JPH06157428A - Aromatic dinitro compound, aromatic diamino compound and their production - Google Patents

Abstract

PURPOSE:To provide a new aromatic diamino compound extremely useful as a raw material for polyimide, etc., having low dielectric constant and excellent moldability and to provide an aromatic dinitro compound useful as a precursor of the diamino compound. CONSTITUTION:The 1,3- or 1,4-bis(3-nitro-5-trifluoromethylphenoxy)benzene expressed by formula I and 1,3- or 1,4-bis(3-amino-5-trifluoromethylphenoxy) benzene expressed by formula II. The compound of formula I can be produced by condensing 3,5-dinitrobenzotrifluoride with resorcinol or hydroquinone in the presence of a base in an aprotic polar solvent. Reduction of the compound of formula I gives the compound of formula II. A polyimide resin usable as an insulation material of a flexible printed circuit board for a highly integrated electronic circuit can be produced by condensing the compound of formula II with 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride.

Description

Detailed Description of the Invention

[0001]

The present invention relates to 1,3- or 1,4
-Bis (3-nitro-5-trifluoromethylphenoxy) benzene, 1,3- or 1,4-bis (3-amino-5-trifluoromethylphenoxy) benzene and a method for producing them. This compound is a useful compound as a starting material for polyimide, polyamide, polyamideimide, bismaleimide, epoxy resin and the like.

[0002]

2. Description of the Related Art Polyimide resins belong to the highest class among organic polymers in various properties such as heat resistance, mechanical properties and adhesiveness, and by utilizing these properties, various heat resistant mechanical parts can be used. It is well known that it is widely used for adhesives, electronic material parts and the like. However, the polyimide resin has a problem that its dielectric constant is higher than that of a low dielectric resin such as Teflon resin. The dielectric constant is a very important factor in the field of electronic materials. The dielectric constant of currently commercialized polyimide resin is 3.5 / 1 for polyimide (trade name, Kapton) composed of 4,4'-diaminodiphenyl ether and pyromellitic dianhydride.
MHz, 4,1'-diaminodiphenyl ether and biphenyl tetracarboxylic acid dianhydride polyimide (trade name, Upilex) 3.5 / 1 MHz,
3,3'-Diaminobenzophenone and benzophenone tetracarboxylic dianhydride (trade name, LRAC-TPI)
Then, it is 3.7 / 1 MHz. Currently, polyimide resin has already been used as an insulating material for flexible printed boards, but with the recent high integration of electronic circuits,
Further, an insulating material having a low dielectric constant, specifically, a polyimide resin having a dielectric constant of 2.9 / 1 MHz or less is desired.

The problem of high permittivity is due to electron transfer in the resin, and it is possible to reduce the permittivity by limiting the transfer of electrons in the polymer main chain.
Specifically, it is known that it is effective to introduce an electron-attracting fluorine atom into the molecular unit of polyimide. For example, aromatic diamines containing a hexafluoroisopropylidene group have been disclosed as polyimide monomers for low dielectric materials (JP-A-1-19065).
2). However, these aromatic diamines have industrial and physical problems such as a multi-step synthetic method and insufficient melt fluidity when molding and processing a polyimide resin obtained from them. There is.

On the other hand, a polyimide having a monomer unit of bis [(trifluoromethyl) aminophenoxy] benzenes as a low dielectric material is disclosed in JP-A-59-18912.
2, described in JP-A-3-6528. However, these are descriptions as one component of polyimide, and in the patent, let alone the physical properties of this diamine compound,
No detailed description of the manufacturing method is given.
The diamine compound described in JP-A-3-6528 is 1,4-bis (4-amino-2-trifluoromethylphenoxy) benzene in which the amino group is in the para position relative to the ether bond. Since all the bonding positions of this compound are in the para position, the obtained polyimide has a rigid structure, and there is a drawback that the melt fluidity during molding is insufficient. Further, the para-position of the bond extends the conjugated system, which may lead to an increase in the dielectric constant.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel compound useful as a raw material for polyimide having low dielectric properties and excellent moldability.

[0006]

Means for Solving the Problems The inventors of the present invention have completed the present invention as a result of extensive studies to solve the above problems. That is, the present invention relates to an aromatic dinitro compound represented by formula (1) (formula 4) and an aromatic diamino compound represented by formula (2) (formula 4). In addition, a method for producing the above aromatic dinitro compound by condensing 3,5-dinitrobenzotrifluoride and resorcin or hydroquinone in the presence of a base in an aprotic polar solvent and the above aromatic diamino compound for reducing the same. The present invention relates to a manufacturing method.

