JP3025952B2 - Fluorine-containing resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-containing resin, and more particularly to a heat-resistant fluorine-containing resin having a low surface free energy which is soluble in various organic solvents, has a high glass transition temperature, and has water and oil repellency. About.

[0002]

2. Description of the Related Art Polyamine resins and polyether resins and methods for producing these resins are disclosed, for example, in the proceedings of the Society of Polymer Science, vol. 43, p. 3168 (1994). Such conventional polyamine resins and polyether resins have high glass transition temperatures, but have poor water and oil repellency because they exhibit high surface free energy,
There are problems with hygroscopicity, tackiness, friction, and the like, and this has been a major factor hindering industrial use of polyamine resins and polyether resins.

[0003]

SUMMARY OF THE INVENTION The present invention relates to a fluorine-containing resin which is soluble in various organic solvents, has a low surface free energy and a high glass transition temperature, is water- and oil-repellent, and is heat-resistant. It is an object to provide a method.

[0004]

Means for Solving the Problems The present inventors have succeeded in obtaining a fluorine-containing resin exhibiting water and oil repellency while maintaining solubility in an organic solvent and a high glass transition temperature. The present invention has been completed.

That is, the present invention provides a compound represented by the general formula (1)

[0006]

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[Wherein, Ar represents a divalent aromatic residue.
Y represents -NH- or -O-. n shows the integer of 10-200. ] The fluorine-containing resin represented by the formula:

The fluorine-containing resin of the present invention is soluble in various organic solvents, has a low surface free energy and a high glass transition temperature, is water- and oil-repellent, and has heat resistance.

The fluororesin of the present invention is soluble in a wide range of organic solvents, has good moldability, and has a high glass transition temperature and a low surface free energy. Great value.

The fluorine-containing resin of the present invention has the following general formula (1)
a)

[0011]

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Wherein Ar and n are as defined above. And a fluorine-containing polyamine resin represented by the following general formula (1b):

[0013]

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Wherein Ar and n are the same as above. And a fluorine-containing polyether resin represented by the formula:

[0015]

DETAILED DESCRIPTION OF THE INVENTION The fluorine-containing polyamine resin represented by the above general formula (1a) is, for example, a compound represented by the following general formula (2)

[0016]

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And a triazine dihalide represented by the general formula (3) H ₂ N—Ar—NH ₂ (3) wherein Ar is the same as defined above. And an aromatic diamine represented by the formula:

Further, the fluorine-containing polyether resin represented by the general formula (1b) comprises a triazine dihalide represented by the general formula (2) and HO—Ar—OH (4) [ In the formula, Ar is the same as described above. And an aromatic diol represented by the following formula:

The halogen atom represented by X in the general formula (2) includes fluorine, chlorine, bromine and iodine atoms. The divalent aromatic group represented by Ar in the general formulas (3) and (4) includes various groups described in Table 1 below.

[0020]

[Table 1]

The fluorine-containing polyamine resin represented by the general formula (1a) is produced from the triazine dihalide represented by the general formula (2) and the aromatic diamine represented by the general formula (3). You. Further, the triazine dihalide of the general formula (2) is used in an amount of 20 to 99 mol%, and the general formula (5)

[0022]

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[Wherein, R represents a hydrogen atom or an alkyl group. X is the same as above. ] Can be used by mixing 80 to 1 mol% of the triazine dihalide represented by the formula (1). When the triazine dihalide of the general formula (5) is used as a mixture, when the amount of the triazine dihalide of the general formula (2) is less than 20 mol%, the fluorine-containing polyamine resin satisfies the water / oil repellency. Disappears.

Specific examples of the aromatic diamine represented by the above general formula (3) include metaphenylenediamine, paraphenylenediamine, 3,3'-diaminobiphenyl,
4,4'-diaminobiphenyl, 3,3'-methylenedianiline, 4,4'-methylenedianiline, 4,4'-
Isopropylidene dianiline, 3,3'-oxydianiline, 4,4'-oxydianiline, 3,4'-oxydianiline, 3,3'-thiodianiline, 4,4'-thiodianiline, 3,3 ' -Carbonyldianiline, 4,
4'-carbonyldianiline, 3,3'-sulfonyldianiline, 4,4'-sulfonyldianiline, 1,4-
Naphthalenediamine, 1,5-naphthalenediamine,
2,6-naphthalenediamine, 2,2-bis (4-aminophenoxyphenyl) propane, 2,2-bis (4-
Aminophenoxyphenyl) hexafluoropropane,
Bis (4-aminophenoxyphenyl) sulfone, 4,
4'-bis (4-aminophenoxy) biphenyl, 1,
3-bis (4-aminophenoxy) benzene, 2,2-
Bis (4-aminophenyl) hexafluoropropane and the like can be exemplified. In the present invention, these aromatic diamines are used alone or in combination of two or more.

