemical 36]

[0103]

[Chemical 37]

Examples thereof include groups represented by the formulas [44] and [45]. -C _3m F _6m-1 [44] [m is the same as m in the general formula [11]] -C _{2m '} F _4m'-1 [45] [m' is the same as m 'in the general formula [12]. same] -C n _{'F 2n'} H [46] [n 'is the general formula [3] n' in the same] examples and, [47], groups of [48] expression.

-C _3m F _6m H [47] [m is the same as m in the general formula [11]] -C _{2m '} F _4m' H [48] [m 'is m'in the general formula [12]. The same as the above] Specific examples of the groups of the general formulas [43] to [48] include the following.

CF ₂ = CF-, CF ₂ = CFCF _2- ,
_{CF 3 CF = CF-, CF 3} CF 2 CF = CF -, (C
_{F 3) 2 C = CF-,} C 6 F 11 -, C 9 F 17 -, C 15 F
_{29 -, C 10 F 19 -} , CF 3 CHFCF 2 -, C 6 F 12 H
_{-, C 9 F 18 H-,} C 4 F 8 H-, C 10 F 20 H-. Further, the following groups can also be used.

CFCl = CF-, CFCl ₂ CF ₂ CF
_{= CF-, CF 3 CCl = CF-} , CCl 2 = CF-,
_{CHCl = CF -, (CF 3} ) 2 CH-, CF 3 CFC
lCFCl-. As described above, the fluorinated aromatic compound of the general formula [I] used in the present application can be produced by various methods, and can be further purified by treatments such as distillation, extraction and adsorption.

The compound represented by the formula [I] can be advantageously used alone or as a mixture of plural kinds thereof as a lubricating oil for a refrigeration system using a refrigerant containing a fluorinated alkane. . Furthermore, the compound represented by the formula [I] can be used as a mixture with other oils.

Other oils that can be used by mixing with the compound represented by the formula [I] are usually selected from those exhibiting a certain degree of solubility in a fluoroalkane-based refrigerant, and examples thereof include perfluoropolyether oil and carboxyl. Group, caboxylate group, amide group, carbonyl-containing group such as ketone group and ester group, hydroxyl group, amino group, imide group, ether group, benzimidazole group, phosphite group,
Examples thereof include perfluoropolyether oils, chlorofluorocarbon oils, fluorinated silicone oils and the like having polar substituents such as phosphine groups, nitrile groups, phosphotriazine groups and triazine groups, and among these, general formula [I ] An appropriate type is selected in consideration of the compatibility with the compound of [] and the viscosity or lubricating characteristics of the resulting lubricating composition.

When the compound represented by the formula [I] is used as a mixture with another oil, the amount of the compound represented by the formula [I] depends on the compatibility of the resulting lubricating composition with a refrigerant and It is selected in consideration of the viscosity of the composition, etc., but is usually in the range of at least 0.1% by weight, preferably 25% by weight or more, more preferably 50% by weight or more based on the total amount of the lubricating oil composition. Is used.

When the compound represented by the formula [I] of the present invention is used alone as a lubricating oil using a refrigerant containing a fluorinated alkane, its viscosity is usually 40%.
Kinematic viscosity in the range of 2 to 500 cst,
The range of 3 to 300 cst is preferably used, the range of 5 to 170 cst is more preferable, and the range of 10 to 150 cst is particularly preferable.

Alternatively, the kinematic viscosity at 100 ° C. is usually 0.5 to 100 cst, preferably 1 to 50 cs.
t, particularly preferably in the range of 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.

When the compound represented by the formula [I] is used as a mixture of a plurality of kinds, or when it is used as a mixture with other oil, the compound represented by the 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 the viscosity range when the compound represented by the above formula [I] is used alone. Further, even when the compound represented by the formula [I] is a solid, the viscosity of the refrigerant composition comprising the fluoroalkane-based refrigerant and the substance is represented by the above various kinematic viscosity formula [I]. It can be used as long as it is the same as the refrigerant composition comprising the compound.

In 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 range, preferably 95 / 5-10 / 90 range,
Particularly preferably, it is in the range of 90/10 to 20/80.
The lubricating oil for a refrigerator of the present invention is added to a normal lubricating oil such as an anticorrosive agent, an antioxidant, a viscosity index improver, a corrosion inhibitor, an oiliness improver, a pour point depressant and an extreme pressure additive. It is also possible to use various additives in an amount usually used.

The fluoroalkane-based refrigerant in the present invention is
The chlorine-containing fluoroalkane-based refrigerant is contained in an amount of 0.01 to 100% by weight, preferably 0.01 to 80% by weight, and more preferably 0.01 to 50% by weight. As the proportion of chlorine-containing fluoroalkane-based refrigerants decreases, the ozone depletion capacity decreases, but it is possible to increase the refrigeration efficiency of the refrigeration cycle by mixing chlorine-containing fluoroalkane-based refrigerants appropriately. .

Chlorine-Containing Fluorinated Alkane System According to the Present Invention
Refrigerant is a low chlorine-containing fluoride that can be used as refrigerant.
Lucan (for example, chlorine-containing fluoride having about 1 to 5 carbon atoms)
Lucan), preferably a chlorine-containing fluoride containing 1 to 3 carbon atoms
It is Lucan. For example, HCFC-22 (CHCl
F₂), CFC-12 (CCl₂F₂), HCFC-1
42b (CClF₂CH₃), HCFC-141b (C
Cl₂FCH₃), HCFC-124a (CClF₂C
HF₂), HCFC-124 (CF ₃CHClF), H
CFC-123a (CHClFCClF₂), HCFC
-123 (CF₃CHCl₂), HCFC-235ca
(CHF₂CF₂CHClF), HCFC-235cd
(CF₃CF₂CH₂Cl), HCFC-235cc
(CClF₂CF₂CH₂F), etc., containing various lower chlorine
Fluorinated alkanes can be exemplified, but are not limited to these.
It is not something that will be done.

In addition, the fluoroalkane-based cooling according to the present invention
The medium is a lower fluoroalkane that can be used as a refrigerant (for example,
For example, fluorinated alkanes with 1 to 5 carbon atoms), especially the carbon number
It is preferred to contain 1-4 hydrofluoroalkanes
Good For example, HFC-32 (CH₂CF₂), HFC
-23 (CHF₃), HFC-134a (CF₃CH₂
F), HFC-134 (CHF₂CHF₂), HFC-
143a (CF₃CH₃), HFC-152a (CH₃
CHF₂), HFC-125 (CF₃CHF₂), HF
C-227ea (CF₃CHFCF₃), HFC-22
7ca (CHF₂CF₂CF₃), CF₃CH₂C
F₃, CF₃CHFCHF₂, CF₃CF₂CH₂F,
CHF₂CF₂CHF₂, CF₃CH₂CHF₂, CF
₃CF₂CH₃, CHF₂CF₂CH₂F, CF₃CF
₂CF₂CH ₃, CF₃CHFCHFCF₃, CF₃C
HFCHFCF₂CF₃Fluorinated methane, etc.
Fluorine, propane fluoride, butane fluoride, etc.
Examples of the compound are alkanes, but are not limited to these.
Not something.

The compound represented by the formula [I] is HCFC-
Chlorine-containing fluoroalkane-based refrigerants such as 22 and HFC-13
Good compatibility with any of the hydrofluoroalkane-based refrigerants such as 4a in a wide temperature range. For example, the formula [I]
The compounds represented by are HFC-134a and HCFC-2.
Fluorinated alkane such as 2 and -10 ° C or lower, -20 ° C or lower,
It is possible to be compatible at -30 ° C or lower, -40 ° C or lower, and further -78 ° C or lower.

The HFC of the compound represented by the formula [1]
-134a and other hydrofluoroalkane-based refrigerants and HC
The upper limit temperature of compatibility with chlorine-containing fluoroalkane-based refrigerants such as FC-22 is 70 ° C or higher, 80 ° C or higher, and further 90
A temperature above ℃ is easily obtained. Therefore, the formula [I]
As a matter of course, the compound of (3) shows the same good compatibility with a mixed solvent of various hydrofluoroalkane-based refrigerants and chlorine-containing fluoroalkane-based refrigerants.

