JP3132783B2 - Aromatic dinitro compound, aromatic diamino compound and method for producing them - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aromatic dinitro compound having a trifluoromethyl group, an aromatic diamino compound and a method for producing the same. These compounds are useful as starting materials for polyimides, polyamides, polyamideimides, bismaleimides and epoxy resins.

[0002]

2. Description of the Related Art In recent years, with the development of electronics, research and development of insulating materials for a multilayer circuit board have been widely pursued. Among organic materials, particularly, polyimide is excellent in heat resistance and dimensional stability, and has a low dielectric constant as compared with inorganic materials. Therefore, polyimide is promising for use as an insulating material. For example, the dielectric constant of polyimide obtained from 4,4'-diaminodiphenyl ether and pyromellitic dianhydride is 3.
The dielectric constant of polyimide obtained from 6/1 kHz, p-phenylenediamine and biphenyltetracarboxylic dianhydride is 3.5 / 1 kHz. However, with the increase in the degree of integration of electronic circuits, an insulating material having a lower dielectric constant, specifically, a material having a dielectric constant reduced to 3.0 / 1 kHz or less, preferably to about 2.8 / 1 kHz is desired. ing. As a technique for lowering the dielectric constant of polyimide, it is known to introduce a fluorine atom into a molecular unit of polyimide. For such a purpose, an aromatic diamine containing a hexafluoroisopropylidene group has been disclosed as a polyimide monomer for a low dielectric constant material (Japanese Unexamined Patent Publication (Kokai) No. Heisei 1).
-190652). However, these aromatic diamines have industrial problems such as a multi-step synthesis method and a lack of heat fluidity when molding and processing a polyimide resin obtained therefrom.

As a diamine having a trifluoromethyl group in the molecule, for example, 4,4′-bis (4-amino-5-trifluoromethylphenyloxy) represented by the following formula (4) ) Biphenyl is disclosed (WO840412).

[0004]

Embedded image However, since this compound has an amino group at the para-position with respect to the rigid biphenyl structure, the resulting polyimide has a rigid structure, and has a drawback that molding processing becomes difficult.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a raw material for polyimide having low dielectric properties and having various properties derived from liquid crystallinity such as high moldability. is there.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, the present invention relates to an aromatic dinitro compound represented by the formula (1) and an aromatic diamino compound represented by the formula (2) (Formula 6).

[0007]

Embedded image In addition, the present invention provides a bis (4) represented by the formula (3)
-Hydroxycumyl) benzene and 2-chloro-5-nitrobenzotrifluoride in the presence of a base in an aprotic polar solvent to prepare an aromatic dinitro compound and an aromatic dinitro compound for reducing the aromatic dinitro compound The present invention relates to a method for producing an aromatic diamino compound.

[0008]

Embedded image The aromatic dinitro compound and the aromatic diamino compound according to the present invention are both novel compounds. The polymer obtained by using the diamino compound of the present invention as a monomer unit has various properties derived from liquid crystallinity such as low solution viscosity, low molding shrinkage, self-reinforcing effect, and low water absorption, and is derived from a trifluoromethyl group. Exhibit low dielectric properties.

The dinitro compound of the present invention is 2-chloro-
It can be produced in high yield by reacting 5-nitrobenzotrifluoride with bis (4-hydroxycumyl) benzene in the presence of a base in an aprotic polar solvent. Both methods for producing 2-chloro-5-nitrobenzotrifluoride and bis (4-hydroxycumyl) benzene as raw materials are known. The former involves nitration of o-chlorobenzotrifluoride, and the latter involves bis (2 -Hydroxypropan-2-yl) benzene can be easily obtained by reacting with phenol in the presence of an acid catalyst. In the method of the present invention, bis (4-hydroxycumyl)
2-chloro-5-nitrobenzotrifluoride may be used in an amount of at least twice equivalent to benzene, and the post-processing is complicated.
In consideration of cost and the like, it is preferable to use 2-2.5 equivalents.

[0010] The base used in the method of the present invention is an alkali metal carbonate, hydrogen carbonate, hydroxide or alkoxide, and potassium carbonate, potassium hydrogen carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, Examples include sodium hydrogencarbonate, lithium carbonate, lithium hydroxide, sodium methoxide, potassium isopropoxide and the like. The amount of these bases used is determined by the amount of bis (4-
It is sufficient that the amount is at least equivalent to the hydroxyl group of (hydroxycumyl) benzene, and specifically, it is sufficient that the amount is 1 to 2 times equivalent. The aprotic polar solvent used in the method of the present invention includes formamide, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylformamide.
N-dimethylacetamide, N-methylpyrrolidone,
Examples thereof include 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and sulfolane. The amount of these solvents used is not particularly limited, but is usually 1 to 10 times the weight of the raw materials.

