JP3440110B2 - Bisphenol derivatives and their production - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel bisphenol derivative and a method for producing the same. More specifically, the present invention is useful as a raw material for high molecular weight polymers used for substrates for optical recording media such as polycarbonate, aromatic polyesters, epoxy resins, polysulfones, optical members, retardation compensation films and the like. The present invention relates to a bisphenol derivative and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Conventionally, bisphenol derivatives obtained by the reaction of phenols with aldehydes or ketones are important compounds as raw materials for various high molecular weight polymers such as polycarbonate, epoxy resin, aromatic polyester, polysulfone and the like. In particular, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) obtained from phenol and acetone is used in large amounts as a raw material for the polymer. In addition, a large number of bisphenol derivatives have been developed to meet various uses of high molecular weight polymers.
Those obtained by selecting the aldehydes or ketones that are the raw materials of the bisphenol derivative include:
1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), 1,1-bis (4-hydroxyphenyl) methane (bisphenol F), 4,4′-
Dihydroxytetraphenylmethane (bisphenol T
P) and the like are known. Further, what is obtained by selecting phenols as a raw material of the bisphenol derivative is 2,2-bis (4-hydroxy-3-) having an alkyl group, an aryl group and a halogen atom in the benzene ring of the bisphenol derivative. Methylphenyl) propane (bisphenol C), 2,2-bis (4-hydroxy-3-cyclohexylphenyl) propane (bisphenol CH), 2,2-bis (4-hydroxy-3-phenylphenyl) propane (bisphenol PH) , 9,
9-bis (4-hydroxyphenyl) fluorene (bisphenol FL) and the like are known. Among these bisphenol derivatives, 4,4'-dihydroxytetraphenylmethane (bisphenol TP), 2,2-bis (4-hydroxy-3-phenylphenyl) propane (bisphenol PH), 9,9-bis (4 -Hydroxyphenyl) fluorene (bisphenol FL) and the like have many phenyl groups, and a high-molecular polymer synthesized from these bisphenol derivatives as a raw material has a large number of phenyl groups in the direction orthogonal to the polymer main chain. Due to the presence of aryl groups such as phenyl groups, it is known to have excellent heat resistance and optical properties, and the development of bisphenol derivatives having more aryl groups such as phenyl groups in the molecule has been desired. .

[0003]

The object of the present invention is to provide a novel bisphenol derivative having more aryl substituents such as phenyl group than bisphenol TP, bisphenol PH and bisphenol FL, and a suitable production method thereof. And

[0004]

Means for Solving the Problems That is, the present invention has the following general formula:

[0005]

[Chemical 5] (Where X is

[0006]

[Chemical 6] And Ar each independently represents an unsubstituted aryl group having 6 to 12 carbon atoms, and R ¹ , R ² , R ³ and R ⁴ each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms or a carbon atom. Represents an unsubstituted aryl group of the formulas 6 to 12, a and b each independently represent an integer of 0 to 4, c and d each independently represent an integer of 0 to 6, Z is a single bond, -O. -, -CO
-, - S- or -SO ₂ - represent. ) Is provided. The bisphenol derivative of the present invention is a novel compound, which is useful as a raw material for high molecular weight polymers such as polycarbonate, epoxy resin, aromatic polyester, and polysulfone, and is used as a substrate for optical recording media, an optical member, and a retardation compensation film. It is preferably used as a raw material for the high-molecular polymer used.

The bisphenol derivative of the present invention has, for example, the following general formula:

[0008]

[Chemical 7] (Wherein Ar is the same as above) and a phenol represented by the following general formula

[0009]

[Chemical 8] (In the formula, R ¹ , R ² , R ³ , R ⁴ , Z, a, b, c and d are the same as the above), and can be produced by reacting.

Examples of the phenols used in the present invention include o-phenylphenol and o- (4-methylphenyl) phenol. Usually, o-phenylphenol is preferably used.

The carbonyl compound used in the present invention includes, for example, fluorenone, anthrone, pentacenone and the like, and usually fluorenone is preferably used.

The reaction between the phenols and the carbonyl compound may be carried out without using a solvent or may be carried out using a solvent. As the solvent to be used, those inert to the reaction, for example, aromatic hydrocarbon solvents such as benzene, toluene, xylene and the like are preferable.

