JPH11152255A - Aromatic diamine and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new aromatic diamine suitable for a raw material for polyamide which is satisfactory to flexibility and moldability and useful as an adhesive. SOLUTION: This compound is shown by formula I (m) and (n) are each 0 or 1;R is shown by formula II (R1 to R4 are each H, a halogen, 1-8C alkyl, aryl, alkenyl, aralkyl or 1-5C alkoxy) to formula V [R5 to R7 are each H, a 1-8C alkyl, aryl, alkenyl, aralkyl or 1-10C, 1-3O ω-alkyloxyoligo(alkylenoxy) alkyl]}, e.g. 3, 3'-domino-4,4'-diphenoxybenzophenone. A compound of formula I is obtained by reducing a compound obtained by condensing a dinitro compound (e.g. 4,4'-dihalogeno-3,-3'-dinitrobenzophenone) with a hydroxy compound shown by the formula; R-OH in the presence of a base in an aprotic polar solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel aromatic diamino compound and a method for producing the same. The novel aromatic diamino compound of the present invention has a novel thermoplastic property,
Not only useful as a raw material for amorphous polyimide rich in solvent solubility, but also other polyamides, polyimides,
It is used as a raw material for polyamideimide, bismaleimide and epoxy resins, and can also be used as a curing agent for other maleimide compounds and epoxy compounds.

[0002]

2. Description of the Related Art In recent years, heat-resistant resin materials have been required to satisfy not only thermal and mechanical performances but also performances such as flexibility and moldability in use as composite materials. As such a material, a polyimide resin has attracted attention. Conventionally, polyimide has excellent properties in mechanical properties, chemical resistance, flame retardancy, electrical properties, etc. in addition to its excellent heat resistance. It is widely used in the field of parts and the like.

[0003] However, while polyimide resins have high performance, they have a drawback that molding processing is difficult. For example, a typical polyimide is an aromatic polyimide obtained from 4,4′-diaminodiphenyl ether and pyromellitic anhydride (Du'pont, trade name “Vesp”)
el ”)

Embedded image A polyimide having a repeating structural unit represented by the following formula is known (manufactured by DuPont: trade names Kapton, Ves)
pel), since this polyimide is insoluble and infusible, a special method called powder sintering molding is used. However, in this method, it is difficult to obtain a processed product having a complicated shape, and in order to obtain a satisfactory molded product, the molded product must be further finished by cutting or the like. Yes, and cannot be used as a polyimide varnish. Therefore, research and development on soluble polyimide or fusible (thermoplastic) polyimide have been widely promoted for the purpose of imparting processability of polyimide.

[0004] Use of soluble polyimides in heat-resistant varnishes, paints, sealants, and the like is expected in the future. Methods for solubilization are summarized in, for example, the Technical Information Association of Japan, "Polyimide Resin" (1991), etc. However, the flexibility of molecular chains can be increased by introducing flexible copolymerization or copolymerization, or by using alkyl groups or the like. Are introduced to increase the interaction with the solvent.
However, many such soluble polyimides
N-methyl-2-pyrrolidone, N, N-dimethylacetamide,
There are problems such as dissolving only in a high boiling point solvent such as cresol (for example, JP-A-61-130342) and containing a sulfone group having high hygroscopicity. Also,
In a series of recent published patent publications, acetone, toluene,
Polyimides soluble in low-boiling solvents such as dichloromethane have been found, but problems such as the inclusion of an alkyl group having poor heat resistance in the molecular chain remain (see, for example, JP-A-1-263116, and JP-A-1-263116). 1-263117,
No. 2-160832).

On the other hand, various meltable (thermoplastic) polyimides have been developed. For example, a method of improving a diamine component as a raw material has been attempted for the purpose of improving the above-mentioned disadvantages. For example, a method is known in which the glass transition temperature and the melt fluidity of a corresponding polyimide are controlled by a bonding group in a monomer unit, a folded structure, and the like. For example, a polyimide having a basic skeleton of the following formula (B) composed of 3,3′-diaminobenzophenone and benzophenonetetracarboxylic dianhydride (NASA,
LARC-TPI) or a polyimide obtained by further improving this polyimide, such as 1,3-bis (3-aminobenzoyl) benzene and various tetracarboxylic dianhydrides (Japanese Patent Application No. 03-223930). Is being developed. However, although these polyimides exhibit excellent heat resistance and adhesiveness, their fluidity at the time of melting is still insufficient, and at present, they are often used mainly in the form of polyamic acid varnish. Such an application method as a varnish has a problem in treating water generated at the time of final heat ring closure using a polyamide acid as a polyimide, and causes problems such as generation of voids in the adhesive layer. For this reason, there are drawbacks that the desired performance is hardly exhibited and that the process of using the adhesive is complicated.

The present inventors have found that the formula (B)

Embedded image With regard to the polyimide having the basic skeleton of (1), a polyimide capable of injection and extrusion molding by adjusting the polymer molecular weight by sealing the terminal of the reactive polymer was found (JP-A-2-018419). However, this polyimide powder also has a melting point around 340 ° C., and has to be made amorphous in order to be subjected to molding and bonding at a low temperature. Further, the polyimide of the above formula (B) can be used as an adhesive having excellent heat resistance, and is currently mainly used for bonding metals, prepregs, ceramics, etc., and as an adhesive for polyimide films for FPC substrates. However, it is expected to develop a wider range of adhesives by utilizing its thermoplasticity.

