JP3496954B2 - 4,4 '"-quarterphenyl-dicarboxylic acid diester - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to novel compounds 4.4 '''-quaterphenyl-dicarboxylic acid diesters. These compounds are highly expected to be useful as raw materials for various industrial raw materials, in particular, liquid crystal compounds for liquid crystal display devices, raw materials for high heat-resistant and chemical-resistant polymer compounds, and additives for modifying polymer compounds.

[0002]

2. Description of the Related Art Conventionally, 4.4 '''-quaterphenyl-dicarboxylic acid and 4.4'''-quaterphenyl-dicarboxylic acid dimethyl ester are known, and they are produced by the following method. There is.

(1) 4-Methyl-4'-iodobiphenyl was heated to 220 ° C. in the presence of a large amount of copper powder to deiodine dimerize, and the yield was 60 to 70%. -Dimethyl quaterphenyl obtained, this material in boiling acetic acid,
A method of obtaining 4.4 '''-quaterphenyl-dicarboxylic acid by oxidizing with a chromic acid-acetic acid solution for 1 to 2 days. At this time, the yield is less than 60% (total yield is about 40%).

(2) 4'-iodobiphenyl-4-carboxylic acid methyl ester in a nitrogen atmosphere in the presence of copper powder, 2
Method for deiodination dimerization at 70 ° C. to obtain 4.4 ″ ′-quaterphenyl-dicarboxylic acid dimethyl ester. The yield at this time is 20%.

The above methods (1) and (2) are performed using, for example, P
ummerer, Seligsberger, Beri
chte, 64 [1931], P2477-2488.

(3) 4'-bromobiphenyl-4-carboxylic acid was added in the presence of methanol and sodium hydroxide to give 5
Debrominated dimerization with% palladium-carbon catalyst, 4.
Method for obtaining 4 '''-quaterphenyl-dicarboxylic acid. At this time, the yield is 65%.

(4) 4'-Bromobiphenyl-4-carboxylic acid methyl ester was debrominated and dimerized with 5% palladium-carbon catalyst in the presence of methanol and sodium methylate to obtain 4.4 "'-quaterphenyl-. Method for obtaining dicarboxylic acid dimethyl ester. Yield 61 at this time
%.

The above methods (3) and (4) are disclosed in Japanese Patent Laid-Open No. 4-139147.

However, whether it is 4.4 '''-quaterphenyl-dicarboxylic acid or 4.4'''-quaterphenyl-dicarboxylic acid dimethyl ester, the melting points are very high (482 ° C. and 356-357 ° C., respectively). In view of its physical properties, an organic solvent such as dimethylformamide, o for separation from the catalyst and purification by recrystallization in the production process.
-A large amount of dichlorobenzene, xylene, toluene, etc. (at atmospheric pressure and boiling point, 100 times or more the weight of the target product) is required. Therefore, there are many problems in terms of safety and hygiene and pollution prevention.

Further, when the above compound is used as a monomer raw material for highly heat resistant plastics (super engineering plastics) or as a modifying additive for a polymer compound, it is poor in compatibility and solubility with other components, and thus is heavy. It is disadvantageous in the condensation reaction.

[0011]

The object of the present invention is to reduce the risk of problems in terms of safety and hygiene and prevention of pollution in the manufacturing process, to facilitate the separation and purification operation, and to use it as a monomer for highly heat-resistant plastics. Alternatively, it is to provide novel 4.4 ′ ″-quaterphenyl-dicarboxylic acid diesters having excellent compatibility and reactivity with other components when used as a modifying additive.

[0012]

According to the invention, the general formula (I)

[0013]

[Chemical 2] There is provided 4,4 ""-quaterphenyl- dicarboxylic acid diester represented by the formula (wherein R represents an alkyl group or a cycloalkyl group having 3 to 12 carbon atoms).

These compounds have a low melting point and exhibit good solvent solubility, and therefore have excellent compatibility and reactivity with other components in the polycondensation reaction.

The compound (I) according to the present invention has the general formula (I
I)

[0016]

[Chemical 3] [In the formula, R represents an alkyl group or a cycloalkyl group having 3 to 12 carbon atoms, and X represents a halogen atom. ] The 4' -halogenobiphenyl-4-carboxylic acid ester represented by the formula [ 4 ] is used in the presence of zinc dust in an inert organic solvent in an inert gas atmosphere, using tetrakistriphenylphosphine-nickel or palladium complex as a catalyst to dehalogenate dihydrogenate. By quantifying, it can be easily obtained in high yield.

