JPH0657240A - Heating medium oil - Google Patents

Abstract

PURPOSE:To provide the heating medium oil having heat stability, a high spontaneous ignition temperature and excellent low-temperature flow and comprising a specified fluoroaromatic compound. CONSTITUTION:The heating medium oil comprises a fluoroaromatic compound of the general formula: R(ORf)n (wherein R is a 6-60C n-valent aromatic residue; n is an integer of 1-4; Rf is a fluorocarbon group or a partially substituted derivative thereof, the number of the carbon atoms of Rf is in the range of 1-25; and the ratio of the number of the fluorine atoms of Rf to the number of the carbon atoms is 0.5 or below). When the n is 2 or greater, the compound of the formula may be composed of two or more kinds of Rf groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel heat carrier oil, and more particularly to a new heat carrier composed of a specific fluorine-containing aromatic compound and having excellent heat stability and low temperature fluidity.

[0002]

2. Description of the Related Art Recent technological advances in the chemical industry have been remarkable, and instead of the direct heating method, the indirect heating method using oil or the like as a heating medium has been used for the textile, paper, food, construction, and chemical systems. Widely used in all industrial fields such as. The heat carrier oil is most commonly used as the heat carrier of this indirect heating method. This heat carrier oil usually has (1) excellent thermal stability, (2) low vapor pressure and high flash point. , (3) Good low temperature fluidity,
(4) It is required to have properties such as no toxicity and no odor, and as the heat carrier oil, mineral oil type and aromatic hydrocarbon type oils have been mainly used conventionally.

[0003]

However, the mineral oil type is not good in heat resistance and has a thermal decomposition point of 160 to 180.
C., the spontaneous ignition temperature is about 230 to 270.degree. The heat resistance of the polyphenyl ether type is better than that of the mineral oil type. For example, phenoxyphenoxydiphenyl has a thermal decomposition temperature of 301 ° C. and a spontaneous ignition temperature of 396 ° C., but it cannot be said to be sufficiently good. Further, the polyphenyl ether type has a defect that the pour point is −15 to + 20 ° C. and the low temperature fluidity which is an important characteristic as a heat medium is poor. An object of the present invention is to provide a heat medium which has particularly excellent thermal stability and high spontaneous ignition temperature, and at the same time has excellent low temperature fluidity.

[0004]

The present invention provides a heating medium comprising a fluorine-containing aromatic compound represented by the general formula 1. That is, the heat carrier oil of the present invention is characterized by comprising the fluorine-containing aromatic compound represented by the general formula 1.

[0005]

Embedded image in R (ORf) _n ...... 1 formula, R represents an aromatic group having 6 to 40 pieces of n-valent carbon.
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 1.0. That is all. Note that n
When is 2 or more, the compound represented by the general formula 1 may be composed of plural kinds of ORf groups.

The contents of the present invention will be described in more detail below. R in the general formula 1 has 6 to 40 carbon atoms, preferably 6 carbon atoms.
-30, more preferably 6-20, n-valent aromatic groups are represented. The aromatic basic means a group containing an aromatic ring, and in the aromatic group, a substituent having 20 or less carbon atoms, preferably 15 or less, and more preferably 10 or less, other than the aromatic ring, It may contain 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 0.2 or more, preferably 0.
It is 3 or more, more preferably 0.5 or more.

The substituent is a monovalent group, and the linking group is a divalent or higher valent group. Examples of these groups are summarized below. An alkyl group, a divalent to tetravalent hydrocarbon group and a divalent to tetravalent aliphatic group. Saturated hydrocarbon groups such as cyclic hydrocarbon groups, unsaturated hydrocarbon groups such as allyl groups, halogenated hydrocarbon groups such as 2-chloroethyl groups, halogen atoms such as chlorine and fluorine, hydroxyl groups, thiol groups, alkoxy groups, Nitrile group, nitro group, ether group, thioether group, ester group, carbonyl group, sulfonyl group, sulfinyl group, carboxyl group, carboxylate group, amino group, thiocarbamate group, amide group, imide group, pyridine group, pyrimidine group, Piperidine group, triazine group, phosphine group, benzimidazole group, phosphite group, triazole group, tetrazole group, thiazole group, thiadiazo Various oxygen-containing such group, nitrogen-containing, phosphorus-containing atom include a polar group-containing sulfur atom. Specific examples of R in the general formula 1 include the followings.

