JPH0637445B2 - Methyl-substituted 2,2-bis [4- (3-aminophenoxy) phenyl] propane and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a methyl-substituted compound of 2,2-bis [4- (3-aminophenoxy) phenyl] propane and a method for producing the same.

More specifically, 2,2-bis [4- (3-nitrophenoxy) phenyl obtained by condensing 4,4'-bisphenol and m-dinitrobenzene in an aprotic polar solvent in the presence of a base. ] 2,2-bis [4- (3-aminophenoxy) obtained by reducing the methyl substitution product of propane
It relates to a methyl-substituted form of phenyl] propane.

The methyl-substituted form of 2,2-bis [4- (3-aminophenoxy) phenyl] propane of the present invention has no known production since there is no example ever produced.

However, due to its structure, it is useful as a raw material for heat-resistant polymer monomers, particularly polyamide, polyimide or polyamide and bismaleimide resin.

(Prior Art) Previously, the present applicant found out that an adhesive having excellent heat resistance can be obtained from a polyimide containing 2,2-bis [4- (3-aminophenoxy) phenyl] propane as a diamine component. Filed (Japanese Patent Application No. Sho 60-186610).

An adhesive having excellent heat resistance can be obtained from the polyimide of the present invention containing the methyl-substituted 2,2-bis [4- (3-aminophenoxy) phenyl] propane as a diamine component.

Conventionally, regarding the substitution reaction of m-dinitrobenzene with phenols, 3-nitrodiphenyl ethers are produced by reacting m-dinitrobenzene with an alkyl metal salt of phenols in a polar organic solvent in the presence of a macrocyclic polyether. There is only a known method for doing so (Japanese Patent Laid-Open No. Sho 5)
4-39030). However, in this case, it is necessary to use a special reagent such as expensive crown ether as a reaction accelerator, and there is a drawback that its recovery is difficult.

As described above, the substitution reaction with m-dinitrobenzene and phenols is expected to be considerably more difficult than the case of alcohols, and under normal conditions considered industrially,
There have been no examples in the past.

(Problems to be Solved by the Invention) That is, an object of the present invention is to provide a compound useful as a raw material for various resins having excellent flexibility and molding processability or a raw material for an adhesive having heat resistance, and a method for producing the same. It is to be.

(Means for Solving Problems) The inventors of the present invention have made extensive studies to achieve the object of the present invention.
As a result, the general formula (III) of the present invention (In the formula, R _{1 to} R ₃ represent a hydrogen atom or a methyl group, and may be the same or different from each other) 2,2-
When a methyl substitution product of bis [4- (3-aminophenoxy) phenyl] propane is used as a polyimide resin raw material, that is, a polyimide resin obtained from a diamine represented by the general formula (III) and pyromellitic dianhydride. As shown in Table-1, the thermal physical properties of No.2 are glass transition temperature (Tg) 220 ~ 260 ℃, 5% weight loss in air is 450 ℃ or more, and tensile shear strength is 300kg / cm. ²
As described above, it has the expected heat resistance and strong adhesive strength. On the other hand, a polyimide resin generally has a high softening temperature and is insoluble in an organic solvent, so that it is often difficult to mold the polyimide resin. However, the 2,2-bis [4]
A polyimide resin obtained from methyl-substituted 3- (3-aminophenoxy) phenyl] propane and pyromellitic dianhydride is generally an aprotic polar solvent generally used exclusively as a polymerization solvent, for example, dimethylacetamide, 1,3-
Both dimethyl-2-imidazolidinone and 1-methyl-2-pyrrolidinone are soluble at room temperature. Therefore, unlike the case of using a solution of a polyamic acid in an organic solvent, since a dehydration cyclization step is not included, it is possible to perform molding advantageously such that foaming and nonuniformity of the film layer do not occur. By the way, 2,2-
Polyimide resins obtained from bis [4- (3-aminophenoxy) phenyl] propane and pyromellitic dianhydride are dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, 1-methyl-2-pyridinone, etc. It is insoluble in the solvent.