According to one embodiment of the method for producing the fluorine-containing polyamine resin represented by the general formula (1), the triazine represented by the general formula (2) is used in an organic solvent in the presence of an acid acceptor. The reaction is carried out by reacting the dihalide with the aromatic diamine represented by the general formula (3) at 0 to 250 ° C. for several minutes to several days. In this method, the molecular weight of the fluorine-containing polyamine resin represented by the general formula (1a) is determined based on the charged amount of the triazine dihalide represented by the general formula (2) and the aromatic diamine represented by the general formula (3). When these reaction components are equimolar, a high molecular weight fluorine-containing polyamine resin represented by the above general formula (1a) can be produced. In the fluorine-containing polyamine resin represented by the general formula (1a), n is from 10 to 200.
The reason for limiting to an integer of n is that if n is less than 10, the properties such as mechanical properties and heat resistance are not sufficient when molded into a film or the like. This is because the sex becomes worse.

The organic solvent used in this method includes
For example, N, N-dimethylacetamide, N-methyl-2
Aprotic polar solvents such as -pyrrolidone, 1,3-dimethyl-2-imidazolidone and tetramethylene sulfone; aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene and benzonitrile; chloroform, dichloromethane and 1,2-dichloroethane ,
Examples thereof include halogen solvents such as 1,1,2,2-tetrachloroethane and dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, and ketone solvents such as acetone and methyl ethyl ketone.

Examples of the acid acceptor that can be used simultaneously with these solvents include, for example, organic bases such as triethylamine and pyridine and inorganic bases such as cesium fluoride, potassium fluoride, sodium carbonate and potassium carbonate.

The fluorinated polyamine resin represented by the general formula (1a) thus produced has solubility, glass transition temperature and repellency depending on the kind of the aromatic diamine represented by the general formula (3) used. The water and oil repellency changes. The general formula (1)
The fluorine-containing polyamine resin represented by a) is, for example, N, N
-Soluble in all or a part of organic solvents such as dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, tetrahydrofuran, dioxane and the like, and a solution casting method from the solution of the fluorine-containing polyamine resin. The film obtained by
It has a high glass transition temperature around 0-210 ° C. and an additional 8
It shows a contact angle of water around 9 to 98 degrees and a contact angle of methylene iodide around 54 to 65 degrees, and has a low surface free energy of 32 to 37 erg / cm ² .

The fluorinated polyether resin represented by the general formula (1b) is made of a triazine dihalide represented by the general formula (2) and an aromatic diol represented by the general formula (4). Manufactured. It is also possible to use 20 to 99 mol% of the triazine dihalide of the above general formula (2) and to mix and use 80 to 1 mol% of the triazine dihalide of the above general formula (5) containing no fluorine atom. it can. When the triazine dihalide of the general formula (5) containing no fluorine atom is used as a mixture, if the triazine dihalide of the general formula (2) is less than 20 mol%, the fluorine-containing polyether resin becomes repellent. Water and oil repellency will not be satisfied.

Specific examples of the aromatic diol represented by the general formula (4) include hydroquinone, resorcinol, biphenol, dihydroxynaphthalene, and bis (4
-Hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2- Bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 3-
(4-hydroxyphenyl) -1,1,3-trimethyl-5-indanol, 1,3- (1,1-dimethyl-4
-Hydroxyphenylmethyl) benzene and the like. In the present invention, these aromatic diols are used alone or as a mixture of two or more.

According to one embodiment of the method for producing the fluorine-containing polyether resin represented by the above general formula (1b), a two-phase system of an organic solvent and an aqueous alkali solution is used in the presence of a phase transfer catalyst in the presence of the above general formula The triazine dihalide represented by (2) and the aromatic diol represented by the general formula (4) are combined with 0
The reaction is carried out at -200 ° C for several minutes to several days. In this method, the molecular weight of the polyether resin represented by the general formula (1b) is limited by the charged amounts of the triazine dihalide represented by the general formula (2) and the aromatic diol represented by the general formula (4). When these reaction components are made into equimolar amounts, the above-mentioned general formula (1b) having a high molecular weight can be obtained.
Can be produced. The reason that n is limited to an integer of 10 to 200 in the fluorine-containing polyether resin represented by the general formula (1b) is that n is 10
If the amount is less than this, the properties such as mechanical properties and heat resistance when formed into a film or the like are not sufficient, and if n exceeds 200, the solubility and formability of the bait such as an organic solvent deteriorate.

The organic solvent used in this method includes
For example, N, N-dimethylacetamide, N-methyl-2
Aprotic polar solvents such as -pyrrolidone, 1,3-dimethyl-2-imidazolidone and tetramethylene sulfone; aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene and benzonitrile; chloroform, dichloromethane and 1,2-dichloroethane ,
Examples thereof include halogen solvents such as 1,1,2,2-tetrachloroethane and dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, and ketone solvents such as acetone and methyl ethyl ketone.