The present invention will be described in more detail.

In the definition of the general formula (II), the alkyl group of R has 3 to 12 carbon atoms. Specific examples of the compound represented by the general formula (II) include 4' -bromobiphenyl-4-carboxylic acid, 4' -iodobiphenyl-4-carboxylic acid and normal propyl ester of 4-chlorobiphenyl-4-carboxylic acid. , Isopropyl ester, normal butyl ester, isobutyl ester, secondary butyl ester, normal pentyl ester, normal octyl ester, 2-ethylhexyl ester,
Examples thereof include normal lauryl ester and cyclohexyl ester.

As the inert organic solvent, N, N-dimethylformamide, N, N-dimethylacetamide, 1,
3-dimethyl-2-imidazolidinone, sulfolane, N
-Methylpyrrolidone, hexane, toluene, xylene,
Examples thereof include o-chlorobenzene and chlorobenzene, but industrially, N, N-dimethylformamide, N, N
-Dimethylacetamide and the like are preferred. The amount thereof used is 1 to 20 times by weight that of the compound of the general formula (II), preferably 1.
It is 5 to 5 times the weight. It should be noted that these solvents may be mixed and used.

The catalyst tetrakistriphenylphosphine-nickel complex or latrakistriphenylphosphine-palladium complex can be prepared individually by a conventional method, but it is prepared in the above solvent prior to the reaction, and then the compound of the general formula (II) is prepared. Can be added to carry out the coupling reaction. Examples of nickel compounds used include nickel (II) chloride, nickel (II) bromide, and nickel (II) iodide. Palladium compounds include palladium (II) chloride, palladium (II) bromide, and iodide. Palladium (II) and the like can be mentioned, and the amount thereof used is 0.1 mol% to 110 mol%, preferably 1 mol% to 15 mol% with respect to the compound of the general formula (II). The suitable amount of triphenylphosphine is 400 mol% to 440 mol% with respect to the nickel compound or the palladium compound.

The amount of zinc powder used as a reducing agent and a halogen scavenger is 50 to 500 mol%, preferably 120 to 300 mol% based on the compound of the general formula (II).

The reaction temperature is 20 to 150 ° C, preferably 40 to 90 ° C. The reaction time is 0.5 to 12 hours, usually 2 to 8 hours.

An inert gas such as helium, nitrogen or argon is used as a reaction atmosphere in order to prevent deactivation of the catalyst, but nitrogen substitution is industrially suitable.

After completion of the reaction, the reaction mixture is cooled, the target substance and unreacted zinc are filtered off, and then an aprotic solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl is used. -2-Imidazolidinone, pyridine, quinoline, etc., or halobenzenes such as chlorobenzene, o-dichlorobenzene, trichlorobenzene, bromobenzene, o-dibromobenzene, tribromobenzene, etc., or aromatic hydrocarbons such as xylene, toluene, etc. The target product is dissolved by heating, and the target product is deposited by cooling the filtrate by hot filtration.
Separate and get. Aromatic hydrocarbons such as xylene and toluene are industrially suitable. Further, the amount of its use depends on the intended product, but 5 to 30 times by weight is sufficient. In this respect, when separating and purifying 4,4 ′ ″-quaterphenyl-dicarboxylic acid or 4,4 ′ ″-quaterphenyl-dicarboxylic acid dimethyl ester of existing compounds, 100 or more times by weight of N, N-, respectively, are separated. Dimethylformamide or o
-Dichlorobenzene and the like are required, and there are safety and health or industrial problems.

[0025]

EXAMPLES Next, examples of the present invention will be described. Example 1 A 100 ml glass reaction flask was equipped with a stirrer, a water cooling tube and a thermometer, and anhydrous nickel chloride 0.58 was used.
g and N, N-dimethylacetamide (15 g) were charged and dissolved in a nitrogen atmosphere at 40 ° C., 5 g of triphenylphosphine and then 4 g of zinc powder were added, and a reddish brown tetrakistriphenylphosphine-nickel complex was produced.