Further, the compound of the formula [I] is added to copper or a metal such as brass, aluminum and carbon steel and HF.
When subjected to a stability test (so-called shielded tube test) of heating in the presence of a mixed refrigerant of a fluorinated alkane such as C-134a and a chlorine-containing fluorinated alkane such as CFC-12, the formula [ The compound of [I] and the mixed refrigerant are stable, and show good results that the metal surface hardly changes. On the other hand, under similar conditions, polar oils such as polyalkylene glycol and ester oils are easily decomposed.

As described above, the compound represented by the formula [I] of the present invention exhibits good compatibility with various fluorinated alkanes containing a chlorine-containing fluoroalkane-based refrigerant in a very wide temperature range, Moreover, it exhibits high stability even in the presence of a chlorine-containing fluoroalkane such as CFC-12. In addition, the compound represented by the general formula [I] has extremely low hygroscopicity, such as polyalkylene glycol or ester oil having high hygroscopicity, which causes deterioration of electric characteristics of oil due to water and HFC-.
There is no problem such as promotion of decomposition of fluorinated alkane such as 134a.

Further, the lubricating properties of the fluorinated aromatic compound of the formula [I] were evaluated in the presence and absence of the fluorinated alkane. In both cases, extreme pressure (baking load),
It was confirmed that both the abrasion resistance and the coefficient of friction show extremely good performance. For example, most of the fluorine-containing aromatic compounds represented by the formula [I] are conventional refrigerating machine oils such as mineral oil,
Alternatively, it showed much better lubricating properties than candidate oils for HFC-134a frozen oils such as polyalkylene glycols and polyester oils.

The above-mentioned lubrication characteristics can be measured by various kinds of testing machines. For example, extreme pressure and abrasion resistance can be measured by a Falex tester, extreme pressure can be measured by a Soda type four-ball friction tester, and soda type can be measured. The friction coefficient is measured by a pendulum type friction tester. Therefore, the compound of general formula [I] is suitable as a refrigerating machine oil for a refrigerant containing a chlorine-containing fluoroalkane-based refrigerant. In addition, the general formula [I]
The compound (1) is also suitable as a refrigerating machine oil in the case of substituting a fluorinated alkane-based refrigerant composition of a refrigerating machine refrigerant composition that has conventionally used a chlorine-containing fluoroalkane-based refrigerant.

According to another aspect of the present invention, a high-purity general formula [I] suitable for a lubricating oil for a refrigerator using a fluoroalkane-based refrigerant containing a chlorine-containing fluoroalkane-based refrigerant is provided. A method for producing the compound represented by That is, in the presence of a base catalyst and a polar solvent, the compound of the general formula [II]
Or a phenol or thiophenol represented by R (XH) _n [II] [wherein X is an O or S atom. R and n are the same as R and n in the general formula [I], respectively. When n is 2 or more, the compound represented by the general formula [II] may be composed of different kinds of XH groups. ] To a fluorinated olefin to synthesize a fluorinated aromatic compound represented by the general formula [I], a base catalyst is added to the phenolic hydroxyl group or thiophenolic thiol group involved in the reaction in an amount of 0.01 The method for producing a high-purity fluorine-containing aromatic compound is characterized by using 1 to 1 times mol and reacting in the presence of 0.2 times to 100 times mol of water with respect to the base catalyst. .

As described above, the fluorine-containing aromatic compound represented by the general formula [I] can be produced by various methods and is not limited by the production method. However, usually, in the manufacturing process, impurities having a similar structure to the target product are often produced as by-products, and purification of the target product by removal thereof is difficult in many cases.

In refrigerating machine oil, even a trace amount of impurities may cause corrosion of metal materials in the refrigerating system,
Extremely high purity is required because it accelerates the decomposition of the refrigerant or has a significant adverse effect on the electrical characteristics of the refrigerating machine oil, such as volume resistance (the characteristics required for a closed refrigerator for a refrigerator, etc.). Therefore, the present inventors have diligently studied various synthetic methods described above in order to synthesize a highly pure fluorine-containing aromatic compound represented by the general formula [I] in a high yield and easily.

As a result, in the presence of a base catalyst and a polar solvent, according to the reaction mode represented by the general formula [3],
When a phenol or thiophenol represented by the general formula [II] is added to a fluorinated olefin to synthesize a fluorinated aromatic compound represented by the general formula [I], a chlorine catalyst is involved in the reaction. 0.1 to 1 times mol, preferably 0.05 to 0.3 times mol, of the phenolic hydroxyl group or the thiophenolic thiol group is used, and
0.2 times to 100 times mol, preferably 1 time to 50 times mol, more preferably 15 times mol of the base catalyst.
It has been found that a highly pure fluorine-containing aromatic compound can be easily synthesized and isolated by reacting it in the presence of a double to 50-fold molar amount of water.

As the base catalyst used in the above reaction,
Various bases are used, examples of which include alkali metal hydroxides such as NaOH and KOH, and NaHC.
Alkali metal bicarbonates such as O ₃ and KHCO ₃ , Na ₂ C
Examples thereof include alkali metal carbonates such as O ₃ and K ₂ CO ₃ , amines such as triethylamine and tributylamine, and alkali metals such as sodium metal and alkaline earth metals.

The fluorinated olefin used in the present method is not particularly limited as long as it is capable of nucleophilic addition of a phenoxy anion or a thiophenoxy anion, and examples thereof include Advance in Fluorine Chromium.
CF ₂ = C shown in emistry, 4 , 50 (1965)
Perfluoroolefins such as F ₂ , CF ₂ ═CFCF ₃ , CF ₂ ═CClF or chlorofluoroolefins, and various fluorine-containing olefin oligomers represented by the general formulas (11) and (12) CF ₂ ═CFOCF ₂ C
Perfluoro vinyl ether represented by F ₂ CF ₃ and the like can be mentioned.

As the polar solvent used in this method, various polar solvents can be used. Examples thereof include dimethyl sulfoxide, dimethylformamide, sulfolane, and the like.
Examples thereof include N-methylpyrrolidone, acetone, tetrahydrofuran, dioxane, tetraglyme and dimethoxyethane. The amount of the polar solvent used is not particularly limited, but is usually 10% by weight to 1000% based on the phenols or thiophenols involved in the reaction.
Wt% is added.

The reaction temperature is usually 0 to 150 ° C., preferably 40 to 100 ° C., and the reaction pressure is usually 0.1 to 2 ° C.
It is carried out at 0 atm, preferably 1-10 atm. The amount of the base catalyst is 0.01 to 1 times mol, preferably 0.05 to 0.3 times mol, based on the phenolic hydroxyl group or thiophenol group in the phenols or thiophenols involved in the reaction.

The amount of water added is usually 0.2 times to 100 times, preferably 1 times to the base catalyst.
A 50-fold molar range, more preferably a 15-fold to 50-fold molar range, is used. If the amount of water added is too small, the selectivity of the target product will be low, and if it is too large, the reaction rate will be slow, making it impractical. Another advantage of the present method is that, in a sufficiently water-added system, after the reaction, an oil layer containing an oil represented by the general formula [I] as a target product as a main component, a polar solvent, and water. , And the catalyst layer mainly composed of a base catalyst is separated into two layers, so that the target substance can be easily separated from the reaction mixture, while the catalyst layer can be recycled and reused as it is.

When the fluorine-containing aromatic compound represented by the general formula [I] is used as a lubricating oil for a refrigeration system, the electrical characteristics are important characteristics other than compatibility, lubrication characteristics and durability. I can name it. In particular, a lubricating oil for a hermetic refrigerator used in a refrigerator or the like for refrigerators is required to have good electric insulation. That is, usually 10
^It is required to have a volume resistivity of ¹¹ Ωcm or more, preferably 10 ¹² Ωcm or more, particularly preferably 10 ¹³ Ωcm or more.

According to the above-mentioned synthetic method, since the desired fluorine-containing aromatic compound is formed with high selectivity, it can be highly purified (for example, simple distillation) by washing with water or simple distillation (for example, simple distillation).
Although it is possible to isolate a fluorine-containing compound (99.9% or more), electric characteristics such as volume resistivity are often insufficient due to the influence of a trace amount of impurities. Therefore, the present inventors have studied various treatment methods for improving electric characteristics and found the following method.

