KR101685673B1 - Poly(biphenylene oxide)s Substituted with Two Trifluoromethyl Groups and Method for Producing Thereof - Google Patents

Abstract

The present invention relates to poly (biphenylene oxide) having excellent physical properties having two trifluoromethyl groups as substituents and a process for producing the poly (biphenylene oxide). More specifically, the present invention relates to a poly (biphenylene oxide) having two trifluoromethyl groups as substituents, (Biphenylene oxide), a copolymer thereof, and a process for producing the same. The poly (biphenylene oxide) having two trifluoromethyl groups as a substituent according to the present invention and the copolymer thereof are excellent in physical properties such as low refractive index, low dielectric constant and high glass transition temperature, Can be very useful.

Description

Poly (biphenylene oxide) s Substituted with Two Trifluoromethyl Groups and Method for Producing the same (Poly (biphenylene oxide) s Substituted with Two Trifluoromethyl Groups and Method for Producing Thereof)

The present invention relates to poly (biphenylene oxide) having excellent physical properties having two trifluoromethyl groups as substituents and a process for producing the poly (biphenylene oxide). More specifically, the present invention relates to a poly (biphenylene oxide) having two trifluoromethyl groups as substituents, (Biphenylene oxide), a copolymer thereof, and a process for producing the same.

The poly (arylene ether) -based polymer having an aromatic derivative and an ether bond has excellent physical properties such as mechanical strength, durability and chemical resistance as well as heat resistance, and is excellent in workability, so that the range and use amount thereof as an engineering plastic are continuously increased and, as a commercial product ^{Udel TM (Poly (ether sulfone)} ), PEEK TM (Poly (ether ether ketone)) ( more than ^{Amoco社), Ultem TM (Poly} (ether imide)), PPO TM (Poly (phenylene oxide ) (Commercially available from GE Corp.).

Among these various high performance polymers, poly (phenylene oxide) made by GE is a polymer polymerized by using an oxidative coupling reaction and has excellent physical properties and is widely used by blending with a general-purpose resin It is an organic polymer material. In general, poly (phenylene oxide) -based polymers can not be converted into main chains due to the specificity of the polymerization mechanism, and only derivatives with different substituents are known.

On the other hand, in the case of using aromatic nucleophilic substitution (S _N Ar) reaction from an activated aromatic dihalide (or dinitro group) and bisphenolate, various types of poly (arylene ether) Polymers can be synthesized, and many studies have been focused on polymer systems made using these reactions.

On the other hand, recent breakthroughs in electronic and optical communication technologies are demanding new materials with better physical properties, and in particular, there is a growing need for materials exhibiting low dielectric constant, birefringence, and low optical loss. In order to meet the needs of these new materials, it is necessary to control the physical properties by controlling the molecular structure as well as the processability. In order to produce a polymer material exhibiting low dielectric constant and birefringence, it is necessary to reduce the content of polar groups in the molecule, Should be designed. Introduction of a perfluoroalkyl group including a trifluoromethyl group into a polymer main chain having a rigid structure is advantageous in that it is possible to obtain a polymer having a rigid structure without degrading the heat resistance of a polymer produced due to stronger carbon- Not only greatly increases the workability including the solubility of the fluorine atom but also the water absorption rate, permittivity, and refractive index (including birefringence) are remarkably lowered due to the low polarizability of fluorine atoms. In addition, the carbon-fluorine bond is advantageous in the application of a plastic optical fiber or an optical waveguide because absorption of light of a wavelength of 1.3 .mu.m or 1.55 .mu.m used in current optical communication is remarkably reduced as compared with carbon-hydrogen bond. Therefore, a high-performance polymer in which a trifluoromethyl group is effectively introduced into a polymer main chain and a manufacturing technique thereof are very important.

(Biphenylene oxide) having one trifluoromethyl group as a substituent has been prepared (Korean Patent Laid-Open No. 10-2003-0049785) to provide a polymer exhibiting excellent physical properties such as dielectric constant and refractive index There have been limitations in meeting the requirements of the electronic and optical communication technologies.

Accordingly, the present inventors have made intensive efforts to provide a novel structure poly (biphenylene oxide) exhibiting properties such as low dielectric constant, low refractive index and low optical loss, and as a result, by introducing two trifluoromethyl groups into the biphenyl structure, , A low refractive index, and a high glass transition temperature, thereby completing the present invention.

It is an object of the present invention to provide a poly (biphenylene oxide) having two trifluoromethyl groups introduced into a biphenyl structure and a copolymer thereof.

It is another object of the present invention to provide a process for preparing the poly (biphenylene oxide) and copolymers thereof.

To achieve the above object, there is provided a poly (biphenylene oxide) having two trifluoromethyl groups introduced into a biphenyl structure.