[0008]

[Chemical 3]

[0009]

[Chemical 4]

[0010]

[Chemical 5]

[0011]

[Chemical 6]

[0012]

[Chemical 7]

[0013]

[Chemical 8]

[0014]

[Chemical 9]

[0015]

[Chemical 10]

The examples of various aromatic groups having at least one aromatic ring which can be used as R in the general formula 1 have been shown above. Among them, the aromatic ring is directly -OR.
In the case of R having a structure linked to the f group, the compound of the general formula 1 which is particularly excellent in stability can be easily synthesized, which is particularly preferable.
The value of n in the general formula 1 depends on the valence of R, and is usually an integer selected from 1, 2, 3, and 4 for reasons such as easiness of synthesis and taking an appropriate viscosity range. , Preferably an integer selected from 1, 2 and 3, and more preferably an integer selected from 1 and 2. When n is 2 or more in the general formula 1, the compound of the general formula 1 is
It may be composed of a plurality of types of Rf.

In the general formula 1, Rf represents a fluorocarbon residue. The fluorocarbon residue means a substituent having a structure in which some or all of the hydrogen atoms of various hydrocarbon groups are substituted with fluorine atoms, and examples thereof include fluoroalkyl groups having a saturated structure, Examples thereof include a fluoroalkenyl group having a saturated structure, a fluoroaryl group having an aromatic nucleus, and a fluoroaraalkyl group. Particularly, a fluoroalkyl group and a fluoroalkenyl group are easy to synthesize and useful.

Rf is a hydrocarbon group in which some or all of hydrogen atoms are substituted with fluorine, and some of the fluorine atoms or hydrogen atoms of the above-mentioned fluorocarbon groups are chlorine atoms, bromine atoms, iodine atoms, etc. Halogen atom, hydroxyl group, alkoxy group, amino group, nitrile group, or
It may be a partially substituted fluorocarbon residue further substituted with various substituents which are stable under the use conditions of the heat carrier oil, such as a carbonyl-containing group such as an ester group, an amide group, an acyl group and a carboxyl group. The number of substituents other than the fluorine atom of the group is 1 of the total number of fluorine atoms or fluorine atoms and hydrogen atoms of the substituted fluorocarbon residue.
It is 50% or less, preferably 100% or less.

It is also possible for the above-mentioned unsubstituted or substituted fluorocarbon to have a structure in which the main chain has at least one ether group. The number of fluorine atoms in Rf /
The ratio of the number of carbon atoms is usually 1.0 or more, 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 low temperature fluidity tends to deteriorate and the stability tends to decrease, such being undesirable.

The number of carbon atoms in Rf is usually in the range of 1 to 25, preferably 1 to 10, and more preferably 1.
The range is from 3 to 3. When the number of carbon atoms in Rf is more than 25, it becomes difficult to obtain or synthesize the raw material, the synthesis and purification become complicated, and the viscosity becomes too high, which is not preferable. Examples of Rf in the substance represented by the general formula 1 used in the present invention are illustrated below. Examples of Rf shown here are examples of Rf in the substance of the general formula 1 synthesized by various methods. However, the present invention is not limited to this.

[0021]

Embedded image ^{_{Z 7 - (CF 2) L1}} - (CH 2) L2 ...... 2 ^{[Z 7 = F, Cl, I} , H: L 1 = 1~18 integer: L ₂
The following are specific examples of the compound represented by the formula: = 0, 1, 2] 2.