To this, N, N-dimethylacetamide 3
15 g of 4'-bromobiphenyl-4-carboxylic acid isobutyl ester dissolved in 0 g was added dropwise, and the mixture was reacted at 70 ° C for 2 hours. Crystals of the target substance were precipitated on the way.

After completion of the reaction, the reaction mixture is cooled to room temperature,
The solid substance (4,4 '''-quaterphenyl-dicarboxylic acid diisobutyl ester and unreacted zinc powder) was collected by filtration, sufficiently washed with isopropyl alcohol and dried. Then, 100 g of xylene was added to the solid, heated under stirring, and hot filtered.

After cooling, the precipitate was filtered, washed with xylene and dried. White scale-like crystal 4,4 '''-quaterphenyl-dicarboxylic acid diisobutyl ester 8.3 g
Got Yield 72.8%. Melting point 202 ° C. Elemental analysis values of this product are shown in the following table.

Elemental analysis value (%) (as C ₃₄ H ₃₄ O ₄ ) Theoretical value C, 80.60: H, 6.76 Measured value C, 80.38: H, 6.71 Infrared absorption spectrogram of the above compound Is shown in FIG.

Example 2 In the same manner as in Example 1 except that 15 g of 4'-bromobiphenyl-4-carboxylic acid isobutyl ester of Example 1 was replaced with 15 g of 4'-bromobiphenyl-4-carboxylic acid normal butyl ester. Manipulate the white scale-like crystals 4,
9.2 g of 4 '''-quarterphenyl-dicarboxylic acid dinormal butyl ester was obtained. Yield 80.7%. Melting point 2
43 ° C.

The elemental analysis values of this product are shown in the following table.

Elemental analysis value (%) (as C ₃₄ H ₃₄ O ₄ ) Theoretical value C, 80.60: H, 6.76 Measured value C, 80.46: H, 6.68 Infrared absorption spectrogram of the above compound Is shown in FIG.

Example 3 Instead of 15 g of 4'-bromobiphenyl-4-carboxylic acid isobutyl ester of Example 1, 15 g of 4'-bromobiphenyl-4-carboxylic acid secondary butyl ester.
Was operated in the same manner as in Example 1 to obtain 9.1 g of 4,4 ′ ″-quarterphenyl-dicarboxylic acid disecondary butyl ester as white flaky crystals. Yield 79.8
%. Melting point 170 [deg.] C.

The elemental analysis values of this product are shown in the following table.

Elemental analysis value (%) (as C ₃₄ H ₃₄ O ₄ ) Theoretical value C, 80.60: H, 6.76 Actual value C, 80.47: H, 6.74 Infrared absorption spectrogram of the above compound Is shown in FIG.

Example 4 A 100 ml glass reaction flask was equipped with a stirrer, a water cooling tube and a thermometer, and anhydrous nickel bromide 0.33 was used.
g and N, N-dimethylacetamide 15 g were charged, dissolved at 100 ° C. under a nitrogen atmosphere, cooled to 40 ° C., triphenylphosphine 1.7 g and then zinc dust 4 g were added,
A reddish-colored tetrakistriphenylphosphine-nickel complex was formed.

To this, N, N-dimethylacetamide 3
16.2 g of 4'-bromobiphenyl-4-carboxylic acid isopropyl ester dissolved in 0 g was added dropwise, and the temperature was 65 ° C.
And reacted for 4 hours. Crystals of the target substance were precipitated on the way.

After completion of the reaction, the reaction mixture is cooled to room temperature,
The solid matter (4,4 '''-quaterphenyl-dicarboxylic acid diisopropyl ester and unreacted zinc powder) was collected by filtration,
It was thoroughly washed with isopropyl alcohol and dried. Then, 100 g of xylene was added to the solid, heated under stirring, and hot filtered. After cooling, the precipitate was filtered, washed with xylene and dried.

White scale-like crystals of 4,4 '''-quaterphenyl-dicarboxylic acid diisopropyl ester 9.7
g was obtained. Yield 79.9%. Melting point 225 [deg.] C.

The elemental analysis values of this product are shown in the following table.

Elemental analysis value (%) (as C ₃₂ H ₃₀ O ₄ ) Theoretical value C, 80.31: H, 6.32 Actual value C, 80.10: H, 6.41 Infrared absorption spectrogram of the above compound Is shown in FIG.