The present invention also provides a monomer for producing the poly (biphenylene oxide).

(A) dissolving the monomer of formula (8) in a polar aprotic solvent, adding potassium carbonate to the solution, and stirring at 80 to 150 ° C to produce a phenoxide salt; And (b) a step of raising the temperature of the solution in which the salt is formed to 80 to 190 DEG C and stirring the poly (biphenylene oxide).

The present invention also provides a poly (biphenylene oxide) copolymer.

(A) dissolving the monomer of formula (9) and the monomer of formula (10) in a polar aprotic solvent at a ratio of 100: 1 to 1: 100, adding potassium carbonate to the solution, Lt; 0 > C to form the phenoxide salt; And (b) a step of raising the temperature of the solution in which the salt is formed to 80 to 190 DEG C and stirring the solution. The poly (biphenylene oxide)

The present invention also provides a poly (arylene ether) copolymer.

The poly (biphenylene oxide) having two trifluoromethyl groups as a substituent according to the present invention and the copolymer thereof are excellent in physical properties such as low refractive index, low dielectric constant and high glass transition temperature, Can be very useful.

FIG. 1 shows the results of a hydrogen atom nuclear magnetic resonance spectroscopy ( ¹ H Nuclear Magnetic Resonance spectrum, ¹ H NMR) of the monomer prepared in Example 3. FIG.
Fig. 2 shows the results of infrared spectroscopy (IR) of the monomers prepared in Example 3 and the poly (biphenylene oxide) prepared in Example 6. Fig.
FIG. 3 shows the results of a hydrogen atom nuclear magnetic resonance spectroscopy ( ¹ H Nuclear Magnetic Resonance spectrum, ¹ H NMR) of the monomer prepared in Example 5. FIG.
4 shows the results of infrared spectroscopy (IR) of the monomers prepared in Example 5 and the poly (biphenylene oxide) prepared in Example 7. Fig.
5 shows the results of a hydrogen atom nuclear magnetic resonance spectroscopy ( ¹ H Nuclear Magnetic Resonance spectrum, ¹ H NMR) of the poly (biphenylene oxide) prepared in Example 7. FIG.
6 shows the results of a hydrogen atom nuclear magnetic resonance spectroscopy ( ¹ H Nuclear Magnetic Resonance spectrum, ¹ H NMR) of the poly (biphenylene oxide) copolymer prepared in Example 10.
Fig. 7 shows the results of thermogravimetric analysis (TGA) of the poly (biphenylene oxide) copolymer prepared in Example 10. Fig.
8 is a graph showing differential scanning calorimetry (DSC) of the poly (biphenylene oxide) copolymer prepared in Example 7 and the poly (biphenylene oxide) copolymer prepared in Examples 8, 9, 10 and 11, Respectively.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

In the present invention, a poly (biphenylene oxide) having two trifluoromethyl groups introduced into a biphenyl structure and a copolymer thereof were prepared to confirm whether the poly (biphenylene oxide) had excellent physical properties.

In one aspect, the present invention relates to a poly (biphenylene oxide) represented by the following general formula (1). In Formula 1, n is an integer of 2 or more and 20,000 or less.

[Chemical Formula 1]

The poly (biphenylene oxide) of the present invention has a simple repeating unit structure in which two trifluoromethyl groups are substituted with side branches as a structure connected to a biphenylene ether. Representative structures include formulas 2, 3, 4, 5, 6 and 7.

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In another aspect, the present invention relates to a monomer represented by the following general formula (8) for producing the poly (biphenylene oxide).

[Chemical Formula 8]

Since the monomer has a hydroxy group capable of reacting within the molecular structure and a nitro leaving group activated by a trifluoromethyl group, a polymerization reaction can be carried out without a comonomer to produce a poly (biphenylene oxide) of the present invention can do. Representative examples of such monomers include 4'-hydroxy-4-nitro-2,6-bis (trifluoromethyl) biphenyl or 4'-hydroxy- (Trifluoromethyl) biphenyl and 4'-hydroxy-4-nitro-2,5-bis (trifluoromethyl) biphenyl and 3'-hydroxy-4- (Trifluoromethyl) biphenyl or 3'-hydroxy-4-nitro-3,5-bis (trifluoromethyl) biphenyl or 3'- And nitro-2,5-bis (trifluoromethyl) biphenyl.

