KR100583016B1 - Terphenyl dihydroxy monomers containing fluorine, and process for preparing them - Google Patents

Abstract

The present invention relates to a fluorine-containing terphenyl dihydroxy monomer and a preparation method thereof, and more particularly, to 2,5-dialkoxy-1,4-benzenediboronic acid and bromobenzene containing fluorine; Prepared by Suzuki cross-coupling reaction, which contains two hydroxyl group functional groups and a fluorine (F) atom at the same time. S _N Ar) relates to a fluorine-containing terphenyl dihydroxy monomer useful as a monomer applied to a polymerization reaction to polymerize a fluorine-containing polymer and a method for preparing the same.

Fluorine-containing terphenyl dihydroxy monomer, fluorine-containing polymer, Suzuki cross coupling, aromatic nucleophilic substitution

Description

Terphenyl dihydroxy monomers containing fluorine, and process for preparing them}             

1 is a GC-MASS spectrum for 1,4-dibromo-2,5-dimethoxybenzene.

FIG. 2 shows ¹ H-NMR spectra for 1,4-dimethoxybenzene, 1,4-dibromo-2,5-dimethoxybenzene and 2,5-dimethoxy-1,4-benzenediboronic acid to be.

3 is FT-IR spectra for 1,4-dimethoxybenzene, 1,4-dibromo-2,5-dimethoxybenzene and 2,5-dimethoxy-1,4-benzenediboronic acid .

4 is GC-MASS spectrum for 6FDMTP.

5 is ¹ H-NMR spectra for 2,5-dimethoxy-1,4-benzenediboronic acid, 4-bromobenzotrifluoride, 6FDMTP and 6FTPDH.

6 is the FT-IR spectra for 6FDMTP and 6FTPDH.

7 is GC-MASS spectrum for 6FTPDH.

8 is a GC-MASS spectrum of 12FDMTP.

FIG. 9 is ¹ H-NMR spectra for 2,5-dimethoxy-1,4-benzenediboronic acid, 3,5-bistrifluoromethylbromobenzene, 12FDMTP, and 12FTPDH.

10 is the FT-IR spectra for 12FDMTP and 12FTPDH.

11 is the GC-MASS spectrum for 12FTPDH.

12 is the GC-MASS spectrum for 14 FDMTP.

FIG. 13 shows 2,5-dimethoxy-1,4-benzenediboronic acid, 1-bromo-2,3,5,6-tetrafluoro-4- (trifluoromethyl) benzene, 14FDMTP and 14FTPDH. ¹ H-NMR spectra for.

14 is the FT-IR spectra for 14FDMTP and 14FTPDH.

15 is the GC-MASS spectrum for 14FTPDH.

The present invention relates to a fluorine-containing terphenyl dihydroxy monomer and a preparation method thereof, and more particularly, to 2,5-dialkoxy-1,4-benzenediboronic acid and bromobenzene containing fluorine; Prepared by Suzuki cross-coupling reaction, which contains two hydroxyl group functional groups and a fluorine (F) atom at the same time. S _N Ar) The present invention relates to a fluorine-containing terphenyl dihydroxy monomer represented by the following Chemical Formula 1, which is applied to a polymerization reaction and is useful as a monomer for polymerizing a fluorine-containing polymer, and a method for preparing the same.

In Chemical Formula 1, R represents a hydrogen atom or an alkyl group of C _{1 to} C ₆ ; X represents a fluorine (F) atom or a C _{1 to} C ₆ fluoroalkyl group; n represents the integer of 1-4 as the number of substituents X.

Fluorine (F) -containing polymers generally have thermal stability, chemical stability, low light loss, low refractive index, low birefringence, and low dielectric constant, and are easy to process and have low moisture absorption. have. In addition, fluorine (F) -containing polymer is well used in the manufacture of devices for optical waveguides because it is well matched with the physical properties required for device manufacturing in the field of information and communication.

Representative fluorine (F) containing polymers include poly (arylene ether) s (hereinafter, abbreviated as 'PAEs'). PAEs are engineering plastics that are used not only for electronic materials but also for aerospace materials, or they are used as fuel cells by sulfonating PAEs.

