JPH08127554A - 3,3'-diphenyl-4,4'-dihydroxybiphenyl derivative and method for producing the same - Google Patents

Abstract

(57) [Abstract] [Objective] 3,3'-diphenyl-4,4'-dihydroxybiphenyl derivative having excellent performance as a monomer of high-performance polymer, especially plastic for optical lens and plastic for optical disk, and method for producing the same I will provide a. [Structure] 3,3'-diphenyl-4,4'-dihydroxybiphenyl is reacted with an alkylene carbonate, an alkylene oxide or a halogenoalkanol, and then acrylic acid, methacrylic acid or an acid halide thereof is reacted to give a compound of the general formula ( 1) [Chemical 1] [In general formula (1), R ₁ and R ₂ are a hydrogen atom or a methyl group, m and n are an integer of 1 to 10, shown. ] The desired 3,3'-diphenyl-4,4'-dihydroxybiphenyl derivative represented by the following formula is produced.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to 3,3'-diphenyl-
The present invention relates to a 4,4'-dihydroxybiphenyl derivative and a method for producing the same. The compound provided by the present invention has excellent performance as a monomer for high-performance polymers, especially plastics for optical lenses and plastics for optical discs, and as a modifier for high-performance polymers, and is drawing attention.

[0002]

2. Description of the Related Art Conventionally, as resin components for plastic lenses, JP-A-60-11513 and JP-A-60-5500 are known.
No. 7, No. 61-127713, No. 61-183306
Various proposals have been made, but further improvement in performance is required in terms of water absorption resistance, solvent crack resistance, refractive index, birefringence, moldability, flexibility and the like.

[0003]

The present inventors have arrived at the present invention as a result of various researches on such demands. That is, according to the present invention, the general formula (1)

[0004]

Embedded image [In general formula (1), R ₁ and R ₂ are a hydrogen atom or a methyl group, m and n are an integer of 1 to 10, shown. ] 3,3'- diphenyl-4,4'- dihydroxy biphenyl derivative represented by these is provided. Furthermore, equation (3)

[0005]

[Chemical 6] By reacting 3,3'-diphenyl-4,4'-dihydroxybiphenyl represented by the following with ethylene carbonate or propylene carbonate, ethylene oxide or propylene oxide or halogenoalkanol,
General formula (2)

[0006]

[Chemical 7] [In the general formula (2), R ₁ , m and n are the same as defined in the general formula (1). ] 3,3'-diphenyl-
A bisalkylene glycol ether compound of 4,4′-dihydroxybiphenyl is produced, and this compound is further reacted with acrylic acid, methacrylic acid, or an acid halide thereof to obtain 3,3 ′ represented by the general formula (1). Methods for making -diphenyl-4,4'-dihydroxybiphenyl and derivatives are provided.

The 3,3'-diphenyl-4,4'-dihydroxybiphenyl derivative represented by the general formula (1) does not contain a halogen atom such as bromine as a monomer for a plastic lens and has a high refractive index. It produces a polymer for lenses that is excellent in weather resistance, water absorption resistance, solvent crack resistance, moldability, and the like.

Next, the manufacturing method of the present invention will be described.

3,3'-diphenyl-4,4'-dihydroxybiphenyl (abbreviated as DHQ-O) represented by the formula (3) is prepared by dissolving 2-phenyl-4-bromophenol in a methanol solvent in an alkali and In the presence of a palladium catalyst,
It can be produced by a debromination dimerization reaction.

The compound represented by the formula (2) (DHQ-O-
Abbreviated as AO) is DHQ-O and ethylene carbonate,
Reacting with ethylene oxide, propylene carbonate or propylene oxide in the presence of a suitable catalyst, or a halogenoalkanol such as 2-chloroethanol, 3-chloro-2-propanol, 2- (2-chloroethoxy) ethanol, 2- It is produced by reacting with [2- (2-chloroethoxy) ethoxy) ethanol or the like in the presence of an acid scavenger. Next, their reaction formulas are shown.

[0011]

Embedded image [In the reaction formula, R ₁ is a hydrogen atom or a methyl group, X is a halogen atom, m and n are integers of 1 to 10, and p is 0, 1
Indicates an integer of -9. ] The reaction represented by the formula 1) will be described later. The reaction shown in Formula 2) is usually carried out in an inert solvent in DH.
Q-O and the selected number of moles of alkylene oxide corresponding to the numerical value of (m + n) (actually a small excess thereof),
It is carried out by heating in a closed reactor in the presence of a catalyst (organic or inorganic base). The reaction shown in Formula 3) is usually carried out by using DHQ-O in an inert solvent and the same amount of halogenoalkanol as in Formula 2) in the presence of an acid scavenger (organic or inorganic base) in a closed reactor. This is done by heating down.

