JP2001206862A - Fluorene compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new multi-functional type fluorene compound. SOLUTION: A fluorene compound characterized by being represented by the general formula (I) (R1 and R2 are each independently hydrogen or a 1 to 6C alkyl, and may be same or different each other), or a salt thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel fluorene compound and relates to a raw material for a polymer material or a resin material, for example,
Raw materials for thermoplastic resins such as polycarbonate and polyarylate, raw materials for thermosetting resins such as epoxy resins, curing agents,
The present invention relates to a novel fluorene compound useful as a modifier or the like.

[0002]

2. Description of the Related Art Bifunctional bisphenols are useful as fluorene compounds useful as raw materials for thermoplastic resins such as polycarbonate and polyarylate, raw materials for thermosetting resins such as epoxy resins, curing agents and modifiers, and the like. Although fluorene and the like are used, further improvements in various properties such as heat resistance, water resistance, chemical resistance, electrical properties, and mechanical properties are required. Therefore, there is a demand for a novel polyfunctional fluorene compound to meet such a demand.

[0003]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a 4- to 6-functional fluorene compound can solve the above-mentioned problems, and have completed the present invention.

[0004] The present invention relates to the following items 1 to 3. Item 1. The following general formula (I)

[0005]

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(Wherein, R ¹ and R ² each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms, and may be the same or different from each other) Or a salt thereof. Item 2. Item 4. The fluorene compound or the salt thereof according to item 1, wherein both R ¹ and R ² are hydrogen. Item 3. A method for producing a fluorene compound of the general formula (I), comprising reacting fluorene (1) with two catechol compounds (2) and (3).

[0007]

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[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the fluorene compound of the present invention, the positions of substituents of two phenyl groups may be different, but are preferably the same.

The alkyl group having 1 to 6 carbon atoms has a straight or branched chain such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl and hexyl. And an alkyl group.

R ¹ and R ² are preferably both hydrogen.

The preferred fluorenone of the present invention is shown below.・ 9,9-bis- (3 ′, 4′-dihydroxyphenyl) -fluorene ・ 9,9-bis- (2 ′, 4′-dihydroxyphenyl) -fluorene ・ 9,9-bis- (3 ′, 5 '-Dihydroxyphenyl) -fluorene 9,9-bis- (2', 3'-dihydroxyphenyl) -fluorene 9,9-bis- (2 ', 6'-dihydroxyphenyl) -fluorene 9,9- Bis- (2 ′, 5′-dihydroxyphenyl) -fluorene The salt of a fluorene compound is prepared by dissolving a fluorene compound in a suitable solvent, and adding 1 or 2 equivalents of a base (alkali metal hydroxide, alkali metal hydride, alkali metal alkoxide). ) And evaporating the solvent.

The fluorene compound of the general formula (I) of the present invention can be produced, for example, according to the following reaction scheme 1. <Reaction process formula 1>

[0013]

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Wherein R ¹ and R ² are as defined above. Fluorenone (1) and catechol (2), (3) are converted to thioacetic acid or β.
-The desired fluorene compound (I) can be obtained by reacting in the presence of mercaptopropionic acid and an acid catalyst (hydrochloric acid or sulfuric acid).

In the reaction, catechol (2) or (3) is added in an amount of 1 mol to an excess each per mol of fluorenone (1), thioacetic acid or β-acid.
-Using appropriate amounts of mercaptopropionic acid and an acid catalyst;
The reaction proceeds advantageously at a temperature of 0 to 120 ° C. for about 20 minutes to 20 hours.

[0016]

The fluorene compound according to the present invention is a raw material of a polymer material or a resin material, for example, polycarbonate,
It is useful as a raw material of a thermoplastic resin such as polyarylate, a raw material of a thermosetting resin such as an epoxy resin, a curing agent, a modifier and the like.

In particular, the novel fluorene compound according to the present invention has four hydroxyl groups as functional groups and can form a cross-linked structure, so that it has heat resistance, water resistance, chemical resistance, Excellent in various characteristics such as electrical characteristics and mechanical characteristics.

Polymer materials and resin materials obtained using the fluorene compound according to the present invention as a raw material are as follows. It has a low dielectric constant and a low dielectric loss tangent, and has excellent dielectric properties. Also, with high heat resistance,
Since it has low water absorption and low moisture absorption, it is possible to improve the heat resistance of a part obtained by molding a polymer material obtained from the fluorene compound according to the present invention as a raw material for use in electronic and electric equipment, and to reduce the amount of water absorption and moisture absorption. In addition, the mechanical strength can be increased.

