JP6594808B2 - Novel fluorene compound and process for producing the same - Google Patents

Description

  The present invention relates to a novel fluorene compound and a method for producing the same.

  The epoxy resin is cured with various curing agents to form a cured product having excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, and the like. Therefore, epoxy resins are used in a wide range of fields such as adhesives, paints, laminates, molding materials and casting materials. Conventionally, bisphenol A type epoxy resins and the like have been known as the most industrially used epoxy resins, but such epoxy resins may have insufficient heat resistance depending on the application.

  Moreover, it has been reported that an epoxy resin having a 9,9-bisphenylfluorene skeleton such as 9,9-bis (4-glycidyloxyphenyl) fluorene improves characteristics such as heat resistance to some extent (Patent Document 1). .

  However, the heat resistance of epoxy resins is still not sufficient, and further research is being conducted.

JP 2005-162785 A

  An object of this invention is to provide the novel fluorene compound with high heat resistance, and its manufacturing method.

  The present inventors have found that an epoxy compound having a specific spiro structure at the 9-position of fluorene has high heat resistance, and have completed the present invention. That is, this invention includes the aspect shown below.

  Item 1. General formula (4):

[Wherein, Ar ¹ and Ar ² are the same or different and each represents an aromatic hydrocarbon ring. R ^D1 , R ^E1 , R ^D2 and R ^E2 are each a hydrogen atom or a general formula (A):

(Y ¹ and Y ² are the same or different and represent an alkylene group. R ^F1 , R ^F2 and R ^F3 are the same or different and represent a hydrogen atom or an alkyl group. P represents an integer of 0 to 10. )
The group represented by these is shown. However, one of R ^D1 and R ^E1 is a group represented by the general formula (A), and the other is a hydrogen atom. One of R ^D2 and R ^E2 is a group represented by the general formula (A), and the other is a hydrogen atom. R ^C1 and R ^C2 are the same or different and each represents an alkyl group, an alkoxy group, an acyl group, a cyano group, a halogen atom, a hydroxy group, an amino group, a nitro group, or a carboxyl group. m represents an integer of 0 to 4. n represents an integer of 0 to 4. ]
A fluorene compound represented by:

Item 2. Item 2. The fluorene compound according to Item 1, wherein R ^D1 and R ^D2 are hydrogen atoms, and R ^E1 and R ^E2 are groups represented by the general formula (A).

Item 3. Item 2. The fluorene compound according to Item 1, wherein R ^D1 and R ^D2 are a group represented by the general formula (A), and R ^E1 and R ^E2 are hydrogen atoms.

  Item 4. Item 4. A cured product of the fluorene compound according to any one of Items 1 to 3.

  According to the present invention, a fluorene compound having extremely high heat resistance can be provided because it has a specific spiro structure at the 9-position of fluorene.

Spiro [fluorene-9,9 '- (1', 8'-diglycidyl oxy benzoxanthene) is a chart showing ¹ H-NMR spectrum (CDCl ₃₎ of the. Spiro [fluorene-9,9 '- (2', 7'-diglycidyl oxy benzoxanthene) is a chart showing ¹ H-NMR Spectrum _{(DMSO-d 6)} of.

  The present invention relates to general formula (4):

[Wherein, Ar ¹ and Ar ² are the same or different and each represents an aromatic hydrocarbon ring. R ^D1 , R ^E1 , R ^D2 and R ^E2 are each a hydrogen atom or a general formula (A):

(Y ¹ and Y ² are the same or different and represent an alkylene group. R ^F1 , R ^F2 and R ^F3 are the same or different and represent a hydrogen atom or an alkyl group. P represents an integer of 0 to 10. )
The group represented by these is shown. However, one of R ^D1 and R ^E1 is a group represented by the general formula (A), and the other is a hydrogen atom. One of R ^D2 and R ^E2 is a group represented by the general formula (A), and the other is a hydrogen atom. R ^C1 and R ^C2 are the same or different and each represents an alkyl group, an alkoxy group, an acyl group, a cyano group, a halogen atom, a hydroxy group, an amino group, a nitro group, or a carboxyl group. m represents an integer of 0 to 4. n represents an integer of 0 to 4. ]
It is related with the fluorene compound represented by these.

Ar ¹ and Ar ^{2 each} represent an aromatic hydrocarbon ring. Specific examples include a benzene ring and a naphthalene ring, and a benzene ring is preferable. Ar ¹ and Ar ² may be the same or different.

