JP2002316970A - Method for producing aromatic polyether polyamines - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently producing an aromatic polyether polyamines extremely effective as a raw material or the like for a highly heat- resistant polyimide by eliminating conventional defects. SOLUTION: An aromatic polyfluoro compounds represented by general formula 1: R1 -(F)n (1) (R1 is a 6-24C monocyclic aromatic group, or noncondensed polycyclic aromatic group obtained by linking aromatic rings directly or by using a cross-linking member; n is an integer of 2-10; with the proviso that the substituted positions of n F-groups are not vicinal positions) are reacted with aromatic aminophenols represented by general formula 2: (OH)o-R2 -(NH2)p (2) (R2 is a 6-24C monocyclic aromatic group, condensed polycyclic aromatic group or noncondensed polycyclic aromatic group obtained by linking aromatic groups directly or by using a cross-linking member; and o and p are each independently an integer of 1-5) in the presence of an alkali metal to convert the whole F group-substituted positions to ether bonds, and to produce the objective aromatic polyether polyamines.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel method for producing polyetherpolyamines useful as raw materials for heat-resistant high-molecular monomers, particularly polyimides, in a simple and high yield.

[0002]

2. Description of the Related Art Polyimide resins are widely used as electric and electronic materials because of their high heat resistance, flame retardancy and excellent electrical insulation. Polyimide is obtained by the reaction of polycarboxylic anhydride and primary polyamine,
In order to satisfy performance such as heat resistance, a polyimide resin using an aromatic polyamine as a raw material occupies the mainstream. Of these, aromatic polyether polyamines such as bis (aminophenoxy) aryls and bis (aminophenoxyphenyl) s are known as one of the highest heat-resistant polymer raw materials among polyimides (U.
SP3845018, USP3879349). As a method for producing aromatic polyether polyamines, for example, a method in which the corresponding chlorinated benzenes or brominated benzenes are synthesized by Ullmann condensation of phenols, a polynitroaryl and a phenol in the presence of an alkali metal are used. A two-step method or the like in which a corresponding poly (nitrophenoxy) aryl is once synthesized by reacting and then subjected to catalytic reduction using a noble metal catalyst or the like is well known. The former Ullmann reaction generally requires a reaction accelerator such as copper and requires a long time at a high temperature. Furthermore, since the yield is low and there are many by-products,
The cost tends to be high, and a large load is required for purification.

In the latter two-stage method, since the number of steps is as large as two, equipment costs are increased, and the condensation reaction of the nitro group is liable to produce tar, thereby decreasing the yield of the subsequent reduction step. A problem occurs and the cost is likely to increase.
That is, in a method for producing an aromatic polyether polyamine which is extremely effective as a highly heat-resistant polyimide raw material, a sufficient production method has not yet been provided, and there is room for improvement.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing aromatic polyether polyamines which overcomes the disadvantages of the prior art.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies on a method for producing an aromatic polyether polyamine which is extremely effective as a highly heat-resistant polyimide raw material and the like. Aromatic polyfluoro compounds and aromatic aminophenols having a specific structure, when reacted in the presence of an alkali metal, found that the desired aromatic polyether polyamines can be produced more efficiently than conventional methods, The present invention has been reached.

That is, the present invention relates to a compound represented by the formula (1) R _1- (F) n (1) wherein R ₁ has 6 to 24 carbon atoms and is a monocyclic aromatic group in one molecule. Or an aromatic group is selected from the group consisting of non-condensed polycyclic aromatic groups which are connected to each other directly or by a bridging member, and n represents an integer of 2 to 10. In addition, n F group substitution positions aromatic polyfluoro compounds containing a specific structure represented by not adjacent to each other), at least the general formula in one molecule (2) (OH) o- R 2 -. (NH2) p (2) (Wherein R ₂ has 6 to 24 carbon atoms, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are directly or mutually linked by a bridge member. Selected from the group consisting of aromatic groups, and o and p independently represent an integer of 1 to 5.) The family aminophenols, reacted with an alkali metal presence, a process for producing an aromatic polyether polyamines, characterized in that for all the F group substitution positions ether bond.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

An aromatic polyfluoro compound having a specific structure represented by the formula (1), which is one of the raw materials used in the present invention, means that at least a fluorine atom as a halogen group bonded to a benzene ring is arbitrarily bonded. Is an aromatic polyfluoro compound in which only two or more fluorine atoms having a mono (poly) fluorophenyl skeleton are bonded. However, those whose fluorine substitution positions are adjacent to each other are excluded. Accordingly, an aromatic polyfluoro compound having any structure may be used as long as this rule is satisfied.