When such a useful compound is reacted with 4,4′-bisphenol and m-dinitrobenzene in an aprotic polar solvent in the presence of a base, 2,2-bis [4- (3-nitrophenoxy) is obtained. ) Phenyl] propane methyl substitution product was obtained in high yield, and by reducing this compound 2,2-
The inventors have found that a methyl-substituted bis [4- (3-aminophenoxy) phenyl] propane can be industrially advantageously produced, and completed the present invention.

That is, the present invention is represented by the general formula (I) (In the formula, R _{1 to} R ₃ represent a hydrogen atom or a methyl group and may be the same or different from each other) 4,4 ′
-General formula (II) obtained by condensing bisphenols and m-dinitrobenzene in the presence of a base in an aprotic polar solvent (Wherein R _{1 to} R ₃ have the same meaning as in the case of the general formula (I)) 2,2-bis [4- (3-nitrophenoxy)
General formula (III) characterized by reducing the methyl-substituted form of (phenyl) propane (In the formula, R _{1 to} R ₃ have the same meaning as in the general formula (I))
And a method for producing a methyl-substituted 2,2-bis [4- (3-aminophenoxy) phenyl] propane represented by the formula, and a methyl-substituted 2,2-bis [4- (3-aminophenoxy) phenyl] propane Is.

2,2-bis [4- (3) represented by the general formula (III) of the present invention
Specific examples of the methyl-substituted derivative of -aminophenoxy) phenyl] propane include 2- [3-methyl-4- (3-aminophenoxy) phenyl] -2- [4- (3-aminophenoxy) phenyl] propane. , 2- [3,5-dimethyl-4- (3-aminophenoxy) phenyl] -2- [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [3,5-dimethyl-4-] (3-aminophenoxy) phenyl] propane and 2,2-bis [3-methyl-4- (3-aminophenoxy) phenyl] propane.

The compound produced as an intermediate by the method of the present invention is a methyl-substituted product of 2,2-bis [4- (3-nitrophenoxy) phenyl] propane represented by the general formula (II).

Specifically, 2- [3-methyl-4- (3-nitrophenoxy) phenyl] -2- [4- (3-nitrophenoxy) phenyl] propane, 2- [3,5-dimethyl-4-]
(3-Nitrophenoxy) phenyl] -2- [4- (3
-Nitrophenoxy) phenyl] propane, 2,2-bis [3,5-dimethyl-4- (3-nitrophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (3-
Nitrophenoxy) phenyl] propane.

The starting materials used in the method of the present invention are m-dinitrobenzene and the above-mentioned general formula (I) 4,
It is a 4'-bisphenol. Specific examples of 4,4′-bisphenol include 2- (4-hydroxy-3-methylphenyl) -2- (4-hydroxyphenyl) propane and 2- (4-hydroxy-3-methylphenyl) propane.
(4-Hydroxy-3,5-dimethylphenyl) -2-
(4-Hydroxyphenyl) propane, 2,2-bis (4
-Hydroxy-3-methylphenyl) propane, 2,2-
It is bis (4-hydroxy-3,5-dimethylphenyl) propane.

The amount of these raw materials used is not particularly limited,
Usually, m-dinitrobenzene is used in an amount of 1.5 to 4.0 times mol with respect to 4,4'-bisphenols. In the method of the present invention, 4,4'-bisphenols represented by the general formula (I) and m-dinitrobenzene are condensed in an aprotic polar solvent in the presence of a base to give the compound represented by the general formula (II). The reaction for producing the methyl substitution product of 2,2-bis [4- (3-nitrophenoxy) phenyl] propane represented (hereinafter referred to as the first step reaction) and further the reaction of 2,2-bis [4- (3-
The methyl-substituted nitrophenoxy) phenyl] propane is reduced to give 2,2-bis [4] represented by the general formula (III).
Reaction for producing methyl substitution product of-(3-aminophenoxy) phenyl] propane (hereinafter referred to as second-stage reaction)
It consists of two reactions.

The bases used in the first stage reaction are alkali metal oxides, hydroxides, carbonates, bicarbonate hydrides and alkoxides.