In order to prepare such PAEs, aromatic nucleophilic substitution (S _N Ar) reactions are usually used. At this time, monomers having dihydroxy functional groups are mainly used. 4,4 '-(hexafluoroisopropylidene) diphenol (6FBPA) is known as a dihydroxy monomer for preparing PAEs, and in view of the industrial utility of fluorine-containing polymers, Lean-containing dihydroxy monomers are extremely rare.

Although PAEs as fluorine (F) -containing polymers have a wide range of industrial applications, such as information communication devices, currently known fluorine-containing dihydroxy monomers are very rare and have many limitations in producing PAEs with better physical and chemical properties. In the present invention, the present invention has been completed by synthesizing a novel monomer which can solve such a problem.

Accordingly, an object of the present invention is to provide a fluorine-containing terphenyl dihydroxy monomer and a preparation method thereof.

The present invention is characterized by a fluorine-containing terphenyl dihydroxy monomer represented by the following formula (1).

[Formula 1]

In Chemical Formula 1, R represents a hydrogen atom or an alkyl group of C _{1 to} C ₆ ; X represents a fluorine (F) atom or a C _{1 to} C ₆ fluoroalkyl group; n represents the integer of 1-4 as the number of substituents X.

Referring to the present invention in more detail as follows.

The new dihydroxy monomer represented by Formula 1 according to the present invention contains fluorine (F), and the polymer prepared by polymerizing the monomer generally has properties such as thermal properties of the fluorine-containing polymer. It has excellent stability and chemical stability as well as low light loss, low refractive index, low dielectric constant, easy processing and low moisture absorption, which can be usefully applied as an information communication device.

More specifically illustrating the fluorine-containing terphenyl dihydroxy monomer represented by Formula 1 according to the present invention, 2 ', 5'-dimethoxy-4,4 "-bis-trifluoromethyl- [1, 1 '; 4', 1 "] terphenyl; 4,4 "-bis-trifluoromethyl- [1,1 ', 4', 1"] terphenyl-2 ', 5'-diol; 2 ', 5'-dimethoxy-3,5,3 ", 5" -tetrakis-trifluoromethyl- [1,1', 4 ', 1 "] terphenyl; 3,5,3", 5 "-Tetrakis-trifluoromethyl- [1,1 ', 4', 1"] terphenyl-2 ', 5'-diol; 2,3,5,6,2 ", 3", 5 ", 6" -octafluoro-2 ', 5'-dimethoxy-4,4 "-bis-trifluoromethyl- [1,1' , 4 ', 1 "] terphenyl; 2,3,5,6,2 ", 3", 5 ", 6" -octafluoro-4,4 "-bis-trifluoromethyl- [1,1 ', 4', 1"] terphenyl -2 ', 5'-diol may be included.

In addition, the present invention includes a method for preparing the monomer represented by the formula (1), briefly showing the production method according to the invention as shown in Scheme 1.

In Scheme 1, R ′ represents an alkyl group of C ₁ to C ₆ ; R represents a hydrogen atom or an alkyl group of C _{1 to} C ₆ ; X represents a fluorine (F) atom or a C _{1 to} C ₆ fluoroalkyl group; n represents the integer of 1-4 as the number of substituents X.

The compound represented by the formula (1) according to the present invention, wherein R is a hydrogen atom, cannot be prepared in one step due to the reaction characteristics between the hydroxyl group and the fluorine atom. Therefore, in the present invention, 1,4-dialkoxybenzene in which an alkoxy group is substituted in place of the hydroxy group is used as a starting material, and after the Suzuki cross coupling reaction with a fluorine-containing material, the alkoxy group is used in the final step of the reaction. A method of converting to a hydroxyl group was adopted.

Referring to the production method of the present invention according to the reaction scheme 1 in more detail.

First, 1,4-dialkoxybenzene represented by the formula (2) is brominated to prepare 1,4-dibromo-2,5-dialkoxybenzene represented by the formula (3). The bromination reaction is carried out at room temperature by conventional methods using bromine (Br ₂ ) and iodine (I ₂ ). As the reaction solvent, a conventional organic solvent is used. Specifically, dichloromethane (CH ₂ Cl ₂ ), acetic acid, toluene, hexane, tetrahydrofuran (THF), N, N -dimethylformamide (DMF), and dimethyl sulfoxide (DMSO) and the like can be used. In addition, after the bromination reaction, an unreacted bromine (Br ₂ ) and iodine (I ₂ ) were treated with an aqueous potassium hydroxide solution or the like.