[0009] Among them, relatively preferred compounds include, for example, 1,3-difluorobenzene,
2,4-difluorotoluene, 1,3,5-trifluorobenzene, 2,4,6-trifluorotoluene, 2,
2'-difluorobiphenyl, 3,3'-difluorobiphenyl, 4,4'-difluorobiphenyl, 2,3 '
-Difluorobiphenyl, 2,4'-difluorobiphenyl, 3,4'-difluorobiphenyl, 4,4'-difluorobiphenyl, bis (2-fluorophenyl) ketone, bis (3-fluorophenyl) ketone, bis (4
-Fluorophenyl) ketone, (2-fluorophenyl) (3-fluorophenyl) ketone, (2-fluorophenyl) (4-fluorophenyl) ketone, (3-fluorophenyl) (4-fluorophenyl) ketone, bis ( 2-fluorophenyl) methane, bis (3-fluorophenyl) methane, bis (4-fluorophenyl) methane, (2-fluorophenyl) (3-fluorophenyl) methane, (2-fluorophenyl) (4-fluorophenyl ) Methane, (3-fluorophenyl) (4-fluorophenyl) methane, bis (2-fluorophenyl) -2,2-propane, bis (3-fluorophenyl) -2,2-propane, bis (4 -Fluorophenyl) -2,2, -propane, (2-fluorophenyl)
(3-fluorophenyl) -2,2, -propane, (2
-Fluorophenyl) (4-fluorophenyl) -2,
2, -propane, (3-fluorophenyl) (4-fluorophenyl) -2,2-propane, bis (2-fluorophenyl) amine, bis (3-fluorophenyl)
Amine, bis (4-fluorophenyl) amine, (2-
Fluorophenyl) (3-fluorophenyl) amine,
(2-fluorophenyl) (4-fluorophenyl) amine, (3-fluorophenyl) (4-fluorophenyl) amine, tris (2-fluorophenyl) amine,
Tris (3-fluorophenyl) amine, tris (4-
Fluoro (phenyl) amine, bis (4-fluorophenyl) sulfide, bis (3-fluorophenyl) sulfone, bis (2-fluorophenyl) ether, bis (3
-Fluorophenyl) ether, bis (4-fluorophenyl) ether, (2-fluorophenyl) (3-fluorophenyl) ether, (2-fluorophenyl)
(4-fluorophenyl) ether, (3-fluorophenyl) (4-fluorophenyl) ether, 1,3
5-tris (2-fluorophenyl) benzene, 1,
3,5-tris (3-fluorophenyl) benzene,
1,3,5-tris (4-fluorophenyl) benzene, 1,2,4-tris (2-fluorophenyl) benzene, 1,2,4-tris (3-fluorophenyl) benzene, 1,2,4 -Tris (4-fluorophenyl)
Examples include benzene, but the present invention is not limited to only these exemplified compounds.

The other raw material, an aromatic aminophenol having a specific structure represented by the formula (2), refers to an aniline structure having an amino group bonded to at least a benzene ring and a phenol structure having a hydroxy group bonded to a benzene ring. The compound is a compound having both of them arbitrarily, and aromatic aminophenols having any structure may be used as long as this rule is satisfied.