One of R ^D1 and R ^E1 is represented by the general formula (A):

[Y ¹ and Y ² are the same or different and each represents an alkylene group. R ^F1 , R ^F2 and R ^F3 are the same or different and each represents a hydrogen atom or an alkyl group. p shows the integer of 0-10. ]
And the other is a hydrogen atom. One of R ^D2 and R ^E2 is a group represented by the general formula (A), and the other is a hydrogen atom. From the viewpoint of easy production, R ^D1 and R ^D2 are preferably the same (that is, R ^E1 and R ^E2 are also the same). That is, the present invention relates to the general formula (4a):

[Wherein, Ar ¹ , Ar ² , R ^C1 , R ^C2 , R ^F1 , R ^F2 , R ^F3 , Y ¹ , Y ² , m, n, and p are the same as described above. ]
And a fluorene compound represented by the general formula (4b):

[Wherein, Ar ¹ , Ar ² , R ^C1 , R ^C2 , R ^F1 , R ^F2 , R ^F3 , Y ¹ , Y ² , m, n, and p are the same as described above. ]
The fluorene compound represented by these is included as a preferable aspect. Among them, from the viewpoint of better heat resistance, R ^D1 and R ^D2 are hydrogen atoms, and R ^E1 and R ^E2 are groups represented by the general formula (A), that is, the general formula (4a) The compound represented by these is preferable.

^Examples of the alkyl group represented by R ^F1 , R ^F2 and R ^F3 include an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms. For example, a methyl group, an ethyl group, an n-propyl group, etc. can be illustrated. This alkyl group has 0 to 6 substituents (preferably 1 to 3) such as an alkoxy group, an acyl group, a cyano group, a halogen atom, a hydroxy group, an amino group, a nitro group, and a carboxy group, which are described later. ).

R ^F1 , R ^F2 and R ^F3 are all preferably hydrogen atoms from the viewpoint of easy production.

Examples of the alkylene group represented by Y ¹ and Y ² include alkylene groups having 1 to 6 (preferably 1 to 4) carbon atoms. For example, a methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, 2-methylbutane-1,3-diyl group and the like can be exemplified. This alkylene group has 0 to 6 substituents (preferably 1 to 3) such as an alkoxy group described later, an acyl group described later, a cyano group, a halogen atom described later, a hydroxy group, an amino group, a nitro group, and a carboxy group. ).

Y ¹ and Y ² are each preferably a methylene group or an ethylene group from the viewpoint of easy production.

  The p is an integer of 0 to 10, an integer of 0 to 5 is preferable from the viewpoint of yield and the like, and 0 is more preferable.

The group represented by the general formula (A) is preferably a glycidyl group from the viewpoint of easy production. That is, it is preferred that R ^F1 , R ^F2 and R ^F3 are all hydrogen, Y ² is all a methylene group, and p is all 0.

R ^C1 and R ^C2 represent an alkyl group, an alkoxy group, an acyl group, a cyano group, a halogen atom, a hydroxy group, an amino group, a nitro group, or a carboxy group. R ^C1 and R ^C2 may be the same or different.

^Examples of the alkyl group represented by R ^C1 and R ^C2 include an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms. For example, a methyl group, an ethyl group, an n-propyl group, etc. can be illustrated. This alkyl group has 0 to 6 substituents (preferably 1 to 3) such as an alkoxy group, an acyl group, a cyano group, a halogen atom, a hydroxy group, an amino group, a nitro group, and a carboxy group, which are described later. ).

^Examples of the alkoxy group represented by R ^C1 and R ^C2 include alkoxy groups having 1 to 6 (preferably 1 to 4) carbon atoms. For example, a methoxy group, an ethoxy group, an n-propoxy group, etc. can be illustrated. This alkoxy group has 0 to 6 substituents such as the above alkyl group, the above alkoxy group, an acyl group described later, a cyano group, a halogen atom described later, a hydroxy group, an amino group, a nitro group, and a carboxy group (preferably 1 ~ 3).

^Examples of the acyl group represented by R ^C1 and R ^C2 include acyl groups having 2 to 7 (preferably 2 to 5) carbon atoms. For example, an acetyl group etc. can be illustrated. This acyl group has 0 to 6 substituents such as the above alkyl group, the above alkoxy group, the above acyl group, a cyano group, a halogen atom, a hydroxy group, an amino group, a nitro group and a carboxy group described below (preferably 1 to 3).