In the above three reactions, the reaction of the formula 2) requires a technique for controlling the number of moles of alkylene oxide added,
The reaction of the formula 3) has a slow reaction rate and requires a technique for suppressing side reactions (in particular, self-ring closure reaction and self-polymerization reaction). On the other hand, the reaction of the formula 1) has a high reaction rate, and the control of the number of added moles is also a container.

Then, DHQ-O is reacted with ethylene carbonate according to the formula 1) to give DHQ-of the general formula (2).
A bis (2-hydroxyethyl ether) compound of O (abbreviated as DHQ-O-EO) is produced, and then the compound is reacted with acrylic acid to prepare a bisacrylic acid ester of DHQ-O-AO (DHQ-AO). An embodiment of the present invention will be described by taking the case of manufacturing (-AC) as an example.

A reactor equipped with a stirrer, a thermometer, a reflux condenser and a charging port is charged with DHQ-O, ethylene carbonate and an inert solvent. The amount of ethylene carbonate used is determined by the number of moles added to DHQ-O. For example, in the general formula (1), 2 mol per 1 mol of DHQ-O when m = n = 1, 4 mol when m = n = 2, and 10 mol or less when m = n = 5. Of ethylene carbonate is used. In practice, the amount used is 1.05 to 2 times, preferably 1.2 to 1.5 times.

The inert solvent is usually used in an amount of 1 to 100 parts, preferably 3 to 20 parts, per 1 part (weight, hereinafter the same) of DHQ-O. The solvent is DHQ-O or / and DHQ-O-
It is not always necessary to completely dissolve EO, and the reaction proceeds sufficiently even in a suspended state. As the inert solvent, ether compounds such as ethylene glycol di-lower alkyl ether, aromatic compounds such as benzene, toluene and xylene,
Examples include non-aqueous polar solvents such as N, N-dimethylacetamide and sulfolane.

The above mixture is heated to reflux temperature or 50 to 130 ° C. with stirring and the catalyst is added. As the catalyst, a basic compound such as an alkali metal hydroxide or carbonate is used. The amount used is 0.1 to DHQ-O.
10% (weight, the same unless otherwise specified). The reaction time is usually 1 to 15 hours, preferably 3 to 6 hours. After completion of the reaction, the reaction mixture is cooled, filtered, washed and dried to obtain DHQ-O-EO.

Then, DHQ-O-EO, a polymerization inhibitor, acrylic acid, a catalyst and an inert solvent are charged into a reactor equipped with a stirrer, a thermometer, an oil / water separator and a reflux condenser.

Acrylic acid is used in an amount of 2 mol equivalent to 1 mol of DHQ-O-EO. As the inert solvent, the same one as in the production of DHQ-O-AO is used. As the catalyst, an acid used in a usual esterification reaction, for example, sulfuric acid, hydrochloric acid, p-toluenesulfonic acid or a strongly acidic ion exchange resin is used. The usage is DHQ
It is usually 2 to 15% with respect to -O-EO.

The polymerization inhibitor is used to prevent acrylic acid itself from being polymerized by heating, and hydroquinone, p-tert-butylcatechol and the like are used, and the amount thereof is 1 to 20 with respect to acrylic acid. %. The reaction temperature varies depending on the solvent used, but is usually 80 to 20.
The temperature is 0 ° C., preferably 100 to 150 ° C., but it is preferable to carry out the reaction while azeotropically removing the reaction product water by an oil-water separator under reflux. The end of the reaction is recognized by the fact that no further water separation can be observed from the oil / water separator. After some aging time, the reaction mixture was cooled, neutralized and washed with weak alkaline water, washed with water, and then the solvent was distilled off preferably under reduced pressure to obtain the desired product DHQ-O-EO-AC. obtain.