The catalyst is an acidic catalyst such as hydrogen chloride,
Sulfuric acid, toluenesulfonic acid, trifluoromethanesulfonic acid, oxalic acid, phosphorus pentachloride, polyphosphoric acid and the like are used, but among these, hydrogen chloride is particularly preferable from the viewpoint of accelerating the reaction and ease of post-treatment. .

The amount of these catalysts used cannot be unconditionally specified because it depends on the type of catalyst used, but when hydrogen chloride is used, it is usually 0.5 to 10 relative to the total amount of phenols and carbonyl compounds. weight%
It is selected in the range of.

In this reaction, it is preferable to use a compound containing a mercapto group as a cocatalyst together with the acidic catalyst. Examples of the compound containing a mercapto group include methyl mercaptan, ethyl mercaptan,
Examples thereof include alkyl mercaptans such as propyl mercaptan, butyl mercaptan, octyl mercaptan, and dodecyl mercaptan, aromatic mercaptans such as thiophenol and thiocresol, and mercapto organic acids such as mercaptoacetic acid (thioglycolic acid) and mercaptopropionic acid. When using these promoters,
It is usually used in the range of 0.1 to 5% by weight based on the total amount of phenols and carbonyl compounds.

Regarding the use ratio of the phenols and the carbonyl compound, it is preferable to use the phenols in excess of the theoretical amount, and usually, the phenols are used in a ratio of 2.2 to 6 mols per mol of the carbonyl compound.

The reaction temperature varies depending on the type of phenols, carbonyl compound and catalyst used,
Although it cannot be specified unconditionally, it is generally selected in the range of 20 to 150 ° C. The reaction pressure is not particularly limited and may be any of reduced pressure, normal pressure and increased pressure, but it is usually advantageous to carry out the reaction under normal pressure. Further, the reaction time is usually about 5 to 200 hours, though it depends on the kinds of raw materials, the kinds and amounts of the catalyst and the cocatalyst, and the reaction temperature.

The obtained bisphenol derivative is useful as a raw material for high molecular weight polymers such as polycarbonate, epoxy resin, aromatic polyester and polysulfone.

For example, a polycarbonate is obtained by reacting the bisphenol derivative with phosgene by a known method. Furthermore, an epoxy resin is obtained by reacting the bisphenol derivative with epichlorohydrin by a known method. In addition, an aromatic polyester is obtained by condensing the bisphenol derivative with an aromatic polycarboxylic acid such as terephthalic acid by a known method, and a polysulfone is obtained by condensing the aromatic polyester with di- (4-chlorophenyl) sulfone.

[0020]

The present invention will be described in more detail below with reference to examples of the present invention and comparative examples thereof, but the present invention is not limited to these examples.

Example 1 510 g (3 mol) of o-phenylphenol and 180 g (1 mol) of fluorenone were mixed and heated to about 90 ° C. to melt, then 10 g of mercaptoacetic acid was added and hydrogen chloride was stirred. The gas was blown in for 30 hours. The reaction mixture was washed 3 times with warm water of about 70 ° C. and the organic phase was washed with 1
The mixture was heated to 190 ° C. under a reduced pressure of 4 mmHg to evaporate the evaporate to obtain 300 g of distillation residue. Then, this was dissolved in 500 ml of methylene chloride, 600 ml of a 2N sodium hydroxide aqueous solution was added, and the mixture was vigorously stirred, followed by cooling with ice to precipitate crystals. The crystals were washed twice with 400 ml of methylene chloride and then with an ice-cooled 2N sodium hydroxide aqueous solution. The crystals were dispersed in 2 liters of 1N hydrochloric acid, stirred vigorously, and dried under reduced pressure to obtain 9,9-bis (4
200 g of -hydroxy-3-phenyl) fluorene (bisphenol derivative) was obtained.

The yield of the obtained bisphenol derivative was 40% based on fluorenone.

¹ H-NMR (acetone d-6 / TMS)
δ (ppm) is 6.9 (d2H), 7.0 (dd2)
H), 7.1 (d2H), 7.3 (m6H), 7.4.
(Dd4H), 7.3-7.6 (m6H), 7.8 (m
2H). The molecular weight (H ⁺ ) was 502.

