JPH0635426B2 - Method for producing 2,4-bis [4- (4-aminophenoxy) phenyl] -2-methylpentane - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing 2,4-bis [4- (4-aminophenoxy) phenyl] -2-methylpentane. More specifically, 4-chloronitrobenzene and 2,4-bis (4-hydroxyphenyl) -4-methyl-1-pentene and / or 2,4-bis (4-hydroxyphenyl) -4-methyl-2-pentene Is reacted in the presence of a base to give 2,4-bis [4- (4-nitrophenoxy) phenyl] -4-methyl-1-pentene and / or 2,
4-bis [4- (4-nitrophenoxy) phenyl]-
It relates to a method for producing 2,4-bis [4- (4-aminophenoxy) phenyl] -2-methylpentane, which comprises producing 4-methyl-2-pentene and further reducing them.

2,4-bis [4- (4-aminophenoxy) phenyl]
-2-Methylpentane (hereinafter abbreviated as BAPP) has no known uses because there has been no example ever produced.

However, as a result of intensive studies on the development of various heat resistant resins, the present inventors have found that the above BAPP is a useful raw material for polyimide resins.

Conventionally, the polyimide resin has high performance, but has a drawback that the molding process is difficult. For example, the most typical aromatic polyimide consisting of 4,4′-diaminodiphenyl ether and pyromellitic dianhydride (Dupont, trade name “Vespel”) is insoluble and infusible, so it is special Use the method. With this method, since a processed product having a complicated shape cannot be obtained, it is necessary to perform processing by cutting or the like, resulting in an increase in cost, which is a major drawback in addition to difficulty in molding. We have
In order to improve these drawbacks, we have investigated various compounds with the expectation that if an aliphatic carbon skeleton or an aromatic ether bond is introduced into the polyimide resin structure, flexibility and molding processability will be improved. did. As a result, according to the present invention
We have found that BAPP imparts the expected performance to the polyimide resins obtained with it.

That is, the polyimide resin composed of BAPP and 3,3′4,4′-benzophenone tetracarboxylic acid anhydride has a relatively low glass transition temperature (Tg) of 201 ° C. and has a heat resistance of 5% weight reduction in air. The temperature was about 500 ° C, and a very useful polyimide resin having satisfactory moldability and thermal stability was obtained. Furthermore, it was surprisingly found that this polyimide resin has a very significant feature that it is soluble in a bulking agent. In the conventional polyimide resin, most of its applications are used in the form of a film such as a flexible printed circuit, but these polyimide films are precursors for most of the various polyimide resins because they are insoluble in solvents. It is manufactured by casting a solvent solution in a state called amic acid, drying the solution, and then subjecting it to dehydration ring closure by high-temperature heat treatment. However, this method has a drawback that small holes called voids are likely to be formed because water is generated at the time of imidization by heating, and it is difficult to obtain a uniform film. However, the polyimide resin using BAPP according to the present invention is aprotic polar solvent, soluble in ether solvents and halogenated hydrocarbon solvents, and the like,
After being imidized in a solvent, it is simply cast and dried to produce a very homogeneous film.

Therefore, the development of the BAPP of the present invention provides an extremely useful polyimide resin having excellent flexibility and film processability.

(Prior Art) Conventionally, 4-chloronitrobenzene and bisphenols are reacted to obtain a bis (4-nitrophenoxy) compound,
An example is known in which this is reduced to produce a bis (4-aminophenoxy) compound. For example, bis (4-nitrophenoxy) biphenyl is obtained from 4-chloronitrobenzene and 4,4'-biphenol, which is reduced to give bis (4
-Aminophenoxy) biphenyl was produced (28th National SAMPE Symposium
ymposium), April issue, 12-14, 728-739 (1983)), 2,2 '
Bis (4-aminophenoxy) phenylpropane is produced from -bis (4-hydroxyphenyl) propane (Rocz Chem 48 1459 (197)
Four)).

However, 2,4-bis (4-hydroxyphenyl) -4-methyl-1-pentene represented by the formula (1) or the formula
2,4-bis (4-hydroxyphenyl) represented by (2)
BAP represented by formula (5) from -4-methyl-2-pentene
There are no known examples of inducing P.