[Chemical Formula 9]

[Chemical formula 10]

Hydroxy-4-nitro-2,6-bis (trifluoromethyl) biphenyl and 3'-hydroxy-4-nitrobenzene in the monomers of poly (biphenylene oxide) -Nitro-2,6-bis (trifluoromethyl) biphenyl oxidizes 4-bromo-3,5-bis (trifluoromethyl) aniline as shown in Scheme 1 below, 4-nitro-2,6-bis (trifluoromethyl) benzene was prepared, and then a methoxynitro compound was prepared by a coupling reaction with 4 or 3-methoxyphenylboronic acid in the presence of palladium catalyst Is produced through a dimerization reaction.

[Reaction Scheme 1]

(A) dissolving the monomer of formula (8) in a polar aprotic solvent, adding potassium carbonate to the solution, and stirring at 80 to 150 ° C to produce a phenoxide salt step; And (b) a step of raising the temperature of the solution in which the salt is formed to 80 to 190 캜 and stirring the solution.

The method for producing the poly (biphenylene oxide) of the present invention from the monomer of the formula (8) is shown in the following reaction formula (2). Specifically, the monomer of Formula 8 is dissolved in a polar aprotic solvent at a concentration of 20 to 50% (monomer weight (g) / amount of solvent (mL)), about 0.5 to 4 equivalents of potassium carbonate as a base is added, And the mixture is stirred at 80 to 150 ° C for 0.5 to 6 hours to form a phenoxide salt. At this time, it is preferable to continuously add a small amount of toluene or benzene or chlorobenzene to remove water generated during the reaction so that the reaction can be effectively performed. Thereafter, the temperature is raised to 80 to 190 ° C. for an effective reaction, and the reaction solution is stirred for 1 to 48 hours. When the polymerization reaction is completely completed, the reaction solution is precipitated in excess water and washed several times with hot water and methanol Then, it is dried in a vacuum oven. By this process all polymers can be obtained in almost quantitative yield.

Examples of polar aprotic solvents that can be used in the above reaction include N-methylpyrrolidone, dimethylsulfoxide, N, N-dimethylacetamide, N, N-dimethylformamide, diphenylsulfone, Sulfolane, 1,3-dimethyltetrahydropyrimidin-2 ( 1H ) -one, hexamethylphosphoramide, and the like.

[Reaction Scheme 2]

In another aspect, the present invention relates to a poly (biphenylene oxide) copolymer represented by the following general formula (11). In the general formula (11), n and m are an integer of 2 or more and 10,000 or less.

(11)

(A) dissolving the monomer of Formula 9 and the monomer of Formula 10 in a polar aprotic solvent at a ratio of 100: 1 to 1: 100, adding potassium carbonate to the solution, , Stirring at a temperature of 80 to 150 DEG C to produce a phenoxide salt; And (b) a step of raising the temperature of the solution in which the salt is formed to 80 to 190 캜 and stirring the solution.

The poly (biphenylene oxide) copolymer according to the present invention is a copolymer of 4'-hydroxy-4-nitro-2,6-bis (trifluoromethyl) biphenyl or 4'- (Trifluoromethyl) biphenyl or 4'-hydroxy-4-nitro-2,5-bis (trifluoromethyl) biphenyl and represented by formula (Trifluoromethyl) biphenyl or 3'-hydroxy-4-nitro-3,5-bis (trifluoromethyl) biphenyl Or 3'-hydroxy-4-nitro-2,5-bis (trifluoromethyl) biphenyl compound at different ratios.

Herein, the method of mixing the compounds represented by the above formulas (9) and (10) at different ratios and performing polymerization is as shown in the following reaction formula (3). Concretely, the mixture of the monomer of formula (9) and the monomer of formula (10) in a ratio of 100 to 0.01 (monomer of formula (9) / monomer of formula (10) )), Dissolved in a polar aprotic solvent, added with about 0.5 to 4 equivalents of potassium carbonate as a base, and stirred at 80 to 150 ° C for 0.5 to 6 hours to form a phenoxide salt. At this time, it is preferable to continuously add a small amount of toluene or benzene or chlorobenzene to remove water generated during the reaction so that the reaction can be effectively performed. Thereafter, the temperature is raised to 80 to 190 ° C. for an effective reaction, and the reaction solution is stirred for 1 to 48 hours. When the polymerization reaction is completely completed, the reaction solution is precipitated in excess water and washed several times with hot water and methanol Then, it is dried in a vacuum oven. By this process all polymers can be obtained in almost quantitative yield.

Polar aprotic solvents that can be used in the above reaction include N, N-dimethylformamide, N, , Sulfolane, 1,3-dimethyltetrahydropyrimidin-2 ( 1H ) -one, hexamethylphosphoramide, and the like.

[Reaction Scheme 3]

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are merely illustrative of the present invention and that the scope of the present invention is not construed as being limited by these embodiments.

The structures and physical properties of the monomers and polymers according to the following examples were confirmed and measured using the following method.