[0007] Conventional polyimide bonding techniques include: 1) a method of applying a polyamic acid varnish as a precursor to the bonding surface, applying pressure and heat, and removing the solvent and imidizing. 2) A method in which a polyimide film is sandwiched between bonding surfaces and bonded by applying pressure and heat. 3) A method in which polyimide powder is suspended in a solvent (eg, alcohol) that is easily volatilized, applied to an adhesive surface, coated by evaporating only the solvent, and then pressurized and heated to adhere. . In particular, the bonding method of 3) has an advantage that it is simple as a bonding method and is often used. However, development of a polyimide applicable to this method is desired. It is clear that adhesion cannot be achieved by this method unless the melting point of the polyimide powder is exceeded.

[0008] A prepreg is prepared by impregnating a polyimide powder suspended in a solvent with carbon cloth or the like, and a composite using the prepreg is often used as a structural base material. Also in this case, a processing temperature exceeding the melting point of the polyimide powder is required as in the case of the bonding method 3). Thus, development of polyimide having good solubility and meltability is demanded from the viewpoint of processing temperature and bonding temperature. As an alternative to the polyimides of formula (B), which have essentially various excellent properties but are insoluble in most organic solvents, they have better solubility in organic solvents and Amorphizing the polyimide powder of the above and providing a polyimide having a lower melting point improves the molding and adhesion performance of the polyimide, and greatly contributes to expansion of the application field, improvement of the application method, and rationalization. The development of such a polyimide largely depends on the development of a novel diamine compound as its monomer.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel aromatic diamino compound which satisfies flexibility and moldability and is suitable as a raw material for a polyimide useful as an adhesive. is there.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, a polyimide containing an aromatic diamine having a specific structure as a monomer component impairs various properties inherent to the polyimide. Without any problem, the present inventors have found that it is a thermoplastic amorphous polyimide which is rich in solubility and has excellent moldability, and completed the present invention.

That is, the present invention provides: 1) Formula (1)

Embedded image [Wherein, m and n are each independently an integer of 0 or 1, and R is

Embedded image (Where R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkenyl group, an aralkyl group, or a C ₁ to C 5
R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group,
An alkenyl group, an aralkyl group or an ω-alkyloxyoligo (alkyleneoxy) alkyl group having 1 to 10 carbon atoms and 1 to 3 oxygen atoms)].

2) Equation (2)

Embedded image Wherein n is independently an integer of 0 or 1, and R ₈ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a phenyl group or a halogen atom. Compound,

3) Equation (3)

Embedded image (Where R ₉ is

Embedded image An aromatic diamino compound represented by:

4) Equation (4)

Embedded image (Where R ₉ is

Embedded image An aromatic diamino compound represented by:

5) Equation (5)

Embedded image (Where R ₉ is

Embedded image Which represents an aromatic diamino compound. Further, a method for producing these aromatic diamino compounds,

6) Equation (6)

Embedded image (Wherein X represents a halogen atom, m and n are each independently an integer of 0 or 1), and a dinitro compound represented by the formula (7) R—OH (7) wherein R is

Embedded image (Where R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkenyl group, an aralkyl group, or a C ₁ to C 5
R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group,
An alkenyl group, an aralkyl group or an ω-alkyloxyoligo (alkyleneoxy) alkyl group having 1 to 10 carbon atoms and 1 to 3 oxygen atoms)] in the presence of a base in the presence of a non-proton. Condensed in a polar solvent, formula (8)

[0017]

Embedded image (Wherein m, n and R are as defined above), and then reducing this compound, the formula (1)

Embedded image (Wherein, m, n and R are as described above).

The aromatic diamine of the present invention has the formula (1)

Embedded image [Wherein, m and n are each independently an integer of 0 or 1, and R is

Embedded image (Where R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkenyl group, an aralkyl group, or a C ₁ to C 5
R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group,
An alkenyl group, an aralkyl group or an ω-alkyloxy oligo (alkyleneoxy) alkyl group having 1 to 10 carbon atoms and 1 to 3 oxygen atoms)]. It is an aromatic diamine.

Preferably, the formula (2)

Embedded image (Wherein n is independently an integer of 0 or 1, and R ₈ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a phenyl group or a halogen atom) It is a diamino compound.

More preferably, the formula (3)

Embedded image (Where R ₉ is

Embedded image An aromatic diamino compound represented by:

Equation (4)

Embedded image (Wherein R ₉ is the same as described above), and a compound represented by the formula (5):

Embedded image (In the formula, R ₉ is the same as described above.)