For example, one aromatic ring may have one or more amino groups and one or more hydroxy groups, but an aromatic ring having one or more amino groups and one or more hydroxy groups. Aromatic ring is direct or alkylene (arylene)
Or a part or all of the hydrogen atoms in the aromatic ring may be substituted with alkyl (aryl) or substituted with a halogen atom other than fluorine. . Examples of relatively preferred compounds among them include, for example, 2-aminophenol, 3-aminophenol, 4-aminophenol,
2,4-diaminophenol, 2,6-diaminophenol, 2-aminonaphthol, 3-aminonaphthol,
4-aminonaphthol, 5-aminonaphthol, 6-aminonaphthol, 7-aminonaphthol, 8-aminonaphthol, 2-amino-2'-hydroxy-biphenyl, 3-amino-3'-hydroxy-biphenyl, 4-aminonaphthol
Amino-4'-hydroxy-biphenyl, 2-amino-
3'-hydroxy-biphenyl, 2-amino-4'-hydroxy-biphenyl, 3-amino-2'-hydroxy-biphenyl, 3-amino-4'-hydroxy-biphenyl, 4-amino-2'-hydroxy-biphenyl , 4
-Amino-3'-hydroxy-biphenyl, 2-aminophenyl-2'-hydroxyphenyl-ketone, 3-aminophenyl-3'-hydroxyphenyl-ketone, 4
-Aminophenyl-4'-hydroxyphenyl-ketone, 2-aminophenyl-3'-hydroxyphenyl-
Ketone, 2-aminophenyl-4'-hydroxyphenyl-ketone, 3-aminophenyl-2'-hydroxyphenyl-ketone, 3-aminophenyl-4'-hydroxyphenyl-ketone, 4-aminophenyl-2'-hydroxy Phenyl-ketone, 4-aminophenyl-3′-
Hydroxyphenyl-ketone, 2-aminophenyl-
2'-hydroxyphenyl-methane, 3-aminophenyl-3'-hydroxyphenyl-methane, 4-aminophenyl-4'-hydroxyphenyl-methane, 2-aminophenyl-3'-hydroxyphenyl-methane, 2-
Aminophenyl-4′-hydroxyphenyl-methane,
3-aminophenyl-2'-hydroxyphenyl-methane, 3-aminophenyl-4'-hydroxyphenyl-
Methane, 4-aminophenyl-2'-hydroxyphenyl-methane, 4-aminophenyl-3'-hydroxyphenyl-methane, 2-aminophenyl-2'-hydroxyphenyl-2,2-propane, 3-aminophenyl-
3'-hydroxyphenyl-2,2-propane, 4-aminophenyl-4'-hydroxyphenyl-2,2-propane, 2-aminophenyl-3'-hydroxyphenyl-2,2-propane, 2-aminophenyl -4'-hydroxyphenyl-2,2-propane, 3-aminophenyl-2'-hydroxyphenyl-2,2-propane,
3-aminophenyl-4'-hydroxyphenyl-2,
2-propane, 4-aminophenyl-2'-hydroxyphenyl-2,2-propane, 4-aminophenyl-
3'-hydroxyphenyl-2,2-propane, 4-aminophenyl-4'-hydroxyphenyl-sulfide, 2-aminophenyl-2'-hydroxyphenyl-
Sulfone, 3-aminophenyl-3'-hydroxyphenyl-sulfone, 4-aminophenyl-4'-hydroxyphenyl-sulfone, 2-aminophenyl-3'-hydroxyphenyl-sulfone, 2-aminophenyl-
4'-hydroxyphenyl-sulfone, 3-aminophenyl-2'-hydroxyphenyl-sulfone, 3-aminophenyl-4'-hydroxyphenyl-sulfone,
-Aminophenyl-2'-hydroxyphenyl-sulfone, 4-aminophenyl-3'-hydroxyphenyl-
Sulfone, 2-aminophenyl-2'-hydroxyphenyl-ether, 3-aminophenyl-3'-hydroxyphenyl-ether, 4-aminophenyl-4'-hydroxyphenyl-ether, 2-aminophenyl-
3'-hydroxyphenyl-ether, 2-aminophenyl-4'-hydroxyphenyl-ether, 3-aminophenyl-2'-hydroxyphenyl-ether, 3
-Aminophenyl-4'-hydroxyphenyl-ether, 4-aminophenyl-2'-hydroxyphenyl-
Ether, 4-aminophenyl-3'-hydroxyphenyl-ether, 2-aminophenyl-2'-hydroxyphenyl-benzene, 3-aminophenyl-3'-hydroxyphenyl-benzene, 4-aminophenyl-
4'-hydroxyphenyl-benzene, 2-aminophenyl-3'-hydroxyphenyl-benzene, 2-aminophenyl-4'-hydroxyphenyl-benzene, 3
-Aminophenyl-2'-hydroxyphenyl-benzene, 3-aminophenyl-4'-hydroxyphenyl-
Benzene, 4-aminophenyl-2'-hydroxyphenyl-benzene, 4-aminophenyl-3'-hydroxyphenyl-benzene, 2-aminophenyl-2'-hydroxyphenyl-amine, 3-aminophenyl-3 '
-Hydroxyphenyl-amine, 4-aminophenyl-
4'-hydroxyphenyl-amine, 2-aminophenyl-3'-hydroxyphenyl-amine, 2-aminophenyl-4'-hydroxyphenyl-amine, 3-aminophenyl-2'-hydroxyphenyl-amine, 3-
Aminophenyl-4′-hydroxyphenyl-amine,
4-aminophenyl-2'-hydroxyphenyl-amine, 4-aminophenyl-3'-hydroxyphenyl-
Amine, (4-aminophenyl) -di (4-hydroxyphenyl) -amine, di (4-aminophenyl)-(4
-Hydroxyphenyl) -amine, (3-aminophenyl) -di (3-hydroxyphenyl) -amine, di (3
-Aminophenyl)-(3-hydroxyphenyl) -amine, (2-aminophenyl) -di (2-hydroxyphenyl) -amine, di (2-aminophenyl)-(2-
(Hydroxyphenyl) -amine, (3-aminophenyl) -di (4-hydroxyphenyl) -amine, di (3
-Aminophenyl)-(4-hydroxyphenyl) -amine, (4-aminophenyl) -di (3-hydroxyphenyl) -amine, di (4-aminophenyl)-(3-
(Hydroxyphenyl) -amine, (4-aminophenyl) -di (2,4-dihydroxyphenyl) -amine,
Di (2,4-diaminophenyl)-(4-hydroxyphenyl) -amine, (4-aminophenyl) -di (4-
(Hydroxyphenyl) -benzene, di (4-aminophenyl)-(4-hydroxyphenyl) -benzene, (3
-Aminophenyl) -di (3-hydroxyphenyl)-
Benzene, di (3-aminophenyl)-(3-hydroxyphenyl) -benzene, (2-aminophenyl) -di (2-hydroxyphenyl) -benzene, di (2-aminophenyl)-(2-hydroxyphenyl) -Benzene, (3-aminophenyl) -di (4-hydroxyphenyl) -benzene, di (3-aminophenyl)-(4-
(Hydroxyphenyl) -benzene, (4-aminophenyl) -di (3-hydroxyphenyl) -benzene, di (4-aminophenyl)-(3-hydroxyphenyl)
-Benzene, (4-aminophenyl) -di (2,4-dihydroxyphenyl) -benzene, di (2,4-diaminophenyl)-(4-hydroxyphenyl) -benzene, and the like. However, the present invention is not limited to only the exemplified compounds.