The structures of the synthesized materials were confirmed by IR (infrared spectroscopy) and NMR (nuclear magnetic resonance spectroscopy). IR charts were obtained from Bruker's EQUINOX-55 FTIR spectrophotometer using KBr and NMR spectra were obtained by dissolving samples in chloroform-d, dimethylsulfoxide-d ₆ , tetrahydrofuran-d ₈ and analyzed using a Bruker Fourier Transform AVANCE 400 spectrometer ≪ / RTI > The molecular weight of the polymer synthesized from the gel permeation chromatography was measured, and a sample was dissolved in tetrahydrofuran and measured using a TDA 302 instrument of VISCOTEK. TGA (Thermogravimetric Analysis) and DSC (Differential Scanning Calorimetry) were measured using a TGA Q500 and DSC Q100 from TA Instruments at a rate of 10 ° C / min. In all cases, it was measured under constant nitrogen flow, and TGA analysis was also performed under constant air flow. The 5% weight loss temperature was obtained from TGA analysis and the glass transition temperature (T _g ) and melting temperature (T _m ) were chosen at the midpoint of the slope of the curve in the DSC chart. The refractive index was measured using a Sairon SPA-4000 prism coupler with a laser having a wavelength of 1310 nm as a light source. A uniform film with a thickness of 4-7 μm was prepared and measured for horizontal and vertical refractive indices at room temperature.

[Comparative Example]

Preparation of poly (biphenylene oxide) having one trifluoromethyl group (Korean Patent Publication No. 10-200-0049785)

In order to confirm whether the poly (biphenylene oxide) having two trifluoromethyl group substituents according to the present invention exhibits excellent physical properties as compared with the poly (biphenylene oxide) having one trifluoromethyl group substituent, An experiment was conducted to prepare poly (biphenylene oxide) using 3'-hydroxy-4-nitro-2- (trifluoromethyl) biphenyl as a monomer containing one fluoromethyl group. 1.643 g (5.801 mmol) of 3'-hydroxy-4-nitro-2- (trifluoromethyl) biphenyl and 1.203 g (8.7 mmol) of potassium carbonate were dissolved in 6 mL of N-methylpyrrolidone, And the mixture was stirred at 135 캜 for 3 hours to form phenoxide. At this time, a constant amount of toluene was continuously added to continuously remove water generated during the reaction through an azeotropic process. The reaction temperature was raised to 190 ° C., and the reaction was carried out for 14 hours. The reaction product was precipitated in excess water and recovered. The product was washed with hot water and methanol several times and dried to obtain a pale yellow poly (biphenylene oxide) g; yield = 99.0%).

FTIR (KBr, cm ^-1 ): 1598 (aromatic C = C); 1250, (COC); 1170-1100 (CF).

It was confirmed that the polymer having one trifluoromethyl group prepared by the above method had a glass transition temperature of 154 캜 and a refractive index of 1.61.

One- Bromo -4-nitro-2,6- Of bis (trifluoromethyl) benzene  synthesis

0.95 g (3.08 mmol) of 4-bromo-3,5-bis (trifluoromethyl) aniline, 0.17 g (0.5 mmol) of tetrabutylammonium hydrogensulfate and 20 g (32.5 mmol) of potassium peroxymonosulfate (OXONE) Are added to a solution of 50 mL of acetone and 50 mL of dichloromethane and reacted at 0 ° C for 1 hour. At this time, the pH of the solution is maintained at 7 to 8 while adding potassium hydroxide. The reaction product was extracted several times with dichloromethane to obtain 1-bromo-4-nitro-2,6-bis (trifluoromethyl) benzene (0.86 g, 2.54 mmol; yield = 83%).

Melting point: 57 ℃

¹ H NMR (CDCl ₃ , 400 MHz, ppm): 8.71 (s, 2H).

_{^{13 C NMR (DMSO-d 6}} , 100 MHz, ppm): 146.62, 132.48 (q, J = 31.9 Hz), 126.71 (q, J = 5.7 Hz), 125.63, 121.68 (q, J = 272.9 Hz).

Synthesis of 4 'methoxy-4-nitro-2,6-bis (trifluoromethyl) biphenyl

, 4 g (11.8 mmol) of 4-methoxyphenylboronic acid, 3.6 g (23.7 mmol) of 4-methoxyphenylboronic acid and 8.15 g (59 mmol) of potassium carbonate, And a catalytic amount (0.682 g) of palladium (0) tetrakistriphenylphosphine were dissolved in 40 mL of toluene, 40 mL of water, and 20 mL of ethanol and refluxed for 35 hours. The reaction was repeated several times with ethyl acetate to obtain 4.47 g (9.5 mmol, yield = 80.5%) of 4'-methoxy-4-nitro-2,6-bis (trifluoromethyl) biphenyl.