[0022]

Embedded image CF ₃ −, CF ₃ CH ₂ —, CF ₃ CH ₂ C
_{H 2 -, F- (CF 2} ) 2 -, F- (CF 2) 3 -, F
_{- (CF 2) 6 -,} F- (CF 2) 10 -, F- (C
_{F 2) 2 -CH 2 -,} F- (CF 2) 4 -CH 2 -, F
_{- (CF 2) 4 -CH 2} CH 2 -, F- (CF 2) 8 -
_{CH 2 CH 2 -, I- (} CF 2) 4 -CH 2 CH 2 -,
_{ClCF 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 -CH 2
_{-, H- (CF 2) 3} CH 2 -, H- (CF 2) 10 -C
_{H 2 -, HCF 2 -,} HCF 2 CH 2 CH 2 -, HCF
_{2 CH 2 -, I- (CF} 2) 2 -CH 2 CH 2 -

[0023]

[Chemical 13]

[0024]

Embedded image F- (CF ₂ CF ₂ O) _{L 3} —CF ₂ CH ₂ — (L ₃ = 1 to 11) ... 4

[0025]

Embedded image F- (CF ₃ CF ₂ CF ₂ O) _{L 4} —CF ₂ CF ₂ CH ₂ — (L ₄ = 1 to 7) ... 5

[0026]

Embedded image CF ₃ CHF—, CH ₃ CF ₂ —, CH ₂ F
_{CF 2 -, CF 2 HCF 2} -, CH 2 F-, CHF 2 C
_{H 2 -, CF 3 CCl 2} -, CF 3 CHCl-, CF 3 CF
_{Cl-, CFCl 2 CF 2 -,} CHFClCF 2 -, C 6 F 6
_{-, CHCl 2 CF 2 -,} CH 3 CHFCH 2 -, CH 2
_{FCH (CH 3) -, CF} 3 CHFCF 2 -, CF 3 C
_{F 2 CHFCF 2 -, HOCH 2} CF 2 CF 2 CH
_{2 -, CH 2 ClCF 2 -} , CF 3 CHClCF 2 -,

[0027]

Embedded image —CZ ³ Z ⁴ CFZ ³ Z ⁴ …… 6 [Z ³ , Z ⁴ = F, Cl, Br, CF ₃ , H]

[0028]

[Chemical 18]

[0029]

Embedded image —CF ₂ CX ¹ X ² H ... 8 [X ¹ , X ² = F, Cl, H]

[0030]

_{Embedded image} —C _{n ′} F _{2n ′ −1} ... 9 [n ′ represents an integer of 2 to 20]
Groups of formulas 0 and 11 are mentioned.

[0031]

Embedded image —C _2m F _6m-1 …… 10 [m: integer of 2 or more, preferably 2 to 6]

[0032]

_{Embedded image} —C _{2m ′} F _4m′-1 …… 11 [m ′: an integer of 2 or more, preferably an integer of 2 to 10]

[0033]

Embedded image —C _{n ′} F _{2n ′} H ...... 12 [n ′ represents an integer of 2 to 20] For example, 1
Groups of formulas 3 and 14 are mentioned.

[0034]

Embedded image —C _3m F _6m H ...... 13 [m: integer of 2 or more, preferably 2 to 6]

[0035]

Embedded image _{-C 2m 'F 4m' H ......} 14 [m ': 2 or more integer, preferably 2 to 10 integer] Specific examples of groups of formula 9-14 are given below.

[0036]

Embedded image CF ₂ ═CF—, CF ₂ ═CFCF ₂ —, C
_{F 3 CF = CF-, CF 3} CF 2 CF = CF -, (CF
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 6 H-, C 10 F 20 H- addition,
Furthermore, the following groups can also be used.

[0037]

Embedded image CFCl = CF-, CFCl ₂ CF ₂ CF = CF
_{-, CF 3 CCl = CF-,} CCl 2 = CF-, CHCl = C
_{F -, (CF 3) 2} CH-, CF 3 CFClCFCl-,

The fluorine-containing aromatic compound represented by the general formula 1 used in the present invention can be synthesized by various methods. In the following, an example of synthesis in the case of n = 1 in the general formula 1 will be illustrated, but the synthesis can be performed by the same method also in the case of n = 2, 3, 4. (1) Reaction of phenols 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. As a typical reaction example, a case where a perfluoroolefin is used as the fluorine-containing olefin is shown as an example, and the following reactions are mentioned.