[0007]

[Chemical 4] 1,3- or 1,4-bis (3-amino-5) of the present invention
-Trifluoromethylphenoxy) benzene has a trifluoromethyl group and an amino group substituted at the meta position with respect to the ether bond group. Therefore, the polyimide resin obtained from this diamine has excellent properties such as moldability due to the bent structure of the polymer molecule and low dielectric constant due to the trifluoromethyl group.

Hereinafter, 1,3- or 1,4-bis (3-nitro-5-trifluoromethylphenoxy) of the present invention
The method for producing benzene and 1,3- or 1,4-bis (3-amino-5-trifluoromethylphenoxy) benzene will be specifically described. 1,3- or 1, of the present invention
4-bis (3-nitro-5-trifluoromethylphenoxy) benzene has a high yield by reacting 3,5-dinitrobenzotrifluoride with resorcin or hydroquinone in the presence of a base in an aprotic polar solvent. Can be manufactured at a rate. The production method of the raw material 3,5-dinitrobenzotrifluoride is known,
Of American Chemical Society (J.Am.Che
m.Soc.) 74 , 3011-14, it is obtained by reacting a mixed acid with benzotrifluoride. In the reaction of the present invention, 3,5-dinitrobenzotrifluoride is used in an amount of 2 equivalents or more with respect to resorcin or hydroquinone, but in consideration of complexity of post-treatment, cost, etc., use 2 to 2.5 equivalents. Is desirable.

The base used in the present invention is an alkali metal carbonate, hydrogen carbonate, hydroxide or alkoxide, which is potassium carbonate, potassium hydrogen carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide or hydrogen carbonate. Sodium, lithium carbonate, lithium hydroxide, sodium methoxide, potassium isopropoxide and the like can be mentioned. The amount of these bases used may be equivalent to or more than the hydroxyl group of the raw material resorcin or hydroquinone, and is preferably 1 to 2 times equivalent. As the aprotic polar solvent used in the present invention, formamide, N-methylformamide, N, N-dimethylformamide, N, N-
Examples thereof include diethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, sulfolane and the like. The amount of these solvents to be used is not particularly limited, but usually 1 to 10 times by weight of the raw material is sufficient.

As a general reaction method of the present invention, a predetermined amount of resorcin or hydroquinone, a base and a solvent are charged, and after resorcin or hydroquinone is converted to an alkali metal salt, 3,5-dinitrobenzotrifluoride is added. Alternatively, all the raw materials containing 3,5-dinitrobenzotrifluoride may be added in advance at the same time, and the temperature may be raised as it is to react. Moreover, the present invention is not limited to these and can be appropriately implemented by other methods. The reaction temperature is usually in the range of 40 to 250 ° C, preferably 80 to 250 ° C.
It is in the range of 180 ° C. In the method of the present invention, a copper powder and a copper compound or a phase transfer catalyst such as a crown ether, polyethylene glycol, a quaternary ammonium salt, or a quaternary phosphonium salt may be used as a catalyst for promoting the reaction. , It's okay. When water is present in the reaction system, it may be removed outside the system by bubbling nitrogen gas or the like during the reaction, but usually, a small amount of benzene, toluene, xylene, chlorobenzene, etc. is used. Then, a method of removing it out of the system by azeotropic distillation is often used. The end point of the reaction can be determined by thin layer chromatography or high performance liquid chromatography while observing the decrease of the raw materials.

1,3- or 1,4-bis (3-amino-5-trifluoromethylphenoxy) benzene can be produced by reducing the dinitro compound obtained by the above production method. The method for reducing the dinitro compound is not particularly limited, and usually a method for reducing a nitro group to an amino group (for example, New Experimental Chemistry Course, Volume 15,
Oxidation and reduction II, Maruzen (1977)) can be applied, but industrially catalytic reduction is preferred. In the case of catalytic reduction, the reduction catalyst used may be a metal catalyst generally used for catalytic reduction, such as nickel, palladium, platinum, rhodium, ruthenium, cobalt or copper. Industrially, it is preferable to use a palladium catalyst. These catalysts can be used in a metal state, but usually, they are used by supporting them on the surface of a carrier such as carbon, barium sulfate, silica gel, alumina, and celite, and Raney catalysts such as nickel, cobalt, and copper. Also used as. The amount of the catalyst used is not particularly limited, but is in the range of 0.01 to 10% by weight as a metal with respect to the dinitro compound as a raw material, and usually 2 to 8% by weight when used in a metal state, the carrier. In the case of being supported on, the range is 0.1 to 5% by weight.