_{^{1 H NMR (DMSO-d 6}} , 400 MHz, ppm): 8.75 (s, 2H), 7.21 (d, 2H, J = 11.17 Hz), 7.01 (d, 2H, J = 11.60 Hz), 3.81 (s, 3H, -OCH _3).

_{^{13 C NMR (DMSO-d 6}} , 100 MHz, ppm): 159.78, 146.82, 146.07, 131.91 (q, J = 30.3 Hz), 130.59, 124.73 (q, J = 5.7 Hz), 123.69, 122.16 (q, J = 273.5), 112.73, 55.13.

Synthesis of 4'-hydroxy-4-nitro-2,6-bis (trifluoromethyl) biphenyl

3 g (8.21 mmol) of the above prepared 4'-methoxy-4-nitro-2,6-bis (trifluoromethyl) biphenyl and 60 mL of dichloromethane were added thereto, Of 1M boron tribromide (BBr ₃ ) was slowly added dropwise. When the addition was completed, the reaction temperature was slowly raised to room temperature and further stirred for 7 hours. The reaction mixture was slowly added dropwise to an excessive amount of ice water to terminate the reaction. The reaction mixture was extracted with dichloromethane and recrystallized from a toluene / n-hexane co-solvent to give pale yellow 4'-hydroxy-4-nitro- Bis (trifluoromethyl) biphenyl (2.89 g, 8.23 mmol, yield> 99%).

Melting point: 140 ℃

FTIR (KBr, cm- ¹ ): 3418 (OH); 1613 (aromatic C = C); 1538, 1335 (NO ₂ ); 1142-1189 (CF).

_{^{1 H NMR (DMSO-d 6}} , 400 MHz, ppm): 9.80 (s, 1H, -OH), 8.74 (s, 2H), 7.07 (d, 2H, J = 8.33 Hz), 6.82 (d, 2H, J = 8.56 Hz).

_{^{13 C NMR (DMSO-d 6}} , 100 MHz, ppm): 158.06, 146.68, 146.58, 131.90 (q, J = 30.2 Hz), 130.45, 124.70 (q, J = 5.6 Hz), 122.17 (q, J = 273.6 Hz), 121.98,114.12.

Synthesis of 3'-methoxy-4-nitro-2,6-bis (trifluoromethyl) biphenyl

7 g (20.63 mmol) of 1-bromo-4-nitro-2,6-bis (trifluoromethyl) benzene, 3.8 g (24.98 mmol) of 3-methoxyphenylboronic acid and 8.61 g (62.3 mmol) And a catalytic amount (1 g) of palladium (0) tetrakistriphenylphosphine were dissolved in 40 mL of toluene, 40 mL of water, and 20 mL of ethanol and refluxed for 31 hours. The reaction was repeated several times with ethyl acetate to obtain 5.94 g (16.26 mmol, yield: 78.8%) of 3'-methoxy-4-nitro-2,6-bis (trifluoromethyl) biphenyl.

_{^{1 H NMR (DMSO-d 6}} , 400 MHz, ppm): 8.76 (s, 2H), 7.37 (t, 1H, J = 7.96 Hz), 7.06 (m, 1H), 6.86 (s, 1H), 6.85 ( d, 1 H, J = 12.16), 3.75 (s, 3H, -OCH ₃ ).

_{^{13 C NMR (DMSO-d 6}} , 100 MHz, ppm): 158.03, 146.89, 145.50, 133.06, 131.58 (q, J = 30.8 Hz), 128.42, 124.71 (q, J = 5.7 Hz), 122.09 (q, J = 273.5 Hz), 121.65, 115.49, 114.38, 55.08.

Synthesis of 3'-hydroxy-4-nitro-2,6-bis (trifluoromethyl) biphenyl

3.44 g (9.42 mmol) of the above prepared 3'-methoxy-4-nitro-2,6-bis (trifluoromethyl) biphenyl and 69 mL of dichloromethane were added thereto, mL of 1 M boron tribromide (BBr ₃ ) was slowly added dropwise. When the addition was completed, the reaction temperature was slowly raised to room temperature and further stirred for 19 hours. The reaction mixture was slowly added dropwise to excess ice water to terminate the reaction. The reaction mixture was extracted with dichloromethane and then passed through a silica gel using ethyl acetate and hexane as a co-solvent to obtain 3'-hydroxy-4-nitro- , 6-bis (trifluoromethyl) biphenyl (3.3 g, 9.40 mmol, yield> 99%).

Melting point: 86 ℃

FTIR (KBr, cm- ¹ ): 3271 (OH); 1610 (aromatic C = C); 1539, 1333 (NO ₂ ); 1141-1187 (CF).