[0039]

[Chemical 28] (Here, Ar ′ represents a monovalent aromatic group, and n ′ represents an integer of 2 to 20) For example, Advance in
Fluorine Chemistry, 4 , 50
(1965) shows reaction examples similar to the formulas 15 and 16 by ionic reaction of various fluorine-containing olefins with phenols or alcohols as described below.

(2) Reaction of Phenols or Thiophenols with Saturated Fluorocarbons Many reactions can be considered as the reaction of the fluorinated aromatic compound by the reaction of phenols with the saturated fluorocarbons. Examples of the reaction method include the following reactions.

[0041]

Ar'O- + RfY → Ar'ORf ... 17 Ar'Y + Rf'O- → Ar'ORf '... 18 (where Y is a halogen atom, -OSO ₂ Me, -OCO.
_{CF 3, -OSO 2 C 5 H} 4 CH 3, -OSO 2 C
F _3, -OSO ₂ CCl _3, represents a likely substituents leaves as an anion such as -OSO ₂ Cl. Ar 'represents a monovalent aromatic group. Rf ′ is the same as Rf in the general formula 1, and Rf
f'x ^- represents what can take anionic structure).

The fluorine-containing aromatic compound represented by the general formula 1 can be synthesized by various methods, and the reactions shown so far are some of the specific examples. Therefore, the method for synthesizing the substance represented by the general formula 1 is not limited to these methods. The heat carrier oil used in the present invention may have the structure represented by the general formula 1, and is not limited by the manufacturing method.

The compound represented by the general formula 1 used in the present invention can be used alone or in combination of plural kinds. Moreover, you may mix and use mineral oil and a well-known synthetic oil as needed. The heat carrier oil of the present invention may be added with known additives such as an antioxidant, a defoaming agent, a detergent dispersant, a rust inhibitor or a pour point depressant, if necessary. Details of these various additives are described in, for example, “Petroleum Product Additives” (Koushobo), edited by Toshio Sakurai.

[0044]

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.

Reference Example 1 To 1200 ml of dimethyl sulfoxide, 56.5 g of potassium hydroxide and 2,2-bis (4-hydroxyphenyl)
Add 600 g of propane and 370 ml of distilled water to 70
Stirred at 3 ° C for 3 hours. This solution was placed in an autoclave having a volume of 5 liters, the system was degassed, and then nitrogen was introduced to return the pressure to normal pressure. Next, heat the inside of the autoclave to 60 ° C,
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. Remove the reaction solution from the autoclave,
After the solvent was distilled off with a rotary evaporator, the obtained oil was washed 5 times with 1 liter of distilled water. Next, vacuum distillation (bp. = 180 ° C., 0.02 mmHg) is performed,
1200 g of colorless and transparent oil [S1] was obtained. (Yield 9
9%) Oil [S1] is used for infrared absorption spectrum analysis, mass spectrometry [m / e 460, 462 (M ⁺ ), 455, 447.
(M ⁺ —CH ₃ )] and ¹⁹ F-NMR spectrum analysis confirmed that this oil [S2] was a compound having the structure shown below.

[0046]

[Chemical 30] ¹⁹ F-NMR spectrum (ppm from internal standard CF ₃ COOH): 78 (2F), 7.5 (4F).

Reference Example 2 To 1200 ml of dimethyl sulfoxide, 56.2 g of potassium hydroxide and 2,2-bis (4-hydroxyphenyl)
600 g of propane was added, and the mixture was stirred at 70 ° C. for 3 hours. This solution was placed in an autoclave having a volume of 5 liters, the system was degassed, and then nitrogen was introduced to return the pressure to normal pressure. Next, the inside of the autoclave was heated to 60 ° C. and tetrafluoroethylene was introduced to start the reaction. Then, 1000 g of colorless and transparent oil [S2] was obtained in exactly the same manner as in Reference Example 1 (yield 97%). b. p. 160 ° C., 0.20 mmHg infrared spectrum analysis, mass spectrometry [(m / e 392
From (M ⁺ ), 377 (M ⁺ —CH ₃ )], it was confirmed that this compound [S2] had a structure shown below.