[0019]

The following examples are provided to further clarify the features of the present invention.

Example 1 Internal volume of 1000 ml equipped with a stirrer, cooling tube and burette
Was charged with 90 g (0.5 mol) of fluorenone having a purity of 99.5% by weight (manufactured by Osaka Gas Chemicals) and 220 g (2.0 mol) of catechol (manufactured by Kishida Chemical Co., Ltd.), 0.4 ml of β-mercaptopropionic acid and 80 ml of 95% sulfuric acid. Was added, and the reaction solution was stirred at 85 ° C. for 1 hour to complete the reaction.

After completion of the reaction, 360 g of methanol or isopropyl alcohol was added to the reaction solution, the mixture was heated to 60 ° C., and stirring was continued for 1 hour. Next, 900 g of pure water was added to precipitate a reaction product. After cooling to room temperature, the reaction product was separated by filtration. The resulting solid was filtered and dried. The resulting compound 9,9-bis- (3 ', 4'-dihydroxyphenyl)-
The yield of fluorene was 153.0 g, and the yield was 80.1%. The structural analysis of the obtained compound is as follows. Molecular ion peak of mass spectrum (m / e): 382 Infrared absorption spectrum (cm ^-1 ): Fluorene skeleton: 745 Phenol: around 3500, 1327, 1199 Aromatic ring: 3065, 1606, 1514, 1449 3-substituted benzene ring: 1115, 1036, 864, 807 ¹ H NMR (CDCl ₃ ) δ: 6.3 (2H, dd), 6.6 (4H,
d), 7.3 (6H, m), 7.8 (2H, dd) Example 2 Fluorenone 90 having a purity of 99.5% by weight was placed in the same container as in Example 1.
g (0.5mol) and catechol (manufactured by Kishida Chemical Co., Ltd.) 220g
(2.0 mol), 0.4 ml of thioacetic acid and 36% hydrochloric acid 8
0 ml was added and the reaction was stirred at 85 ° C. for 1 hour to complete the reaction. After completion of the reaction, 360 g of methanol or isopropyl alcohol was added to the reaction solution, the mixture was heated to 60 ° C., and stirring was continued for 1 hour. Next, 900 g of pure water was added to precipitate a reaction product. After cooling to room temperature, the reaction product was separated by filtration. The resulting solid was filtered and dried. The resulting compound 9,9-bis- (3 ', 4'-dihydroxyphenyl)-
The yield of fluorene was 156.8 g, and the yield was 82.1%. Example 3 Fluorenone 90 having a purity of 99.5% by weight was placed in the same container as in Example 1.
g (0.5mol) and 132g catechol (Kishida Chemical Co., Ltd.)
(1.2 mol) and 270 g of toluene were added, 0.4 ml of β-mercaptopropionic acid and 80 ml of 95% sulfuric acid were added, and the reaction solution was stirred at 85 ° C. for 1 hour to complete the reaction.

After the completion of the reaction, 180 g of methanol or isopropyl alcohol was added to the reaction solution, the mixture was heated to 60 ° C., and stirring was continued for 1 hour. Next, 900 g of pure water was added to precipitate a reaction product. After cooling to room temperature, the reaction product was separated by filtration. The resulting solid was filtered and dried. The resulting compound 9,9-bis- (3 ', 4'-dihydroxyphenyl)-
The yield of fluorene was 153.8 g, and the yield was 80.5%.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yasuhiro Suda 4-1-2, Hirano-cho, Chuo-ku, Osaka-shi, Osaka F-term in Osaka Gas Co., Ltd. (reference) 4H006 AA01 AA02 AB49 AC25 AC41 AD15 AD17 BA28 BA36 BA37 BA52 BA66 BB11 BC10 BC19 FC56 FG40 4H039 CA60 CD40 CL25 4J029 AA10 AB07 AC01 AE01 BC09 BD08

Claims (3)

[Claims] 1. A compound represented by the following general formula (I): (Wherein, R ¹ and R ² each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms, and may be the same or different from each other). Compound or salt thereof. 2. The method of claim ^1, wherein R ¹ and R ² are both hydrogen.
Or the salt thereof. 3. A method comprising reacting fluorene (1) with two catechol compounds (2) and (3) in the presence of thioacetic acid or β-mercaptopropionic acid and an acid catalyst (hydrochloric acid or sulfuric acid). A method for producing a fluorene compound of the general formula (I). Embedded image