Example 5 In place of 16.2 g of 4'-bromobiphenyl-4-carboxylic acid isopropyl ester of Example 4, 16.2 g of 4'-bromobiphenyl-4-carboxylic acid normal propyl ester was used. A dimerization reaction was performed in the same manner as in 4. After completion of the reaction, the reaction mixture was cooled to room temperature, and the solid matter (4,4 '''-quaterphenyl-dicarboxylic acid dinormalpropyl ester and unreacted zinc powder) was collected by filtration, sufficiently washed with isopropyl alcohol and dried. It was Then, 200 g of xylene was added to the solid, and the solid was heated with stirring and hot filtered. After cooling, the precipitate was filtered, washed with xylene and dried. 9.5 g of white scaly crystals of 4,4 ″ ′-quaterphenyl-dicarboxylic acid dinormalpropyl ester were obtained. Yield 78.3%. Melting point 266
° C.

The elemental analysis values of this product are shown in the following table.

Elemental analysis value (%) (as C ₃₂ H ₃₀ O ₄ ) Theoretical value C, 80.31: H, 6.32 Actual value C, 80.22: H, 6.38 Infrared absorption spectrogram of the above compound Is shown in FIG.

Example 6 In place of 16.2 g of 4'-bromobiphenyl-4-carboxylic acid isopropyl ester of Example 4, 17.4 g of 4'-bromobiphenyl-4-carboxylic acid normal pentyl ester was used. The same procedure as in Example 4 was performed to obtain 10.3 g of 4,4 ′ ″-quaterphenyl-dicarboxylic acid dinormal pentyl ester as white scale crystals. Yield 76.9%. Melting point 229 [deg.] C.

The elemental analysis values of this product are shown in the following table.

Elemental analysis value (%) (as C ₃₆ H ₃₈ O ₄ ) Theoretical value C, 80.87: H, 7.16 Measured value C, 79.95: H, 7.20 Infrared absorption spectrogram of the above compound Is shown in FIG.

Example 7 In place of 16.2 g of 4'-bromobiphenyl-4-carboxylic acid isopropyl ester of Example 4, 19.45 g of 4'-bromobiphenyl-4-carboxylic acid normal octyl ester was used. The same operation as in Example 4 was performed to obtain 12.3 g of 4,4 ′ ″-quaterphenyl-dicarboxylic acid dinormaloctyl ester as white flaky crystals. Yield 79.6%. Melting point 198 [deg.] C.

The elemental analysis values of this product are shown in the following table.

Elemental analysis value (%) (as C ₄₂ H ₅₀ O ₄ ) Theoretical value C, 81.51: H, 8.14 Measured value C, 80.34: H, 8.31 Infrared absorption spectrogram of the above compound Is shown in FIG.

Example 8 In place of 16.2 g of 4'-bromobiphenyl-4-carboxylic acid isopropyl ester of Example 4, 19.45 g of 4'-bromobiphenyl-4-carboxylic acid-2-ethylhexyl ester was used. It operated like Example 4.
At this time, crystals of the target substance did not precipitate during the reaction.

After the completion of the reaction, crystals were precipitated while the reaction mixture was cooled to room temperature. Therefore, the same operation as in Example 4 was carried out, and white scale-like crystals of 4,4 "'-quaterphenyl-dicarboxylic acid were obtained. 10.6 g of acid di-2-ethylhexyl ester was obtained. Yield 68.6%. Melting point 76
° C.

The elemental analysis values of this product are shown in the following table.

Elemental analysis value (%) (as C ₄₂ H ₅₀ O ₄ ) Theoretical value C, 81.51: H, 8.14 Measured value C, 81.03: H, 8.28 Infrared absorption spectrogram of the above compound Is shown in FIG.

Example 9 In place of 16.2 g of 4'-bromobiphenyl-4-carboxylic acid isopropyl ester of Example 4, 22.25 g of 4'-bromobiphenyl-4-carboxylic acid normal lauryl ester was used. The same operation as in Example 4 was performed to obtain 14.9 g of 4,4 ′ ″-quaterphenyl-dicarboxylic acid dinormal lauryl ester as white scale crystals. Yield 81.6%. Melting point 181 [deg.] C.

The elemental analysis values of this product are shown in the following table.

Elemental analysis value (%) (as C ₅₀ H ₆₆ O ₄ ) Theoretical value C, 82.15: H, 9.10 Actual value C, 81.05: H, 9.03 Infrared absorption spectrogram of the above compound Is shown in FIG.