Specifically, sodium oxide, lithium oxide, potassium hydroxide, sodium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium-t-butoxide, sodium methoxide. , Sodium ethoxide, etc. are used. Of course, these may be used alone or in combination of two or more kinds. The amount of base is not particularly limited,
It may be 1 to 5 times by mole, and preferably 1.5 to 3 times by mole with respect to the raw material bisphenol. During this reaction, quaternary ammonium salt, quaternary phosphonium salt, macrocyclic polyether such as crown ether, nitrogen-containing macrocyclic polyether such as cryptate, phase transfer catalyst such as polyethylene glycol and its alkyl ether, copper Powder and copper salt may be added as a reaction accelerator.

An aprotic polar solvent is used as the reaction solvent. Specifically, N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, dimethyl sulfone, sulfolane,
1-methyl-2-pyrrolidinone, 1,3-dimethyl-2-
Examples include imidazolidinone N, N, N ', N'-tetramethylurea, hexamethylphosphotriamide, and 1,3-dimethyl-3,4,5,6-tetrahydro-2 (HI) -pyrimidine. . The amount of these solvents used is not particularly limited, but usually, 1 to 10 times by weight of the raw material is sufficient.

There are no particular restrictions on the method of charging the raw materials when carrying out the reaction, but for example, (1) m-dinitrobenzene is prepared after charging a predetermined amount of bisphenol, a base and a solvent to prepare an alkali metal salt of bisphenol in advance. And a method of charging all the starting materials containing (2) m-dinitrobenzene from the beginning and reacting as it is, and the method is not particularly limited as the reaction proceeds.

Using an alkali metal oxide or hydroxide as a base, water generated in the reaction system is gradually removed out of the system during the reaction by, for example, aeration of nitrogen gas, or benzene, toluene, xylene, or chlorine. A method in which a small amount of benzene or the like is used to remove it outside the system as an azeotropic mixture is used.

On the other hand, when hydrogencarbonate or carbonate is used, dehydration operation is not particularly required.

The reaction temperature is usually 100 to 240 ° C., preferably 120 to
It is in the range of 180 ° C. The end point of the reaction can be determined by thin layer chromatography, high performance liquid chromatography and the like.

After completion of the reaction, the solvent is distilled off, or the reaction solution is directly discharged into water to obtain a target crude product. Although this crude product can be purified by recrystallization or the like, it can usually be used as it is for the second stage reaction. Second
The reduction method applied in the step reaction is not particularly limited, and is usually a method of reducing a nitro group to an amino group (eg, New Experimental Chemistry Course, Vol. 15, Oxidation and Reduction (II) Maruzen (1977)).
Can be applied, but catalytic reduction or hydrazine reduction is industrially preferable. As the reduction catalyst used in the case of catalytic reduction, a metal catalyst generally used in catalytic reduction, for example, nickel, palladium, platinum rhodium, cobalt,
Copper or the like can be used. It is industrially preferable to use a palladium catalyst.

These catalysts can be used in a metal state, but usually, they are used by supporting them on a carrier surface such as carbon, barium sulfate, silica gel, alumina, and Celite, and nickel, cobalt, copper, etc. are used as Raney catalysts. Is also used. The amount of the catalyst used is not particularly limited, but 0.01% as a metal relative to the methyl substitution product of the starting material 2,2-bis [4- (3-nitrophenoxy) phenyl] propane.
The range is from 10 to 10% by weight, usually 2 to 8% by weight when used in a metal state, and 0 when loaded on a carrier.
It is in the range of 1 to 5% by weight.

The reaction solvent is not particularly limited as long as it is inert to the reaction, for example, alcohols such as methanol, ethanol, isopropyl alcohol, glycols such as ethylene glycol and propylene glycol, ethers, dioxane, Tetrahydrofuran, ethers such as methyl cellosolve, benzene, toluene, aromatic hydrocarbons such as xylene, ethyl acetate, esters such as butyl acetate, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1, Halogenated hydrocarbons such as 2-trichloroethane and tetrachloroethane and N, N-dimethylformamide and dimethyl sulfoxide can be used. If the reaction progresses slowly when using a reaction solvent that is immiscible with water, 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 not particularly limited as long as it is sufficient to suspend or completely dissolve the raw material, but 0.5 to 10 times by weight of the raw material is usually sufficient.

The reaction temperature is not particularly limited, generally 20 to 200 ° C.
In the range of 20 to 100 ° C. is particularly preferable.

The reaction pressure is usually from atmospheric pressure to 50 kg / cm ^{1 -G} .