In the method of the present invention, as a catalyst for accelerating the reaction, copper powder and copper-based compound or crown ether, polyethylene glycol, quaternary ammonium salt,
There is no harm in using a phase transfer catalyst such as a quaternary phosphonium salt. The reaction temperature is usually 40 to 250
° C, but preferably in the range of 80 to 180 ° C. The reaction time is 0.5-30 hours, preferably 1-1.
0 hours. As a general reaction method of the present invention, a predetermined amount of bis (4-hydroxycumyl) benzene, a base and a solvent are charged, and bis (4-hydroxycumyl) benzene is converted into an alkali metal salt. The reaction is carried out by adding -chloro-5-nitrobenzotrifluoride or by simultaneously adding all the raw materials containing 2-chloro-5-nitrobenzotrifluoride in advance and raising the temperature as it is. You may. Further, the present invention is not limited to these, and can be appropriately implemented by other methods.

As a method for removing water in the reaction system, nitrogen gas or the like is passed through the reaction system to remove water during the reaction.
There is a method of exhausting outside the system, but in general, benzene,
A method is often used in which a small amount of toluene, xylene, chlorobenzene or the like is used and removed from the system by azeotropic distillation. The end point of the reaction can be determined by thin-layer chromatography or high-performance liquid chromatography, etc., while observing the reduction of the raw materials. After completion of the reaction, the mixture is concentrated or discharged directly into water or the like to obtain a crude dinitro compound. It can be purified by recrystallization or sludge with a solvent.

The diamino compound of the present invention 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 may be a usual method for reducing a nitro group to an amino group, for example, a method described in Shin-Jikken Kagaku Koza, Vol. 15, Oxidation and Reduction II, Maruzen (1977). Applicable, but
Industrially, catalytic reduction is preferred. In the case of catalytic reduction, as the reduction catalyst used, a metal catalyst generally used for catalytic reduction, for example, nickel, palladium, platinum,
Rhodium, ruthenium, cobalt, copper and the like can be used. Industrially, it is preferable to use a palladium catalyst. These catalysts can be used in the form of a metal, but are usually used by being supported on a carrier surface 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 to be used is not particularly limited, but is in the range of 0.01 to 10% by weight as a metal with respect to the raw material dinitro compound, and usually 2 to 8% by weight when used in a metal state, When supported on a carrier, the content is in the range of 0.1 to 5% by weight.

The reaction solvent used in the reduction reaction of the present invention is not particularly limited as long as it is inert to the reaction. For example, alcohols such as methanol, ethanol and isopropyl alcohol, ethylene glycol and propylene Glycols such as glycol, ethers, dioxane, tetrahydrofuran, ethers such as methyl cellosolve are preferable, and in some cases, hexane, aliphatic hydrocarbons such as cyclohexane, benzene,
Aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane,
Halogenated hydrocarbons such as 1,2-trichloroethane and tetrachloroethane, and N, N-dimethylformamide can also be used. When a reaction solvent that is immiscible with water is used and the progress of the reaction is slow, the reaction is accelerated by adding a commonly used phase transfer catalyst such as a quaternary ammonium salt or a quaternary phosphonium salt. be able to. The amount of the solvent used is sufficient to suspend or completely dissolve the raw materials, and is not particularly limited, but is usually 0.5 to 10 times the weight of the raw materials.

The reaction temperature is not particularly limited, and is 20 to 20.
It is in the range of 0 ° C, but preferably in the range of 20 to 100 ° C. The reaction pressure is from normal pressure to about 50 atm.
The reaction time is 0.5 to 30 hours, preferably 1 to 10 hours. The reaction is usually carried out by adding a catalyst in a state where the raw materials are dissolved or suspended in a solvent, and then introducing hydrogen at a predetermined temperature under stirring to perform a reduction reaction. The end point of the reaction can 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 is removed, and then the reaction solvent is distilled off to obtain the desired product.