As the phase transfer catalyst, for example, quaternary ammonium salts, quaternary phosphonium salts, crown ethers, cryptands and the like are used. More specifically,
Tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetramethylammonium sulfate, benzyltriethylammonium chloride, decyltrimethylammonium bromide, dodecyltrimethylammonium bromide, cetyltrimethylammonium chloride, Cetyltrimethylammonium bromide, cetyltributylammonium bromide, tetrabutylphosphonium bromide, cetyltributylphosphonium bromide, 15-crown-5,18-crown-6, benzo-18-crown-6, dibenzo-18-crown-6, dibenzo- 24-crown-8 and the like. The use amount of these catalysts is not particularly limited, but is, for example, 1 mol% to 100 mol% based on the triazine dihalide represented by the general formula (2).

According to another embodiment of the method for producing the fluorine-containing polyether resin represented by the general formula (1b), the compound represented by the general formula (2) is prepared in an organic solvent in the presence of an acid acceptor. By reacting the triazine dihalide represented by the formula (1) with the aromatic diol represented by the general formula (4) at 0 to 250 ° C for several minutes to several days.

The organic solvent used in this method includes
For example, N, N-dimethylacetamide, N-methyl-2
Aprotic polar solvents such as -pyrrolidone, 1,3-dimethyl-2-imidazolidone and tetramethylene sulfone; aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene and benzonitrile; chloroform, dichloromethane and 1,2-dichloroethane ,
Examples thereof include halogen solvents such as 1,1,2,2-tetrachloroethane and dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, and ketone solvents such as acetone and methyl ethyl ketone.

Examples of the acid acceptor that can be used simultaneously with these solvents include, for example, organic bases such as triethylamine and pyridine and inorganic bases such as cesium fluoride, potassium fluoride, sodium carbonate and potassium carbonate.

The fluorinated polyether resin represented by the general formula (1b) thus produced is obtained by using the general formula (4)
The solubility, glass transition temperature, and water / oil repellency change depending on the type of aromatic diol represented by The general formula (1)
The fluorine-containing polyether resin represented by b) is, for example, N,
It becomes soluble in all or a part of an organic solvent such as N-dimethylformamide, N-methyl-2-pyrrolidone, tetrahydrofuran, dioxane, chloroform and the like, and a colorless transparent film is formed from a solution of the fluorine-containing polyether resin by a solution casting method. give. This cast film is 140
It has a high glass transition temperature around ~ 205 ° C,
It has a contact angle of water around ９８98 degrees and a contact angle of methylene iodide around 58 to 63 degrees, and has a low surface free energy of 34 to 36 erg / cm ² .

[0038]

EXAMPLES The present invention will be further clarified with reference to examples and comparative examples.

Example 1 4 ml of distilled and purified N-methyl-2-pyrrolidone and 0.778 g of bis (4-aminophenoxyphenyl) hexafluoropropane were placed in a 100 ml eggplant flask.
(1.5 mmol) and dissolved at room temperature with stirring. Next, 2- {4- [2,2-bis (trifluoromethyl) -3,3,4,4,5,5,5-heptafluoropentyl] anilino} -4,6-dichloro-1,3 ,
0.860 g (1.5 mmol) of 5-triazine was added at room temperature, the reaction temperature was raised to 80 ° C., and the mixture was reacted by stirring at the same temperature for 24 hours under a nitrogen stream. After the reaction, the reaction solution was poured into 400 ml of methanol to precipitate a polymer, which was separated by filtration. After washing the polymer with hot methanol,
It dried under reduced pressure at 80 degreeC for 12 hours. The yield was 96%. As a result of infrared absorption spectrum and elemental analysis of this polymer, it was confirmed that the polymer had a structure represented by the following formula as a repeating unit.

[0040]

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Infrared absorption spectrum 1579 cm ^-1 (C
^{= N), 1250~1220cm -1 (C} -F) elemental analysis (C ₄₃ H ₂₅ F ₁₉ N as ₆ O ₂₎ C H N calc (%) 50.70 2.47 8.25 Found (% ) 51.27 3.04 8.49 The properties of this polymer are shown below.

(1) Intrinsic viscosity: 0.55 dl / g (N-
(2) Molecular weight Number average molecular weight (Mn): 53000 Weight average molecular weight (Mw): 85,000 Molecular weight distribution (Mw / Mn): 1.6 In methyl-2-pyrrolidone, measured at a concentration of 0.5 g / dl at 30 ° C. .

Example 2 0.456 g (3.0 mmol) of reagent grade cesium fluoride was placed in a 100 ml eggplant flask and heated and dried using a drier under a stream of nitrogen. 4 ml of distilled and purified N-methyl-2-pyrrolidone and 0.778 g of bis (4-aminophenoxyphenyl) hexafluoropropane
(1.5 mmol) and dissolved at room temperature with stirring.