(Problems to be Solved by the Invention) The present inventors are the raw materials of this useful polyimide resin.
The method of manufacturing BAPP was earnestly studied. As a result, 4-
2,4-bis (4-hydroxyphenyl) -4-methyl-1-pentene or 2,4-obtained as a linear dimer of chloronitrobenzene and 4-isopropenylphenyl
The present invention has been completed by finding that the target BAPP can be easily produced in a high yield from the two steps of condensation and reduction of bis (4-hydroxyphenyl) -4-methyl-2-pentene.

That is, the present invention relates to 4-chlorobenzene and formula (1) 2,4-bis (4-hydroxyphenyl)-
4-methyl-1-pentene and / or formula (2) 2,4-bis (4-hydroxyphenyl)-
4-methyl-2-pentene was reacted in the presence of a base to give the compound of formula (3) 2,4-bis [4- (4-nitrophenoxy) phenyl] -4-methyl-1-pentene represented by and / or formula (4) 2,4-bis [4- (4-nitrophenoxy) phenyl] -4-methylpentene represented by
Equation (5) characterized by reducing these The method for producing 2,4-bis [4- (aminophenoxy) phenyl] -2-methylpentane represented by

The present invention will be specifically described. In order to obtain the target compound, BAPP, by the method of the present invention, a condensation step and a reduction step are performed.

First, in the condensation step, 4-chloronitrobenzene as a raw material, 2,4-bis (4-hydroxyphenyl) -4-methyl-1-pentene represented by the formula (1) and 2,4-bis represented by the formula (2). Bis (4-hydroxyphenyl) -4-methyl-2-pentene or a mixture of these bisphenols is reacted with a solvent in the presence of a base. as a result,
2,4-bis (4-hydroxyphenyl) -4-methyl-
From 1-pentene, 2,4-bis [4- represented by the formula (3)
(4-Nitrophenoxy) phenyl] -4-methyl-1
-Pentene is 2,4-bis (4-hydroxyphenyl)
From -4-methyl-2-pentene, 2,4-bis [4-
(4-Nitrophenoxy) phenyl] -4-methyl-2
-Pentene is produced and from the mixed bisphenols a corresponding proportion of the nitrophenoxy form is produced.

Any of these nitrophenoxy compounds can be led to the target BAPP in the subsequent reduction step. That is, by the reduction method of the present invention, 2,4-bis [4- (4-nitrophenoxy) phenyl] -4-methyl-1-pentene and 2,4
-Bis [4- (4-nitrophenoxy) phenyl] -4
In the case of -methyl-2-pentene, the nitro group becomes an amino group and the unsaturated bond is reduced to a saturated bond. Therefore, the mixture can be used as a target product regardless of the mixture composition.

The starting materials used in this condensation step are 2,4-bis (4-hydroxyphenyl) -4-methyl-1-pentene and 2,4
-Bis (4-hydroxyphenyl) -4-methyl-2-
Pentene or a mixture thereof is obtained as a linear dimer of 4-isopropenylphenol (JP-A-50-3515).
0).

The other raw material, 4-chloronitrobenzene, is used in a molar amount of 2 to 3 times that of the above-mentioned two kinds of bisphenol compounds and their mixture. It is preferably carried out in the range of 2.1 to 2.4 times by mole.

Examples of the base used in this condensation step include alkali metal carbonates, hydrogen carbonates, hydroxides and alkoxides, such as potassium carbonate, sodium carbonate, potassium hydrogen carbonate, potassium hydroxide, sodium hydroxide, lithium hydroxide. , Sodium methoxide, potassium isopropoxide and the like. Of these, potassium carbonate, sodium hydroxide and potassium hydroxide are preferable.

The amount of the base used is 2 equivalents or more, preferably 2.2 to 3 equivalents, relative to the raw material bisphenol.

As the solvent used in the condensation process, a usual aprotic polar solvent is used. They are, for example, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-
2-imidazolidinone, hexamethylphosphortriamide, sulfolane and the like. Further, using an organic solvent immiscible with water, for example, benzene, toluene, xylene, chlorobenzene, 1,2-dichloroethane, 1,1,2-trichloroethane, etc., to react in a heterogeneous system of the organic solvent layer and the aqueous layer. You can also The amount of the solvent used in these homogeneous and heterogeneous systems is not particularly limited, but it is usually sufficient to use 1 to 15 times by weight of the raw material.