Application Example 1 70 g (0.25 mol) of bisphenol A was dissolved in 550 ml of an 8% strength sodium hydroxide aqueous solution, and 250 ml of this and methylene chloride were introduced into a reactor with a baffle plate.
900 ml / with vigorous stirring while maintaining at around 0 ° C
Phosgene gas was blown in for 15 minutes at a rate of min. After the gas blowing was stopped, the mixture was allowed to stand and separate to obtain a methylene chloride solution of an oligomer of a polycarbonate having a chloroformate terminal and a polymerization degree of 2 to 3.

Next, 245 ml of this oligomer solution was diluted to 450 ml with methylene chloride, and 33.6 g (0.067 mol) of 9,9-bis (4-hydroxy-3-phenyl) fluorene obtained in Example 1 was diluted. In 150 ml of 10% aqueous potassium hydroxide solution, p-tert-butylphenol 0.1 as a terminal stopper (molecular weight modifier)
5 g and 3 m of 10% triethylamine aqueous solution as a catalyst
1 was introduced into a reactor equipped with a baffle, and the polycondensation reaction was carried out with vigorous stirring.

After completion of the reaction, 1 liter of methylene chloride was added to the organic layer to dilute it, and the organic layer was washed with water, diluted hydrochloric acid and water in this order and then poured into methanol to obtain a polycarbonate polymer.

The polymer thus obtained had a reduced viscosity [η _sp / c] of 0.78 dl / g at 20 ° C. in a solution of methylene chloride in a concentration of 0.5 g / dl. Further, the ¹ H-NMR spectrum analysis revealed that the content of the structural unit derived from 9,9-bis (4-hydroxy-3-phenyl) fluorene was 15 mol% and the glass transition temperature was 181 ° C.

Application Example 2 9,9-bis (4-hydroxy-3) obtained in Example 1
-Phenyl) fluorene 126 g (0.25 mol), 10% concentration aqueous potassium hydroxide solution 550 ml, methylene chloride 400 ml, p as a terminal stopper (molecular weight regulator)
-Tert-Butylphenol 0.15 g and 10% triethylamine aqueous solution 3 ml as a catalyst were introduced into a reactor equipped with a baffle, and phosgene gas was added at a rate of 340 ml / min while maintaining the temperature of the reaction liquid at around 10 ° C.
The polycondensation reaction was carried out while blowing for a minute and stirring vigorously.

After the reaction was completed, 1 liter of methylene chloride was added to the organic layer to dilute it, and the organic layer was washed with water, diluted hydrochloric acid and water in this order, and then poured into methanol to obtain a polycarbonate polymer.

The polymer thus obtained had a reduced viscosity [η _sp / c] of 0.80 dl / g at 20 ° C. in a solution of methylene chloride in a concentration of 0.5 g / dl, and had a glass transition. The temperature was 258 ° C.

[0031]

The bisphenol derivative of the present invention is a novel compound obtained by condensing a specific phenol and a carbonyl compound in the presence of an acidic catalyst, has a large number of aryl groups, and has a heat-resistant use. It is also useful as a polymer raw material suitable for optical applications.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI C07D 335/10 C07D 335/10 C08G 64/06 C08G 64/06 (58) Fields investigated (Int.Cl. ⁷ , DB name) C07C 13/547 C07C 39/17 C07C 37/20 C07D 311/78 C07D 311/80 C07D 335/04 C07D 335/10 C08G 64/06 CAPLUS (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. The following general formula: (In the formula, X is And Ar each independently represents an unsubstituted aryl group having 6 to 12 carbon atoms, and R ¹ , R ² , R ³ and R ⁴ each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms or a carbon atom. Represents an unsubstituted aryl group of the formulas 6 to 12, a and b each independently represent an integer of 0 to 4, c and d each independently represent an integer of 0 to 6, Z is a single bond, -O. -, -CO
-, - S- or -SO ₂ - represent. ) A bisphenol derivative represented by. 2. The following general formula: (Wherein Ar represents an unsubstituted aryl group having 6 to 12 carbon atoms), and a phenol represented by the following general formula: (In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms or an unsubstituted aryl group having 6 to 12 carbon atoms; And b are independently 0 to
4 represents an integer of 4, c and d each independently represent an integer of 0 to 6, and Z represents a single bond, -O-, -CO-, -S- or -SO _2- . 3. A method for producing a bisphenol derivative according to claim 1, wherein a carbonyl compound represented by the formula (1) is reacted.