_{^{1 H NMR (DMSO-d 6}} , 400 MHz, ppm): 9.69 (s, 1H, -OH), 8.76 (s, 2H), 7.24 (t, 1H, J = 8.20 Hz), 6.88 (m, 1H) , 6.69 (d, 1 H, J = 6.98 Hz), 6.68 (s, 1 H).

_{^{13 C NMR (DMSO-d 6}} , 100 MHz, ppm): 156.10, 146.87, 145.69, 132.94, 131.30 (q, J = 30.5 Hz), 128.36, 124.89 (q, J = 5.7 Hz), 122.14 (q, J = 273.6), 120.09, 116.35, 116.15.

Preparation of poly (biphenylene oxide) (1)

0.8038 g (2.29 mmol) of 4'-hydroxy-4-nitro-2,6-bis (trifluoromethyl) biphenyl and 0.47 g (3.4 mmol) of potassium carbonate were added to 4 mL of N-methylpyrrolidone After dissolving, the mixture was stirred at 135 캜 for 3 hours to form phenoxide. At this time, a constant amount of toluene was continuously added to continuously remove water generated during the reaction through an azeotropic process. The reaction temperature was raised to 175 ° C and allowed to react for 14 hours. The reaction product was precipitated in excess water and recovered. The product was washed several times with hot water and methanol and dried to obtain a pale yellow poly (biphenylene oxide) ; Yield = 93.8%).

FTIR (KBr, cm ^-1 ): 1603 (aromatic C = C); 1295, 1261, 1235 (COC); 1135-1186 (CF).

Preparation of poly (biphenylene oxide) (2)

0.4986 g (1.42 mmol) of 3'-hydroxy-4-nitro-2,6-bis (trifluoromethyl) biphenyl and 0.216 g (1.57 mmol) of potassium carbonate were added to 4 mL of N-methylpyrrolidone After dissolving, the mixture was stirred at 135 캜 for 3 hours to form phenoxide. At this time, a constant amount of toluene was continuously added to continuously remove water generated during the reaction through an azeotropic process. The reaction temperature was raised to 175 ° C and reacted for 14 hours. The reaction product was precipitated in excess water and recovered. The product was washed several times with hot water and methanol and dried to obtain black poly (biphenylene oxide) (0.4982 g ; Yield> 99%).

In order to confirm the excellent physical properties of the poly (biphenylene oxide) into which the two trifluoromethyl groups were introduced according to the present invention, the one trifluoromethyl group-introduced polymer obtained in Comparative Example 1 was compared with the polymer The polymer in which the trifluoromethyl group obtained in Example 1 was introduced had a glass transition temperature of 154 ° C and a refractive index of 1.61, while the polymer having two trifluoromethyl groups obtained in Example 7 had a glass transition temperature of 169 ° C Temperature and a refractive index of 1.50. This is an experimental result showing that the introduction of two trifluoromethyl groups greatly contributes to the increase of the physical properties.

FTIR (KBr, cm ^-1 ): 1610, 1585 (aromatic C = C); 1287, 1268 (COC); 1133-1189 (CF).

The comparative poly (biphenylene oxide)
(KR 10-2003-0049785) The poly (biphenylene oxide) Glass transition temperature 154 ℃  169 ° C Refractive index 1.61 1.50

Preparation of poly (biphenylene oxide) copolymer (1)

0.6017 g (1.71 mmol) of 3'-hydroxy-4-nitro-2,6-bis (trifluoromethyl) biphenyl, 0.2010 g (0.57 mmol) of biphenyl and 0.346 g (2.506 mmol) of potassium carbonate were dissolved in 4 mL of N-methylpyrrolidone and stirred at 135 ° C for 3 hours to form phenoxide. At this time, a constant amount of toluene was continuously added to continuously remove water generated during the reaction through an azeotropic process. The reaction temperature was raised to 175 ° C., and the reaction was carried out for 14 hours. The reaction product was precipitated in excess water and recovered. The reaction product was washed several times with hot water and methanol and dried to obtain a pale yellow poly (biphenylene oxide) copolymer (0.68934 g; Yield = 99%). FTIR (KBr, cm ^-1 ): 1605, 1584 (aromatic C = C); 1293, 1261, 1233 (COC); 1136-1186 (CF).