Then, 1,4-dibromo-2,5-dialkoxybenzene represented by Formula 3 is converted to 2,5-dialkoxy-1,4-benzenediboronic acid represented by Formula 4 . The reaction of converting the bromo compound into the boronic acid compound is carried out by refluxing the bromo compound together with magnesium (Mg), dibromoethane and tetrahydrofuran at a temperature of 70 to 90 ° C., and thus a Grignard reagent. After the preparation, trimethylborate was added while maintaining the temperature at -90 to -50 ° C, stirred at room temperature, hydrolyzed at -30 to 10 ° C, and neutralized with sulfuric acid to obtain the desired boronic acid compound.

Subsequently, the 2,5-dialkoxy-1,4-benzenediboronic ester represented by Formula 4 is substituted with fluorine-substituted bromobenzene represented by Formula 5 and Suzuki cross coupling. Reaction produces the target compound represented by the formula (1) wherein R is an alkyl group. Suzuki cross-coupling reaction is carried out in the range of reaction temperature 60 ~ 140 ℃ by a conventional method under alkali metal base and palladium catalyst. The alkali metal base may be specifically selected from sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and the like. As the palladium catalyst, palladium tetrakistriphenylphosphine (Pd (PPh ₃ ) ₄ ), palladium acetate, palladium chloride and the like can be used. As the reaction solvent, a conventional organic solvent is used. Specifically, tetrahydrofuran (THF), N, N -dimethylformamide (DMF), toluene, pentane, dioxane, ethylene glycol, dimethyl ether (DME), and dimethylacetate Amide (DMA) or the like can be used.

In addition, in order to synthesize the compound represented by the formula (1) wherein R is a hydrogen atom, a suitable acid such as hydrochloric acid, bromic acid / acetic acid, iodic acid, trifluoroacetic acid, aluminum chloride, aluminum bromide, aluminum iodide Hydrolysis reaction is carried out using selected from id, boron trichloride, boron tribromide, phenyl boron dichloride, boron triiodide, boron trifluoride and the like. As a specific example, acid hydrolysis may be performed by heating at a temperature of 100 to 150 ° C. using bromic acid / acetic acid.

The reaction of each step constituting the preparation method according to the present invention described above is only a known method, but the specific fluorine-containing dihydroxy monomer can be efficiently formed by specifically configuring the selection of reactants and the introduction order of substituents. It is characterized by the method of obtaining.

On the other hand, the novel monomer represented by the formula (1) according to the present invention is a structural feature containing a fluorine atom and a hydroxyl group, it can be usefully applied to fluorine-containing polymer polymerization by the aromatic nucleophilic substitution reaction.

The present invention as described above will be described in more detail based on the following examples, but the present invention is not limited thereto.

Example 1 Preparation of 1,4-Dibromo-2,5-dimethoxybenzene

1,4-dimethoxybenzene (74.5 mmol), iodine (I ₂ ; 0.61 mmol) and dichloromethane were added to a three-necked round flask substituted with nitrogen, and then blocked with light using a dropping funnel with blocking funnel. (Br ₂ ; 178.8 mmol) was slowly dropped from room temperature. After the dropping, the reaction was refluxed for one hour while maintaining the temperature of the reactor at room temperature. After the reaction, the reactants were poured into 5M aqueous potassium dihydroxy (KOH) solution to remove unreacted iodine and bromine, and the salts were removed with water during the extraction process using dichloromethane and water. . Magnesium sulfate was also used to remove the small amount of water remaining. Dichloromethane in the filtrate was removed using a vacuum concentrator. The product obtained was vacuum dried at 40 ° C. and the yield was very high, above 99%. The final product was obtained as a white solid with a melting point of 144-149 ° C.