The reaction temperature is usually in the range of 70 to 220 ° C, preferably 80 to 180 ° C.

The end point of this reaction can be determined by thin layer chromatography or high performance liquid chromatography while observing the reduction of unreacted intermediates.

As a general embodiment of this condensation step, in a homogeneous reaction using an aprotic polar solvent, a predetermined amount of bisphenol, a base and a solvent are charged to prepare an alkali metal salt of bisphenol and then 4-chloronitrobenzene. May be added and reacted, or all the raw materials containing 4-chloronitrobenzene may be simultaneously added in advance and the temperature may be raised as it is to react. Of course, the present invention is not limited to these and can be appropriately implemented by other modes. The post-treatment method after the reaction can be carried out by concentrating the solvent or directly adding it to water or the like to obtain the intermediate compound. In the method of conducting the condensation in a heterogeneous system using an organic solvent immiscible with water, a general phase transfer catalyst such as quaternary ammonium salt, quaternary phosphonium salt or crown ether is used. For example, triethylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium bromide, tetraphenylphosphonium chloride, trioctylethylphosphonium chloride, 18-crown-6-ether and the like are used. Industrially inexpensive quaternary ammonium salts are often used. The amount of contact used is usually in the range of 0.1 to 30% by weight, preferably 1 to 10%, based on the raw materials.

In this reaction, in order to accelerate the reaction, it is possible to raise the temperature and carry out under slightly pressurized conditions. The post-treatment method after completion of the reaction is to remove the aqueous layer by liquid separation and then perform steam distillation to obtain an intermediate compound, or recover the solvent as it is to obtain an intermediate compound.

Next, this intermediate compound is reduced to lead to a desired product. In this reduction step, catalytic reduction is performed in a solvent in the presence of a reduction catalyst.

As the solvent, water, alcohols such as methanol, ethanol, isopropanol, isobutanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, propylene glycol, diglyme, tetraglyme, dioxane, tetrahydrofuran, glycols, ethers are preferably used. And sometimes hexane,
Cyclohexane, benzene, toluene, ethyl acetate, butyl acetate, dichloromethane, 1,2-dichloroethane, 1,
Aliphatic hydrocarbons such as 1,2-trichloroethane, aromatic hydrocarbons, esters and halogenated hydrocarbons can also be used. These solvents may be used alone or in combination of two or more. The amount of the solvent used is not particularly limited, but usually 1 to 15 times the weight of the raw material is sufficient.

As the reduction catalyst, commonly used reduction catalysts such as palladium, platinum, rhodium, ruthenium, Raney nickel, copper, iron and the like can be used. These catalysts can be used in a metal state, but they are usually used by supporting them on the surface of a carrier such as carbon, barium sulfate, silica gel and alumina. Industrially, palladium or platinum catalyst supported on activated carbon or Raney nickel catalyst is used.

The amount of these catalysts used was 0.
It is in the range of 01 to 30% by weight, and is usually in the range of 0.05 to 5% by weight when used by being supported on a carrier.

The reaction temperature is generally in the range of 1 to 150 ° C, particularly 10
The range of -100 ° C is preferred.

In the catalytic reduction method, the reaction pressure is usually 50 kg.
Any pressure below / cm ² is sufficient, and there is no inconvenience at normal pressure.

In a general embodiment of this reduction step, a solvent is added to the intermediate compound obtained in the condensation step to dissolve or suspend it, and then a catalyst used in the reduction reaction is added to carry out reduction.

The reaction is carried out until the absorption of hydrogen gas is quantified or the absorption of hydrogen gas is stopped.

The progress of the reaction can be known by thin layer chromatography or high performance liquid chromatography.

After completion of the reaction, the target BAPP can be obtained by concentrating the solvent or diluting it with water or the like.

(Operation and Effect) The present invention provides a novel and useful method for producing a diamine monomer.

According to this method, the diamine monomer can be produced in a high yield with inexpensive raw materials. Since the polyimide resin obtained from this diamine monomer has a relatively low glass transition temperature and is soluble in a solvent, it has satisfactory performance in terms of molding processability and film processability. Therefore, the development of the industrial manufacturing method of BAPP makes it possible to inexpensively supply a large amount of highly functional polyimide resin.