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 be determined by the amount of absorbed hydrogen, thin layer chromatography or the like.

On the other hand, in the case of hydrazine reduction, hydrazine may be used in a small excess with respect to the theoretical amount, and preferably 1.2 to 2 times the amount of hydrazine is used to carry out the reduction reaction.

As the catalyst, the above metal catalyst generally used for catalytic reduction is used. Industrially palladium / carbon,
A catalyst in which platinum / carbon or ferric chloride is adsorbed on activated carbon is preferable. The amount of the catalyst used is not particularly limited, and methyl substitution of 2,2-bis [4- (3-nitrophenoxy) phenyl] propane which is a usual raw material As a metal to the body 0.01 ~
It is in the range of 30% by weight.

As the reaction solvent, the same solvent as in the case of catalytic reduction can be used. The reaction temperature is not particularly limited and is generally in the range of 20 to 150 ° C, particularly preferably 40 to 100 ° C. In the reaction, the catalyst is usually added in a state where the raw materials are dissolved or suspended in a solvent, and then hydrazine is added dropwise at a predetermined temperature under stirring to carry out a reduction reaction. The end point of the reaction can be determined by thin layer chromatography or high performance liquid chromatography.

After completion of the reaction, the reaction solution is heated to remove the catalyst, and then the solvent is distilled off if necessary to obtain the target 2,2-bis [4-
A crude product of methyl-substituted (3-aminophenoxy) phenyl] propane is obtained. This crude product can be purified by recrystallisation or isolation as the hydrochloride salt.

(Action and Effect) The present invention is a novel diamine compound useful as a monomer of a heat-resistant polymer such as polyamide, polyimide, polyamide or bismaleimide resin, 2,2-bis [4- (3
A methyl substitution product of -aminophenoxy) phenyl] propane and adding a reaction accelerator such as a phase transfer catalyst to the condensation reaction of bisphenols with m-dinitrobenzene, which has been considered to be difficult. The methyl substitution product of 2,2-bis [4- (3-nitrophenoxy) phenyl] propane can be produced by performing the same procedure without any further treatment, and further it can be relatively easily reduced by a conventional method to obtain a good yield. It is manufactured by. That is, the present invention is extremely significant industrially.

(Examples) Hereinafter, the present invention will be specifically described with reference to Examples.

Example 1 1 In a glass reaction vessel, 2,2-bis (4-hydroxy-)
71 g (0.25 mol) of 3,5-dimethylphenyl) propane, 100.9 g (0.6 mol) of m-dinitrobenzene 82.8 g of potassium carbonate and N, N-dimethylformamide 66.
Charge 0 ml and react at 140-150 ° C for 15 hours. After completion of the reaction, the mixture was cooled to remove KNO ₂ , then the solvent of the liquid was distilled off under reduced pressure, then cooled to 90 ° C., charged with 700 ml of water, and stirred for 1.0 hour. A dark brown crystal of 2-bis [3,5-dimethyl-4- (3-nitrophenoxy) phenyl] propane was obtained. Then, the crystals were placed in a glass reaction vessel, 13 g of activated carbon, 1.3 g of ferric chloride hexahydrate and 550 ml of methyl cellosolve.
Was charged and stirred under reflux for 30 minutes, then 50 g (1.0 mol) of hydrazine hydrate was added dropwise at 70 to 80 ° C. over 2 hours, and further stirred at 70 to 80 ° C. for 7 hours. To remove the catalyst and distill off the methyl cellosolve 3
250 g of 0% hydrochloric acid aqueous solution was added, and then methanol 1
Add 20 ml and add 30 g of salt and stir for 20
Crystals precipitate when cooled to ~ 25 ° C.
Add 560 ml of 50% aqueous methanol solution, and add salt and 50
Crystals are precipitated by adding g and cooling to 20 to 25 ° C. with stirring. Separately, the crystals are neutralized with ammonia water in water, washed with water, dried and recrystallized from a mixed solvent of toluene and n-heptane. 2,2-bis [3,5-dimethyl-4-
Fine brown crystals of (3-aminophenoxy) phenyl] propane were obtained.

Yield 88.5 g (yield 76%) mp 112-114 ° C The purity determined by high performance liquid chromatography was 99.5%.