Preparation of poly (biphenylene oxide) copolymer (2)

(1.48 mmol) of 4'-hydroxy-4-nitro-2,6-bis (trifluoromethyl) biphenyl, 3'- (0.75 mmol) of potassium carbonate and 0.348 g (2.518 mmol) of potassium carbonate were dissolved in 4 mL of N-methylpyrrolidone and stirred at 135 占 폚 for 3 hours to form phenoxide. At this time, a constant amount of toluene was continuously added to continuously remove water generated during the reaction through an azeotropic process. The reaction temperature was raised to 175 ° C and allowed to react for 14 hours, then precipitated in excess water and recovered, washed several times with hot water and methanol, and dried. The resulting polymer was dissolved in tetrahydrofuran and then re-dissolved in methanol to obtain a brown poly (biphenylene oxide) copolymer (0.6325 g; yield = 93%).

FTIR (KBr, cm ^-1 ): 1605, 1584 (aromatic C = C); 1294, 1261, 1232 (COC); 1134-1187 (CF).

_{^{1 H NMR (DMSO-d 6}} , 400 MHz, ppm): 7.71 (4H), 7.63 (2H), 7.53 (1H), 7.37 (4H), 7.31 (1H), 7.20 (5H), 7.11 (1H).

Preparation of poly (biphenylene oxide) copolymer (3)

4-nitro-4-nitro-2,6-bis (trifluoromethyl) biphenyl was obtained by reacting 0.4004 g (1.14 mmol) of 4'- (1.14 mmol) of potassium carbonate and 0.348 g (2.518 mmol) of potassium carbonate were dissolved in 4 mL of N-methylpyrrolidone and stirred at 135 占 폚 for 3 hours to form phenoxide. At this time, a constant amount of toluene was continuously added to continuously remove water generated during the reaction through an azeotropic process. The reaction temperature was raised to 175 ° C and allowed to react for 14 hours, then precipitated in excess water and recovered, washed several times with hot water and methanol, and dried. The resulting polymer was dissolved in tetrahydrofuran and then re-dissolved in methanol to obtain a brown poly (biphenylene oxide) copolymer (0.5538 g, yield = 80%).

FTIR (KBr, cm ^-1 ): 1606, 1583 (aromatic C = C); 1294, 1261, 1230 (COC); 1133-1188 (CF).

_{^{1 H NMR (DMSO-d 6}} , 400 MHz, ppm): 7.71 (2H), 7.63 (2H), 7.53 (1H), 7.37 (2H), 7.31 (1H), 7.20 (3H), 7.11 (1H).

Preparation of poly (biphenylene oxide) copolymer (4)

(0.571 mmol), 3'-hydroxy-4-nitro-2,6-bis (trifluoromethyl) (1.71 mmol) and potassium carbonate (0.348 g, 2.518 mmol) were dissolved in 4 mL of N-methylpyrrolidone, and the mixture was stirred at 135 占 폚 for 3 hours to form phenoxide. At this time, a constant amount of toluene was continuously added to continuously remove water generated during the reaction through an azeotropic process. The reaction temperature was raised to 175 ° C and allowed to react for 14 hours, then precipitated in excess water and recovered, washed several times with hot water and methanol, and dried. The resulting polymer was dissolved in tetrahydrofuran and then re-dissolved in methanol to obtain a brown poly (biphenylene oxide) copolymer (0.57457 g, yield = 83%).

FTIR (KBr, cm ^-1 ): 1607, 1583 (aromatic C = C); 1293, 1262, 1227 (COC); 1136-1188 (CF).

_{^{1 H NMR (DMSO-d 6}} , 400 MHz, ppm): 7.71 (2H), 7.63 (6H), 7.52 (3H), 7.37 (2H), 7.27 (3H), 7.19 (5H), 7.11 (3H).

Comparison of physical properties of poly (biphenylene oxide) and poly (biphenylene oxide) copolymers

As shown in Table 1, the poly (biphenylene oxide) of the present invention in which two trifluoromethyl groups are substituted has a high crystallinity, so that the melting temperature can be observed. Also, by controlling the ratio of the poly (biphenylene oxide) copolymer, the crystallinity of the polymer is lowered to obtain a polymer having a high molecular weight. In the polymer, only a clear glass transition temperature is observed without the melting temperature. Also, as shown in Table 2, the poly (biphenylene oxide) of the present invention does not show good solubility in an organic solvent, but the poly (biphenylene oxide) copolymer shows a very good solubility in an organic solvent. In the case of Examples 9, 10 and 11, the poly (biphenylene oxide) copolymer is prepared by reacting the poly (biphenylene oxide) copolymer with N, N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), tetrahydrofuran And a nonpolar organic solvent such as ethyl acetate. Thus, a polymer capable of forming a strong film was obtained.