That is, the high-purity fluorine-containing aromatic compound obtained by the above-mentioned method was applied to silica gel, zeolite, frass earth, activated clay, bauxite, alumina, magnesia, charcoal, bone charcoal, activated carbon, or silica silicate gel,
It is preferably selected from activated carbon, silica gel, activated alumina, silica-alumina, activated clay, and zeolite by contacting with at least one inorganic or organic adsorbent for various polar substances such as ion exchangers such as zirconium oxide gel. By contacting with at least one adsorbent, particularly preferably by contacting with at least one adsorbent selected from activated carbon, silica gel and zeolite, the electrical characteristics are remarkably improved and the volume resistivity is 10 ¹² Ωcm or more. , Or 10 ¹³
It was found that a high-purity fluorine-containing aromatic compound having an Ωcm or more can be easily obtained.

As the contact method, the adsorbent may be dispersed in a fluorinated aromatic compound or a solution thereof, or the fluorinated aromatic compound or a solution thereof may be passed through a column having the adsorbent as a packing material. Contact purification treatment may be performed accordingly. According to the present purification method, a fluorine-containing aromatic compound having an extremely high purity (for example, 99.9% or more), showing no adverse effects on metal materials and refrigerants, and showing good electric characteristics can be easily obtained.

As described above, since the fluorine-containing aromatic compound represented by the general formula [I] generally exhibits good lubricating characteristics, refrigeration using a fluoroalkane containing a chlorine-containing fluoroalkane-based refrigerant as a refrigerant. It is useful not only as a lubricating oil for machines but also as a general lubricating oil. Among them, in particular, the polyvalent fluorine-containing aromatic compound represented by the general formula [III] can be synthesized 1) using inexpensive synthetic raw materials and with high yield economically. , It shows particularly excellent lubrication properties 3), and because it has excellent compatibility with various hydrocarbon solvents, it is easy to apply, wash, and mix the substance 4), It has excellent compatibility with fluorine-based oils (for example, hydrocarbon-based oils, polyalkylene glycols, ester-based oils, etc.), so it has many characteristics such as being usable as a mixed oil with these oils. And is particularly useful.

R ′ (XRf ′) n ′ [III] [wherein, X is an O or S atom. R'represents the same aromatic group as R in general formula [I], provided that the number of carbon atoms in R'is 6 to 30. n'represents an integer of 2 to 4. Rf ′ is the same as Rf in the general formula [I], provided that the number of carbon atoms in Rf ′ is 1 to 3.

The compound of the general formula [III] may be composed of plural kinds of XRf ′. R'and XRf '
Are directly linked by the aromatic ring portion in R '. ] 1) will be described in more detail with specific examples.
For example, the substance of the general formula [III] includes polyhydric phenol and C
F ₂ = CF ₂ , CF ₂ = CFCl, CF ₂ = CFCF ₃
It is synthesized in a high yield by a reaction with an inexpensive fluoroolefin which is industrially produced in large quantities.

Alternatively, the substance of the general formula [III] is polyvalent.
Phenol and HCFC-22 (CF ₂HCl) and CFC
-113 (CF₂ClCFCl₂) Inexpensive chlorof
It is also synthesized in high yield by reaction with luorocarbons.
It In addition, CF₃CH₂OH, CF₃CF₂CH
₂OH and other industrially mass-produced inexpensive fluorine-containing foot
It is also synthesized using elementary alcohol.

Explaining in more detail with respect to 2), the substances of the general formula [III] exhibit extremely good lubricating characteristics, and they are more excellent than turbine oil (containing additives) which is a typical high performance lubricating oil. Excellent extreme pressure resistance, abrasion resistance,
It has been confirmed to exhibit a coefficient of friction. General formula [II
Examples of the compound represented by I] include the following compounds.

R15

[0143]

[Chemical 38]

R16

[0145]

[Chemical Formula 39]

[0146]

EXAMPLES The present invention will be specifically described below with reference to examples, but the scope of the present invention is not limited to the examples. The kinematic viscosity of the lubricating oil of the present invention can be determined by measuring the viscosity with various viscometers. For example, as the viscometer to be used, for example, Uberode viscometer, Ostwald viscometer, capillary viscometer such as Canon-Fenske viscometer,
A rotational viscometer or a falling ball type viscometer can be mentioned, but in the present application, an E type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.) was used.

(Reference Reaction Example 1) 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. This potassium alkoxide (18.9 g) and bisphenol A (56.0 g) were dissolved in dimethyl sulfoxide (200 ml) and placed 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 chlorotrifluoroethylene was introduced to start the reaction. Chlorotrifluoroethylene was supplied so that the system internal pressure (gauge pressure) was maintained at ² to 3 kg / cm ^2, and the reaction was carried out for about 5 hours. The solution after the reaction was poured into a large amount of water, and 1,1,2-trichloro-1,2,2-trifluoroethane (hereinafter abbreviated as CFC-113) was added to the separated reaction product to give 50 parts.
0 ml was added. The CFC-113 layer was washed twice with distilled water, dried and the solvent was removed to obtain 131 g of a colorless transparent oil (containing 91.5 wt% of [S1]).

After simple distillation (bp. 0.02 mmHg, 18
(0 ℃) Separated using silica gel column and
Was isolated [S1]. Infrared absorption spectrum analysis, quality
Quantitative analysis [m / e 460, 462 (M⁺) 445, 44
7 (M⁺-CH₃)〕and ¹⁹F-NMR spectrum
According to the analysis, this oil [S1] has the structure shown below.
It was confirmed to be a compound.

[S1]

[0151]

[Chemical 40]

¹⁹ F-NMR spectrum (CF ₃ COOH
Ppm): 78 (2F), 7.5 (4F) (Reference Reaction Example 2) The reaction was conducted in the same manner as in Reference Reaction Example 1 except that tetrafluoroethylene was used instead of chlorotrifluoroethylene. Oil (9 [S2]
113 g (containing 0.1 wt%) was obtained. After simple distillation (bp.
(0.20 mmHg, 160 ° C.), a separation treatment was performed using a silica gel column to isolate oil [S2].

Infrared absorption spectrum analysis, mass spectrometry [m
/ E 392 (M ⁺ ), 377 (M ⁺ -CH ₃ )] It was confirmed that this compound [S2] was a compound having the structure shown below. [S2]

[0154]

[Chemical 41]

(Reference Reaction Example 3) 10 g of bisphenol A
Was dissolved in 10 ml of tetrahydrofuran, 10 g of triethylamine was added thereto, and the mixture was placed in a 200 ml capacity micro-bomb. This micropombe was cooled to −78 ° C., the pressure inside the micropombe was reduced, 60 g of hexafluoropropane was introduced, and then heated to 60 ° C.
Reacted for hours. After the reaction, 100 ml of R-113 was added to the reaction mixture obtained by removing tetrahydrofuran and excess triethylamine by an evaporator to form a solution, which was washed once with dilute hydrochloric acid and twice with distilled water.

By removing the solvent of the R-113 phase with an evaporator, 12 g of a colorless transparent oil [S3] was obtained.
Obtained (yield 55%). When this mixture was analyzed by gas chromatography, several peaks were observed. Therefore, oil [S3] was subjected to separation treatment using a silica gel column, and samples obtained from each fraction were subjected to mass spectrometry and infrared absorption spectrum. Analysis, ¹⁹ F-N
MR spectrum analysis was performed. The results are shown in Table 1.

[0157]

[Table 1]

A) Internal standard CF ₃ COOH b) [S3]

[0159]

[Chemical 42]

[S3A]

[0161]

[Chemical 43]

[S3B]

[0163]

[Chemical 44]

[S3C]

[0165]

[Chemical formula 45]

The oil [S3] is the compound [A], [B] or [C] shown in Table 1 (molar ratio A / B / C = 4/4 /
2) which is a mixture of compound [A] and has a cis-cis form, a cis-trans form and a trans-trans form depending on the structural isomers of the pentafluoropropenyl group, and compound [B] contains Similarly, it was confirmed that there were cis and trans forms.

Reference Reaction Example 4 17 g of potassium alkoxide of bisphenol A synthesized by the same method as in Reference Reaction Example 1 was dissolved in 100 ml of dimethyl sulfoxide, 28 g of R-113 was added, and the mixture was heated to 60 ° C. for about 5 minutes.
Reacted for 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 then the solvent was removed to obtain 13.4 g of a colorless transparent oil [S4] (yield 28.5%).

When this oil was analyzed by gas chromatography, three peaks were observed. Therefore, the oil [S4] was subjected to separation treatment using a silica gel column, and the samples obtained from each fraction were subjected to mass spectrometry and infrared spectroscopy. Absorption spectrum analysis and NMR spectrum analysis were performed. The results are shown in Table 2.