IR (KBrcm ^-1 ): 1220 (ether bond) 3440 and 3350 (NH ₄
Group) Example 2 1 In a glass reaction vessel, 2,2-bis (4-hydroxy-)
3-methylphenyl) propane 64 g (0.25 mol), m
-Dinitrobenzene 100.9 g (0.6 mol), potassium carbonate 82.8 g, N, N-dimethylformamide 650
Charge ml and react at 145 to 150 ° C. for 8 hours. After completion of the reaction, the mixture was cooled and discharged into water to give 2,2-bis [3-methyl-
The tar-like substance of 4- (3-nitrophenoxy) phenyl] propane was separated, this tar-like substance was washed with water, and then charged into a 1-glass reaction vessel, and further 12 g of activated carbon and ferric chloride hexahydrate. 1.2 g and methyl cellosolve 63
Charge 0 ml and stir for 30 minutes under reflux. Then 70-8
50 g (1.0 mol) of hydrazine hydrate was added dropwise at 0 ° C. over 2 hours, and the mixture was stirred under reflux for 6 hours. After completion of the reaction, the catalyst was removed by cooling and the methyl cellosolve was distilled off.
% Methanol aqueous solution (500 ml) and concentrated hydrochloric acid (62.5 g) are added and dissolved by heating. Further, 60 g of sodium chloride is added and cooled to 20 to 25 ° C. to precipitate crystals. After separating this, 450 ml of a 20% aqueous methanol solution was added again to dissolve by heating, 45 g of sodium chloride was added, and crystals were precipitated by cooling to 20 to 25 ° C. with stirring. Separated from this, the crystals obtained by neutralizing with ammonia water in water and washing with excess water were added with toluene and dissolved by heating, and then the aqueous layer was separated. Then, crystals were precipitated by adding n-heptane. Separately dried and 2,2-bis [3
A slightly brown crystal of -methyl-4- (3-aminophenoxy) phenyl] propane was obtained.

Yield 79.5 g (yield 72.6%) mp 146-148 ° C The purity determined by high performance liquid chromatography was 99.6%.

IR (K _B rcm ^-1 ): 1225 (ether bond) 3470 and 3390 (NH ₂
Group) Example 3 1 In a glass reaction vessel, 2- (4-hydroxy-3-methylphenyl) -2- (4-hydroxyphenyl) propane 60.5 g (0.25 mol), m-dinitrobenzene 100.9
g (0.6 mol), potassium carbonate (82.8 g) and N, N-dimethylformamide (650 ml) were charged and the temperature was 140 to 150 ° C.
React for 12 hours, cool after completion of the reaction, and discharge into water 3 to obtain crude 2- [3-methyl-4- (3-nitrophenoxy).
The tar of phenyl] -2- [4- (3-nitrophenoxy) phenyl] propane was separated. The tar-like substance is washed with water, then charged into a glass container, 12 g of activated carbon, 1.2 g of ferric chloride hexahydrate and 600 ml of isopropyl alcohol are charged, and the mixture is stirred under reflux for 30 minutes. Next, at 70-80 ° C, 50 g of hydrazine hydrate (1.
(0 mol) was added dropwise over 2 hours and the mixture was stirred under reflux for 6 hours. After cooling, the catalyst was removed and methyl cellosolve was distilled off to obtain 500 ml of 10% aqueous methanol solution and 62.6 g of concentrated hydrochloric acid.
Add 50 g of salt and heat to dissolve.
Crystals precipitate when cooled to -25 ° C. After this 1
When 450 ml of 0% aqueous methanol solution was added and dissolved by heating, 45 g of sodium chloride was added and cooled to 20 to 25 ° C. with stirring to precipitate crystals. Separate this, add toluene and neutralize with ammonia water with stirring, heat and dissolve to separate the aqueous layer.

Then, n-heptane is added to precipitate crystals. The precipitated crystals are separated and dried to give 2- [3-methyl-4- (3-
A slightly brown crystal of aminophenoxy) phenyl] -2- [4- (3-aminophenoxy) phenyl] propane was obtained.

Yield 74.8 g (yield 70.5%) mp 114-116 ° C. Purity by high performance liquid chromatography was 99.3%.