[0048]

[Chemical 31]

Examples 1 and 2 Compounds [S1] and [S obtained from Reference Examples 1 and 2 above
In order to evaluate the thermal stability of 2], the thermal decomposition point (exothermic start temperature in air) and the spontaneous ignition temperature were measured. The thermal decomposition point was measured using an autoclave type high pressure DSC. The spontaneous ignition temperature was measured by a test based on ASTM D 2155-66 (oil drop method).

Comparative Examples 1 to 4 Mineral oil (aromatic carbon content 0%, 4.3%, 8.6%) and polyphenyl ether (phenoxyphenyldiphenyl) were treated in the same manner as in Example 1 to obtain a thermal decomposition point. And the spontaneous ignition temperature was measured. The results are shown in Table 1.

[0051]

[Table 1] As is clear from Table 1, the heat carrier oil [S1] of the present invention,
[S2] has extremely good thermal stability as compared with mineral oil and polyphenyl ether, and has a much higher spontaneous ignition temperature, and is suitable as a heat carrier oil.

Examples 3 and 4 Compounds [S1] and [S] obtained from Reference Examples 1 and 2 above.
2] Reservoir for evaluating low temperature fluidity, JIS K2269
The pour point was measured according to the method described in 1. Also,
Viscosity at 40 ℃ E type rotational viscometer (Tokyo Keiki Co., Ltd.)
Was measured using. The results are shown in Table 2.

Comparative Example 5 The pour point of the polyphenyl ether oil was measured in the same manner as in Example 3. The results are shown in Table 2. As is clear from Table 2, the heat carrier oils [S1] and [S2] of the present invention have a lower pour point than the polyphenyl ether oil and can be used at lower temperatures.

[0054]

[Table 2]

Comparative Examples 5 to 18 The heat carrier oils [S3] to [S16] shown in Table 3 are also useful because they have suitable viscosities as heat carrier oils. The viscosity was measured in the same manner as in Example 3. [S3] ~
For the method of synthesizing the compound of [S16], refer to Reference Example 3 to
16 shows.

[0056]

[Table 3]

Reference Example 3 10 g of bisphenol A was added to 10 ml of tetrahydrofuran.
10 g of triethylamine was added to this, and 20
It was placed in a 0 ml capacity micro-bomb. After cooling this micro bomb to -78 degreeC and decompressing the inside of the micro bomb, 60 g of hexafluoropropene was introduced, and then heated to 60 degree C and reacted for 5 hours. After the reaction, the reaction mixture obtained by removing tetrahydrofuran and excess triethylamine with an evaporator was added with R-11.
100 ml of 3 was added to form a solution, which was then 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 colorless transparent oil [S3] was obtained (yield 55%). When this mixture was analyzed by gas chromatography,
Since several peaks were observed, oil [S3] was subjected to a separation treatment with a silica gel column, and samples obtained from each fraction were subjected to mass spectrometry, infrared absorption spectrum analysis, and ¹⁹ F-NMR spectrum analysis ( Table 4).

[0058]

[Table 4]

As a result, the oil [S3] was prepared from the compounds [A], [B] and [C] shown in Table 1 (molar ratio A / B / C = 4 /
4/2), and the compound [A] has cis-cis, cis-trans, and trans-trans isomers depending on the structural isomers of the pentafluoropropenyl group, and the same applies to the compound [B]. It was confirmed that there are cis and trans isomers.