M _n
(X 10 ³ ) M _w
(X 10 ³ ) PDI
5% weight reduction temperature 10% weight reduction temperature T _g
(° C) T _m
(° C) Nitrogen stream Air stream Nitrogen stream Air stream Example 6 - - - 430 398 486 465 - 405 Example 7 9.3 ^s 20.8 ^s 2.23 ^s 394 377 516 474 169 337 Example 8 9.3 ^s 26.4 ^s 2.85 ^s 500 457 542 511 208 403
429 Example 9 34.9 58.6 1.68 432 416 522 499 192 - Example 10 70.6 143.3 2.03 505 475 534 516 187 - Example 11 24.6 42.0 1.70 463 399 521 480 176 -

S means the melting portion of each polymer.

Example 6 Example 7 Example 8 Example 9 Incidental example 10 Example 11 toluene - - - + - - ++ Nucleic acid - - - - - - CHCl ₃ - + - - ++ + - ++ THF - + - + - ++ ++ ++ EA - - - + - ++ ++ Cyclohexanone - + - - ++ ++ ++ Acetone - - - + - ++ ++ Acetonitrile - - - - - - Anisol - + - - ++ + - + - Methanol - - - - - - Diethyl ether - - - - - + - 1,4-dioxane - + - + - ++ ++ ++ DMAc - + - - + - ++ ++ DMF - + - + - ++ ++ ++ DMSO - + - - + - + - + - NMP - + - + - ++ ++ ++ DMPU - + - + - ++ ++ ++ ODCB - + - + - ++ + - ++

* Solubility: ++ Good recording at room temperature, + - Partial recording, - Not recording

CHCl _3: chloroform

THF: tetrahydrofuran

EA: ethyl acetate

DMAc: N, N-dimethylacetamide

DMF: N, N-dimethylformamide

DMSO: Dimethyl sulfoxide

NMP: N-methylpyrrolidone

DMPU: 1,3-dimethyltetrahydropyrimidin-2 ( 1H ) -one

ODCB: o -dichlorobenzene

In addition, as shown in Table 3, the synthesized polymer exhibits low birefringence with low refractive index in all cases. This is due to the fact that the two large trifluromethyl groups interfere with the crystallization of the polymers as well as the low polarizability of the fluorine atoms contained in the polymer.

n _TE n _TM Birefringence Thickness (μm) Example 9 1.5084 1.4988 0.0096 4.15 Example 10 1.5028 1.4880 0.0148 6.50 Example 11 1.5052 1.4957 0.0095 4.51

n _TE : in-plane refractive index, n _TM : out-of-plane refractive index, birefringence = n _TE -n _TM

Having described specific portions of the present invention in detail, those skilled in the art will appreciate that these specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby Will be clear. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (7)

A poly (biphenylene oxide) comprising a repeating unit represented by the following formula (1).
[Chemical Formula 1]

In Formula 1, n is an integer of 2 or more and 20,000 or less.
A monomer represented by the following general formula (8) for producing the poly (biphenylene oxide) of claim 1.
[Chemical Formula 8]

A process for preparing a poly (biphenylene oxide) of formula (1) according to claim 1, comprising the steps of:
(a) dissolving the monomer of formula (8) of claim 2 in a polar aprotic solvent, adding potassium carbonate to the solution, and stirring at 80 to 150 ° C to form a phenoxide salt; And
(b) a step of raising the temperature of the solution in which the salt is formed to 80 to 190 ° C and stirring.
4. The process of claim 3, wherein the polar aprotic solvent is selected from the group consisting of N-methylpyrrolidone, dimethylsulfoxide, N, N-dimethylacetamide, N, N- dimethylformamide, diphenylsulfone, 1,3-dimethyltetrahydropyrimidin-2 (1 H ) -one, and hexamethylphosphoramide. ≪ Desc / Clms Page number 20 >
A poly (biphenylene oxide) copolymer comprising a repeating unit represented by the following formula (11).
(11)

In Formula 11, n and m are an integer of 2 or more and 10,000 or less.
A process for preparing a poly (biphenylene oxide) copolymer of formula (11) according to claim 5 comprising the steps of:
(a) a monomer of the following formula (9) and a monomer of the following formula (10) are dissolved in a polar aprotic solvent at a ratio of 100: 1 to 1: 100, potassium carbonate is added to the solution, To form a phenoxide salt; And
(b) a step of raising the temperature of the solution in which the salt is formed to 80 to 190 ° C and stirring.
[Chemical Formula 9]

[Chemical formula 10]

7. The process of claim 6 wherein the polar aprotic solvent is selected from the group consisting of N-methyl pyrrolidone, dimethyl sulfoxide, N, N-dimethylacetamide, N, N- dimethylformamide, diphenylsulfone, sulfolane, 1,3-dimethyltetrahydropyrimidin-2 (1 H ) -one, and hexamethylphosphoramide. 2. A process for preparing a poly (biphenylene oxide) copolymer comprising the steps of:

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