IR (K _B rcm ^-1 ): 1225 (ether bond) 3440 and 3360 (NH
₄ groups) Example 4 1 2- (4-hydroxy-3,5-
Dimethylphenyl) -2- (4-hydroxyphenyl)
Propane 64 g (0.25 mol), m-dinitrobenzene 10
0.9 g (0.6 mol), potassium carbonate 82.8 g and N, N-
Charge 630 ml of dimethylformamide to 140-150
React at 14 ° C for 14 hours. After completion of the reaction, the mixture was cooled and discharged into 3000 ml of water, and the tar-like substance of crude 2- [3,5-dimethyl-4- (3-nitrophenoxy) phenyl] -2- [4- (3-nitrophenoxy) phenyl] propane was collected. separated.

This tar-like material is washed with water, then charged into one glass container, and further 12 g of activated carbon and 1.2 g of ferric chloride hexahydrate.
Then, 630 ml of methyl cellosolve are charged and the mixture is stirred under reflux for 30 minutes. Then, at 70-80 ° C, hydrazine hydrate 50
g (1.0 mol) was added dropwise over 2 hours and the mixture was stirred under reflux for 8 hours. After cooling, the catalyst was removed and the methyl cellosolve was distilled off to obtain 500 ml of 25% aqueous methanol solution and concentrated hydrochloric acid.
2.5 g was added and dissolved by heating, and 50 g of sodium chloride was further added and cooled to 20 to 25 ° C. with stirring to precipitate crystals. After separating this, 400 ml of 25% aqueous methanol solution was added and dissolved by heating, 40 g of sodium chloride was added, and the mixture was cooled to 20 to 25 ° C. with stirring to precipitate crystals. Separated from this, the crystals obtained by neutralizing with ammonia water in water, excess, and washing with water were added with toluene to dissolve by heating, the aqueous layer was separated, and then n-heptane was added to precipitate crystals. The precipitated crystal was separated and dried to obtain a slightly brown crystal of 2- [3,5-dimethyl-4- (3-aminophenoxy) phenyl] -2- [4- (3-aminophenoxyphenyl] propane.

The yield was 82.1 g (yield 75%), and the purity was 99.2% by mp137-139 ° C high performance liquid chromatography.

IR (K _B rcm ^-1 ): 1230 (ether bond) 3450 and 3370 (NH
₂ groups) Example 5 1 2- (4-hydroxy-3-methylphenyl) -2- (4-hydroxyphenyl) propane 60.5 g (0.25 mol) and m-dinitrobenzene 100.9 in a glass reaction vessel.
g (0.6 mol), potassium carbonate (82.8 g) and sulfolane (630 ml) were charged and reacted at 150 to 160 ° C. for 15 hours. After completion of the reaction, post-treatment and purification were carried out in the same manner as in Example 3-2- [3-methyl- 4- (3-aminophenoxy) phenyl] -2- [4- (3-aminophenoxy)
A slightly brown crystal of phenyl] propane was obtained.

Yield 72.6 g (yield 68.5%) mp 114-116 ° C. Purity 99.3% (by high performance liquid chromatography) Example 6 1 2- (4-hydroxy-3,5-
Dimethylphenyl) -2- (4-hydroxyphenyl)
Propane 64 g (0.25 mol), m-dinitrobenzene 10
0.9 g, 82.8 g of potassium carbonate and 650 ml of dimethyl sulfoxide are charged and the reaction is carried out at 150 to 160 ° C. for 8 hours. After completion of the reaction, post-treatment and purification were carried out in the same manner as in Example 4 to give 2- [3,5-dimethyl-4- (3-aminophenoxy) phenyl] -2- [4- (3-aminophenoxy) phenyl]. A slightly brown crystal of propane was obtained. Yield 7
7.9 g (yield 71.2%), mp 137-139 ° C, purity 99.2% (by high performance liquid chromatography).