[0020]

EXAMPLES Next, examples of the present invention will be described. Example 1 In a 1.000 ml reactor (stirrer, reflux condenser with oil / water separator, thermometer and charging equipment), 300 g of xylene,
33.8 g (0.1 mol) of DHQ-O and 26.0 g (0.3 mol) of ethylene carbonate were charged, and 1 with stirring.
At 20 to 130 ° C., 3 g of anhydrous potassium carbonate powder was added over about 30 minutes. After the addition was completed, the temperature was kept at the same temperature for 5 hours for reaction. The reaction mixture was cooled, the precipitate was filtered off, washed with water, washed with 50 ml of methanol and dried at about 80 ° C. to obtain 32 g of DHQ-O-EO as an off-white crystalline powder. Yield 74.7% [vs DHQ-O, in general formula (2),
m = n = 1, R ₁ = H]. Melting point 171 [deg.] C.

In a 500 ml reactor (equipped with a stirrer, a reflux condenser with an oil / water separator and a thermometer), the DHQ-OE was placed.
O12.6g (0.03mol), acrylic acid 5.6g
(0.078 mol), 100 g of toluene, 1 g of sulfuric acid and 0.5 g of hydroquinone were charged, heated under reflux with stirring (108 to 110 ° C.), and reacted while separating generated water. After maintaining at the same temperature for 6 hours, the reaction mixture was cooled, 50 g of water was added and the mixture was washed with water, further washed with 50 g of a 5% sodium carbonate aqueous solution for neutralization, and again washed with 50 g of water.
After that, toluene was distilled off under reduced pressure to recover the light brown resinous object [in the general formula (1), R ₁ = R ₂ = H, m = n =
1] 12.7 g was obtained. Yield 80.4% (vs DHQ-O
-EO). Purity 94.6% (by liquid chromatography).

The elemental analysis values of this product are shown in Table 1.

Table 1 ────────────────────────────── C (%) H (%) ────── ──────────────────────── Measured value 76.01 5.80 Calculated value 76.39 5.66 (as C ₃₄ H ₃₀ O ₆ ) ─ ───────────────────────────── In addition, the infrared absorption spectrogram (KBr tablet method) of this product is shown in FIG.

Example 2 In a reactor similar to that of Example 1, 15.2 g of DHQ-O was added.
(0.045 mol), N-methylpyrrolidone (50 g) and toluene (20 g) were charged, and the mixture was added from a dropping funnel at about 90 ° C. to 2
21.6 g of 0% sodium hydroxide aqueous solution was added over 1 hour. Further heating was continued, and a dehydration reaction was carried out while azeotropically distilling toluene-water to produce a sodium salt of DHQ-O. After about 8 hours, it is cooled and then at about 30 ° C. 2- [2-
(2-chloroethoxy) ethoxy] ethanol 18 g
(0.107 mol) was added. The mixture was heated again and kept at about 145 ° C. for 10 hours, and then N-methylpyrrolidone and toluene were collected by distillation under reduced pressure. To the residue was added 100 g of toluene, 7.7 g of acrylic acid (0.106 mol), 0.5 g of hydroquinone and 1 g of sulfuric acid,
The reaction product water was removed to the outside of the system while heating under reflux at about 110 ° C., and the reaction was allowed to proceed for 24 hours.

After completion of the reaction, the reaction mixture was cooled, 50 g of ethyl acetate was added thereto, washed with 50 g of water, further washed with 50 g of 10% sodium carbonate aqueous solution, and then washed with 50 g of water. After that, toluene and ethyl acetate are distilled off under reduced pressure and recovered to obtain a light brown resinous target product at room temperature [in the general formula (1), R ₁ = R ₂ =
H, m = n = 3] was obtained. Yield 24.3g. Yield 76.
2% (vs DHQ-O). Purity 93.2% (by liquid chromatography).

The elemental analysis values of this product are shown in Table 2.

Table 2 ────────────────────────────── C (%) H (%) ────── ──────────────────────── Measured value 70.36 6.83 Calculated value 70.97 6.52 (as C ₄₂ H ₄₆ O ₁₀ ) ─ ───────────────────────────── In addition, the infrared absorption spectrogram of this product is shown in FIG.

Example 3 DHQ-O-EO obtained in the same manner as in Example 1
8.5 g (0.02 mol), methacrylic acid 4.1 g
(0.047 mol), 100 g of toluene, 1 g of sulfuric acid and 0.5 g of hydroxy were charged into a reactor similar to that used in the esterification reaction of Example 1, and the reaction product water was heated under reflux at 108 to 110 ° C. under stirring. The reaction was performed while removing it to the outside of the system. After reacting for 24 hours, the reaction mixture was cooled, 50 g of ethyl acetate was added, washed with 50 g of water, further washed with 10% aqueous sodium carbonate solution and then with 50 g of water, and distilled under reduced pressure to recover toluene and ethyl acetate. And a light brown resinous object [in the general formula (1), R ₁ = H, R ₂ = CH
₃ , m = n = 1] was obtained. Yield 6.2g. Yield 55.4
% (Vs. DHQ-O). Purity 91.1% (by liquid chromatography).