Structural analysis was performed through GC-MASS, ¹ H-NMR, and FT-IR. As can be seen in the GC-MASS spectrum of FIG. 1, parent ions were found at 296, and the aliphatic bromine compound was found to be 1: 1 at 79 and 81 in bromine. It should also appear between 294. The reason for this is both when the substituted bromine in 1,4-dibromo-2,5-dimethoxybenzene is substituted for a substance having an atomic weight of 79, and when 79 and 81 are substituted one by one. This is because three cases occur when a substance having an atomic weight of 81 is substituted. In addition, it can be seen that the peaks in which the methyl group (-CH ₃ ) is separated by one appear at 279, 281, and 283. Even in the ¹ H-NMR spectrum of FIG. 2, bromine having an electronegativity greater than hydrogen is substituted to reduce the electron density of the protons, thereby reducing the local diamagnetic shielding of the protons. It could be confirmed that. In addition, the FT-IR spectrum of FIG. 3 shows that the 1968 and 1867 cm ^-1 peaks that appeared in the starting material 1,4-dimethoxybenzene disappeared after the reaction. These two peaks were 2000 to 1667 cm. ^The peaks appearing in the substituted benzene compounds in the para- position found in the ⁻¹ region, but two peaks disappeared after the reaction. And it was confirmed through the 1793, 1700 cm ^-1 peak that the four substances are substituted in the position of C-1, C-2, C-4, C-5 of the benzene after the reaction.

Example 2: Preparation of 2,5-dimethoxy-1,4-benzenediboronic acid

Into a nitrogen-substituted three-necked round flask equipped with a condenser, a dropping funnel and a magnetic stub, magnesium (Mg) was added and heated to completely remove water, followed by tetrahydrofuran (10 mL) and dibromoethane (0.1 a little mL) was added and activated. At this time, after the magnesium is activated, the solution color changes from the transparent color to the dark brown color, and then gradually turns to 1,4-dibromo-2,5-dimethoxybenzene dissolved in tetrahydrofuran and tetrahydrofuran. After the addition, the mixture was refluxed at a temperature of 80 ° C. for one hour. After making the acetone bath using dry ice and acetone and maintaining the temperature of the reactor to -60 ℃, trimethyl borate was added little by little using a dropping funnel for 20 to 30 minutes. After removing the acetone bath and raising the temperature of the reactor to room temperature, tetrahydrofuran (40 mL) was added, and maintained for 24 hours. The temperature of the reactor was maintained at 0 ° C. or lower, followed by hydrolysis by addition of water, followed by neutralization of the compound by addition of aqueous sulfuric acid solution (33.6 mL of sulfuric acid in 680 mL of water). After neutralization, the reaction product was extracted with an organic layer using diethyl ether, and then residual water was removed using magnesium sulfate. The diethyl ether in the filtrate was removed using a vacuum concentrator, and then recrystallized using a mixture of acetonitrile and water to obtain a final product. The obtained product was vacuum dried at 60 ° C., and the yield was 52%. The final product was obtained as a white solid, with a melting point of 250 ° C. or higher.

Structure analysis was performed through element analysis (EA) analysis, ¹ H-NMR, ¹³ C-NMR, FT-IR. As a result of EA analysis, the carbon (C) and hydrogen (H) values of the 2,5-dimethoxy-1,4-benzenediboronic acid were measured as 43.68 and 5.38, respectively, and the molecular formula (C ₈ H ₁₂ B ₂ O ₆ ) Is almost identical to 42.55, 5.36. In the ¹ H-NMR spectrum of FIG. 2, the hydroxy (-OH) peak was newly appeared at 7.80 ppm, and the hydrogen peak and the methyl group peak of benzene were exactly shown, and the area ratio of the peaks was also exactly the same. It was confirmed that 5-dimethoxy-1,4-benzenediboronic acid was synthesized. In addition, ¹³ C-NMR spectra showed that the carbon peaks of different environments appeared at 55.84, 116.86, 124.56, and 157.47 ppm, respectively. In the FT-IR spectrum of FIG. 3, the hydroxy (-OH) peak, which was not seen in 1,4-dibromo-2,5-dimethoxybenzene, appeared exactly at 3366 cm ⁻¹ , showing boronic acid (-B It was confirmed that the (OH) ₂ ) group was formed. The EA analysis, ¹ H-NMR, ¹³ C-NMR, FT-IR was confirmed that the 2,5-dimethoxy-1,4-benzenediboronic acid was synthesized.