Next, 2- {4- [2,2-bis (trifluoromethyl) -3,3,4,4,5,5,5-heptafluoropentyl] anilino} -4,6-dichloro-
0.860 g (1.5 mmol) of 1,3,5-triazine was added at room temperature, the reaction temperature was raised to 80 ° C., and the mixture was reacted at that temperature with stirring under a nitrogen stream for 24 hours.
After the reaction, the reaction solution was poured into 400 ml of methanol,
The polymer was precipitated and filtered. After washing the polymer with hot methanol, the polymer was dried under reduced pressure at 80 ° C. for 12 hours. The yield is 9
6%. As a result of infrared absorption spectrum and elemental analysis of this polymer, it was confirmed that the polymer had a structure represented by the following formula as a repeating unit.

[0045]

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Infrared absorption spectrum 1579 cm ^-1 (C
^{= N), 1250~1220cm -1 (C} -F) elemental analysis (C ₄₃ H ₂₅ F ₁₉ N as ₆ O ₂₎ C H N calc (%) 50.70 2.47 8.25 Found (% ) 51.11 2.70 8.23 The properties of this polymer are shown below.

(1) Intrinsic viscosity: 0.60 dl / g (N-
(Measured at 30 ° C. in methyl-2-pyrrolidone at a concentration of 0.5 g / dl) (2) Molecular weight Number average molecular weight (Mn): 60000 Weight average molecular weight (Mw): 96,000 Molecular weight distribution (Mw / Mn): 1.6 (3) Glass transition temperature (differential scanning calorimetry): 177 ° C (4) 10% weight loss temperature (thermal balance measurement): 410 ° C
(In air), 420 ° C. (in nitrogen) This polyamine resin is N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-
A pale yellow transparent cast film was prepared from a solution of the polyamine resin in N-methyl-2-pyrrolidone, which was soluble in an organic solvent such as pyrrolidone, dimethylsulfoxide, tetrahydrofuran, and 1,4-dioxane. The tensile strength, elongation at break, and tensile modulus of the film are 64M, respectively.
Pa, 7.7%, and 1.1 GPa. The contact angles of water and methylene iodide with this film were 90 ° and 64 °, respectively, and the surface free energy calculated from these contact angles was 35 erg / cm ² .

Example 3 In a 100 ml eggplant flask, 4 ml of distilled and purified N-methyl-2-pyrrolidone and 0.616 g (1.5 mmol) of bis (4-aminophenoxyphenyl) propane were added.
Was added and dissolved at room temperature with stirring. Next, 2-
{4- [2,2-bis (trifluoromethyl) -3,
3,4,4,5,5,5-heptafluoropentyl] anilino} -4,6-dichloro-1,3,5-triazine 0.860 g (1.5 mmol) was added at room temperature, and the reaction temperature was raised to 80 ° C. The reaction was stirred for 24 hours under a nitrogen stream at the same temperature. After the reaction, the reaction solution is
The mixture was poured into ml of methanol to precipitate a polymer, which was separated by filtration. The polymer was washed with hot methanol and dried under reduced pressure at 80 ° C. for 12 hours. The yield was 98%. As a result of infrared absorption spectrum and elemental analysis of this polymer, it was confirmed that the polymer had a structure represented by the following formula as a repeating unit.

[0049]

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Infrared absorption spectrum 1579 cm ^-1 (C
= N), 1250-1220 cm ^-1 (C-F) Elemental analysis (as C ₄₃ H ₃₁ F ₁₃ N ₆ O ₂ ) Calculated value for CH N (%) 56.71 3.43 9.23 Actual value (%) ) 56.44 3.48 9.74 The properties of this polymer are shown below.

(1) Intrinsic viscosity: 0.55 dl / g (N-
(Measured in methyl-2-pyrrolidone at 30 ° C. at a concentration of 0.5 g / dl) (2) Molecular weight Number average molecular weight (Mn): 51000 Weight average molecular weight (Mw): 117000 Molecular weight distribution (Mw / Mn): 2.3 .

Example 4 In a 100 ml eggplant flask, 0.456 g (3.0 mmol) of reagent grade cesium fluoride was placed and dried by heating under a stream of nitrogen. 4 ml of distilled and purified N-methyl-2-pyrrolidone and 0.616 g (1.5 mmol) of bis (4-aminophenoxyphenyl) propane were added and dissolved at room temperature with stirring. Next, 2- {4- [2,2-
Bis (trifluoromethyl) -3,3,4,4,5
5,5-heptafluoropentyl] anilino-4,6
-0.860 g of dichloro-1,3,5-triazine
(1.5 mmol) was added at room temperature, the reaction temperature was raised to 80 ° C., and the mixture was reacted at that temperature with stirring under a nitrogen stream for 24 hours. After the reaction, the reaction solution was poured into 400 ml of methanol to precipitate a polymer, which was separated by filtration. After washing the polymer with hot methanol, the polymer was dried under reduced pressure at 80 ° C. for 12 hours. The yield was 98%. As a result of infrared absorption spectrum and elemental analysis of this polymer, it was confirmed that the polymer had a structure represented by the following formula as a repeating unit.