[0169]

[Table 2]

A) Internal standard CF ₃ COOH b) [S4]

[0171]

[Chemical formula 46]

[S4D]

[0173]

[Chemical 47]

[S4E]

[0175]

[Chemical 48]

[S4F]

[0177]

[Chemical 49]

Oil [S4] is compound [D], [E],
It was confirmed that the mixture was [F] (molar ratio D / E / F = 3/5/2). (Reference reaction example 5) 2,2-instead of bisphenol A
Oil [S5] was obtained in exactly the same manner as in Reference Reaction Example 1 except that bis (4-hydroxy-3-methylphenyl) propane was used and tetrafluoroethylene was used instead of chlorotrifluoroethylene (yield 77 %).

Infrared absorption spectrum analysis and mass spectrometry results [m / e 456 (M ⁺ ), 441 (M ⁺ -C)
From H ₃ )], it was confirmed that [S5] was a compound having the structure shown below.

[S5]

[Chemical 50]

Reference Reaction Example 6 Oil [S6] was obtained in exactly the same manner as in Reference Reaction Example 3 except that p-α-cumylphenol was used in place of bisphenol A (yield 8
6%). [S6]

[0182]

[Chemical 51]

From the results of gas chromatography analysis and mass spectrometry, the oil [S6] was identified as a mixture of the compounds [G] and [H] (molar ratio G / H = 5/5). [S6-G, H]

[0184]

[Chemical 52]

Reference Reaction Example 7 Oil [S7] was prepared in the same manner as in Reference Reaction Example 3 except that 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane was used in place of bisphenol A. Was obtained (yield 46%). From the results of infrared absorption spectrum analysis and mass spectrometry, [S
7] was confirmed to be a compound having the structure shown below.

[S7]

[0187]

[Chemical 53]

M = 0, 1 n = 0, 1 (Reference Reaction Example 8) Instead of bisphenol A, bis (4
A highly viscous oil [S8] was obtained in exactly the same manner as in Reference Reaction Example 3 except that -hydroxyphenyl) sulfone was used (yield 41%).

From the results of infrared absorption spectrum analysis and mass spectrometry, it was identified that [S8] was a compound having the structure shown below. [S8]

[0190]

[Chemical 54]

M = 0, 1 n = 0, 1 (Reference Reaction Example 9) Exactly the same as Reference Reaction Example 3 except that bis (3,5-dimethyl-4-hydroxyphenyl) sulfone was used in place of bisphenol A. Then 10
A solid substance [S9] was obtained at ℃ (yield 97%).

From the results of infrared absorption spectrum analysis and mass spectrometry, it was identified that [S9] was a compound having the structure shown below. [S9]

[0193]

[Chemical 55]

M = 0, 1 n = 0, 1 (Reference Reaction Example 10) Oil [S10] was obtained in exactly the same manner as Reference Reaction Example 3 except that dodecylphenol was used in place of bisphenol A (yield 80 %). From the results of infrared absorption spectrum analysis and mass spectrometry, it was identified that [S10] was a compound having the structure shown below.

[S10]

[0196]

[Chemical 56]

N = 0, 1 (Reference Reaction Example 11) Instead of hexafluoropropene, the following hexafluoropropene dimer, R17:

[0198]

[Chemical 57]

Oil [S11] was obtained in exactly the same manner as in Reference Reaction Example 3 except that the above compound was used (yield 79%). [S11]

[0200]

[Chemical 58]

From the results of gas chromatography analysis and mass spectrometry, m = 0, 1 n = 0, 1
The mixture [S11] was identified as a mixture of the mixtures [I], [J] and [K] (molar ratio I / J / K = 4.8 / 4.7 / 0.5). m = 0 n = 0 [S11-I] m = 0 n = 0 [S11-J] m = 1 n = 1 [S11-K] (Reference Reaction Example 12) 10 g of bisphenol A was dissolved in 10 ml of tetrahydrofuran. Triethylamine (15 g) was added, and the mixture was placed in a four-necked flask equipped with a reflux cooling type stirrer. To this, 180 g of hexafluoropropene trimer C ₉ F 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-11
After the three phases were purified by a silica gel column and the solvent was removed by an evaporator, 47 g of oil [S12] was obtained (yield 97%). From the results of infrared absorption spectrum analysis and mass spectrometry, [S12] was identified as a compound having the structure shown below.

[S12]

[0204]

[Chemical 59]

M = 0, 1 n = 0, 1 (Reference Reaction Example 13) An oil [S13] was obtained in exactly the same manner as Reference Reaction Example 12 except that nonylphenol was used in place of bisphenol A (yield 70 %). From the results of infrared absorption spectrum analysis and mass spectrometry, [S13]
Was identified as a compound having the structure shown below.

[S13]

[0207]

[Chemical 60]

N = 0, 1 (Reference Reaction Example 14) An oil [S14] was obtained in exactly the same manner as Reference Reaction Example 9 except that dodecylphenol was used instead of bisphenol A (yield 69%). From the results of infrared absorption spectrum analysis and mass spectrometry, [S14]
Was identified as a compound having the structure shown below.

[S14]

[0210]

[Chemical formula 61]

N = 0, 1 (Reference reaction example 15) Instead of bisphenol A, p-α
-Oil [S15] was obtained in exactly the same manner as in Reference Reaction Example 12 except that cumylphenol was used (yield 70
%). From the results of infrared absorption spectrum analysis and mass spectrometry, it was identified that [S15] was a compound having the structure shown below.

[S15]

[0213]

[Chemical formula 62]

N = 0, 1 (Reference reaction example 16) 7.1 g of sodium hydroxide was added to water 2
After dissolving in 0.7 g, 4.0 g of bisphenol A and 13.8 g of dimethyl sulfoxide were added, and the mixture was charged into a 100 ml capacity micro-bomb. -78 this micro cylinder
After cooling to 0 ° C. and reducing the pressure in the bomb, 7.8 g of chlorodifluoromethane (R22) was introduced. After reacting at 70 ° C. for 10 hours, 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 R-113 layer was washed twice with distilled water, then purified by a silica gel column and the solvent was removed to obtain 1.1 g of oil [S16] (yield 18%). Mass spectrometry [m / e 328 (M ⁺ ), 313
(M ⁺ —CH ₃ )] and infrared absorption spectrum analysis results show that oil [S16] has the following structure. .

[S16]

[0217]

[Chemical formula 63]

(Reference Reaction Example 17) Bisphenol A10
After dissolving g in 60 ml of tetrahydrofuran, 15 g of triethylamine was added, 40 ml of a tetrahydrofuran solution containing 7.2 g of 2-ethylhexanoic acid chloride was further added dropwise, and the mixture was gradually added with a funnel. After reacting for 10 hours at room temperature, tetrahydrofuran and excess triethylamine were removed by an evaporator. The remaining reaction product was transferred to a 200 ml capacity micropombe and used as a reference reaction example 3.
It was reacted with hexafluoropropene by a method similar to that to obtain 1.6 g of oil [S17] (yield 7.5
%).

As a result of infrared absorption spectrum analysis and mass spectrometry, the compound [S17] was identified to be a compound having the structure shown below. [S17]

[0220]

[Chemical 64]

N = 0, 1 (Reference Reaction Example 18) Oil obtained in Reference Reaction Example 3 [S3]
10.8 g was put into a 200-volume micropombe, 5.4 g of sulfuryl chloride SO ₂ Cl ₂ was added, and then 100 ° C.
And reacted for 4 days. After the reaction, the solution was poured into a large amount of water, 100 ml of Freon 113 was added to the separated reaction product to form a solution, and the lower layer was separated. After washing with a 10% aqueous sodium bicarbonate solution and distilled water, the product was purified by a silica gel column to obtain 9.65 g of an oily substance.

The infrared absorption spectrum of this oily substance is based on the stretching vibration of -CF = CF- of [S3].
The absorption at 59 cm ^-1 has disappeared, indicating that a chlorine adduct such as [S18] is formed. [S1
8]

[0223]

[Chemical 65]

(Here, RfCl is -CClFCClF
CF ₃ or -CF ₂ CHFCF _3. (Reference reaction example 19) Sodium borohydride NaBH ₄
8 g of the mixture [S4] obtained in Reference Reaction Example 4 was added to a solution prepared by suspending 7 g in 100 ml of dimethyl sulfoxide,
The reaction was carried out at 85 ° C for 16 hours. After the reaction, 100 ml of R-113 was added to the reaction mixture obtained by removing dimethyl sulfoxide with an evaporator to obtain a solution. After washing this with distilled water, the R-113 phase was purified by a silica gel column to obtain 3.5 g of colorless transparent oil [S19] (yield 55%).