Specifically, 3,3'-diamino-4,4'-diphenoxybenzophenone, 4,4'-diamino-5,5'-diphenoxybenzophenone, 3,4'-diamino-4,5 '-Diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone, 3,4'-diamino-5 '-Phenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 4,4'-diamino-5,5'-dibiphenoxybenzophenone, 3,4'-diamino-4,5'-dibi Phenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 4,4'-diamino-5-biphenoxybenzophenone, 3,4'-diamino-4-biphenoxybenzophenone, 3,4'-diamino-5 '-Biphenoxyben Phenone, 1,3-bis (3-amino-4-phenoxybenzoyl)
Benzene, 1,4-bis (3-amino-4-phenoxybenzoyl) benzene, 1,3-bis (4-amino-5-phenoxybenzoyl) benzene, 1,4-bis (4-amino-5-phenoxybenzoyl) ) Benzene, 1,3-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,4-bis (3-amino-4-
(Biphenoxybenzoyl) benzene, 1,3-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,4-bis (4
-Amino-5-biphenoxybenzoyl) benzene and the like.

These aromatic diamines may be used alone or in combination of two or more. Such an aromatic diamino compound can be produced, for example, by the following method. That is, equation (6)

Embedded image (Wherein X represents a halogen atom, m and n are each independently an integer of 0 or 1). An aromatic halogenodinitro compound represented by the formula (7) R-OH (7) , R is

Embedded image (Where R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkenyl group, an aralkyl group, or a C ₁ to C 5
R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group,
An alkenyl group, an aralkyl group or an ω-alkyloxyoligo (alkyleneoxy) alkyl group having 1 to 10 carbon atoms and 1 to 3 oxygen atoms)] in the presence of a base in the presence of a non-proton. Condensed in a polar solvent having the formula (8)

Embedded image (Wherein m, n and R are as defined above), and the compound is reduced to obtain an aromatic dinitro compound of the formula (1)

Embedded image (Wherein, m, n and R are as defined above) can be produced.

The aromatic halogenodinitro compound of the formula (6) used for producing the aromatic dinitro compound of the formula (8) used in this method is preferably a compound of the formula (6-1)

Embedded image (Wherein X represents a halogen atom), for example, 4,4′-dihalogeno-3,3′-dinitrobenzophenone represented by the formula (6-2)

Embedded image (Wherein X represents a halogen atom), for example, a monohalogenodinitrobenzophenone, for example, 4-halogeno-
As 3,3 '(or 4')-dinitrobenzophenone, 4-chloro-3,3 '(or 4')-dinitrobenzophenone, 4-bromo-3,3 '(or 4')-
Dinitrobenzophenone, 4-fluoro-3,3 '(or 4')-dinitrobenzophenone, 4-iodo-
3,3 ′ (or 4 ′)-dinitrobenzophenone, preferably 4-chloro-3,3 ′ (or 4 ′)-dinitrobenzophenone, and formula (6)
-3)

Embedded image (Wherein X represents a halogen atom)
(Or 1,4) -bis (3-nitro-4-halogenobenzoyl) benzene, for example, 1,3 (or 1,4)
-Bis (3-nitro-4-chlorobenzoyl) benzene, 1,3 (or 1,4) -bis (3-nitro-4-
Fluorobenzoyl) benzene, 1,3 (or 1,
4) -bis (3-nitro-4-bromobenzoyl) benzene, 1,3 (or 1,4) -bis (3-nitro-
4-iodobenzoyl) benzene and the like, and preferably 1,3 (or 1,4) -bis (3-nitro-4).
-Chlorobenzoyl) benzene.

The aromatic dinitro compound of the formula (8) can be produced at a high yield by reacting the corresponding aromatic halogenodinitro compound with a phenol or alcohol in an aprotic polar solvent in the presence of a base. Can be manufactured at a rate. The aromatic halogenodinitro compound used as a raw material in this method, for example, 4,4′-dihalogeno-3,3′-dinitrobenzophenone is a known method described in JP-A-58-112256, It is easily obtained by nitration of dihalogenobenzophenone. Other aromatic dinitro compounds can be produced according to these methods.

Examples of the phenols include phenol; alkylphenols such as cresol and dimethylphenol;
Alkoxyphenols such as guaiacol and dimethoxyphenol; chlorophenol, fluorophenol,
Halogenophenols such as dichlorophenol and difluorophenol; arylphenols such as phenylphenol and diphenylphenol; phenoxyphenol;
Aryloxyphenols such as diphenoxyphenol; polycyclic phenols such as naphthol and anthrol and their alkyl, alkoxy, halogeno and aryl derivatives; and phenols having two or more substituents include halogenoalkylphenol and halogenoaryl Phenols substituted by plural kinds of substituents such as phenol and polycyclic phenols can also be used.

Alcohols include alkyl alcohols such as methanol, ethanol, isopropyl alcohol and tert-butyl alcohol; ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether;
Oligoethylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether; arylalkyl alcohols such as benzyl alcohol; alkenyl alcohols such as propenyl alcohol and isopropenyl alcohol can be used. Phenols and alcohols are not limited to these exemplified compounds.

When the aromatic halogenodinitro compound of the formula (6) is an aromatic monohalogenodinitro compound, the amount of these phenols or alcohols used is 1.0 to 1.5 per mole of the aromatic halogenodinitro compound. Moles, preferably 1.0
3 to 1.3 mol, and in the case of an aromatic dihalogenodinitro compound, 2.0 to 3.0 mol,
Preferably it is 2.05-2.6 mol.