Example 3: Preparation of 2 ', 5'-dimethoxy-4,4 "-bis-trifluoromethyl- [1,1', 4 ', 1"] terphenyl (6FDMTP)

2,5-dimethoxy-1,4-benzenediboronic acid (6.64 mmol), 4-bromobenzotrifluoride (12.28 mmol) in a two-necked round flask equipped with a condenser, a magnetic stub, and a nitrogen-substituted round flask; Tetrahydrofuran (50 mL) and 2 M aqueous potassium carbonate solution (25 mL) were added, followed by palladium tetrakistriphenylphosphine (Pd (PPh ₃ ) ₄ ; 5 mol%) as a catalyst. The reaction mixture was allowed to react the reactor for 8 hours at a temperature of 80 ° C. in a nitrogen atmosphere. After the reaction, the mixture was extracted with dichloromethane and washed several times with water. Magnesium sulfate was also used to remove the small amount of water remaining. Dichloromethane in the filtrate was removed using a vacuum concentrator, and then the unreacted material was removed by column chromatography, and then again purified by dichloromethane to obtain a more pure final product. The product obtained was vacuum dried at 60 ° C. and the yield was as high as 92% or more. The final product was obtained as a white solid, with a melting point of 192 to 194 ° C.

Structural analysis was performed using GC-MASS, ¹ H-NMR, ¹⁹ F-NMR, and FT-IR. The parent ion seen in the GC-MASS spectrum of FIG. 4 was very large at 426, and the peak at which one methyl group (-CH ₃ ) was separated from the peak at 411 was shown at 396, respectively. In the ¹ H-NMR spectrum of FIG. 5, the boronic acid peak disappeared and hydrogen peaks in 4-bromobenzotrifluoride were formed at 7.70 and 6.98 ppm after the reaction, respectively, indicating that 6FDMTP was synthesized. Their area ratio was also correct. In addition, in the ¹⁹ F-NMR spectrum, a new fluorine peak appeared at -59.74 ppm, indicating that the Suzuki cross coupling reaction was successful. In the FT-IR spectrum of FIG. 6, the substitution of the trifluoromethylbenzene group was successful by the disappearance of the hydroxyl group of the boronic acid group and the newly appearing 1122 cm ^-1 corresponding to the CF peak of the trifluoromethyl group. 6FDMTP was confirmed that the synthesis. From the above analysis results, it was found that the Suzuki cross coupling reaction was successful.

Example 4: Preparation of 4,4 "-bis-trifluoromethyl- [1,1 ', 4', 1"] terphenyl-2 ', 5'-diol (6FTPDH)

6FDMTP and acetic acid were added to a nitrogen-substituted two-necked round flask equipped with a condenser, a dropping funnel and a magnetic stub, and HBr was slowly added using a dropping funnel and reacted at 125 ° C. for 48 hours. The reaction was then precipitated in water and filtered to give the final product. The product obtained was vacuum dried at 60 ° C. and obtained as a white solid. The yield was very high at 96% and the melting point was obtained from 188 to 190 ℃.

Structural analysis was performed using GC-MASS, ¹ H-NMR, ¹⁹ F-NMR, and FT-IR. The parent ions seen in the GC-MASS spectrum of FIG. 7 were very large at 398. As a result of the ¹ H-NMR spectrum of FIG. 5, the hydrogen peak of the methyl group, which appeared at 3.81 ppm of 6FDMTP, disappeared in 6FTPDH, and the peak corresponding to the hydroxyl group appeared at 4.75 ppm, indicating that 6FTPDH was successfully synthesized. In addition, ¹⁹ F-NMR spectral results showed a fluorine peak at -59.89 ppm but little change in peak. Analysis of the FT-IR of Figure 6 was able to confirm the peak by the hydroxyl group at 3338 cm ^-1 , and confirmed the synthesis of the designed material by disappearing the CH peaks of the methyl group appeared in the range of 2900 ~ 3000 cm ^-1 Could.

Example 5: Preparation of 2 ', 5'-dimethoxy-3,5,3 ", 5" -tetrakis-trifluoromethyl- [1,1', 4 ', 1 "] terphenyl (12FDMTP)

In the same manner as in Example 3, except that 3,5-bistrifluoromethylbromobenzene was used instead of 4-bromobenzotrifluoride as a starting material. The yield was 95% or more, and melting | fusing point was obtained at 193-195 degreeC.