[0053]

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Infrared absorption spectrum 1579 cm ^-1 (C
= N), 1250-1220 cm ^-1 (C-F) Elemental analysis (as C ₄₃ H ₃₁ F ₁₃ N ₆ O ₂ ) Calculated value for CH N (%) 56.71 3.43 9.23 Actual value (%) ) 56.55 3.39 9.54 The properties of this polymer are shown below.

(1) Intrinsic viscosity: 0.80 dl / g (N-
(Measured in methyl-2-pyrrolidone at 30 ° C. at a concentration of 0.5 g / dl) (2) Molecular weight Number average molecular weight (Mn): 65,000 Weight average molecular weight (Mw): 124000 Molecular weight distribution (Mw / Mn): 1.9 (3) Glass transition temperature (differential scanning calorimetry): 176 ° C (4) 10% weight loss temperature (thermobalance measurement): 395 ° C
(In air), 395 ° C. (in nitrogen) The polyamine resin comprises N-methyl-2-pyrrolidone,
Soluble in organic solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, tetrahydrofuran,
A pale yellow transparent cast film was prepared from the N-methyl-2-pyrrolidone solution of the polyamine resin. The tensile strength, elongation at break, and tensile modulus of the film were 58 MPa, 7.5%, and 1.0 GPa, respectively. Also,
The contact angle of water and methylene iodide to this film is
At 89 and 61 degrees, respectively, the surface free energy calculated from these contact angles was 36 erg / cm ² .

Example 5 In a 100 ml eggplant-shaped flask, 0.456 g (3.0 mmol) of reagent grade cesium fluoride was placed and dried by heating under a nitrogen stream. 4 ml of distilled and purified N-methyl-2-pyrrolidone and 0.649 g (1.5 mmol) of bis (4-aminophenoxyphenyl) sulfone were added and dissolved at room temperature with stirring. Next, 2- {4- [2,2-
Bis (trifluoromethyl) -3,3,4,4,5
5,5-heptafluoropentyl] anilino) -4,6
-0.860 g of dichloro-1,3,5-triazine
(1.5 mmol) was added at room temperature, the reaction temperature was raised to 80 ° C., and the mixture was reacted at that temperature with stirring under a nitrogen stream for 24 hours. After the reaction, the reaction solution was poured into 400 ml of methanol to precipitate a polymer, which was separated by filtration. After washing the polymer with hot methanol, the polymer was dried under reduced pressure at 80 ° C. for 12 hours. The yield was 98%. As a result of infrared absorption spectrum and elemental analysis of this polymer, it was confirmed that the polymer had a structure represented by the following formula as a repeating unit.

[0057]

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Infrared absorption spectrum 1579 cm ^-1 (C
^{= N), 1250~1220cm -1 (C} -F) elemental analysis _{(C 40 H 25 F 13 N} 6 O 4 S) C H N calc (%) 51.51 2.70 9.01 Found (% ) 51.01 2.70 9.18 The properties of this polymer are shown below.

(1) Intrinsic viscosity: 0.55 dl / g (N-
(2) Molecular weight Number average molecular weight (Mn): 45000 Weight average molecular weight (Mw): 99000 Molecular weight distribution (Mw / Mn): 2.2 in methyl-2-pyrrolidone at a concentration of 0.5 g / dl at 30 ° C. (3) Glass transition temperature (differential scanning calorimetry): 210 ° C (4) 10% weight loss temperature (thermobalance measurement): 380 ° C
(In air), 390 ° C. (in nitrogen) The polyamine resin comprises N-methyl-2-pyrrolidone,
It is soluble in organic solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, and dioxane, and is used to form a pale yellow transparent cast film from a solution of the polyamine resin in N-methyl-2-pyrrolidone. Produced. Tensile strength of the film,
The elongation at break and the tensile modulus are 67 MPa, respectively.
It was 8.6% and 1.2 GPa. The contact angles of water and methylene iodide with this film were 91
In degrees and 57 degrees, the surface free energy calculated from these contact angles was 37 erg / cm ² .

Example 6 0.456 g (3.0 mmol) of reagent grade cesium fluoride was placed in a 100 ml eggplant-shaped flask, and ripened and dried under a nitrogen stream. 4 ml of distilled and purified N-methyl-2-pyrrolidone, 0.2 g of dried calcium chloride and 4,
4'-bis (4-aminophenoxy) biphenyl 0.5
53 g (1.5 mmol) was added and dissolved at room temperature with stirring. Next, 2- {4- [2,2-bis (trifluoromethyl) -3,3,4,4,5,5,5-heptafluoropentyl] anilino} -4,6-dichloro-
0.860 g (1.5 mmol) of 1,3,5-triazine was added at room temperature, the reaction temperature was raised to 80 ° C., and the mixture was reacted at that temperature with stirring under a nitrogen stream for 24 hours.
After the reaction, the reaction solution was poured into 400 ml of methanol,
The polymer was precipitated and filtered. After washing the polymer with hot methanol, the polymer was dried under reduced pressure at 80 ° C. for 12 hours. The yield is 9
8%. As a result of infrared absorption spectrum and elemental analysis of this polymer, it was confirmed that the polymer had a structure represented by the following formula as a repeating unit.