The base to be used is an alkali metal carbonate, hydrogencarbonate, hydroxide or alkoxide. Potassium carbonate, potassium hydrogencarbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogencarbonate, Examples thereof include lithium carbonate, lithium hydroxide, sodium methoxide, and potassium isopropoxide.
The amounts of these bases used are determined by the formulas (6) and (6-
It suffices that the amount be at least equivalent to the halogen group of the aromatic halogenodinitro compound such as 1), (6-2) or (6-3), and more specifically, 1 to 2 times equivalent.

The aprotic polar solvents used include formamide, N-methylformamide, N,
N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide, sulfolane, tetrahydrofuran and the like. The use amount of these solvents is not particularly limited, but usually 1 to 10 times the weight of the raw material is sufficient. As a catalyst for accelerating the reaction, a copper powder and a copper-based compound or a phase transfer catalyst such as crown ether, polyethylene glycol, quaternary ammonium salt and quaternary phosphonium salt may be used at all. The reaction temperature is usually in the range of -10 to 250C, preferably in the range of -5 to 180C. Reaction time is 0.5 ~
It is 30 hours, preferably 1 to 10 hours.

As a general method of this reaction, a predetermined amount of a phenol compound or an alcohol compound, a base and a solvent are charged, and the phenol compound or the alcohol compound is converted into an alkali metal salt. Aromatic dinitro compounds, for example, 4,4'-dihalogeno-3,3'-
The reaction is carried out by adding dinitrobenzophenone, or an aromatic dinitro compound of the formula (6), for example, 4,4′-dihalogeno-3,3′-dinitrobenzophenone is charged into a solvent and adjusted there beforehand. Or a method in which an aromatic dinitro compound of the formula (16), for example, 4,4′-dihalogeno-3,3′-dinitrobenzophenone is used. It may be added simultaneously, and the reaction may be performed by raising the temperature as it is. 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, there is a method in which nitrogen gas or the like is passed through the reaction system to exhaust the reaction system during the reaction, but generally, benzene, toluene, xylene, A method of using a small amount of chlorobenzene or the like and 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, 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.

By the above reaction, the above formula (8)

Embedded image (Wherein m, n and R are as defined above), for example, the formula (8-1)

Embedded image Formula (8-2)

Embedded image Or equation (8-3)

Embedded image Is obtained.

Equations (8-1), (8-2) and (8-
In 3), R is as described above, but preferably includes the following.

Embedded image

The aromatic dinitro compound obtained by the above reaction is reduced to obtain an aromatic diamino compound. That is,
The aromatic diamino compound of the present invention can be produced by reducing the corresponding aromatic dinitro compound obtained by the above production method. The method for reducing the aromatic dinitro compound is not particularly limited, and a usual method for reducing a nitro group to an amino group, for example, a new laboratory chemistry lecture, 15
Volume, oxidation and reduction II, the method described in Maruzen (1977) can be applied, but catalytic reduction is preferred from an industrial viewpoint.

In the case of catalytic reduction, a metal catalyst generally used for catalytic reduction, for example, nickel, palladium, platinum, rhodium, ruthenium, cobalt, copper or the like can be used as the reduction catalyst. 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. Also used as a catalyst. The amount of the catalyst used is not particularly limited, but is 0.01 to 10 as a metal with respect to the raw material dinitro compound.
%, Usually 2 to 8% by weight when used in a metal state, and 0.5 to 8% by weight when supported on a carrier.
It is in the range of 5% by weight.

In the case of iron powder reduction, the reaction temperature is from 0 to 1
It is in the range of 50 ° C, but preferably in the range of 0 to 70 ° C. In this case, the reaction is carried out by a method in which a raw material and a catalytic amount of hydrochloric acid are dissolved or suspended in a solvent and iron powder is gradually added to carry out a reduction reaction, or a raw material containing iron powder is charged in a reaction solvent in advance. Then, any method of performing a reduction reaction may be used.

The reaction solvent used in the reduction reaction is not particularly limited as long as it is inert to the reaction. For example, alcohols such as methanol, ethanol, isopropyl alcohol and the like, ethylene glycol, propylene glycol and the like can be used. Glycols, ethers, dioxane, tetrahydrofuran, ethers such as methyl cellosolve are preferred, in some cases, hexane, aliphatic hydrocarbons such as cyclohexane, benzene, toluene,
Aromatic hydrocarbons such as xylene, esters such as ethyl acetate and butyl acetate, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,2-trichloroethane, and tetrachloroethane Or
N, N-dimethylformamide and the like can also be used. When a reaction solvent that is immiscible with water is used, if the progress of the reaction is slow, 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 materials, and is not particularly limited. Usually, 0.5 to 10 times the weight of the raw materials is sufficient.

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 material is 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 also be determined by the amount of hydrogen absorption or thin-layer chromatography or high-performance liquid chromatography. 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.