[0016]

EXAMPLES Hereinafter, the method of the present invention will be described in more detail with reference to examples. The present invention is not limited by this. Example 1 N, N-dimethylformamide (DMF) 700 was placed in a four-necked flask equipped with a thermometer, a reflux condenser, and a stirrer.
ml, toluene 30 ml, 2-chloro-5-nitrobenzotrifluoride 87 g (0.386 mol), 1,
63.6 g of 3-bis (4-hydroxycumyl) benzene
(0.184 mol), 53.3 g of potassium carbonate (0.
386 mol), and the mixture was heated to 110 ° C. with stirring and then aged at 110 ° C. for 4 hours. After the completion of the reaction, the mixture was cooled to 80 ° C. and filtered to remove inorganic salts. 30 ml of water was added to the filtrate, and the mixture was cooled to room temperature to crystallize the desired product. The precipitated crystals were separated by filtration and sludged with isopropyl alcohol to obtain 1,3-bis [4- (4-nitro-2-trifluoromethylphenoxy) cumyl] benzene as a target product. Melting point: 127.4-128.4 ° C. Yield: 120 g, 90% yield ¹ H-NMR δ (CDCl ₃ , ppm) 1.69 (s, 12H (1)), 6.90 (d, 4H (2))
), 6.94-7.34 (m, 4H (3)), 7.26
(D, 4H (4)), 7.18 (d, 2H (5)), 8.2
8 (dd, 2H (6)), 8.58 (d, 2H (7)) (1) to (7) indicate the positions of the following formula (8).

[0017]

Embedded image Elemental analysis _{(C 38 H 30 N 2 O} 6 F 6) C H N F Calculated (%) 62.98 4.17 3.87 15.73 Found (%) 62.89 4.29 3.70 15 .66

Example 2 A reducing device equipped with a thermometer, a reflux condenser, and a stirrer was used.
90 g of 1,3-bis [4- (4-nitro-1-trifluoromethylphenoxy) cumyl] benzene (0.124
mol), 500 ml of methyl cellosolve and 5% -P
d / C 5g (50% water-containing product)
The reaction was performed at 0 to 80 ° C for 4 hours. After the completion of the reaction, the catalyst was filtered off, and the filtrate was concentrated under reduced pressure to give 1,3-bis [4
-(4-amino-2-trifluoromethylphenoxy)
Cumyl] benzene was obtained. 118.5-119.2
° C., yield 73.4 g, 89% yield _{^{1 H-NMR δ (CDCl 3}} , ppm) 1.86 (s, 12H (1)), 3.71 (s, 4H (2)
), 6.76-7.45 (m, 10H (3)), 6.9
5 (d, 4H (4)), 7.29 (d, 4H (5)) (1) to (5) indicate the positions of the following formula (9).

[0019]

Embedded image Elemental analysis _{(C 38 H 34 N 2 O} 2 F 6) C H N F Calculated (%) 68.67 5.16 4.21 17.15 Found (%) 68.78 5.22 4.15 17 .01

Example of Use The diamino compound obtained in Example 2, pyromellitic dianhydride (PMDA), diphenyl ether tetracarboxylic dianhydride (ODPA) and 2,2-bis (3,4
-Dicarboxyphenyl) -1,1,1,3,3,3-
Hexafluoropropane dianhydride (6F-BA) was respectively condensed to obtain a polyimide. Physical properties of the obtained polyimide are shown in Table 1 below.

[0021]

[Table 1] Further, a polyimide comprising the diamino compound of the present invention and pyromellitic dianhydride and a commercially available polyether sulfone (PES, manufactured by ICI, trade name: VICTREXPES)
4100P) is shown in the following (Table 2) when mixed at a weight ratio of 7/3.

[0022]

[Table 2] By mixing the polyimide using the diamino compound of the present invention with PES, the melt viscosity was significantly reduced. or,
The obtained strands were oriented in the extrusion direction, and fibrous fibrils were observed. For example, properties unique to liquid crystalline polymers were observed.

[0023]

The aromatic diamino compound obtained by the present invention is useful as a raw material for polyimide, which has excellent moldability and low dielectric properties.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C07C 205/38 C07C 201/12 C07C 213/02 C07C 217/90 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] An aromatic dinitro compound represented by the formula (1): Embedded image 2. An aromatic diamino compound represented by the formula (2). Embedded image 3. The bis (4-) represented by the formula (3)
(Hydroxycumyl) benzene and 2. The method for producing an aromatic dinitro compound according to claim 1, wherein the condensation with 2-chloro-5-nitrobenzotrifluoride is carried out in the presence of a base in an aprotic polar solvent. 4. An aromatic dinitro compound represented by the formula (1): The method for producing an aromatic diamino compound according to claim 2, wherein the reduction is carried out.