Examples of the halogen atom represented by R ^C1 and R ^C2 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The amino group represented by R ^C1 and R ^{C2 represents} 0 to 0 substituents such as the alkyl group, the alkoxy group, an acyl group, a cyano group, a halogen atom, a hydroxy group, an amino group, a nitro group, and a carboxy group described later. It can also have 6 pieces (preferably 1 to 3 pieces).

The carboxy group represented by R ^C1 and R ^C2 has 0 to 6 substituents such as the alkyl group, the alkoxy group, an acyl group, a cyano group, a halogen atom, a hydroxy group, an amino group, and a nitro group described below ( (Preferably 1 to 3).

  The m and n are integers of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 from the viewpoint of yield and the like.

  The compound represented by the general formula (4) is represented by the general formula (1):

[Wherein, Ar ¹ , Ar ² , R ^C1 , R ^C2 , m and n are the same as defined above. R ^A1 , R ^B1 , R ^A2 and R ^B2 represent a hydroxyl group or a hydrogen atom. However, one of R ^A1 and R ^B1 is a hydroxyl group and the other is a hydrogen atom. One of R ^A2 and R ^B2 is a hydroxyl group and the other is a hydrogen atom. ]
From the compound represented by the following reaction formula 1:

[In the formula, Ar ¹ , Ar ² , R ^A1 , R ^A2 , R ^B1 , R ^B2 , R ^C1 , R ^C2 , R ^D1 , R ^D2 , R ^E1 , R ^E2 , R ^F1 , R ^F2 , R ^F3 , Y ¹ , Y ² , m, n and p are the same as above. X represents a halogen atom. ]
Can be produced by the method described in 1. above.

  Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The amount of the compound represented by the general formula (5) can be used in an excess amount relative to 1 mol of the compound represented by the general formula (1), and the amount of the solvent can also be used. Specifically, for example, 5 to 20 mol is preferable, and 7 to 15 mol is more preferable.

  The reaction between the compound represented by the general formula (1) and the compound represented by the general formula (5) is preferably performed in the presence of a base. As the base, for example, a metal hydroxide such as sodium hydroxide or potassium hydroxide can be used. The amount of the base used is preferably 2 to 20 mol, more preferably 3 to 10 mol, per 1 mol of the compound represented by the general formula (1).

  In the reaction, the compound represented by the general formula (5) can be used as a solvent, or a solvent can be used separately. Examples of the solvent include methyl isobutyl ketone, dioxane, dimethyl sulfoxide, dimethylformamide and the like.

  The compound represented by the general formula (1) has the following reaction formula 2:

[In the formula, Ar ¹ , Ar ² , R ^A1 , R ^A2 , R ^B1 , R ^B2 , R ^C1 , R ^C2 , m and n are the same as defined above. In R ^A and R ^B , R ^A represents R ^A1 and R ^B represents R ^B1 , or R ^A represents R ^A2 and R ^B represents R ^B2 . ]
It can be produced by the reaction described in 1.

  The reaction between the compound represented by the general formula (2) and the compound represented by the general formula (3) can be performed, for example, in the presence of an acid, using a promoter as necessary. The compounds represented by the general formulas (2) and (3) are known compounds or can be easily produced by known methods.

  1-20 mol is preferable with respect to 1 mol of compounds represented by General formula (2), and, as for the usage-amount of the compound represented by General formula (3), 2-10 mol is more preferable.

  Examples of acid conditions include concentrated sulfuric acid and concentrated hydrochloric acid. 1-10 mol is preferable with respect to 1 mol of compounds represented by General formula (2), and, as for the usage-amount of these acids, 2-5 mol is more preferable.

  Examples of the cocatalyst include organic acids having a mercapto group such as 3-mercaptopropanoic acid. The amount of the cocatalyst used is preferably 0.001 to 5 mol, more preferably 0.01 to 1 mol, per 1 mol of the compound represented by the general formula (2).

  The reaction is preferably performed in the presence of a solvent. Examples of the solvent include ether solvents such as 1,4-dioxane. The amount of the solvent used is preferably 1 to 25 parts by weight and more preferably 2 to 10 parts by weight with respect to 1 part by weight of the compound of the general formula (2).

  The reaction temperature in the reaction is usually 50 to 100 ° C., preferably 60 to 80 ° C., and the reaction time is usually 1 to 24 hours, preferably 2 to 12 hours.

  In addition, the produced | generated compound can also be isolate | separated and refine | purified by separation methods, such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, etc., or a combination means combining these.