By using the aromatic diamino compound described above, for example, a polyimide having the following repeating structural unit can be obtained. Equation (9)

Embedded image (Wherein, m and n are each independently an integer of 0 or 1, R ₈ represents a hydrogen atom, an alkyl group having 1 to 4 prime numbers, an alkoxy group, a phenyl group, or a halogen atom;
Has 2 to 27 carbon atoms, an aliphatic group, a cycloaliphatic group,
A tetravalent group selected from the group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or by a crosslinking member ), A repeating structural unit represented by

Equation (10)

Embedded image (Where R ₉ is

Embedded image And Ar is the same as in the formula (9)),

Equation (11)

Embedded image (Wherein R ₉ and Ar are the same as those of the formula (10)),

Equation (12)

Embedded image (Wherein R ₉ and Ar are the same as those of the formula (10)).

[0044]

The present invention will be described in more detail with reference to Synthesis Examples and Examples, which should not be construed as limiting the present invention. Synthesis Example 1 (Synthesis of 3,3′-dinitro-4,4′-diphenoxybenzophenone) N, N-dimethylformamide (DM) was placed in a four-necked flask equipped with a thermometer, a reflux condenser, and a stirrer.
F) 150 g, toluene 20 g, 4,4'-dichloro {3,3 '
-80 g of dinitrobenzophenone (0.235 mo
1), 45.5 g (0.483 mol) of phenol, and 39 g (0.282 mol) of potassium carbonate were charged, and the mixture was heated to 130 ° C. with stirring and then aged at 130 ° C. for 5 hours. After completion of the reaction, the mixture was cooled to 80 ° C. and filtered to remove the inorganic temperature. 60 g 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 methanol to obtain 3,3′-dinitro-4,4′-diphenoxybenzophenone as a target product. 111.0-112.8
° C., yield 92 g, 86% yield _{^{1 H-NMR δ (CDCl 3}} , ppm): 7.175 (d, 4H (1)), 7.19~7.69
(M, 6H (2)) 7.57 (d, 2H (3)), 8.06 (dd, 2H (4))
8.52 (d, 2H (5)) (1) to (5) represent positions in the following formula.

Embedded image Elemental analysis _{(C 25 H 16 N 2 O} 7)

Example 1 (Synthesis of 3,3'-diamino-4,4'-diphenoxybenzophenone) A reducing device equipped with a thermometer, a reflux condenser and a stirrer was charged with 3,3'-dinitro-4, 60 g (0.131 mol) of 4'-diphenoxybenzophenone, 150 g of methyl cellosolve and 3.0 g of 5% -Pd / C (50% water-containing product) were charged and reacted at 70 to 80 ° C. for 4 hours in a hydrogen atmosphere. After completion of the reaction, the catalyst was filtered off and the filtrate was concentrated under reduced pressure to obtain 3,3′-diamino-4,4′-diphenoxybenzophenone as pale yellow crystals. 153.3-154.0 ° C, 45 g, 86
^{% 1 H-NMR δ (CDCl} 3, ppm): 4.17 (s, 4H (1)), 6.96 (d, 4H (2)) 7.12~7.63 (m, 6H (3) ), 7.21-7.
25 (m, 4H (4)) 7.43 (d, 2H (5)) (1) to (5) represent positions in the following formula.

Embedded image Elemental analysis _{(C 25 H 20 N 2 O} 3)

Example 2 (Synthesis of 3,3'-diamino-4-phenoxybenzophenone) [First-stage reaction] A 4-chloro-chloroform was placed in a glass reactor equipped with a stirrer, a thermometer and a reflux condenser. 61.3 g (0.2 mol) of 3,3'-dinitrobenzophenone, phenol 1
9.7 g (0.21 mol), potassium carbonate 16.6 g
(0.12 mol), N, N-dimethylformamide 22
0 g and 15 g of toluene were charged, and the mixture was heated to 140 ° C. with stirring, and then aged at 140 ° C. for 3 hours. After the completion of the reaction, the mixture was cooled to 100 ° C. and filtered to remove inorganic salts. 200 g of water and 50 g of methanol were added to the filtrate, and the mixture was cooled to room temperature, whereupon crystals were precipitated. This was filtered and washed with isopropyl alcohol to give 69.1 g of 3,3'-dinitro-4-phenoxybenzophenone (94.8% yield).
I got The purity by high performance liquid chromatography is 9
9.7%. Melting point: 135.1-136.0 ° C. The IR spectrum is shown in FIG.

[Reaction of Second Stage] 54.6 g of the above 3,3'-dinitro-4-phenoxybenzophenone was placed in a glass sealed container equipped with a stirrer, thermometer and reflux condenser.
(0.15 mol), 1.1 g of a 5% palladium / alumina catalyst (NE Chemcat) and 270 g of N, N-dimethylformamide were charged, and hydrogen was stirred at a temperature of 40 to 50 ° C. while stirring. When introduced, 19.9 L of hydrogen was absorbed in about 8 hours. After the completion of the reaction, the reaction solution was filtered at the same temperature to remove the catalyst. Next, the filtrate was concentrated under reduced pressure to obtain 37.0 g (81.2% yield) of 3,3′-diamino-4-phenoxybenzophenone as pale yellow crystals. 99.1% purity by high performance chromatography
Met. The melting point is 111.6-113.0 ° C. FIG. 2 shows the IR spectrum. Elemental analysis _{(C 19 H 16 N 2 O} 2)