The alkali metal used in the present invention is a basic substance containing an alkali metal. Specific examples of the compound include, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium hydroxide. , Alkali metal hydroxides such as lithium hydroxide, sodium carbonate,
Alkali metal carbonates such as sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, calcium carbonate, magnesium carbonate, etc., alkali metal hydrides such as sodium hydride, potassium hydride, magnesium hydride, calcium hydride, sodium, potassium, magnesium , Alkali metal such as calcium, sodium methylate,
Examples thereof include alkali metal alkoxylates such as potassium t-butoxide, and alkali metal weak acid salts such as sodium acetate, sodium monohydrogen phosphate and potassium monohydrogen phosphate, but the present invention is limited to only these exemplified compounds. Not something.

[0013] The aromatic polyether polyamines obtained by the method of the present invention refer to aromatic compounds having at least two or more ether groups directly bonded to at least two aromatic rings and one or more amino groups directly bonded to two or more aromatic rings in one molecule. Aromatic polyether polyamines having any structure may be used as long as they satisfy this rule. For example, some or all of the hydrogen atoms on the aromatic ring may be substituted with an alkyl (aryl) group, a hetero group, or the like. Some examples of these aromatic polyether polyamines include, for example, bis (aminophenoxy) benzene, tris (aminophenoxy) benzene, bis (aminophenoxy) biphenyl, bis (aminophenoxyphenyl) methane, bis (amino) Phenoxyphenyl) -2,
2-propane, bis (aminophenoxyphenyl) cyclohexane, bis (aminophenoxyphenyl) ether, bis (aminophenoxyphenyl) sulfide, bis (aminophenoxyphenyl) sulfone, bis (aminophenoxyphenyl) amine, tris (aminophenoxyphenyl) Examples include amines, but the present invention is not limited to only these listed compounds.