The reaction solvent used in the method of the present invention is not particularly limited as long as it is inert to the reaction, and examples thereof include alcohols such as methanol, ethanol and isopropyl alcohol, ethylene glycol, Glycols such as propylene glycol, ethers such as ether, dioxane, tetrahydrofuran and methyl cellosolve are preferable, but in some cases, aliphatic hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene. Esters such as ethyl acetate and butyl acetate, and aprotic polar solvents such as N, N-dimethylformamide can also be used. When a reaction solvent that is immiscible with water is used and the reaction proceeds slowly, it can be accelerated by adding a commonly used phase transfer catalyst such as a quaternary ammonium salt or a quaternary phosphonium salt. . The amount of the solvent used is sufficient to suspend or completely dissolve the raw material and is not particularly limited, but usually 0.5 to 10 times by weight of the raw material is sufficient.

The reaction temperature is not particularly limited and may be 20 to 20.
The temperature is in the range of 0 ° C, but is preferably in the range of 20 to 100 ° C. The reaction pressure is about atmospheric pressure to 50 atm. In the reaction, a catalyst is usually added in a state where raw materials are dissolved or suspended in a solvent, and then hydrogen is introduced at a predetermined temperature with stirring to carry out a reduction reaction. The end point of the reaction can also be determined by the amount of absorbed hydrogen, thin layer chromatography, high performance liquid chromatography, or the like. After completion of the reaction, the catalyst used for the reduction was removed, and then the reaction solvent was distilled off to give 1,3- or 1,4-bis (3-
Amino-5-trifluoromethylphenoxy) benzene is obtained. The obtained product can be further purified by a commonly used purification method such as purification as a hydrochloride.

[0014]

EXAMPLES The method of the present invention will now be described in more detail by way of examples, but the present invention is not limited thereto. Example 1 In a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, DMF 500 ml, toluene 50 ml, 3,5-
Dinitrobenzotrifluoride 80g (0.339m
ol), 18.7 g of resorcin (0.169 mo
1) and 28.1 g (0.203 mol) of potassium carbonate were charged respectively, and the temperature was raised to 110 ° C. with stirring, and then 1
It was aged at 10 ° C for 5 hours. After the reaction was completed, it was cooled to room temperature and filtered to remove inorganic salts. The filtrate was concentrated to obtain the target product, 1,3-bis (3-nitro-5-trifluoromethylphenoxy) benzene. Yield 72 g, 87% yield elemental analysis _{(C 20 H 10 N 2 O} 6 F 6) C H N F Calculated (%) 49.20 2.06 5.74 23.34 Found (%) 49.17 2.10 5.78 23.29 ¹ H-NMR δ (CDCl ₃ , ppm) 6.82 to 6.96 (2H (1), m), 7.02 to 7.04 (2H (2), m) ), 7.45 to 7.54 (1H (3), m), 7.61 to 7.63 (1H (4), m), 7.98 to 8.03 (2H (5), m), 8.23 to 8.35 (2H (6), m) (1) to (6) represent the positions of the following formula (Formula 5).

[0015]

[Chemical 5]

Example 2 A reducing device equipped with a thermometer, a reflux condenser, and a stirrer,
72 g (0.147 mol) of 1,3-bis (3-nitro-5-trifluoromethylphenoxy) benzene, 500 ml of isopropyl alcohol and 5% Pd / C (5
(0% water-containing product) (7.2 g) was charged, and in a hydrogen atmosphere at 50 ° C.
And reacted for 5 hours. After completion of the reaction, the catalyst was filtered off, the filtrate was concentrated under reduced pressure, 200 g of isopropanol was added to the residue to dissolve it, and 400 g of 36% HCl was added to the solution to precipitate the desired product as a hydrochloride. 150 g of water and 200 g of 1,2-dichloroethane (EDC) were obtained.
Suspended in water, neutralized with 28% ammonia water, separated,
After washing the EDC layer with water, the solvent was distilled off to obtain 1,3-bis (3-amino-5-trifluoromethylphenoxy) benzene as a brown viscous liquid. Yield 33.8 g, yield 53.7% Elemental analysis _{(C 20 H 14 N 2 O} 2 F 6) C H N F Calculated (%) 56.08 3.29 6.54 26.61 Found (% ^{) 56.12 3.26 6.57 26.57 1 H-} NMR δ (CDCl 3, ppm) 3.85 (4H (1), S), 6.41~6.45 (2H (2), m ), 6.61 to 6.70 (4H (3), m), 6.73 to 6.77 (2H (4), m), 6.82 to 6.96 (1H (5), m), 7.16 to 7.40 (1H (6), m) (1) to (6) represent the positions of the following formula (Formula 6).