Example 3 (Synthesis of 3,4'-diamino-4-biphenoxybenzophenone) [First-stage reaction] 4-Chloro was placed in a glass reactor equipped with a stirrer, thermometer and reflux condenser. 61.3 g (0.2 mol) of -3,4'-dinitrobenzophenone, 35.7 g (0.21 mol) of p-phenylphenol, 16.6 g (0.12 mol) of potassium carbonate, and N, N-dimethyl After charging 235 g of formamide and heating to 140 ° C. with stirring, the mixture was heated at 140 to 150 ° C. for 1 hour 3 hours.
Aged for 0 minutes. After the completion of the reaction, the mixture was cooled to 100 ° C. and filtered to remove inorganic salts. Water was added to the filtrate, and the mixture was cooled to room temperature, whereupon crystals precipitated. This was filtered and washed with isopropyl alcohol to obtain 3,3.8′-dinitro-4-biphenoxybenzophenone (73.8 g, yield 83.8%). The purity by high performance liquid chromatography was 99.5%. The melting point was 139.6 to 140.6 ° C. The IR spectrum is shown in FIG.

[Second Stage Reaction] In a glass sealed container equipped with a stirrer, thermometer and reflux condenser, 44.0 g of the above 3,4′-dinitro-4-biphenoxybenzophenone was placed.
(0.1 mol), 3.5 g of 5% palladium / alumina catalyst (NE Chemcat Co.) and 220 g of N, N-dimethylformamide were charged, and hydrogen was stirred at a temperature of 40 to 50 ° C. while stirring. Was introduced, 12.2 L of hydrogen was absorbed in about 9 hours. After the completion of the reaction, the reaction solution was filtered at the same temperature to remove the catalyst. Next, 70 g of water was added to the filtrate, and 31.8 g of 3,4'-diamino-4-biphenoxybenzophenone as pale brown crystals (yield 83.6).
%). The purity by high performance liquid chromatography was 99.1%. Melting point: 244.8-245.1 ° C. Elemental analysis (C ₂₅ H ₂₀ N ₂ O ₂ ) FIG. 4 shows the IR spectrum.

Example 4 (Synthesis of 1,3'-bis (3-amino-4-phenoxybenzoyl) benzene) [First reaction] A glass reactor equipped with a stirrer, thermometer and reflux condenser 1,3'-bis (3-nitro-4
-Chlorobenzoyl) benzene 89.0 g (0.2 mo
l), 59.3 g (0.63 mol) of phenol, 33.2 g (0.24 mol) of potassium carbonate and N, N-
After charging 450 g of dimethylformamide, the mixture was heated to 110 ° C. with stirring, and then aged at 110 to 120 ° C. for 1 hour and 30 minutes. After completion of the reaction, the mixture was filtered at the same temperature to remove inorganic salts, cooled to 80 ° C., cooled by dropping 225 g of water to room temperature, and crystals were precipitated. This was filtered and recrystallized from 2-methoxy alcohol to give 10
3.7 g (92.5% yield) of 1,3-bis (3-nitro-4-phenoxybenzoyl) benzene was obtained. The purity by high performance liquid chromatography was 99.8%. Melting point: 162.3-163.8 ° C. An IR spectrum is shown in FIG.

[Second Stage Reaction] The above-mentioned 1,3- was placed in a glass sealed container equipped with a stirrer, thermometer and reflux condenser.
56.1 g (0.1 mol) of bis (3-nitro-4-phenoxybenzoyl) benzene, 2.0 g of 5% palladium / alumina catalyst (NE Chemcat) and 200 g of N, N-dimethylformamide were charged. , 25
When hydrogen was introduced while stirring at a temperature of ° C, 12.21 L of hydrogen was absorbed in about 20 hours. After the completion of the reaction, the reaction solution was filtered at the same temperature to remove the catalyst. Next, 150 g of water was added to the filtrate to obtain pale brown crystals. This was recrystallized from toluene to give 39.1 g (yield 78.1%) of 1,3 ′.
-Bis (3-amino-4-phenoxybenzoyl) benzene was obtained. The purity by high performance liquid chromatography was 98.8%. Melting point 128.0-129.0 ° C Elemental analysis FIG. 6 shows the IR spectrum.