Reference Example 4 Bisphenol A synthesized by the same method as in Reference Example 1
17 g of potassium alkoxide of 1 was dissolved in 100 ml of dimethyl sulfoxide, and 28 g of R-113 was added.
The mixture was heated to 0 ° C. and reacted for about 5 hours. After the reaction, the solution was poured into a large amount of water, and R-113 was added to 100 m in the separated reaction product.
1 was added. 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 recognized. Therefore, the oil [S4] was subjected to a separation treatment using a silica gel column, and the samples obtained from each fraction were subjected to mass spectrometry and infrared absorption. Spectral analysis and ¹⁹ F-NMR spectral analysis were performed. The results are shown in Table 5. It was confirmed that the oil [S4] was a mixture of compounds ... [D], [E], and [F] (molar ratio D / E / F = 3/5/2).

[0062]

[Table 5]

Reference Example 5 Completely the same as Reference Example 1 except that 2,2-bis (4-hydroxy-3-methylphenyl) propane was used instead of bisphenol A and tetrafluoroethylene was used instead of chlorotrifluoroethylene. Similarly, oil [S
5] was obtained (yield 77%). Infrared absorption spectrum analysis and mass spectrometry results [m / e 456 (M ⁺ ), 441 (M
⁺ Than -CH _3)] of [S5] was confirmed to be a compound having a structure shown below.

[0064]

[Chemical 32] Reference Example 6 The same procedure as in Reference Example 3 was performed except that p-α-cumylphenol was used in place of bisphenol A, and the oil [S
6] was obtained (yield 86%).

[0065]

[Chemical 33] From the results of gas chromatography analysis and mass spectrometry, the oil [S6] was identified as compounds [G] and [H] (molar ratio G / H =
It was identified as a mixture of 5/5).

[0066]

[Chemical 34]

Reference Example 7 An oil [S7] was obtained in the same manner as in Reference Example 3 except that 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane was used instead of bisphenol A ( Yield 46%). From the results of infrared absorption spectrum analysis and mass spectrometry, it was confirmed that [S7] was a compound having the structure shown below.

[0068]

[Chemical 35]

Reference Example 8 An oil [S8] was obtained in exactly the same manner as in Reference Example 3 except that dodecylphenol was used instead of bisphenol A (yield 80%). From the results of infrared absorption spectrum analysis and mass spectrometry, it was confirmed that [S8] was a compound having the structure shown below.

[0070]

[Chemical 36]

Reference Example 9 An oil [S9] was obtained in exactly the same manner as Reference Example 12 except that nonylphenol was used instead of bisphenol A (yield 70%).

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

[0073]

[Chemical 37]

Reference Example 10 Oil [S10] was prepared in the same manner as in Reference Example 9 except that dodecylphenol was used instead of bisphenol A.
Was obtained (yield 69%). From the results of infrared absorption spectrum analysis and mass spectrometry, it was confirmed that [S10] was a compound having the structure shown below.

[0075]

[Chemical 38]

Reference Example 11 An oil [S11] was obtained in exactly the same manner as Reference Example 12 except that p-α-cumylphenol was used instead of bisphenol A (yield 70%). From the results of infrared absorption spectrum analysis and mass spectrometry, [S11] was identified as a compound having the structure shown below.

[0077]

[Chemical Formula 39]

Reference Example 12 After dissolving 7.1 g of sodium hydroxide in 20.7 g of water, 4.0 g of bisphenol A and dimethyl sulfoxide 13.
8 g was added, and the mixture was placed in a 100-ml capacity micro cylinder. This micro cylinder was cooled to −78 ° C., and the inside of the cylinder was decompressed, followed by chlorodifluoromethane (R22) 7.8.
g was introduced. After reacting at 70 ° C. for 10 hours, the reaction solution was poured into a large amount of water, and the separated reaction product was subjected to R-113.
100 ml was added. 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 [S12] (yield 18%). Mass spectrometry [m / e 328 (M ⁺ ),
313 (M ⁺ —CH ₃ )] and the results of infrared absorption spectrum analysis, it was confirmed that oil [S16] had the following structure.