Structural analysis was performed using GC-MASS, ¹ H-NMR, ¹⁹ F-NMR, and FT-IR. The parent ion seen in the GC-MASS spectrum of FIG. 8 was very large at 562, and the peak at which one methyl group was separated was 547. In the ¹ H-NMR spectrum of FIG. 9, the boronic acid peak disappeared and hydrogen peaks in 3,5-bistrifluoromethylbromobenzene were formed at 7.87 and 8.01 ppm after the reaction, respectively, confirming that 12FDMTP was synthesized. The area ratio of the hydrogen peaks, respectively, was also correct. In addition, a new fluorine peak was confirmed at -60.03 ppm in the result of ¹⁹ F-NMR spectrum, indicating that the Suzuki cross coupling reaction was successful. In the FT-IR spectrum of FIG. 10, the substitution of the trifluoromethylbenzene group was successful by the disappearance of the hydroxyl group of the boronic acid group and the newly appearing 1118 cm ⁻¹ corresponding to the CF peak of the trifluoromethyl group. 12FDMTP was confirmed that the synthesis. From the above analysis results, it was found that the Suzuki cross coupling reaction was successful.

Example 6 Preparation of 3,5,3 ", 5" -Tetrakis-trifluoromethyl- [1,1 ', 4', 1 "] terphenyl-2 ', 5'-diol (12FTPDH)

In the same manner as in Example 4, except that 2 ', 5'-dimethoxy-4,4 "-bis-trifluoromethyl- [1,1'; 4 ', 1"] ter as a starting material 2 ', 5'-dimethoxy-3,5,3 ", 5" -tetrakis-trifluoromethyl- [1,1', 4 ', 1 "] terphenyl was used instead of phenyl. The yield was 93 It was more than%, and melting | fusing point was obtained from 176-178 degreeC.

Structural analysis was performed through GC-MASS, ¹ H-NMR, and FT-IR. The parent ion seen in the GC-MASS spectrum of FIG. 11 was very large at 534. In the ¹ H-NMR spectrum of FIG. 9, the hydrogen peak of the methyl group, which appeared at 3.85 ppm of 12FDMTP, disappeared in 12FTPDH, and the peak corresponding to the hydroxyl group appeared at 4.77 ppm, indicating that 12FTPDH was successfully synthesized. As a result of the analysis of FT-IR of FIG. 10, the peak by the hydroxyl group was found at 3503 cm ⁻¹ , and the CH peaks of the methyl group disappeared from 2900 to 3000 cm ⁻¹ . .

Example 7 2,3,5,6,2 ", 3", 5 ", 6" -octafluoro-2 ', 5'-dimethoxy-4,4 "-bis-trifluoromethyl- [ Preparation of 1,1 ', 4', 1 "] terphenyl (14FDMTP)

The same procedure as in Example 3 was carried out, except that 1-bromo-2,3,5,6-tetrafluoro-4- (trifluoromethyl) benzene was used instead of 4-bromobenzotrifluoride as a starting material. Was used. The yield was more than 90%, the melting point was obtained at 235 ~ 239 ℃.

Structural analysis was performed using GC-MASS, ¹ H-NMR, ¹⁹ F-NMR, and FT-IR. The parent ion seen in the GC-MASS spectrum of FIG. 12 was very large at 570, and the peak at which the methyl group was separated was 555. In the ¹ H-NMR spectrum results of FIG. 13, the electronegativity of the boronic acid peak disappeared and substituted in 1-bromo-2,3,5,6-tetrafluoro-4- (trifluoromethyl) benzene It was confirmed that the hydrogen peak of the methyl group shifted to the low field by the largest fluorine, and the fluorine peaks substituted with aliphatic in the ¹⁹ F-NMR spectrum were centered around -135.06 and -138.25 ppm, respectively. It was confirmed that 12FDMTP was synthesized by substituting with an aromatic to form a fluorine peak of the trifluoromethyl group as a triple peak around -53.51 ppm, and the area ratio of each fluorine peak was also accurate. It was confirmed that the hydroxy group of the boronic acid group disappeared in the FT-IR spectra of FIGS. 3 and 14. From the above analysis results, it was found that the Suzuki cross coupling reaction was successful.