Example 5 (Synthesis of 1,3'-bis (3-amino-4-biphenoxybenzoyl) benzene) [First-stage reaction] A glass reaction equipped with a stirrer, thermometer and reflux condenser Add 1,3-bis (3-nitro-4-
Chlorobenzoyl) benzene 44.5 g, p-phenylphenol 35.7 g (0.21 mol), potassium carbonate 16.6 g (0.12 mol) and 220 g of N,
After N-dimethylformamide was charged and the temperature was raised to 90 ° C. with stirring, aging was further performed for 3 hours. After the reaction,
After filtration at the same temperature to remove inorganic salts, water was added to precipitate crystals. This was recrystallized from toluene to obtain 64.7 g (yield 90.5%) of 1,3-bis (3-nitro-4-biphenoxybenzoyl) benzene. The purity by high performance liquid chromatography was 99.2%. Melting point 190.6-191.6 ° C

[Second Stage Reaction] The above-mentioned 1,3-A was placed in a glass reactor equipped with a stirrer, thermometer and reflux condenser.
Bis (3-nitro-4-biphenoxybenzoyl) benzene 35.7 g (0.05 mol), iron powder 33.5 g
(0.06 mol) and 400 g of a 90% aqueous 2-methoxyethanol solution were charged, and the internal temperature was raised to 50 ° C. Next, 1.1 g of 35% hydrochloric acid was added to 30 g of 90% 2-
What was dissolved in methoxyethanol was added dropwise over 2 hours. Further, stirring was continued for 15 hours to complete the reaction. At this time, the internal temperature was kept at 50 to 60 ° C. 250g after the end of the reaction
Of water and cooled to 25 ° C.
g of N, N-dimethylformamide was added, the temperature was raised to 110 ° C., and the mixture was filtered. Water was added thereto and the mixture was cooled to 25 ° C. to obtain crystals. This was recrystallized from toluene to obtain 26.2 g (80.2% yield) of 1,3'-bis (3-amino-4-biphenoxybenzoyl) benzene.
The purity by high performance liquid chromatography was 98.8%. Melting point 186.7-187.8 ° C Elemental analysis FIG. 7 shows the IR spectrum.

Example 6 (Synthesis of 3,3'-diamino-4,4'-dimethoxybenzophenone) [First reaction] Tetrahydrofuran was placed in a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer. (THF)
500 g and 100 g (0.293 mol) of 4,4′-dichloro {3,3′-dinitrobenzophenone were respectively charged,
After cooling to 0 ° C. with stirring, sodium methoxide 3
4.8 g (28% methanol solution, 0.645 mol) in 2
After dropwise addition over time, the mixture was aged at 20 ° C. for 5 hours. After the completion of the reaction, insolubles were removed by filtration, the filtrate was heated to 60 ° C., 990 g of water was added, and the mixture was cooled to room temperature to crystallize the desired product. Further, an insoluble matter obtained by filtration was sludged with 300 g of water to obtain an intended substance. The obtained crystals were recrystallized from 1,2-dichloroethane (EDC) to give the desired product 3,3.
3′-Dinitro-4,4′-dimethoxybenzophenone was obtained. Melting point 189.0-189.9 ° C., yield 84 g, yield 86% ¹ H-NMR δ (DMSO-d ₆ , ppm) : 4.05 (s, 6H (1)), 7.53 (d, 2H). (2)) 8.06 (dd, 2H (3)), 8.26 (d, 2H (4) (1) to (4) represent positions in the following formula.

Embedded image Elemental analysis _{(C 15 H 12 N 2 O} 7)

[Second-stage reaction] 3,3'-dinitro-4,4'- was placed in a reducing apparatus equipped with a thermometer, a reflux condenser and a stirrer.
84 g of dimethoxybenzophenone (0.253 mo
l), N, N-dimethylformamide (DMF) 420
The g and _{5% -Pd / Al 2 O 3} 2.52g charged and reacted for 3 hours under 45 to 55 ° C. a hydrogen atmosphere. After completion of the reaction, the catalyst was removed by filtration, the filtrate was heated to 80 ° C.,
5 g was added and cooled to room temperature to crystallize the desired product. The precipitated crystals are separated by filtration, and isopropyl alcohol (IPA)
To give 3,3'-diamino-4,4'-dimethoxybenzophenone as pale yellow crystals. Melting point 128.2-129.2 ° C, yield 27 g, yield 39
% Elemental analysis _{(C 15 H 16 N 2 O} 3) FIG. 8 shows the IR spectrum.

Reference Example A container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube was charged with 3,
3'-diamino-4,4'-diphenoxybenzophenone 3
9.65 g (0.1 mol), 31,58 g (0.09 g) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride
8 mol), 0.592 g (0.004 m) of phthalic anhydride
ol), 1.40 g of γ-picoline, m-cresol 28
4.92 g was charged and heated to 150 ° C. while stirring under a nitrogen atmosphere. Thereafter, the reaction was carried out at 150 ° C. for 4 hours, during which time about 3.6 ml of water was distilled out.

After the completion of the reaction, the reaction mixture was cooled to room temperature, discharged into about 2 L of methyl ethyl ketone, and the polyimide powder was separated by filtration. After washing this polyimide powder with methyl ethyl ketone, it was dried in air at 50 ° C. for 24 hours and in nitrogen at 230 ° C. for 4 hours to obtain 66.25 g of polyimide powder (yield 97.1%).
I got The logarithmic viscosity of the polyimide powder thus obtained was 0.56 dl / g. The glass transition temperature of this polyimide powder was 246 ° C., and the 5% weight loss temperature was 524.
° C and the X-ray diffraction pattern (XRD) showed amorphous. The infrared absorption spectrum of this polyimide powder is shown in FIG. This spectrum diagram, the absorption near 1780 cm ^-1 and 1720 cm ^-1 imide characteristic absorption bands were remarkably observed. The elemental analysis values of the obtained polyimide powder were as follows.