Example 7 1 Crude 2,2-bis [3-methyl-4- (3-nitrophenoxy) phenyl] propane (0.25 mol) produced in the same manner as in Example 2 was placed in a glass closed container at 5% Pd /. c7
g, and 500 ml of methyl cellosolve. 60
When hydrogen was introduced with vigorous stirring at ˜65 ° C., it was not absorbed any more in 10 hours, and the reaction was completed. Post-treatment and purification were carried out in the same manner as in Example 2 to obtain fine brown crystals of granular crystals of 2,2-bis [3-methyl-4- (3-aminophenoxy) phenyl] propane. Yield 79.9
g (yield 73%).

mp 146-148 ° C, purity 99.5% (by high performance liquid chromatography).

Example 8 1 Crude 2- [3-methyl-4- (3-nitrophenoxy) produced in the same manner as in Example 3 in a glass closed container.
Phenyl] -2- [4- (3-nitrophenoxy) phenyl] propane (0.25 mol) is charged along with 7 g of 5% Pd / c and 500 ml of methyl cellosolve. When hydrogen was introduced with vigorous stirring at 60 to 65 ° C., the reaction was terminated after 9 hours without any further absorption. Post-treatment and purification were carried out in the same manner as in Example 2, and 2- [3-methyl-4- (3
A slightly brown crystal of -aminophenoxy) phenyl] -2- [4- (3-aminophenoxy) phenyl] propane was obtained. Yield 74.2 (Yield 70%), mp114-116 ° C, Purity: 9
9.5% (by high performance liquid chromatography).

Reference Example 1 In a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 2- [4- (3-aminophenoxy) phenyl]-
21.2 g (0.05 mol) of 2- [4- (3-aminophenoxy) -3-methylphenyl] propane and 95.8 g of N, N-dimethylacetamide were charged, cooled to around 0 ° C., and dried under a nitrogen atmosphere. 8.72 g (0.04 mol) of pyromellitic acid was added in 4 portions while paying attention to the rise in the solution temperature, and after stirring at 0 ° C for about 2 hours, the solution was returned to room temperature and further pyromellitic anhydride was added under a nitrogen atmosphere. Acid 2.02g (0.0093
Mol) was added, followed by stirring under a nitrogen atmosphere for about 20 hours.

The polyamic acid thus obtained had an inherent viscosity of 2.10 dl / g.

A part of the polyamic acid solution was taken, cast on a glass plate, and then heated at 100 ° C., 200 ° C., and 300 ° C. for 1 hour to obtain a polyimide film. The glass transition temperature of this polyimide film is 229 ° C, 5% in air
The weight loss temperature was 475 ° C.

This polyimide film was inserted between cold-rolled steel plates preheated to 130 ° C. and pressure-bonded at 320 ° C. for 20 minutes at 20 kg / cm ² . The tensile shear bond strength of this product at room temperature was 300 kg / cm ² , and when it was further measured at a high temperature of 240 ° C., it was 210 kg / cm ² . Reference Examples 2 to 4 In the same manner as in Reference Example 1, the diamine was replaced, and a polyimide was obtained in the same manner, and the physical properties thereof were measured. The results are shown in Table-1.
It was shown to.

Reference Example 5 In Reference Example 1, 2- [4- (3-aminophenoxy) phenyl] -2- [4- (3-aminophenoxy)
2,2 ′ instead of -3-methylphenyl] propane
Using -bis [4- (3-aminophenoxy) phenyl] propane, a polyimide was obtained in the same manner as in Reference Example 1,
Its physical properties were measured. The results are shown in Table-1.

Claims (2)

[Claims] 1. General formula (III) (In the formula, R _{1 to} R ₃ represent a hydrogen atom or a methyl group, and may be the same or different from each other) 2,
A methyl-substituted form of 2-bis [4- (3-aminophenoxy) phenyl] propane. 2. The general formula (I) (In the formula, R _{1 to} R ₃ represent a hydrogen atom or a methyl group, and may be the same or different from each other)
General formula (II) obtained by condensing 4,4′-bisphenol and m-dinitrobenzene in the presence of a base in an aprotic polar solvent. (In the formula, R _{1 to} R ₃ have the same meaning as in the general formula (I))
Represented by the general formula (III), which is characterized by reducing a methyl-substituted derivative of 2,2-bis [4- (3-nitrophenoxy) phenyl] propane. (In the formula, R _{1 to} R ₃ have the same meaning as in the general formula (I))
A method for producing a methyl-substituted derivative of 2,2-bis [4- (3-aminophenoxy) phenyl] propane represented by