[0061]

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Infrared absorption spectrum 1579 cm ^-1 (C
^{= N), 1250~1220cm -1 (C} -F) elemental analysis (C ₄₀ H ₂₅ F ₁₃ as the N ₆ O ₂₎ C H N calc (%) 55.31 2.90 9.67 Found (% 54.53 3.01 9.56 The properties of this polymer are shown below.

(1) Intrinsic viscosity: 1.14 dl / g (N-
(Measured in methyl-2-pyrrolidone at 30 ° C. at a concentration of 0.5 g / dl) (2) Molecular weight Number average molecular weight (Mn): 115000 Weight average molecular weight (Mw): 184000 Molecular weight distribution (Mw / Mn): 1.6 (3) Glass transition temperature (differential scanning calorimetry): 189 ° C (4) 10% weight loss temperature (thermobalance measurement): 380 ° C
(In air), 395 ° C. (in nitrogen) The polyamine resin comprises N-methyl-2-pyrrolidone,
It was soluble in organic solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, and tetrahydrofuran, and a pale yellow transparent cast film was prepared from a solution of the polyamine resin in N-methyl-2-pyrrolidone. . Tensile strength of film, elongation at break,
Tensile modulus was 71 MPa, 10.2%, 1.
It was 0 GPa. The contact angles of water and methylene iodide with this film were 94 degrees and 60 degrees, respectively.
The surface free energy calculated from these contact angles is 3
It was 5 erg / cm ² .

Example 7 0.456 g (3.0 mmol) of reagent grade cesium fluoride was placed in a 100 ml eggplant-shaped flask and dried by heating under a nitrogen stream. 4 ml of distilled and purified N-methyl-2-pyrrolidone, 0.2 g of dried calcium chloride and 1,3
0.438 g of bis (4-aminophenoxy) benzene
(1.5 mmol) and dissolved at room temperature with stirring. Next, 2- {4- [2,2-bis (trifluoromethyl) -3,3,4,4,5,5,5-heptafluoropentyl] anilino} -4,6-dichloro-1,3 ,
0.860 g (1.5 mmol) of 5-triazine was added at room temperature, the reaction temperature was raised to 80 ° C, and the reaction was carried out by stirring at the same temperature for 24 hours under a nitrogen stream. After the reaction, the reaction solution was poured into 400 ml of methanol to precipitate a polymer, which was separated by filtration. After washing the polymer with hot methanol,
It dried under reduced pressure at 80 degreeC for 12 hours. The yield was 84%. As a result of infrared absorption spectrum and elemental analysis of this polymer, it was confirmed that the polymer had a structure represented by the following formula as a repeating unit.

[0065]

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Infrared absorption spectrum 1579 cm ^-1 (C
^{= N), 1250~1220cm -1 (C} -F) elemental analysis _{(C 34 H 21 F 13 N} 6 O 2 as) C H N calc (%) 51.52 2.67 10.60 Found (% 50.96 2.95 10.58 The properties of this polymer are shown below.

(1) Intrinsic viscosity: 0.83 dl / g (N-
(Measured in methyl-2-pyrrolidone at 30 ° C. at a concentration of 0.5 g / dl) (2) Molecular weight Number average molecular weight (Mn): 66000 Weight average molecular weight (Mw): 165000 Molecular weight distribution (Mw / Mn): 2.5 (3) Glass transition temperature (differential scanning calorimetry): 159 ° C (4) 10% weight loss temperature (thermobalance measurement): 370 ° C
(In air), 370 ° C. (in nitrogen) The polyamine resin is N-methyl-2-pyrrolidone,
It was soluble in organic solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, and tetrahydrofuran, and a pale yellow transparent cast film was prepared from a solution of the polyamine resin in N-methyl-2-pyrrolidone. . Tensile strength of film, elongation at break,
Tensile modulus was 54 MPa, 7.3%, 1.0
GPa. The contact angles of water and methylene iodide with this film were 98 ° and 62 °, respectively, and the surface free energy calculated from these contact angles was 32 °.
erg / cm ² .