[0079]

[Chemical 40]

Reference Example 13 10 g of bisphenol A was added to 60 ml of tetrahydrofuran.
15 g of triethylamine was added, and then 40 ml of a tetrahydrofuran solution containing 7.2 g of 2-ethylhexanoic acid chloride was 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 micro bomb and reacted with hexafluoropropene in the same manner as in Reference Example 3 to obtain 1.6 g of oil [S13] (yield 7.5%). As a result of infrared absorption spectrum analysis and mass spectrometry, it was confirmed that [S13] was a compound having the structure shown below.

[0081]

[Chemical 41]

Reference Example 14 200 ml of 10.8 g of the oil [S3] obtained in Reference Example 3 was used.
Put in a micro-bomb of capacity, sulfuryl chloride SO ₂ Cl
After adding 5.4 g of ₂ , the mixture was reacted at 100 ° C. for 4 days. After the reaction, a large amount of the solution was poured into 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 with a silica gel column to give an oily substance of 9.6.
5 g was obtained. 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 [S14] is formed.

[0083]

[Chemical 42]

Reference Example 15 8 g of the mixture [S4] obtained in Reference Example 4 was added to a solution prepared by suspending 7 g of sodium borohydride NaBH _{4 in} 100 ml of dimethyl sulfoxide, and reacted at 85 ° C. for 16 hours. After the reaction, the reaction mixture obtained by removing dimethyl sulfoxide with an evaporator was mixed with 100 R-113.
ml was added to give a solution. After washing this with distilled water, R-11
The three phases were purified by a silica gel column to obtain 3.5 g of colorless transparent oil [S15] (yield 55%). Gas chromatography analysis and mass spectrometry [m / e 428
As a result of (M ⁺ ), 413 (M ⁺ —CH ₃ )], it was confirmed that the oil [S15] was a compound having the following structure.

[0085]

[Chemical 43]

Reference Example 16 A solution of hexafluoropropene oligomer acid fluoride F [CF (CF ₃ ) CF ₂ O] _{5 to 8} CF (CF was added to a solution prepared by dispersing 10 g of sodium carbonate in 25 ml of diglyme.
₃ ) Add 25 g of COF (manufactured by US PCR) and react at 80 ° C. for 5 hours. After the reaction, diglyme was distilled off, and the residue was refined with silica gel to obtain 15.4 g of oil [G16].

0.54 g of potassium alkoxide of bisphenol A and 0.50 g of bisphenol A synthesized by the same method as in Reference Example 1 were added to dimethyl sulfoxide 3
11 g of compound [G16]
10 ml of 3 di (trifluoromethyl) benzene solution was added and reacted at 80 ° C. for 3 hours. After distilling off dimethyl sulfoxide, an oil refined with a silica gel column [S1
6] was obtained (yield about 80%). As a result of infrared absorption spectrum analysis and mass spectrometry, it was confirmed that [G16] [S16] was a mixture of substances having the structures shown below.

[0088]

[Chemical 44]

The data of the mass spectrometry of [S16] are shown below. m / e (M ⁺ ) n ₁ = n ₂ = 5 2088 n ₁ = 5, n ₂ = 6 2254 n ₁ = 5, n ₂ = 7 or n ₁ = n ₂ = 6 2420 n ₁ = 5, n ₂ = 8 or n ₁ = 6, n ₂ = 7 2586 n ₁ = 6, n ₂ = 8 or n ₁ = n ₂ = 7 2752 n ₁ = 7 n ₂ = 8 2918 n ₁ = n ₂ = 8 3084

Claims (1)

[Claims] 1. A heat carrier oil comprising a fluorine-containing aromatic compound represented by the general formula 1. ## STR1 ## R (ORf) _n ...... 1 (wherein, R represents an n-valent aromatic group having 6 to 60 carbon atoms. N represents an integer of 1 to 4. Rf represents a fluorocarbon group, Or a partial substitution product thereof, wherein 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 0.5 or more.
When n is 2 or more, the compound represented by the general formula 1 may be composed of a plurality of ORf groups. )