Example 10 4'-Bromobiphenyl-4-carboxylic acid cyclohexyl ester 1 was used in place of 16.2 g of 4'-bromobiphenyl-4-carboxylic acid isopropyl ester of Example 4.
The same procedure as in Example 4 was carried out using 7.95 g to obtain 11.8 g of 4,4 ′ ″-quaterphenyl-dicarboxylic acid dicyclohexyl ester as white scale crystals. Yield 8
5%. Melting point 246 [deg.] C.

The elemental analysis values of this product are shown in the following table.

Elemental analysis value (%) (as C ₃₈ H ₃₈ O ₄ ) Theoretical value C, 81.69: H, 6.86 Measured value C, 80.83: H, 6.77 Infrared absorption spectrogram of the above compound Is shown in FIG.

Comparative Example 1 The above-mentioned conventional method (4) (JP-A-4-139147).
In accordance with 4'-bromobiphenyl-4-carboxylic acid methyl ester 8.7 g (0.03 mol), methanol 55
g, 28% by weight sodium methylate 10 g and 5%
0.7 g of a palladium-carbon catalyst was charged into a reaction vessel and reacted at the boiling point for 9 hours with stirring. The reaction mixture was then cooled to room temperature, the pH was adjusted to 2 with aqueous hydrochloric acid, the solid (a mixture of 4,4 '''-quaterphenyl-dicarboxylic acid dimethyl ester and the catalyst) was filtered off, and water and methanol were added. After thorough washing, 1 liter (amount required for heating dissolution) of o-dichlorobenzene was added to the solid matter and heated,
It was filtered hot. After cooling, the precipitate was filtered, washed with methanol and dried. 3.5 g of 4,4 '''-quaterphenyl-dicarboxylic acid dimethyl ester as white powdery crystals was obtained.
Yield 54.7%. Melting point 357 [deg.] C.

Comparative Example 2 In the same manner as in Example 1 except that 15 g of 4′-bromobiphenyl-4-carboxylic acid isobutyl ester of Example 1 was replaced by 13.7 g of 4′-bromobiphenyl-4-carboxylic acid ethyl ester. It operated and the dimerization reaction was performed. After completion of the reaction, the reaction mixture was cooled to room temperature and solid (4,4 '''
-Quarterphenyl-dicarboxylic acid diethyl ester and unreacted zinc) were filtered off, washed thoroughly with ethanol and dried. Thereafter, 1000 g (the amount required for heating dissolution) of xylene was added to the solid, and the mixture was heated with stirring and hot filtered. After cooling, the precipitate was filtered, washed with xylene and dried. 7.1 g of 4,4 '''-quaterphenyl-dicarboxylic acid diethyl ester as white powdery crystals was obtained. Yield 70.3%. Melting point 303 [deg.] C.

Reference Example (Solubility Comparison Test) Solubility comparison test for each of the 4,4 ′ ″-quaterphenyl-dicarboxylic acid diesters obtained in Examples 1-10 and Comparative Examples 1-2 was conducted.

A stirrer and a reflux condenser were attached to a glass flask, 5 g of a sample was put therein, and the point at which the crystals were completely dissolved under the boiling point of xylene (atmospheric pressure) was measured while adding xylene dropwise thereto. Table 1 shows the weight ratio of xylene to the sample (xylene g / sample g) and the melting point required at that time.

[0065]

[Table 1] R ₁ in the above Table 1 shows the general formula of the corresponding group R of formula (I).

As is clear from Table 1, the four of the present invention
The 4 '''-quaterphenyl-dicarboxylic acid diester is the 4,4'''-quaterphenyl- of Comparative Examples 1-2.
When compared with dicarboxylic acid diesters, they exhibit remarkably excellent solubility in xylene, which is industrially inexpensive as a solvent, has relatively low toxicity, and is easily recovered. It also has a significantly lower melting point. This shows the convenience and advantage in the step of separating and extracting and purifying 4,4 ′ ″-quaterphenyl-dicarboxylic acid diester of the present invention. Further, when used as a monomer raw material of a high-performance polymer compound or as a modifying additive, compatibility and solubility with other components are important factors. During the reaction, undissolved substances are left outside the reaction system, and smooth polymerization cannot be performed, and the physical properties of the produced polymer are greatly adversely affected. In addition, it is unfavorable from an industrial point of view because it leads to an unnecessarily large size of a stirring device and the like. However, the 4,4 '''-quaterphenyl of the present invention-
The dicarboxylic acid diester was 4,4 ″ ′-in Comparative Examples 1-2.
As described above, it exhibits excellent solubility even in xylene as compared with quaterphenyl-dicarboxylic acid diester, and has a remarkably low melting point.