Gas Chromatographic Analysis and Mass Spectrometry [m / e 428 (M ⁺ ), 413 (M ⁺ —CH ₃ )]
As a result, the oil [S19] was identified as a compound having the following structure. [S19]

[0226]

[Chemical formula 66]

Reference Reaction Example 20 The procedure of Reference Reaction Example 3 was repeated except that 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -3-heptene was used in place of bisphenol A. To obtain oil [S20] (yield 93%). Gas chromatography analysis and mass spectrometry results, the ratio of saturated groups to unsaturated groups, i.e. -CF ₂ CHFC
F ₃ / -CF = was _{CF-CF 3 = 42/58} .

[S20]

[0229]

[Chemical formula 67]

(Here, Rf ₁ , Rf ₂ and Rf ₃ are −
Is CF ₂ CHFCF ₃ or -CF = CF-CF _3. (Reference Reaction Example 21) An oil [S21] was obtained in exactly the same manner as in Reference Reaction Example 3 except that the compound [G21] was used instead of bisphenol A (yield 70%).

As a result of gas chromatography analysis and mass spectrometry, the ratio of saturated groups to unsaturated groups, that is, --CF ₂ CHFC
It was _{F 3 / -CF = CF-CF} 3 = 46/54. [G21], [S21]

[0232]

[Chemical 68]

(Here, Rf ₁ , Rf ₂ , Rf ₃ and Rf
_4, -CF ₂ CHFCF ₃ or -CF = CF-CF ₃
Is. (Reference Reaction Example 22) Acid fluoride F [CF (CF ₃ ) CF of hexafluoropropene oligomer was added to a solution prepared by dispersing 10 g of sodium carbonate in 25 ml of diglyme.
₂ O] 25 g of _5-8 CF (CF ₃ ) COF (manufactured by US PCR) is added and reacted at 80 ° C. for 5 hours.

After the reaction, diglyme was distilled off and the silica gel column was purified to give oil [G22] at 15.4.
g was obtained. 0.54 g of potassium alkoxide of bisphenol A and 0.50 g of bisphenol A synthesized by the same method as in Reference Reaction Example 1 were added to 3 m of dimethyl sulfoxide.
11 g of 1,3 of compound [G22]
10 ml of di (trifluoromethyl) benzene solution was added, and the mixture was reacted at 80 ° C. for 3 hours.

After distilling off dimethyl sulfoxide, the product was purified with a silica gel column to obtain 9.7 g of oil [S22] (yield about 80%). As a result of infrared absorption spectrum analysis and mass spectrometry, it was confirmed that [G22] [S22] was a mixture of substances having the structures shown below. [G22], [S22]

[0236]

[Chemical 69]

(Here, Rf ₀₁ is R23

[0238]

[Chemical 70]

Rf ₀₂ is R24

[Chemical 71]

It is. ) The data of [S22] mass spectrometry is shown below.

[0241]

[Table 3]

Reference Reaction Example 23 Except that 1,1-difluoro-1,2,2,2-tetrachloroethane was used in place of R-113, exactly the same as Reference Reaction Example 4,
A solid substance [S23-] was obtained (yield = 55%).
Oil [S23-] was added to a solution prepared by suspending 9 g of lithium aluminum hydroxide in 200 ml of tetrahydrofuran.
Is added 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,
Purification by toluene-phase silica gel gave 3.5 g of colorless transparent oil (yield 50%).

From the results of infrared absorption spectrum analysis and mass spectrometry, it was identified that [S23-] and [S23-] are compounds having the structures shown below. [S23-,]

[0244]

[Chemical 72]

M / e 356 (M ⁺ ), 341 (M ⁺ —CH ₃ ) (Reference Reaction Example 24) By the same method as in Reference Reaction Example 22 except that thiophenol was used instead of bisphenol A, Oil [S24] was obtained (yield about 70).
%). As a result of infrared absorption spectrum analysis, gas chromatography analysis and mass spectrometry, it was confirmed that [S24] was a mixture of substances having the structures shown below.

[S24]

[0247]

[Chemical formula 73]

Mass spectrometry data is shown below.

[0249]

[Table 4]

(Reference Reaction Example 25) 2,2-bis [p-
(2-Hydroxyethoxy) phenyl] -propane 7.
A solution prepared by diluting 13 g of hexafluoropropenediethylamine with dichloromethane was added dropwise to 60 ml of a dichloromethane solution containing 9 g dissolved therein at 0 to 5 ° C. After reacting for 4 hours at room temperature, the reaction mixture was poured into a 10 wt% potassium carbonate aqueous solution, and the oil layer was washed with water and dried over sodium sulfate. Separately distilled to obtain a colorless transparent oily substance [S
25] was obtained.

Infrared absorption spectrum analysis and mass spectrometry [m / e 320 (M ⁺ ), 305 (M ⁺ -CH ₃ )]
From this, it was confirmed that this substance [S25] was a compound having the structure shown below. [S25]

[0252]

[Chemical 74]

(Reference Reaction Example 26) Alkoxide 1 of bisphenol A synthesized by the same method as Reference Reaction Example 1
3.3 g and ethyl p-toluenesulfonate (30.0 g) were reacted in a dimethyl sulfoxide (200 ml) solvent.
The solvent was distilled off and the residue was purified by a silica gel column to obtain 6.6 g of a white solid compound [S26].

As a result of infrared absorption spectrum analysis and mass analysis, [m / e 284 (M ⁺ ), 269 (M ⁺ -C)
H ₃ )], it was identified that [S26] was a compound having the structure shown below. [S26]

[0255]

[Chemical 75]

(Example 1) <Compatibility test> Oil obtained in Reference Reaction Example 1 [S1]
And various fluorinated alkanes (HFC-134a, HFC-1
34, HFC-152a) was examined for compatibility by the following method.

First, 0.2 g of oil [S1] was placed in a glass tube, and each glass tube was cooled with liquid nitrogen and depressurized, and then about 1.5 g of HFC-134a was introduced. After sealing the glass tube, put it in a temperature-controlled water bath, and after the temperature reaches equilibrium, visually check the compatibility of [S1] and fluorinated alkanes. The range was measured. The low temperature region below room temperature was cooled in a methanol refrigerant and measured by the same method.

The results are shown in Table 3 together with the result of Comparative Example 1. Further, the kinematic viscosities of the oil [S1] at 40 ° C. and 100 ° C. were measured to be 56.8 cst and 5.3, respectively.
It was 4 cst. Example 2 The compatibility of the oil [S2] obtained in Reference Reaction Example 2 with the various fluoroalkanes was examined in the same manner as in Example 1, and the results are shown in Table 5 together with the results of Comparative Example 1.

[0259]

[Table 5]

[0260]

[Table 6]

* 1: CF ₃ manufactured by Montefluos
_{O (-CF 2 CF 2 O)} m1 - (CF 2 O) m2 -CF
₃ * 2: Compatibility is not found within the range of measurement conditions (-79 ° C to 90 ° C). * 3 [S2-1]

[0262]

[Chemical 76]

The oil [S2] has a temperature of 40 ° C and 100 ° C.
The kinematic viscosities at 26.2 cst and 3.40 cs, respectively.
It was t. Comparative Examples 1 to 4 The compatibility of commercially available perfluoropolyether and 2,2-bis (4-ethoxyphenyl) propane with the various fluorinated alkanes was examined in the same manner as in Example 1, and the results were 40. Table 5 together with the kinematic viscosity at ℃
~ 6.

In Tables 3 to 5, 11, 12, and 14, M
n means a number average molecular weight. In addition, n and m _{1 to mn}
Means a positive integer. Comparative Examples 5 to 8 The compatibility of commercially available perfluoropolyether and polyoxyalkylene glycol with HFC-134a was examined in the same manner as in Example 1, and the results are shown in Table 7 together with the kinematic viscosity at 40 ° C.