  Since the fluorene compound of the present invention has a dibenzo [c, h] xanthene ring as a spiro ring at the 9-position of fluorene, it is considered to have high heat resistance.

  Since the fluorene compound represented by the general formula (4) of the present invention has two epoxy groups, it can be suitably used as a raw material for the epoxy resin. Therefore, the compound represented by the general formula (4) of the present invention can be cured with a conventionally known epoxy resin curing agent or the like to obtain a cured product.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

  In the following, the weight reduction temperature, melting point, and weight reduction rate are 30 to 500 ° C. in a nitrogen atmosphere using a thermal analysis / differential thermogravimetric simultaneous measurement device TG / DTA 6200 (manufactured by SSI Nanotechnology). Measured at the measurement temperature.

Reference example 1
Preparation of spiro [fluorene-9,9 '-(1', 8'-dihydroxybenzoxanthene)]

  In a 300 mL separable flask, 9 parts by weight of 9-fluorenone (0.05 mol, manufactured by Osaka Gas Chemical Co., Ltd.), 24 parts by weight of 1,5-dihydroxynaphthalene (0.15 mol, manufactured by Kanto Chemical Co., Inc.), 3 -After charging 0.3 parts by weight of mercaptopropionic acid and 80 parts by weight of 1,4-dioxane, 12.8 parts by weight of sulfuric acid was added dropwise and stirred at 80 ° C for 12 hours. The remaining amount of 9-fluorenone as a raw material was measured by HPLC (Hitachi HPLC D-7000, solvent: acetonitrile: 0.1 wt% phosphoric acid aqueous solution = 55/45 to 95/5), and the conversion was 99.5. % Was confirmed. After confirmation, 100 parts by weight of methyl isobutyl ketone (MIBK) was added to the reaction solution to dissolve it, and the mixture was washed 3 times with water. After concentrating the organic layer, the resulting black solid was recrystallized using 300 g of a mixed solvent of acetone / methanol = 1/2, whereby spiro [fluorene 9,9 ′-(1 ′, 8′-dihydroxydibenzo]. Xanthene)] 13.5 parts by weight (yield 58.1%) was obtained as a gray solid.

The physicochemical properties of spiro [fluorene 9,9 ′-(1 ′, 8′-dihydroxydibenzoxanthene)] are as follows.
Mass spectrum: (m / z) 464
FT-IR (cm ⁻¹ ): 3530, 3049, 1602, 1509, 1372, 1230, 813, 785
¹ H-NMR (CDCl ₃ ): δ (ppm)
3.8 (2H, broadcast), 6.4 (2H, d), 6.9 (2H, d), 7.1-7.6 (10H, m), 7.9 (2H, d), 8 .3 (2H, d)
5% weight loss temperature: 430 ° C
Melting point: None (decomposition).

Reference example 2
Preparation of spiro [fluorene-9,9 '-(2', 7'-dihydroxybenzoxanthene)]

  In a 300 mL separable flask, 9 parts by weight of 9-fluorenone (0.05 mol, manufactured by Osaka Gas Chemical Co., Ltd.), 24 parts by weight of 1,6-dihydroxynaphthalene (0.15 mol, manufactured by Kanto Chemical Co., Inc.), 3 -After charging 0.3 parts by weight of mercaptopropionic acid and 40 parts by weight of 1,4-dioxane, 13.2 parts by weight of sulfuric acid was added dropwise and stirred at 60 ° C for 3 hours. The remaining amount of 9-fluorenone as a raw material was measured by HPLC (Hitachi HPLC D-7000, solvent: acetonitrile: 0.1 wt% phosphoric acid aqueous solution = 55/45 to 95/5), and the conversion was 99.5. % Was confirmed. After confirmation, 100 parts by weight of methyl isobutyl ketone (MIBK) was added to the resulting reaction solution to dissolve it, and washed with water. After concentrating the organic layer, the obtained black solid was washed with toluene, so that 14.6 parts by weight of spiro [fluorene 9,9 ′-(2 ′, 9′-dihydroxydibenzoxanthene)] was obtained (yield: 62. 9%) was obtained as a gray solid.

The physicochemical properties of spiro [fluorene 9,9 ′-(2 ′, 9′-dihydroxydibenzoxanthene)] are as follows.
Mass spectrum: (m / z) 464
FT-IR (cm ⁻¹ ): 3562, 3064, 1607, 1523, 1376, 1261, 827, 787
¹ H-NMR (DMSO): δ (ppm)
6.2 (2H, d), 7.1-7.2 (8H, m), 7.3 (2H, dd), 7.4 (2H, t), 8.0 (2H, d), 8 .6 (2H, d), 9.9 (2H, broadcast)
5% weight loss temperature: 383.2 ° C
Melting point: 353.2 ° C.