The method for producing BAPP of the present invention has a high purity in a simple working process,
It is an industrially suitable production method that can be produced in high yield.

(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 A reactor equipped with a stirrer, thermometer, reflux condenser and water separator is equipped with 2,4-bis (4-hydroxyphenyl) -4-.
Methyl-1-pentene (Mitsui Toatsu Chemicals, mp129.5-131
℃) 76.1g (0.25mol), 96% flake caustic soda
22.9 g (0.55 mol), 30 m of benzene and 250 m of dimethyl sulfoxide were charged, and the temperature was raised while nitrogen gas was being passed through to carry out azeotropic dehydration in the refluxed state of benzene. Then, 86.7 g (0.55 mol) of 4-chloronitrobenzene was added, and the reaction was carried out at a temperature of 100 to 110 ° C for 5 hours. After the reaction was completed, the solvent was recovered by concentrating under reduced pressure and then water 500m
Discharged to. The light brown powder that has precipitated is dried and dried.
126.9 g of 2,4-bis [4- (4-nitrophenoxy) phenyl] -4-methyl-1-pentene were obtained (yield 99.4
%).

It was recrystallized from methyl cellosolve to give pure white needles.
2,4-bis [4- (4-nitrophenoxy) phenyl]
-4-Methyl-1-pentene was obtained. Melting point is 139-140 ℃
The results of elemental analysis are as follows.