Example 8 In a 100 ml eggplant-shaped flask, 0.456 g (3.0 mmol) of reagent grade cesium fluoride was placed and dried by heating under a nitrogen stream. 4 ml of distilled and purified N-methyl-2-pyrrolidone, 0.2 g of dried calcium chloride and 0.300 g of bis (4-aminophenyl) ether (1.5 g
mmol) was added and dissolved at room temperature with stirring. Next, 2- {4- [2,2-bis (trifluoromethyl)
−3,3,4,4,5,5,5-heptafluoropentyl] anilino} -4,6-dichloro-1,3,5-triazine 0.860 g (1.5 mmol) was added at room temperature,
The reaction temperature was raised to 80 ° C., and the mixture was stirred at that temperature for 24 hours under a nitrogen stream to cause a reaction. After the reaction, the reaction solution was poured into 400 ml of methanol to precipitate a polymer, which was separated by filtration. After washing the polymer with hot methanol, the polymer was dried under reduced pressure at 80 ° C. for 12 hours. The yield was 94%. As a result of infrared absorption spectrum and elemental analysis of this polymer, it was confirmed that the polymer had a structure represented by the following formula as a repeating unit.

[0069]

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Infrared absorption spectrum 1579 cm ^-1 (C
^{= N), 1250~1220cm -1 (C} -F) elemental analysis _{(C 28 H 17 F 13 N} 6 O as) C H N calc (%) 48.01 2.45 12.00 Found (%) 47.27 2.45 12.00 The properties of this polymer are shown below.

(1) Intrinsic viscosity: 0.62 dl / g (N-
(Measured in methyl-2-pyrrolidone at 30 ° C. at a concentration of 0.5 g / dl) (2) Molecular weight Number average molecular weight (Mn): 62,000 Weight average molecular weight (Mw): 149000 Molecular weight distribution (Mw / Mn): 2.4 (3) Glass transition temperature (differential scanning calorimetry): 209 ° C (4) 10% weight loss temperature (thermobalance measurement): 400 ° C
(In air), 400 ° C. (in nitrogen) The polyamine resin is N-methyl-2-pyrrolidone,
It was soluble in organic solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, and tetrahydrofuran, and a pale yellow transparent cast film was prepared from a solution of the polyamine resin in N-methyl-2-pyrrolidone. . Tensile strength of film, elongation at break,
Tensile modulus was 29 MPa, 2.5% and 1.2 MPa, respectively.
GPa. The contact angles of water and methylene iodide with this film were 95 ° and 54 °, respectively, and the surface free energy calculated from these contact angles was 37 °.
erg / cm ² .

Example 9 0.951 g of 2,2-bis (3-phenyl-4-hydroxyphenyl) propane was placed in a 100 ml eggplant flask.
(2.5 mmol), 0.27 g (0.75 mmol) of cetyltrimethylammonium bromide and 5.1 ml of a 1 molar aqueous sodium hydroxide solution were added and dissolved.
To this solution was added 2- {4- [2,2-bis (trifluoromethyl) -3,3,4,4,5,5,5-heptafluoropentyl] anilino} -4,6-dichloro-1, 3,
1.433 g (2.5 mmol) of 5-triazine in 5 m
A solution dissolved in 1 of chloroform was added. The reaction was carried out with vigorous stirring at 20 ° C. for 12 hours. 400 reaction solution
The mixture was poured into ml of methanol, and a polyether resin was precipitated and separated by filtration. After washing with hot methanol, it was dried under reduced pressure at 80 ° C. for 12 hours. The yield of polyether resin was 96%. As a result of infrared absorption spectrum and elemental analysis of this resin, it was confirmed that the resin had a structure represented by the following formula as a repeating unit.

[0073]

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Infrared absorption spectrum 1575 cm ^-1 (C
^{= N), 1250~1220cm -1 (C} -F) elemental analysis _{(C 43 H 29 F 13 N} 4 O 2 as) C H N calc (%) 58.64 3.32 6.36 Found (% ) 58.08 3.59 6.63 The properties of this resin are shown below.

(1) Intrinsic viscosity: 0.63 dl / g (N-
(Measured in methyl-2-pyrrolidone at a concentration of 0.5 g / dl at 30 ° C.) (2) Molecular weight Number average molecular weight (Mn): 40000 Weight average molecular weight (Mw): 92000 Molecular weight distribution (Mw / Mn): 2.3 (3) Glass transition temperature (differential scanning calorimetry): 163 ° C (4) 10% weight loss temperature (thermobalance measurement): 425 ° C
(In air), 425 ° C. (in nitrogen) This polyether resin is selected from the group consisting of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, tetrahydrofuran, 1,4-dioxane, chloroform and the like. A colorless transparent cast film was produced from a solution of the polyether resin in tetrahydrofuran, which was soluble in an organic solvent. The tensile strength, elongation at break, and tensile modulus of the film were 39 MPa and 2.3, respectively.
%, 1.7 GPa. The contact angles of water and methylene iodide with this film were 94 degrees and 6 degrees, respectively.
At 3 degrees, the surface free energy calculated from these contact angles was 34 erg / cm ² .