Example 1
Preparation of spiro [fluorene-9,9 '-(1', 8'-diglycidyloxybenzoxanthene)]

  In a 500 mL separable flask, 46.5 parts by weight (0.1 mole) of spiro [fluorene 9,9 ′-(1 ′, 8′-dihydroxydibenzoxanthene)], 92 parts by weight of epichlorohydrin (1 mole, Kanto) Chemical Co., Ltd.) and 163 parts by weight of dimethyl sulfoxide were added and then heated to 80 ° C. to dissolve the raw material. Thereafter, 40 parts by weight of sodium hydroxide (0.3 mol, manufactured by Kanto Chemical Co., Inc.) was added in 10 portions and stirred at 80 ° C. for 12 hours. After removing the residue by filtration, dimethyl sulfoxide and epichlorohydrin were distilled off under reduced pressure. The obtained crystals were washed with water and dried under reduced pressure at 90 ° C. overnight to obtain spiro [fluorene-9,9 ′-(1 ′, 8′-diglycidyloxybenzoxanthene)].

FIG. 1 shows a ¹ H-NMR spectrum (CDCl ₃ ) of spiro [fluorene-9,9 ′-(1 ′, 8′-diglycidyloxybenzoxanthene)]. The mass spectrum is as follows.
Mass spectrum: 576.

  When the weight loss rate of spiro [fluorene-9,9 '-(1', 8'-diglycidyloxybenzoxanthene)] at 500 ° C was measured, the weight was decreased by 28.25%.

Example 2
Preparation of spiro [fluorene-9,9 '-(2', 7'-diglycidyloxybenzoxanthene)]

  In a 300 mL separable flask, 10 parts by weight of spiro [fluorene-9,9 ′-(2 ′, 7′-dihydroxydibenzoxanthene)] (0.02 mol, manufactured by Osaka Gas Chemical Co., Ltd.), epichlorohydrin After charging 19.9 parts by weight (0.215 mol, manufactured by Kanto Chemical Co., Inc.) and 40 parts by weight of methyl isobutyl ketone, the temperature was raised to 80 ° C. to dissolve the raw materials. Thereafter, 2.6 parts by weight of sodium hydroxide (0.06 mol, manufactured by Kanto Chemical Co., Inc.) was added in 10 portions and stirred at 80 ° C. for 13 hours. After removing the residue by filtration, methyl isobutyl ketone and epichlorohydrin were distilled off under reduced pressure. The obtained crystals were washed with water and dried under reduced pressure at 90 ° C. overnight to obtain spiro [fluorene-9,9 ′-(2 ′, 7′-diglycidyloxybenzoxanthene)].

The ¹ H-NMR spectrum (DMSO-d ₆ ) of spiro [fluorene-9,9 ′-(2 ′, 7′-diglycidyloxybenzoxanthene)] is shown in FIG.

  When the weight loss rate of spiro [fluorene-9,9 '-(2', 7'-diglycidyloxybenzoxanthene)] at 500 ° C was measured, the weight was reduced by 43.56%.

Comparative Example 1
9,9'-bis (6-glycidyloxy-2-naphthyl) fluorene

  When the weight loss rate of 9,9'-bis (6-glycidyloxy-2-naphthyl) fluorene at 500 ° C. was measured, the weight was reduced by 63.54%.

Claims (4)

Formula (4 a) or (4b):
[Wherein, Ar ¹ and Ar ² are the same or different and each represents an aromatic hydrocarbon ring . R ^C1 and R ^C2 are the same or different and each represents an alkyl group, an alkoxy group, an acyl group, a cyano group, a halogen atom, a hydroxy group, an amino group, a nitro group, or a carboxyl group. Y ¹ and Y ² are the same or different and each represents an alkylene group. R ^F1 , R ^F2 and R ^F3 are the same or different and each represents a hydrogen atom or an alkyl group. m represents an integer of 0 to 4. n represents an integer of 0 to 4. p shows the integer of 0-10. ]
A fluorene compound represented by: It expresses before following general formula (4a), fluorene compound according to claim 1. It expresses before following general formula (4b), fluorene compound according to claim 1. Hardened | cured material of the fluorene compound in any one of Claims 1-3.