An embodiment of the present invention relates to a method for preparing an aromatic polyfluoro compound having a specific structure represented by the formula (1) and an aromatic aminophenol having a specific structure represented by the formula (2) in the presence of an alkali metal. It is a reaction. More specifically, for example, a polar solvent and an aromatic aminophenol having a specific structure represented by the formula (2) are charged into a reactor equipped with a reflux condenser, and the mixture is stirred under vigorous stirring to give an alkali. The metal is gradually charged to form an alkali metal salt of an aromatic aminophenol. Next, when there is water in the system, an azeotropic solvent is charged, heated to reflux, and the water azeotropically separated into the reflux unit is separated and removed from the system. There is a method in which an aromatic polyfluoro compound is added and reacted to obtain a desired aromatic polyether polyamine. Solvents relatively preferably used as the azeotropic solvent include, for example, toluene, xylene, benzene, chlorobenzene, dichlorobenzene, nitrobenzene, hexane, dichloroethane and the like.

[0015] In addition to the above azeotropic solvents, other solvents are suitably used as necessary. Among them, when a polar solvent is used, favorable results may be obtained. Here, if a part of the polar solvent is exemplified, for example, protic polar solvents such as methanol, ethanol, isopropanol, methoxyethanol, ethylene glycol and polyethylene glycol, acetonitrile, N, N-dimethylformamide, N, N- Dimethylacetamide, dimethylsulfoxide, dimethylsulfone, sulfolane,
Aprotic polar solvents such as N-methylpyrrolidone and 1,3-dimethyl-2-imidazolidinone;
The present invention is not limited to only the solvents exemplified above. Also, an aromatic aminophenol having a specific structure represented by the formula (2) is charged into the azeotropic solvent shown above, and an aqueous alkali metal solution is gradually charged with stirring, and then heated to reflux, and refluxed. Similarly, by separating and removing water azeotropically discharged from the vessel outside the system, an aromatic polyfluoro compound having the specific structure described in Formula (1) dissolved in the polar solvent is added and reacted. Aromatic polyether polyamines can be obtained.

The reaction temperature at the time of reacting the aromatic polyfluoro compound with the alkali metal salt of the aromatic aminophenol is not particularly limited since it greatly varies depending on the structure of each raw material and the kind of the alkali metal used. However, about 50 to 300 ° C, preferably 80 to 300 ° C,
More preferably, it is 100 to 250 ° C. These reactions can be monitored by chromatography or the like.

[0017]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Example 1 240 g (2.2 mol) of 3-aminophenol, 1 L of 1,3-dimethyl-2-imidazolidinone and toluene were placed in a 2 L four-necked flask equipped with a stirrer, a reflux condenser and a Dean-Stark trap. 100 ml was charged and stirred at room temperature.
g (2.2 mol) was added dropwise at an internal temperature of 25 to 50 ° C. Then, the temperature was raised and the mixture was heated and refluxed. Water was drawn into the trap according to the heating and reflux, and the dehydration reaction was allowed to proceed. The reaction was continued until there was no more water distilled in the trap. At this time, the temperature inside the reaction solution rose to 85 ° C to 113 ° C. Next, 4,4 '
-190 g (1.0 mol) of difluorobiphenyl in 1,3
-Dissolved in 500 ml of dimethyl-2-imidazolidinone and added dropwise to the reaction solution. After completion of the dropping, the temperature of the reaction solution is increased,
The toluene in the reaction solution was distilled into a trap via a reflux device, and solvent exchange was performed. At this time, the temperature inside the reaction solution was 200
℃ and stirred for 24 hours. After completion of the reaction, the mixture was cooled to room temperature, and the reaction solution was gradually dropped into 2 L of vigorously stirred ice water. The precipitated crystals are separated by filtration, dried under reduced pressure, and
4,4'-bis (3-aminophenoxy) -biphenyl 3
19 g (yield 85%) was obtained. The purity by high performance liquid chromatography was 98.1%.