[0017]

[Chemical 6]

Example 3 In a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, DMF 250 ml, toluene 50 ml, 3,5-
50 g of dinitrobenzotrifluoride (0.212 m
ol), 11.7 g of hydroquinone (0.106 mo)
1) and 17.6 g (0.127 mol) of potassium carbonate were charged respectively, and the temperature was raised to 120 ° C. with stirring, and then 1
Aged at 20 ° C. for 8 hours. After the reaction was completed, it was cooled to 80 ° C. and filtered to remove inorganic salts. 180 ml of water in the filtrate
Was added and cooled to room temperature to crystallize the desired product. The crystallized crystals were separated by filtration, and recrystallized from isopropyl alcohol to give the desired product, 1,4-bis (3-nitro-5-5).
Trifluoromethylphenoxy) benzene was obtained. Mp 162.8 to 163.3 ° C. Yield 36.5 g, 70.5% yield elemental analysis _{(C 20 H 10 N 2 O} 6 F 6) C H N F Calculated (%) 49.20 2.06 5 .74 23.34 measured value (%) 49.15 2.10 5.72 23.30 ¹ H-NMR δ (CDCl ₃ , ppm) 7.20 (4H (1), S), 7.60 to 7. .62 (2H (2), m), 7.69 to 8.01 (1H (3), m), 7.21 (2H (4), s) (1) to (4) The position of 7) is shown.

[0019]

[Chemical 7]

Example 4 A reducing device equipped with a thermometer, a reflux condenser, and a stirrer,
1,4-bis (3-nitro-5-trifluoromethylphenoxy) benzene 36.5 g (0.0747mo)
1), N, N, -dimethyformamide (250 ml) and Pd-alumina (1.8 g) were charged, and the mixture was charged with hydrogen under an atmosphere of 50.
The reaction was carried out at ℃ for 6 hours. After completion of the reaction, the catalyst was filtered off and the filtrate was concentrated under reduced pressure to give white crystals of 1,4-bis (3-amino-).
5-Trifluoromethylphenoxy) benzene was obtained.
Melting point 157.4 to 158.0 ° C. Yield 36.5 g, Yield 70.5% Elemental analysis (C ₂₀ H ₁₄ N ₂ O ₂ F ₆ ) C H N F calculated value (%) 56.08 3.296 .54 26.61 actual value (%) 56.04 3.32 6.56 26.56 ¹ H-NMR δ (DMSO, ppm) 5.72 (4H (1), S), 6.39 to 6. 41 (4H (2), m), 6.63 (2H (3), s), 7.12 (4H (4), s) (1) to (4) are represented by the following formula (Formula 8). Show.

[0021]

[Chemical 8]

Example of use 1,3-bis (3-amino-5) obtained in Examples 2 and 3
-Trifluoromethylphenoxy) benzene (m-AP
B-2CF _3), 1,4- bis (3-nitro-5-trifluoromethylphenoxy) benzene (m-APB-2
CF ₃ ) of polyimide obtained by condensing 2,2, -bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, respectively. The physical properties are shown in Table 1 (Table 1).

[0023]

[Table 1] Tg (glass transition temperature): measured by DSC η (viscosity): polyimide 0.5 g / 100 cc-N, N-dimethylacetamide, measured at 35 ° C Dielectric constant: measured by ASTM D150-87 at 23 ° C, humidity 50%

[0024]

INDUSTRIAL APPLICABILITY The present invention provides a novel aromatic dinitro compound, aromatic diamino compound and a method for producing them. The aromatic diamino compound of the present invention is
It is extremely useful as a raw material for polyimide and the like, which has low dielectric properties and excellent moldability.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (4)

[Claims] 1. 1,3- or 1,4-bis (3-nitro-5-trifluoromethylphenoxy) benzene represented by the formula (1) (formula 1). [Chemical 1] 2. 1,3- or 1,4-bis (3-amino-5-trifluoromethylphenoxy) benzene represented by the formula (2) (formula 2). [Chemical 2] 3. 1,3- or 1 according to claim 1, wherein 3,5-dinitrobenzotrifluoride and resorcin or hydroquinone are condensed in the presence of a base in an aprotic polar solvent. , 4-bis (3-
Method for producing nitro-5-trifluoromethylphenoxy) benzene. 4. The 1,3- or 1,4-bis (3-amino-5) according to claim 2, wherein the aromatic dinitro compound represented by the formula (1) (formula 3) is reduced. -Method for producing trifluoromethylphenoxy) benzene. [Chemical 3]