Example 8 2,3,5,6,2 ", 3", 5 ", 6" -octafluoro-4,4 "-bis-trifluoromethyl- [1,1 ', 4', 1 Preparation of "] terphenyl-2 ', 5'-diol (14FTPDH)

In the same manner as in Example 4, except that 2 ', 5'-dimethoxy-4,4 "-bis-trifluoromethyl- [1,1'; 4 ', 1"] ter as a starting material 2,3,5,6,2 ", 3", 5 ", 6" -octafluoro-2 ', 5'-dimethoxy-4,4 "-bis-trifluoromethyl- [1, instead of phenyl 1 ', 4', 1 "] terphenyl was used. The yield was 95% or more, and melting | fusing point was obtained at 218-222 degreeC.

Structural analysis was performed through GC-MASS, ¹ H-NMR, and FT-IR. The parent ion seen in the GC-MASS spectrum of FIG. 15 was very large at 542. In the ¹ H-NMR spectrum results of FIG. 13, the hydrogen peak of the methyl group, which appeared at 3.80 ppm of 14FDMTP, disappeared in 14FTPDH, and the peak corresponding to the hydroxyl group appeared at 5.04 ppm, indicating that 14FTPDH was successfully synthesized. Analysis of the FT-IR of FIG. 14 confirmed the synthesis of the designed material by confirming the hydroxy peak without hydrogen bonding and the hydroxy peak with hydrogen bonding at 3482 and 3588 cm ⁻¹ .

Since the new monomers according to the present invention contain fluorine, polymers prepared using these monomers generally have physical properties and optical properties of polymers containing fluorine and thus are useful as information and communication device materials. Contribute to development.

Claims (4)

Fluorine-containing terphenyl dihydroxy monomer, characterized in that represented by the following formula (1): [Formula 1]

In Chemical Formula 1, R represents a hydrogen atom or an alkyl group of C _{1 to} C ₆ ; X represents a fluorine (F) atom or a C _{1 to} C ₆ fluoroalkyl group; n represents the integer of 1-4 as the number of substituents X. According to claim 1, wherein the compound represented by the formula (1) 2 ', 5'-dimethoxy-4,4 "-bis-trifluoromethyl- [1,1'; 4 ', 1"] terphenyl, 4,4 "-bis-trifluoromethyl- [1,1 ', 4', 1"] terphenyl-2 ', 5'-diol, 2 ', 5'-dimethoxy-3,5,3 ", 5" -tetrakis-trifluoromethyl- [1,1', 4 ', 1 "] terphenyl, 3,5,3 ", 5" -tetrakis-trifluoromethyl- [1,1 ', 4', 1 "] terphenyl-2 ', 5'-diol, 2,3,5,6,2 ", 3", 5 ", 6" -octafluoro-2 ', 5'-dimethoxy-4,4 "-bis-trifluoromethyl- [1,1' , 4 ', 1 "] terphenyl, and 2,3,5,6,2 ", 3", 5 ", 6" -octafluoro-4,4 "-bis-trifluoromethyl- [1,1 ', 4', 1"] terphenyl -2 ', 5'-diol Fluorine-containing terphenyl dihydroxy monomer, characterized in that selected from. A process of brominating 1,4-dialkoxybenzene represented by the following formula (2) to prepare 1,4-dibromo-2,5-dialkoxybenzene represented by the following formula (3), The bromine (Br) substituent of 1,4-dibromo-2,5-dialkoxybenzene represented by the following formula (3) is converted to boronic acid, and 2,5-dialkoxy-1 represented by the following formula (4) Preparing a 4-benzenediboronic acid, Suzuki cross-coupling reaction of 2,5-dialkoxy-1,4-benzenediboronic acid represented by the following formula (4) with fluorine (F) -containing bromobenzene represented by the following formula (5) Process for preparing the indicated fluorine-containing terphenyl dihydroxy monomer Manufacturing method characterized in that comprises a:

In the above scheme, R 'represents an alkyl group having _{1 to 6} carbon atoms; R represents a hydrogen atom or an alkyl group of C _{1 to} C ₆ ; X represents a fluorine (F) atom or a C _{1 to} C ₆ fluoroalkyl group; n represents the integer of 1-4 as the number of substituents X. The compound of claim 3, wherein R is a C ₁ to C ₆ alkyl group of the compound represented by the formula (1) produced by the Suzuki cross-coupling reaction is hydrolyzed with an acid solution to convert into a compound wherein R is a hydrogen atom. Rice production method characterized in that the process is further included.

Images