When the flow start temperature of this polyimide powder was measured using a Koka type flow tester, flow was observed at 325 ° C. Further, the molding stability of the polyimide was measured while changing the residence time in the cylinder of the flow tester. The result at a temperature of 380 ° C. and a load of 100 kg is shown in FIG. Even if the residence time in the cylinder becomes longer, the melt viscosity hardly changes, indicating that the molding stability is good. Using this polyimide powder, an adhesion test (Lap Shear Strength) was performed. The tensile shear adhesion strength was 152 kg at a pressing temperature of 280 ° C.
/ Cm ^2, 300 was 332kg / cm ² at 230kg / cm ^2, 350 ℃ at ° C.. Furthermore, when a solvent solubility test of this polyimide powder was performed at room temperature, 20 wt.
%, Chloroform, dichloromethane, carbon tetrachloride, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, cresol (io-,
m-, p-).

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of 3,3′-dinitro-4-phenoxybenzophenone obtained in Example 2.

FIG. 2 is an infrared absorption spectrum diagram of 3,3′-diamino-4-phenoxybenzophenone obtained in Example 2.

FIG. 3 is an infrared absorption spectrum of 3,4′-dinitro-4-biphenoxybenzophenone obtained in Example 3.

FIG. 4 is an infrared absorption spectrum of 3,4′-diamino-4-biphenoxybenzophenone obtained in Example 3.

FIG. 5 is an infrared absorption spectrum of 1,3-bis (3-nitro-4-phenoxybenzoyl) benzene obtained in Example 4.

FIG. 6 is an infrared absorption spectrum of 1,3-bis (3-amino-4-phenoxybenzoyl) benzene obtained in Example 4.

FIG. 7 is an infrared absorption spectrum of 1,3-bis (3-amino-4-biphenoxybenzoyl) benzene obtained in Example 5.

FIG. 8 is an infrared absorption spectrum of 3,3′-diamino-4,4′-dimethoxybenzophenone obtained in Example 6.

FIG. 9 is an infrared absorption spectrum of the polyimide powder obtained in Reference Example.

FIG. 10 is a diagram showing the relationship between the residence time of a polyimide powder obtained in a reference example in a cylinder of a flow tester and the viscosity.

 ──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. Hei 5-30082 (32) Priority date Hei 5 (1993) February 19 (33) Priority claim country Japan (JP) (31) Priority Claim Number Japanese Patent Application No. 5-56977 (32) Priority Date Hei 5 (1993) March 17 (33) Priority Country Japan (JP) (72) Inventor Tadashi Asanuma 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Inside Chemical Company (72) Inventor Yuko Ishihara 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Chemical Co., Ltd. Inventor Keisaburo Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture, within Mitsui Chemicals Co., Ltd. (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemicals, Inc.

Claims (6)

[Claims] (1) Formula (1) [Wherein, m and n are each independently an integer of 0 or 1, and R is (Where R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkenyl group, an aralkyl group, or a C ₁ to C 5
R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group,
An alkenyl group, an aralkyl group, or an ω-alkyloxyoligo (alkyleneoxy) alkyl group having 1 to 10 carbon atoms and 1 to 3 oxygen atoms). 2. The aromatic diamino compound of the formula (1) is a compound of the formula (2) Wherein n is independently an integer of 0 or 1, and R ₈ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a phenyl group or a halogen atom. The aromatic diamino compound according to claim 1. 3. The aromatic diamino compound of the formula (1) is a compound of the formula (3): (Wherein R ₉ is The aromatic diamino compound according to claim 1, which is represented by: 4. The aromatic diamino compound of the formula (1) is a compound of the formula (4) (Wherein R ₉ is The aromatic diamino compound according to claim 1, which is represented by: 5. The aromatic diamino compound of the formula (1) is a compound of the formula (5) (Wherein R ₉ is The aromatic diamino compound according to claim 1, which is represented by: 6. Formula (6) Wherein X represents a halogen atom, and m and n each independently represent an integer of 0 or 1. The dinitro compound represented by the formula (7) R-OH (7) wherein R is Formula 11 (Where R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having an integer of 1 to 8, an aryl group, an alkenyl group, an aralkyl group, or an alkoxy group having 1 to 5 carbon atoms. R ₅ , R ₆ , and R ₇ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkenyl group, an aralkyl group, or a group having 1 to 10 carbon atoms and 1 to 3 oxygen atoms. OH-alkyloxy oligo (alkyleneoxy) alkyl group) is condensed in an aprotic polar solvent in the presence of a base to give a compound of formula (8) Wherein m and n are each independently an integer of 0 or 1, and R is (Here, R ₁ , R ₂ , R ₃ , and R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkenyl group, an aralkyl group, or a group having 1 to 5 carbon atoms.
R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group,
An alkenyl group, an aralkyl group or an ω-alkyloxyoligo (alkyleneoxy) alkyl group having 1 to 10 carbon atoms and 1 to 3 oxygen atoms), to obtain an aromatic dinitro compound. Formula (1) characterized by reduction (Wherein, R, m and n are as defined above).