The elemental analysis values of this product were as shown in Table 3.

Table 3 ────────────────────────────── C (%) H (%) ────── ──────────────────────── Measured value 76.33 6.54 Calculated value 76.85 6.09 (as C ₃₆ H ₃₄ O ₆ ) ─ ───────────────────────────── In addition, the infrared absorption spectrogram of this product is shown in FIG.

[0031]

EFFECTS OF THE INVENTION 3,3'-Diphenyl-4,4'-, which has excellent performance as a monomer for high-performance polymers, particularly optical plastic lenses and plastics for optical disks, and as a modifier for high-performance polymers. Provided are a dihydroxybiphenyl derivative and a method for producing the same.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrogram of a DHQ-O derivative obtained in Example 1 (in the general formula (1), R ₁ = R ₂ = H, and m = n = 1).

FIG. 2 is an infrared absorption spectrogram of the DHQ-O derivative obtained in Example 2 (in the general formula (1), R ₁ = R ₂ = H, and m = n = 3).

FIG. 3 is an infrared absorption spectrogram of the DHQ-O derivative obtained in Example 3 [in the general formula (1), R ₁ = H, R ₂ = CH ₃ , and m = n = 1]. In each figure, the vertical axis represents transmittance (%) and the horizontal axis represents wavelength (cm ^-1 ).
Are shown respectively.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 9, 1995

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction content]

[0006]

[Chemical 7] [In the general formula (2), R ₁ , m and n are the same as defined in the general formula (1). ] 3,3'-diphenyl-
A bisalkylene glycol ether compound of 4,4′-dihydroxybiphenyl is produced, and this compound is further reacted with acrylic acid, methacrylic acid, or an acid halide thereof to obtain 3,3 ′ represented by the general formula (1). A method of making a -diphenyl-4,4'-dihydroxybiphenyl derivative is provided.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction content]

In the above three reactions, the reaction of the formula 2) requires a technique for controlling the number of moles of alkylene oxide added,
The reaction of the formula 3) has a slow reaction rate and requires a technique for suppressing side reactions (in particular, self-ring closure reaction and self-polymerization reaction). In contrast 1) of the reaction is faster the reaction rate, the control of the molar number of addition is also easy.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

Then, DHQ-O is reacted with ethylene carbonate according to the formula 1) to give DHQ-of the general formula (2).
O bis (2-hydroxyethyl ether) compound (manufactured (DHQ-O-EO hereinafter), followed by reacting said compound with acrylic acid, DHQ-O-E-bis acrylic esters of O (DHQ- The embodiment of the present invention will be described by taking the case of producing AO-AC) as an example.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

A reactor equipped with a stirrer, a thermometer, a reflux condenser and a charging port is charged with DHQ-O, ethylene carbonate and an inert solvent. The amount of ethylene carbonate used is determined by the number of moles added to DHQ-O. For example, in the general formula (1), 2 mol per 1 mol of DHQ-O when m = n = 1, 4 mol when m = n = 2, 10 mol when m = n = 5 , A similar amount of ethylene carbonate is used. In practice, the amount used is 1.05 to 2 times, preferably 1.2 to 1.5 times.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

Acrylic acid is used in an amount of 2 mol equivalent to 1 mol of DHQ-O-EO. Inert solvents are the same as in the preparation of the above DHQ-O-E O is used. As the catalyst, an acid used in a usual esterification reaction, for example, sulfuric acid, hydrochloric acid, p-toluenesulfonic acid or a strongly acidic ion exchange resin is used. The usage is DHQ
It is usually 2 to 15% with respect to -O-EO.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

[0020]

EXAMPLES Next, examples of the present invention will be described. Example 1 In a 1,000 ml reactor (stirrer, reflux condenser with oil / water separator, thermometer and charging equipment), 300 g of xylene,
33.8 g (0.1 mol) of DHQ-O and 26.0 g (0.3 mol) of ethylene carbonate were charged, and 1 with stirring.
At 20 to 130 ° C., 3 g of anhydrous potassium carbonate powder was added over about 30 minutes. After the addition was completed, the temperature was kept at the same temperature for 5 hours for reaction. The reaction mixture was cooled, the precipitate was filtered off, washed with water, washed with 50 ml of methanol and dried at about 80 ° C. to obtain 32 g of DHQ-O-EO as an off-white crystalline powder. Yield 74.7% [vs DHQ-O, in general formula (2),
m = n = 1, R ₁ = H]. Melting point 171 [deg.] C.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