[0265]

[Table 7]

* 1 manufactured by Du Pont [S2-2]

[0267]

[Chemical 77]

* 2 manufactured by Daikin Industries, Ltd. [S2-
3]

[0269]

[Chemical 78]

* 3 [S2-4)

[0271]

[Chemical 79]

Tables 5-6. From Table 7, the following is found regarding the compatibility with various fluorinated alkanes. That is, the commercially available perfluoropolyether has insufficient compatibility in the low temperature region, while the polyoxyalkylene glycol is
There is a problem of compatibility in the high temperature region. In comparison with them, the oil of the present invention shows good compatibility with various fluorinated alkanes in a wide temperature range from a low temperature region to a high temperature region.

[S26], which has a structure similar to the oil of the present invention shown in Comparative Example 4, but does not contain a fluorine atom, is almost compatible with fluorinated alkanes such as HFC-134a. Not shown. From this fact, it is clear that the alkyl group bonded to the aromatic group by an ether bond contains a fluorine atom, which is an essential requirement for compatibility development.

(Examples 3 to 23) Reference reaction examples 3 to 7 and 1
The compatibility of HFC-134a with various oils obtained in 0 to 23 was examined in the same manner as in Example 1, and the result was 40 ° C.
It shows in Tables 8-9 with the kinematic viscosity in.

[0275]

[Table 8]

[0276]

[Table 9]

(Examples 24 and 25) The compatibility of the alkane compounds obtained in Reference Reaction Examples 8 and 9 with HFC-134a was the same as in Example 1. As a result, both the lubricants [S8] and [S9] showed compatibility with HFC-134a in the entire temperature range of -78 ° C to 90 ° C measured.

(Examples 26 to 28) The oil [S5] obtained in Reference Reaction Example 5 and the oil [S2] obtained in Reference Reaction Example 2 were mixed at various weight ratios.
The results of examining the compatibility with FC-134a in the same manner as in Example 1 are shown in Table 10 together with the kinematic viscosity at 40 ° C.

[0279]

[Table 10]

(Examples 29 to 30) The solid substance [S4-D] at 10 ° C. obtained in Reference Reaction Example 4 and Reference Reaction Example 2
Regarding the oil obtained by mixing the oil [S2] obtained in 1. at various weight ratios, the compatibility with HFC-134a was determined in Example 1.
Table 11 shows the results of the same examination as above, together with the kinematic viscosity at 40 ° C.

[0281]

[Table 11]

(Examples 32 to 34) Oils obtained by mixing the oil [S7] obtained in Reference Reaction Example 7 and the oil [S3] obtained in Reference Reaction Example 3 at various weight ratios were tested.
The results of examining the compatibility with FC-134a in the same manner as in Example 1 are shown in Table 12 together with the kinematic viscosity at 40 ° C.

[0283]

[Table 12]

(Example 35) The oil [S11] obtained in Reference Reaction Example 11 and the oil [S3] obtained in Reference Reaction Example 3 were mixed in a weight ratio [S7] / [S3] = 30/70. The compatibility of the above oil with HFC-134a was examined in the same manner as in Example 1. As a result, it was found that the lower limit of the compatible temperature range was −78 ° C. and the upper limit was 90 ° C. or higher. The kinematic viscosity at 40 ° C. of this mixed oil was 21 cst.

(Example 36) Regarding oil obtained by mixing the oil [S2] obtained in Reference Reaction Example 2 with polypropylene glycol (number average molecular weight Mn = 1000) in a weight ratio [S2] / polypropylene glycol = 50/50 ,
As a result of examining the compatibility with HFC-134a in the same manner as in Example 1, it was found that the lower limit of the compatible temperature range was -70 ° C and the upper limit thereof was 85 ° C.

The kinematic viscosity of this mixed oil at 40 ° C. was 77.7 cst. The lower limit of the compatibility temperature range of polypropylene glycol and HFC-134a is -7.
It is 8 ° C or lower, and the upper limit is 62 ° C. It is clear that the compatibility (maximum temperature) of polypropylene glycol was improved by mixing with oil [S2]. (Example 37) Oil obtained in Reference Reaction Example 2 [S2]
HFC-13 was prepared by mixing ester oil (Unistar registered trademark H407R manufactured by NOF CORPORATION) with a weight ratio [S2] / ester oil = 50/50.
As a result of examining the compatibility with 4a in the same manner as in Example 1, it was found that the lower limit of the compatible temperature range was −28 ° C. and the upper limit thereof was 90 ° C. or higher. The kinematic viscosity at 40 ° C was 28.7 cst.

Unistar H407R is a full ester obtained by the reaction of pentaerythritol and a synthetic fatty acid having 7 carbon atoms, and the kinematic viscosity at 40 ° C. is 21.9 cst.
Indicates. Also, Unistar H407R HFC-13
The lower limit of the compatible temperature range with 4a is -1 ° C and the upper limit is 85 ° C. From the above results, it is clear that the compatibility (lower limit temperature) of Unistar H407R was improved by mixing with oil [S2].

(Examples 38 to 43) <Heat Resistance Evaluation (Shield Tube Test)> 0.6 ml of refined oil [S1] in a glass tube, HFC-1
34a and iron, copper, and aluminum test pieces were added, and the sealed refrigerant composition was heated at 175 ° C. for 10 days.
As a result of observing the change of the hue of the refrigerant composition and the surface of the metal piece, no change was observed in the hue of the refrigerant composition and the state of the metal surface. Further, the viscosity and infrared absorption spectrum of oil [S2] were not changed at all.

Table 13 shows the results of evaluation of the heat resistance of various compounds of the present invention by the shield tube test in the same manner as described above. From this result, it was found that the compound of the present invention exhibits sufficient heat resistance.

[0290]

[Table 13]

(Examples 44 and 45) <Lubrication Property Test> (Farex Test) Using a Falex tester, the oil temperature at the start of the test was 20 ° C.
Under the conditions described above, after operating for 3 minutes under a load of 300 pounds, the applied load is increased by 100 pounds, and each load is operated for 1 minute until baking. The baking load was measured by this method.

The wear amount was measured by the following method. Similar to the measurement of the baking load, first, the refrigerant gas (HRC-134a) is blown into the oil to be measured at an amount of about 10 l / hr.
For about 15 minutes. Furthermore, under the condition that the oil temperature at the start of the test was 20 ° C. under the blowing of the refrigerant gas, the load was increased to 400 lbs after operating for 5 minutes under the load of 250 lbs, and the gear was set to maintain 400 lbs. Operate for 30 minutes while adjusting the pressure. The difference between the number of teeth of the gear when the pressure was reduced to 100 pounds and the weight of 400 pounds was again applied, and the difference between the number of teeth when initially set was taken as a measure of the amount of wear.

<Soda-type four-ball test> Using a Soda-type four-ball tester, the oil temperature at the start of the test was 200 rpm at an oil temperature of 20 ° C.
The load oil pressure is 49.0 kPa / min (0.5 kgf / c
It was raised until seizure occurred at a rate of m ² ) and the pass limit (hydraulic pressure) was determined. <Soda-type pendulum test> The Soda-type pendulum tester was used to measure the oil temperature at the start of the test at 20 ° C.

Table 14 shows the results of measuring the baking load, the amount of wear, and the coefficient of friction of various oils used in the present invention by the above method, together with the results of Comparative Examples 9 to 12. (Comparative Examples 9 to 12) Table 14 shows the results of measuring the baking load, wear amount and friction coefficient of commercially available mineral oil, polyoxyalkylene glycol, ester oil and turbine oil in the same manner as in Examples 44 and 45. Show.

[0295]

[Table 14]

* 1: Nippon San Oil Co., Ltd .: Naphthenic mineral oil * 2: Nippon Oil & Fats Co., Ltd .: Ester oil (full ester obtained by reaction of trimethylolpropane and Yang fatty acid having 12 to 14 carbon atoms) * 3 : Showa Shell Sekiyu Co., Ltd .: Turbine oil (with additives) * 4: Measured while blowing the refrigerant gas CFC-12 * 5: Measured while blowing the refrigerant gas HFC-134a * 6: [S2-5]

[0297]

[Chemical 80]

From Table 12, various oils of the present invention are
-12 mineral oil (registered trademark SUNISO 3GS manufactured by Sun Oil Co., Ltd.), polyoxyalkylene glycol and ester oils listed as candidate oils for refrigerating machine oil for HFC-134a, and various additives. It can be seen that, as compared with the high-performance lubricating oil containing the oil (terrace oil 32 manufactured by Showa Shell Sekiyu KK), all of the extreme pressure resistance, abrasion resistance, and friction coefficient are excellent.