Next, in a closed reduction reactor equipped with a stirrer and a thermometer, 10.21 g (0.02 mol) of 2,4-bis [4- (4-nitrophenoxy) phenyl] -4-methyl-1-pentene was prepared, % Pd / C catalyst 0.3g and ethanol 30m
Was charged, and hydrogen gas was introduced with vigorous stirring. When the reaction was carried out at a reaction temperature of 60 to 70 ° C. for 8 hours, 3150 m of hydrogen was absorbed and further absorption was not observed, so the reaction was terminated. After completion of the reaction, the catalyst palladium carbon was removed, and the solvent was recovered by concentrating with an evaporator. Next, 6.5 g of concentrated hydrochloric acid and 80 parts of water are added to this residue.
After m was added, the mixture was heated and dissolved, the mixture was slowly cooled to precipitate crystals of 2,4-bis [4- (4-aminophenoxy) phenyl] -2-methylpentane hydrochloride. After taking this, it was neutralized with aqueous ammonia in 50 m of isopropanol. When left to cool, white needle-like crystals were precipitated. This is the desired product, 2,4-bis [4- (4-aminophenoxy) phenyl] -2-methylpentane,
After filtration, washing and drying, 7.3 g (yield 80.6%) was obtained. Melting point 1
05.5 ~ 107 ℃ NMR spectrum measurement solvent: acetone -D ₆ Measurement temperature: room temperature 0.8~1.5ppm (9H multiplet) 2.0~2.3ppm (2H multiplet) 2.3~2.8ppm (1H multiplet) 3.0~4.3ppm (4H singlet) 6.4 -7.4ppm (16H multiplet) MS spectrum (M / e) M ⁺ 452,226,212,108 Example 2 A reactor equipped with a stirrer, thermometer and reflux condenser
4-bis (4-hydroxyphenyl) -4-methyl-2
-Pentene (Mitsui Toatsu Chemicals, mp162.5-165.5 ℃) 6.71
g (0.025 mol), 4-chloronitrobenzene 8.67g
(0.055 mol), anhydrous potassium carbide 4.14 g (0.03 mol)
And 35 m of N, N-dimethylformamide are charged,
The reaction was carried out while bubbling nitrogen gas through. The reaction was carried out with stirring at a temperature of 150 to 155 ° C. for 8 hours. After completion of the reaction, the reaction solution was cooled and then poured into 200 m of water to give 2,4-bis [4- (4-nitrophenoxy), a pale yellow resinous product.
Phenyl] -4-methyl-2-pentene separated into the lower layer. Next, the above-mentioned 2,4-bis [4- (4-nitrophenoxy) phenyl] -4-methyl-2-pentene and 10% Pt were added to the same reduction reactor as in Example 1 except that the upper water was decanted.
/ C catalyst (0.1 g) and isopropanol (30 m) were charged, and hydrogen gas was introduced with vigorous stirring. When the reaction was carried out at a reaction temperature of 50 to 60 ° C. for 12 hours, 3145 m of hydrogen was absorbed and further absorption was not observed, so the reaction was terminated. After the completion of the reaction, the catalyst was heated to remove platinum carbon as a catalyst, 15 m of pure water was added and the mixture was allowed to stand, and white needle-like crystals were precipitated. This is the desired product, 2,4-bis [4- (4-aminophenoxy) phenyl] -2-methylpentane, which was dried over and dried to obtain 9.5 g (yield 8
4.0%). Melting point 105-107 ° C MS spectrum (M / e) M ⁺ 452,226,212,108 Example 3 32.1 g (0.55 mol) of 96% potassium caustic as a base and 1,3-dimethyl-2-imidazolidinone 350 m as a solvent
2,4-bis [4- (4-nitrophenoxy), an intermediate compound, was subjected to the condensation reaction in the same manner as in Example 1 except that
126.6 g of phenyl] -4-methyl-1-pentene was obtained (yield 99.2%). Next, in the reduction reactor, 10.21 g (0.02 mol) of 2,4-bis [4- (4-nitrophenoxy) phenyl] -4-methyl-1-pentene, 0.5 g of 5% Pd / C catalyst and methyl cellosolve were added. 50 m was charged, and hydrogen was introduced at a temperature of 40 to 50 ° C. for reduction. Post-treatment after completion of the reaction was performed in the same manner as in Example 1 to obtain 6.9 g (yield: 76.2%) of the desired product. Melting point 105-107 ° C Example 4 13.41 g (0.05 mol) of 2,4-bis (4-hydroxyphenyl) -4-methyl-1-pentene in an autoclave equipped with a stirrer and a thermometer, 6.14 g of 96% potassium caustic
(0.105 mol), 4-chloronitrobenzene 17.34 g (0.
(11 mol), 50 m of water, 50 m of toluene and 1 g of trioctylmethylammonium chloride as a catalyst were charged, and the reaction was carried out at a temperature of 130 to 140 ° C. for 12 hours. After completion of the reaction, the lower layer was extracted and the organic layer was distilled by steam to recover the solvent. After cooling, get the residue and get 100m
Was recrystallized from methyl cellosolve to give 18 g of 2,4-bis [4- (4-nitrophenoxy) phenyl] -4-methyl-1-pentene (yield 70.6%). 2 g of Raney nickel catalyst and 50 g of diglyme were added to this intermediate compound.
It was charged into the autoclave for reduction together with the temperature of 80
The reduction reaction was carried out at ˜90 ° C. and hydrogen pressure of 30 kg / cm ^{2 for} 1 hour. Post-treatment after the reaction was carried out in the same manner as in Example 1 to obtain 12.4 g of the desired product (total yield: 54.8%).

Example 5 2,4-bis (4-hydroxyphenyl) -4-methyl-
1-pentene and 2,4-bis (4-hydroxyphenyl)
A crude dinitro compound was obtained in the same manner as in Example 1 by using 67.1 g of an isomer mixture of -4-methyl-2-pentene in a gas chromatographic ratio of 93: 7. 2,4-bis [4- (4-aminophenoxy) phenyl] -2-methylpentane was obtained. yield
86.3 g (yield 76.3%), melting point 105-107 ° C

Claims (1)

[Claims] 1. A compound of formula (1) and 4-chloronitrobenzene. 2,4-bis (4-hydroxyphenyl) represented by
-4-Methyl-1-pentene and / or formula (2) 2,4-bis (4-hydroxyphenyl) represented by
-4-Methyl-2-pentene is reacted in the presence of a base to give a compound of formula (3) 2,4-bis [4- (4-nitrophenoxy) phenyl] -4-methyl-1-pentene represented by and / or formula (4) 2,4-bis [4- (4-nitrophenoxy) phenyl] -4-methyl-2-pentene represented by
Furthermore, formula (5) characterized by reducing these A method for producing 2,4-bis [4- (4-aminophenoxy) phenyl] -2-methylpentane represented by