In a 500 ml reactor (equipped with a stirrer, a reflux condenser with an oil / water separator and a thermometer), the DHQ-OE was placed.
O12.6g (0.03mol), acrylic acid 5.6g
(0.078 mol), 100 g of toluene, 1 g of sulfuric acid and 0.5 g of hydroquinone were charged, heated under reflux with stirring (108 to 110 ° C.), and reacted while separating generated water. After maintaining at the same temperature for 6 hours, the reaction mixture was cooled, 50 g of water was added and the mixture was washed with water, further washed with 50 g of a 5% sodium carbonate aqueous solution to neutralize, and again washed with 50 g of water.
After that, toluene was distilled off under reduced pressure to recover the light brown resinous object [in the general formula (1), R ₁ = R ₂ = H, m = n =
1] 12.7 g was obtained. Yield 80.4% (vs DHQ-O
-EO). Purity 94.6% (by liquid chromatography).

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction content]

Example 3 DHQ-O-EO obtained in the same manner as in Example 1
8.5 g (0.02 mol), methacrylic acid 4.1 g
(0.047 mol), toluene 100 g, a sulfuric acid 1g and <br/> hydroxamate non 0.5g, were charged into a reactor similar to the esterification reaction of Example 1, stirring with heating under reflux at 108-110 ° C. , The reaction product water was removed from the system to carry out the reaction. After reacting for 24 hours, the reaction mixture was cooled, 50 g of ethyl acetate was added, washed with 50 g of water, further washed with 10% aqueous sodium carbonate solution and then with 50 g of water, and distilled under reduced pressure to recover toluene and ethyl acetate. And a light brown resinous object [in the general formula (1), R ₁ = H, R ₂ = CH
₃ , m = n = 1] was obtained. Yield 6.2g. Yield 55.4
% (Vs. DHQ-O). Purity 91.1% (by liquid chromatography).

Claims (7)

[Claims] 1. A compound represented by the general formula (1): [In general formula (1), R ₁ and R ₂ are a hydrogen atom or a methyl group, m and n are an integer of 1 to 10, shown. ] 3,3'- diphenyl-4,4'- dihydroxy biphenyl derivative represented by these. 2. In the general formula (1), R ₁ and R ₂ are hydrogen atoms, and m and n are 1 to 5, 3,3′-diphenyl-4,4′-. Dihydroxybiphenyl derivative. 3. In the general formula (1), R ₁ is a hydrogen atom, R ₂ is a methyl group, and m and n are 1 to 5, 3,3′-diphenyl-. 4,4'-
Dihydroxybiphenyl derivative. 4. A general formula (2): [In the general formula (2), R ₁ , m and n are the same as defined in the general formula (1). ] 3,3'-diphenyl-
The 3,3'-diphenyl-4,4,4 according to claim 1, characterized in that a bisalkylene glycol ether compound of 4,4'-dihydroxybiphenyl is reacted with acrylic acid, methacrylic acid or an acid halide thereof. 4'-
Process for producing dihydroxybiphenyl derivative. 5. A formula (3): 3,3′-diphenyl-4,4′-dihydroxybiphenyl represented by the formula, and 3,3′-diphenyl-4, represented by the general formula (2), obtained by reacting ethylene carbonate or propylene carbonate. A bisalkylene glycol ether compound of 4'-dihydroxybiphenyl is reacted with acrylic acid, methacrylic acid or an acid halide thereof, 3,3 'represented by the general formula (1) according to claim 1. -Diphenyl-4,4'-
Process for producing dihydroxybiphenyl derivative. 6. The production method according to claim 5, wherein ethylene oxide or propylene oxide is reacted instead of ethylene carbonate or propylene carbonate. 7. Instead of ethylene carbonate or propylene carbonate, a compound represented by the general formula (4): [In the general formula (4), X is a halogen atom, and p is 0, 1 to 1
R ₁ represents an integer of 9 and has the same meaning as in formula (1). ] The manufacturing method of Claim 5 which makes halogenoalkanol shown by these react.