Therefore, the various oils of the present invention are useful not only as refrigerating machine oil but also as general lubricating oil. In addition, the results in Table 12 show that the general formula [I] containing a chlorine atom was used.
It is shown that the compound (1) has particularly excellent lubricity. (Examples 46 to 53, Comparative Examples 13 to 15) <Water absorption amount> Equilibrium water absorption when various oils and polypropylene glycol used in the present invention are allowed to stand in a thermo-hygrostat at 40 ° C and a relative humidity of 80%. The result of measuring the amount,
24 hours under the conditions of 25 ° C. and 80% relative humidity of the ester oil described in JP-A-3-179909.
It is shown in Table 13 together with the amount of water absorption after standing.

From Table 13, the oil of the present invention is the same as the conventional HFC.
It can be seen that, as compared with polyoxyalkylene glycol or ester oil, which is a candidate for refrigerating machine oil of -134a, it has low water absorption and is suitable as a lubricating oil for a refrigerating machine. (Example 54) <Method for producing high-purity fluorine-containing aromatic compound> Bisphenol A60 was placed in a reaction vessel (500 ml micropombe).
g, 5.65 g of potassium hydroxide, 120 ml of dimethyl sulfoxide and 44 ml of water were added and dissolved. 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 chlorotrifluoroethylene was introduced to start the reaction. System pressure (gauge pressure) is 2
Chlorotrifluoroethylene was supplied so as to be maintained at ˜3 kg / cm ² and reacted for about 5 hours.

At the end of the reaction, two layers were separated into an oil layer containing the objective product oil as the main component and a catalyst layer containing dimethyl sulfoxide, water and potassium hydroxide as the main components.
Thoroughly wash the oil layer with distilled water, 0.02mmHg18
Distillation at 0 ° C. gives 100% of the desired product [S1].
g was obtained. On the other hand, dimethyl sulfoxide from the catalyst layer,
After distilling off the water, washing well with distilled water, and then distilling, 20 g of the desired product [S1] was obtained. Total yield of desired product is 12
It became 0 g (yield 99%).

As a result of analyzing the oil obtained by this method by gas chromatography, the purity of the desired product was 99.
It was 5%. (Examples 55 to 57) The reaction between bisphenol A and chlorotrifluoroethylene was examined in the same manner as in Example 54 while changing the amount of water added, the type of catalyst and the type of reaction solvent. The results are shown in Table 15 together with the results of Comparative Example 16.

[0303]

[Table 15]

* 1 Described in JP-A-3-1799091 * 2 [S2-6]

[0305]

[Chemical 81]

(Example 58) As a result of carrying out the reaction in the same manner as in Example 54, except that tetrafluoroethylene was used instead of chlorotrifluoroethylene and the amount of water added was changed from 44 ml to 5 ml. 98 g of the desired product [S2] was obtained. As a result of analyzing the oil obtained by this method by gas chromatography, the purity of the desired product was 99.9%.

Comparative Example 16 The results of Reference Reaction Example 1 are shown in Table 16 together with the results of the gas chromatography analysis.

[0308]

[Table 16]

* 1) KOH, NaOH as a base catalyst
In the case of using, the water generated by the reaction with the phenolic acid is treated as the addition amount of water and added. Table 16 shows that the addition of water improves the purity of the desired product. (Example 59) <Electrical properties> The volume resistivity of the oil [S1] obtained in Reference Reaction Example 1 was measured by a method according to JIS C2101 (electrical insulating oil test). The volume resistivity of the oil [S1] at 20 ° C. was 3.0 × 10 ¹¹ Ωcm.

(Example 60) As a result of measurement by the same method as in Example 59, the oil obtained in Reference Reaction Example 2 [S
2] has a volume resistivity at 20 ° C. of 5.7 × 10 ¹¹
Ωcm was shown. (Example 61) The oil [S4] obtained in Reference Reaction Example 4 was measured by the same method as in Example 59.
The volume resistivity of the sample was 4.0 × 10 ¹² Ωcm.

(Example 62) As a result of measurement by the same method as in Example 59, the oil [S
5] has a volume resistivity at 20 ° C. of 2.9 × 10 ¹²
Ωcm was shown. (Example 63) As a result of measurement by the same method as in Example 59, 2 of oil [S11] obtained in Reference Reaction Example 11 was obtained.
The volume resistivity at 0 ° C. was 1.4 × 10 ¹² Ωcm.

(Example 64) <Purification method of highly pure fluorine-containing aromatic compound> A suspension prepared by dispersing 100 g of activated carbon (Calgon CPG manufactured by Toyo Calgon Co., Ltd.) dried in vacuum at 150 ° C for 3 hours in 400 g of R-113. To the oil [S1] 20 obtained in Example 54.
0 g was added, and the mixture was stirred at room temperature overnight. After filtering the activated carbon,
R-113 was distilled off, and the oil was subjected to simple distillation to obtain 140 g of a colorless transparent oil.

As a result of analyzing the oil obtained by this purification method by gas chromatography, the purity was improved from 99.5% to 99.88%. In addition, the volume resistivity of the oil before and after refining at 20 ° C. was measured by the same method as in Example 59. As a result, the volume resistivity of 1.0 × 10 ¹¹ Ωcm before the refining was measured by the refining treatment. 2.
It was found that it was greatly improved to 2 × 10 ¹³ Ωcm.

Further, regarding the refined oil, JIS
The dielectric breakdown voltage was also measured by the method based on C2101, and a high value of 50 kV / 2.5 cm or more was shown. The above results are shown in Table 17 together with the results of Comparative Examples 17 to 20. (Example 65) Oil [S2] 1 obtained in Example 58
20 g of R-113 was dissolved in 120 g, and the solution was added to 4 g.
The column was treated with a column containing 500 g of silica gel (Wako gel C-200 manufactured by Wako Pure Chemical Industries, Ltd.) dried at 00 ° C. for 3 hours as a packing material.

R-113 was distilled off from the treated solution,
By simple distillation with oil, 108 g of colorless transparent oil was obtained. As a result of analyzing the oil obtained by this purification method by gas chromatography, the purity was improved from 99.9% to 99.97%. Further, the volume resistivity and the dielectric breakdown voltage were measured by the same methods as in Examples 59 and 64. The results are shown in Table 17 together with the results of Comparative Examples 17 to 20.

Comparative Examples 17 to 20 The volume resistivity and dielectric breakdown voltage of polypropylene glycol, perfluoropolyether, and mineral oil were measured in exactly the same manner as in Examples 59 and 64, and the results are disclosed in JP-A-3-128991. It is shown in Table 17 together with the specific volume resistivity of the ester-based oil described.

[0317]

[Table 17]

* 1 manufactured by Du Pont [S2-6]

[0319]

[Chemical formula 82]

* 2 Nippon San Oil Co., Ltd. naphthenic mineral oil * 3 Ester oil described in JP-A-3-128991 * 4 Volume resistivity before refining * 5 [S2-5]

[0321]

[Chemical 83]

The oil obtained according to the present invention is HFC-134.
Compared with polypropylene glycol, which is listed as a candidate oil for the refrigerating machine oil for a, both volume resistivity and dielectric breakdown voltage are sufficiently high and good. Further, it is almost equivalent to the volume specific resistivity of the ester oil described in JP-A-3-128991. Also, Kr
ytox 143AY and SUNISO 3GS (both of which have insufficient compatibility with fluorinated alkanes,
Although it cannot be used as a lubricating oil for refrigerators that use fluorinated alkanes as a refrigerant, it is considered to be the oil with the best electrical characteristics), [S1] [S2] is Krytox.
It exhibits a volume resistivity between 143AY and SUNISO 3GS, and has a dielectric breakdown voltage superior to that of both Krytox 143AY and SUNISO 3GS.

(Examples 66 to 70) Oil [S1] obtained in Example 54 and oil [S] obtained in Example 59.
The purification treatment of [2] was carried out in the same manner as in Example 61 using various adsorbents. The results are shown in Table 18.

[0324]

[Table 18]

* 1: Silica-alumina manufactured by Mizusawa Chemical Co., Ltd. * 2: Activated white clay manufactured by Japan Activated Shirato Co., Ltd. * 3: Alumina manufactured by Nacalai Chemical Co., Ltd. * 4: Zeolite manufactured by Wako Pure Chemical Industries, Ltd. Table 15 , 16, activated carbon as an adsorbent, silica gel,
It can be seen that activated alumina, silica-alumina, activated clay and zeolite are effective in improving the electrical characteristics of oil.