This shows good compatibility and solubility with other components of the 4,4 '''-quaterphenyl-dicarboxylic acid diester of the present invention, which is simple and advantageous in polycondensation reaction and the like. It shows sex.

[0068]

INDUSTRIAL APPLICABILITY The present invention provides 4,4 ″ ′-quaterphenyl-dicarboxylic acid diester which is industrially inexpensive, has relatively low toxicity, and can be easily recovered and easily separated and purified with xylene or the like. It Furthermore, when used as a super engineering plastic monomer or as a modifying additive for super engineering plastics, etc., it has excellent compatibility and solubility with other components. The conditions are simple and extremely advantageous.

Further, the polycondensate obtained above is 4,
Compared with the case of using 4 '''-quaterphenyl-dimethyl ester or diethyl ester, a polymer having a high degree of polymerization and a good molecular weight distribution was obtained, and the modified additive composition had high uniformity and both were physically , Extremely excellent in chemical properties can be obtained.

[Brief description of drawings]

1 is an infrared absorption spectrogram of 4,4 ′ ″-quaterphenyl-dicarboxylic acid diester obtained in Example 1. FIG.

FIG. 2 is an infrared absorption spectrogram of 4,4 ′ ″-quaterphenyl-dicarboxylic acid diester obtained in Example 2.

FIG. 3 is an infrared absorption spectrogram of 4,4 ′ ″-quaterphenyl-dicarboxylic acid diester obtained in Example 3.

FIG. 4 is an infrared absorption spectrogram of 4,4 ′ ″-quaterphenyl-dicarboxylic acid diester obtained in Example 4.

5 is an infrared absorption spectrogram of 4,4 ′ ″-quaterphenyl-dicarboxylic acid diester obtained in Example 5. FIG.

FIG. 6 is an infrared absorption spectrogram of 4,4 ′ ″-quaterphenyl-dicarboxylic acid diester obtained in Example 6.

FIG. 7 is an infrared absorption spectrogram of 4,4 ′ ″-quaterphenyl-dicarboxylic acid diester obtained in Example 7.

FIG. 8 is an infrared absorption spectrogram of 4,4 ′ ″-quaterphenyl-dicarboxylic acid diester obtained in Example 8.

FIG. 9 is an infrared absorption spectrogram of 4,4 ′ ″-quaterphenyl-dicarboxylic acid diester obtained in Example 9.

FIG. 10 is an infrared absorption spectrogram of 4,4 ′ ″-quaterphenyl-dicarboxylic acid diester obtained in Example 10.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenichi Ikemoto 962-7 Nakamura, Nagasu-cho, Tamana-gun, Kumamoto Prefecture (72) Inventor Shin Osuga 2-3-3-29-403 (72) invention, Wakayamadai, Shimamoto-cho, Mishima-gun, Osaka Kazuo Tsuchiyama 13-8-403 Shin-Ashiya, Suita-shi, Osaka (56) Reference JP-A-4-139147 (JP, A) JP-A-5-17409 (JP, A) JP-A-6-239979 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C07C 69/76 C07C 67/347 C07B 61/00 330 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A compound represented by the general formula (I): 4,4 ′ ″-quaterphenyl- dicarboxylic acid diesters represented by the formula (wherein R represents an alkyl group or a cycloalkyl group having 3 to 12 carbon atoms). 2. R in the general formula (I) is selected from the group consisting of a normal propyl group, a normal butyl group, an isobutyl group, a secondary butyl group, a normal pentyl group, a normal octyl group, a 2-ethylhexyl group and a normal lauryl group. 4.4 '''-Quaterphenyl-dicarboxylic acid diesters according to claim 1. 3. The 4.4 ′ ″-quaterphenyl-dicarboxylic acid diesters according to claim 1, wherein R in the general formula (I) is a cyclohexyl group.