Example 2 A 2-L four-necked flask equipped with a stirrer, a reflux condenser and a Dean-Stark trap was charged with 240 g (2.2 mol) of 3-aminophenol and 500 ml of toluene and stirred at room temperature. 180 g (2.2 mol) of a 49% aqueous solution of sodium hydroxide was added dropwise thereto at an internal temperature of 25 to 50 ° C. Then, the temperature was raised and the mixture was heated and refluxed. Water was drawn into the trap according to the heating and reflux, and the dehydration reaction was allowed to proceed. The reaction was continued until there was no more water distilled in the trap. At this time, the temperature inside the reaction solution rose to 85 ° C to 113 ° C. next,
190 g (1.0 mol) of 4,4'-difluorobiphenyl
Was dissolved in 1 L of 1,3-dimethyl-2-imidazolidinone and added dropwise to the reaction solution. After completion of the dropwise addition, the temperature of the reaction solution was raised, and toluene in the reaction solution was distilled into a trap via a reflux device to exchange the solvent. At this time, the temperature inside the reaction solution was 2
The temperature was set to 00 ° C., and the mixture was stirred for 24 hours. After completion of the reaction, the mixture was cooled to room temperature, and the reaction solution was gradually dropped into 2 L of vigorously stirred ice water. The precipitated crystals were separated by filtration and dried under reduced pressure to obtain 309 g (yield 84%) of the target 4,4'-bis (3-aminophenoxy) -biphenyl. The purity by high performance liquid chromatography was 99.2%.

EXAMPLE 3 14.3 g (0.13 mol) of 3-aminophenol was placed in a 100 ml flask equipped with a stirrer and a reflux condenser.
11.8 g of 9% by weight aqueous sodium hydroxide solution (0.14 g)
Mol), 1,3-dimethyl-2-imidazolidinone 50
g of toluene and 30 g of toluene, the temperature was increased while passing nitrogen gas through with stirring, and the water in the reaction system was removed with a reflux device in a refluxing state of toluene. After cooling to room temperature, an autoclave equipped with a 100 ml stirring device was added. (Manufactured by Hastelloy C). Next, 5 g of 1,3-difluorobenzene (0.0 g)
(4 mol) was added, the reactor was closed, the inside of the reactor was replaced with nitrogen, and then the temperature of the autoclave was raised to 200 ° C, and the temperature at 200 ° C was maintained for 30 hours. After the reaction is completed, cool to room temperature,
The reaction mass was discharged into a beaker stirring 500 ml of water. After the discharged mass was extracted with 300 ml of toluene, the toluene layer was washed with water, dehydrated by adding magnesium sulfate, magnesium sulfate was filtered off, and toluene was distilled off by an evaporator to obtain 1,3-bis (3- 11.8 g of aminophenoxy) benzene (APB) (yield
92%). Purity by gas chromatography is 9
It was 7.8%. 10 g of isopropanol was added to 5 g of the crude product, and the mixture was heated and cooled to recrystallize. The crystals were filtered, washed with water and dried to obtain APB as white needle crystals. The purity by gas chromatography was 99.5%.

Comparative Example 1 The starting material of Example 1, 4,4'-difluorobiphenyl was
When a similar reaction was performed in place of 4'-diiodobiphenyl, a complicated mixture was obtained, and the desired 4,4'-bis (3
The yield of -aminophenoxy) -biphenyl was 4%.

Comparative Example 2 The starting material of Example 1, 4,4'-difluorobiphenyl
When a similar reaction was carried out in place of 4'-dibromobiphenyl, a complex mixture was obtained, and the desired 4,4'-bis (3
The yield of -aminophenoxy) -biphenyl was 34%.

[0022]

According to the present invention, aromatic polyether polyamines can be easily synthesized at an extremely high yield.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H006 AA02 AB46 AC43 BE10 BJ50 BP60 BU46

Claims (3)

[Claims] 1. A compound represented by the general formula (1) R _1- (F) n (1) wherein R ₁ has 6 to 24 carbon atoms and is a monocyclic aromatic group or an aromatic group. The group is selected from the group consisting of non-fused polycyclic aromatic groups in which the groups are connected to each other directly or by a bridging member, n represents an integer of 2 to 10. In addition, n F group substitution positions are adjacent to each other. . not matching an aromatic polyfluoro compounds including the specific structure represented by), at least the general formula in one molecule (2) (OH) o- R 2 - (NH2) p (2) ( wherein R ₂ has 6 to 24 carbon atoms, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which the aromatic groups are directly or mutually linked by a bridge member. And o and p each independently represent an integer of 1 to 5). The Lumpur compound, is reacted with an alkali metal presence, aromatic polyether polyamines manufacturing method, characterized in that for all the F group substitution positions ether bond. 2. The method according to claim 1, wherein the aromatic polyfluoro compound having the specific structure represented by the general formula (1) is difluorobiphenyl or difluorobenzene. 3. The method according to claim 1, wherein the aromatic aminophenol having a specific structure represented by the general formula (2) is an aminophenol.