(Examples 71 to 75) Regarding the compatibility of the oil [S2] and HFC-134a obtained in Reference Reaction Example 2, the mixing ratio of the oil and HFC-134a was changed, and the compatibility was exactly the same as in Example 1. Compatibility tests were carried out by the method. The results are shown in Table 19.

[0327]

[Table 19]

From Table 19, the oil [S2] of the present invention is H
It can be seen that it is freely compatible with FC-134a in a wide temperature range. (Example 76) Oil obtained in Reference Reaction Example 2 [S2]
And polypropylene glycol (number average molecular weight Mn = 10
00) was completely compatible with the mixing ratio ([S2] / polypropylene glycol weight ratio) = 50/50. The kinematic viscosity at 40 ° C. of this mixed oil was 77.7 cst.

(Example 77) The oil [S2] obtained in Reference Reaction Example 2 and an ester oil (UNISTAR H407R manufactured by NOF CORPORATION) were mixed at a mixing ratio ([S2] / ester oil weight ratio) of 50/50. Completely compatible with. The kinematic viscosity of this mixed oil at 40 ° C. was 28.7 cst.

(Example 78) The mixing ratio ([S1] / mineral oil weight ratio) of oil [S1] obtained in Reference Reaction Example 1 and mineral oil (naphthenic mineral oil SUNISO 3GS manufactured by Nippon San Oil Co., Ltd.) = 50/50. Completely compatible with. The kinematic viscosity of this mixed oil at 40 ° C. was 34.5 cst.

Example 79 The compatibility of the oil [S2] obtained in Reference Reaction Example 2 with HFC-125 (CF ₃ CHCF ₂ ) was examined by the same method as in Example 1, and it was found that they were compatible with each other. It was found that the lower limit of the temperature range was −78 ° C. or lower and the upper limit was 90 ° C. or higher. (Example 80) Oil obtained in Reference Reaction Example 2 [S2]
And HFC-227ea (CF ₃ CHFCF ₃ ) were examined in the same manner as in Example 1, and as a result, the lower limit of the compatible temperature range was −78 ° C. or lower and the upper limit was 90 ° C.
It turned out that it was above.

Example 81 The compatibility of the oil [S2] obtained in Reference Reaction Example 2 and HFC-32 (CH ₂ F ₂ ) was examined in the same manner as in Example 1, and it was found that It was found that the lower limit of the temperature range was −78 ° C. or lower and the upper limit was 90 ° C. or higher. (Example 82) The oil obtained in Reference Reaction Example 22 [S2
As a result of examining the compatibility between [2] and perfluoropropane by the same method as in Example 1, it was found that the lower limit of the compatible temperature range was −78 ° C. or lower and the upper limit was 90 ° C. or higher.

Example 83 The compatibility of the oil [S1] and HFC-32 obtained in Reference Reaction Example 1 was examined in the same manner as in Example 1. As a result, the lower limit of the compatibility temperature range was-. It was found to be 56 ° C and the upper limit was 90 ° C or higher. Comparative Example 21 Oil obtained in Reference Reaction Example 25 [S2
5] and HFC-134a were examined in the same manner as in Example 1. As a result, it was found that they were not compatible in the temperature range of −78 ° C. to 90 ° C.

(Comparative Example 22) Fomblin Y-06 and HFC
As a result of investigating the compatibility of -32 by the same method as in Example 1, it was found that no compatibility was obtained at 20 ° C or lower. As described above, it is understood that the fluorinated aromatic compound of the present invention exhibits good compatibility with various lower fluorinated alkanes that can be used as a refrigerant.

(Example 84) <Compatibility test> The oil [S1] obtained in the reference reaction example and various fluorinated alkanes (HFC-134a, HFC-3).
2, HFC-32 / HFC-125 (weight ratio 60/4
0), HCFC-22, and CFC-12) were examined by the same method as in Example 1.

The results are shown in Table 2 together with the result of Comparative Example 23.
It shows in 0. (Example 85) The compatibility of the oil [S2] obtained in Reference Example 2 with the various fluorinated alkanes was examined in the same manner as in Example 1 and the results are shown in Table 20. From Table 20, the following can be understood regarding the compatibility with various fluorinated alkanes. That is,
INDUSTRIAL APPLICABILITY The oil of the present invention shows good compatibility with a chlorine-containing fluoroalkane-based refrigerant such as HCFC-22 and a hydrofluoroalkane-based refrigerant such as HFC-134a in a wide temperature range, and is naturally good with a mixed refrigerant thereof. Show good compatibility.

(Example 86) The oil [S2] obtained in Reference Example 2 and HFC-134a / CFC-12 (weight ratio 5
0/50) mixed refrigerant and HFC-32 / HCFC-2
The compatibility with the mixed refrigerant of 2 (weight ratio 50/50) was examined in the same manner as in Example 1, and as a result, in each case, it was compatible in the temperature range of −78 ° C. or lower to + 90 ° C. or higher.

(Example 87) <Heat resistance evaluation (shield tube test)> 0.6 ml of refined oil [S1] in a glass tube, a test piece of iron, copper and aluminum and 1 CFC-12 as a refrigerant.
After heating the refrigerant composition containing 0 wt% of HFC-134a and sealing the tube at 175 ° C. for 10 days, the hue of the refrigerant composition and the surface of the metal piece were observed. No change was seen in the surface condition. Further, the viscosity of the oil [S1] and the infrared absorption spectrum were not changed at all. The results are shown in Comparative Example 24,
The results of 25 are shown in Table 21.

Table 21 shows the results of evaluation of the heat resistance of the oil [S2] of the present invention by the same method as described above. (Examples 88 and 89) HCFC-22 was used as a refrigerant in 10
Other than using HFC-32 containing wt%,
The heat resistance was evaluated by the same method as in Examples 86 and 87. The results are shown in Table 22 together with the results of Comparative Examples 26 and 27.

Table 22 shows the results of evaluation of the heat resistance of the oil [S2] of the present invention by the same method as above. (Example 90) Except that HFC-134a containing 10% by weight of HCFC-124 was used as the refrigerant,
The heat resistance was evaluated in the same manner as in Examples 86 and 87. As a result, neither the hue of the refrigerant composition nor the state of the metal surface was changed. Further, the viscosity of the oil [S1] and the infrared absorption spectrum did not change at all.

From the above-mentioned shield tube test results, ester oil and polypropylene glycol were remarkably decomposed in the presence of a fluoroalkane-based refrigerant containing CFC-12 or HCFC-22. It can be seen that the oil of the present invention is stable and has not been decomposed at all. (Comparative Example 23) Table 20 shows the results of examining the compatibility between mineral oil (naphthenic mineral oil SUNISO 3GS manufactured by Nippon San Oil Co., Ltd.) and the various fluorinated alkanes in the same manner as in Example 1.

(Comparative Examples 24 and 25) Regarding the heat resistance of commercially available ester oils and polypropylene glycol,
The results evaluated in the same manner as in Examples 86 and 87 are shown in Table 21.
Shown in. In Tables 21 and 22, Mn means a number average molecular weight. Further, n means an integer.

(Comparative Examples 26 and 27) Regarding heat resistance of commercially available ester oils and polyalkylene glycols,
The results evaluated in the same manner as in Examples 88 and 89 are shown in Table 22.
Shown in.

[0344]

[Table 20]

[0345]

[Table 21]

[0346]

[Table 22]

[0347]

According to the present invention, when a compound containing a fluorine-containing group and an aromatic group as essential constituents is used as a lubricating oil for a refrigeration system using a refrigerant containing a chlorine-containing fluoroalkane and a fluoroalkane, a low temperature range is obtained. To a high temperature range, it shows good compatibility with the refrigerant and can be used stably.

Further, this lubricating oil has heat resistance, lubricating characteristics,
It has excellent physical properties such as low temperature hygroscopicity and electrical insulation.
It can be an excellent lubricating oil for refrigeration systems.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C10N 40:30

Claims (1)

[Claims] 1. A refrigerant composition comprising a fluorine-containing aromatic compound represented by the general formula [I] and a fluoroalkane-based refrigerant, wherein the fluoroalkane-based refrigerant contains chlorine-containing fluoroalkane-based refrigerant. At least 0.01 to 100% by weight. 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 0.6. That is all. When n is 2 or more, the compound represented by the general formula [I] may be composed of plural kinds of XRf groups. ]