Example 10 In a 100 ml eggplant-shaped flask, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane 0.74
1 g (2.5 mmol), 0.27 g (0.75 mmol) of cetyltrimethylammonium bromide and 5.1 ml of a 1 molar aqueous sodium hydroxide solution were added and dissolved. To this solution was added 2- {4- [2,2-bis (trifluoromethyl) -3,3,4,4,5,5,5-heptafluoropentyl] anilino} -4,6-dichloro-1,
A solution of 1.433 g (2.5 mmol) of 3,5-triazine in 5 ml of chloroform was added. 20
The mixture was reacted with vigorous stirring at 12 ° C. for 12 hours. Reaction solution 4
The mixture was poured into 00 ml of methanol to precipitate a polyether resin, which was separated by filtration. After washing with hot methanol, 12
It dried under reduced pressure for hours. 99% yield of polyether resin
Met. As a result of infrared absorption spectrum and elemental analysis of this resin, it was confirmed that the resin had a structure represented by the following formula as a repeating unit.

[0077]

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Infrared absorption spectrum 1575 cm ^-1 (C
^{= N), 1250~1220cm -1 (C} -F) elemental analysis _{(C 36 H 29 F 13 N} 4 O 2 as) C H N calc (%) 54.28 3.67 7.03 Found (% ) 53.91 3.67 7.01 The properties of this resin are shown below.

(1) Intrinsic viscosity: 0.60 dl / g (measured in tetrahydrofuran at 30 ° C. at a concentration of 0.5 g / dl) (2) Molecular weight Number average molecular weight (Mn): 43000 Weight average molecular weight (Mw): 108000 Molecular weight distribution (Mw / Mn): 2.5 (3) Glass transition temperature (differential scanning calorimetry): 192 ° C (4) 10% weight loss temperature (thermobalance measurement): 415 ° C
(In air), 415 ° C. (in nitrogen) This polyether resin is made of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, tetrahydrofuran, 1,4-dioxane, chloroform, etc. A colorless transparent cast film was produced from a solution of the polyether resin in tetrahydrofuran, which was soluble in an organic solvent. The tensile strength, elongation at break, and tensile modulus of the film were 49 MPa and 4.7, respectively.
%, 1.0 GPa. The contact angles of water and methylene iodide with this film were 98 degrees and 5 degrees, respectively.
At 8 degrees, the surface free energy calculated from these contact angles was 34 erg / cm ² .

Example 11 0.866 g (2.5 mmol) of α, α'-bis (4-hydroxyphenyl) -1,3-diisopropylbenzene and 0.27 g of cetyltrimethylammonium bromide were placed in a 100 ml eggplant flask. (0.75 mmol) and 5.1 ml of 1 molar aqueous sodium hydroxide solution was added to dissolve. To this solution was added 2- {4- [2,2-bis (trifluoromethyl) -3,3,4,4,5,5,
5-heptafluoropentyl] anilino} -4,6-dichloro-1,3,5-triazine 1.433 g (2.5
(Mmol) in 5 ml of chloroform. The reaction was carried out with vigorous stirring at 20 ° C. for 12 hours.
The reaction solution was poured into 400 ml of methanol to precipitate a polyether resin, which was separated by filtration. After washing with hot methanol,
It dried under reduced pressure at 80 degreeC for 12 hours. The yield of polyether resin was 87%. As a result of infrared absorption spectrum and elemental analysis of this resin, it was confirmed that the resin had a structure represented by the following formula as a repeating unit.

[0081]

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Infrared absorption spectrum 1579 cm ^-1 (C
= N), 1250-1220 cm ^-1 (CF) The characteristics of this resin are shown below.

(1) Intrinsic viscosity: 0.35 dl / g (measured in tetrahydrofuran at 30 ° C. at a concentration of 0.5 g / dl) (2) Molecular weight Number average molecular weight (Mn): 28,000 Weight average molecular weight (Mw): 59000 Molecular weight distribution (Mw / Mn): 2.1 (3) Glass transition temperature (differential scanning calorimetry): 140 ° C. (4) 10% weight loss temperature (thermobalance measurement): 410 ° C.
(In air), 420 ° C. (in nitrogen) This polyether resin is selected from N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, tetrahydrofuran, 1,4-dioxane, chloroform and the like. A colorless transparent cast film was produced from a solution of the polyether resin in tetrahydrofuran, which was soluble in an organic solvent.

Example 12 0.841 g of 2,2-bis (4-hydroxyphenyl) hexafluoropropane was placed in a 100 ml eggplant-shaped flask.
(2.5 mmol), 0.27 g (0.75 mmol) of cetyltrimethylammonium bromide and 5.1 ml of a 1 molar aqueous sodium hydroxide solution were added and dissolved.
To this solution was added 2- {4- [2,2-bis (trifluoromethyl) -3,3,4,4,5,5,5-heptafluoropentyl] anilino} -4,6-dichloro-1, 3,
1.433 g (2.5 mmol) of 5-triazine in 5 m
A solution dissolved in 1 of chloroform was added. The reaction was carried out with vigorous stirring at 20 ° C. for 12 hours. 400 reaction solution
The mixture was poured into ml of methanol to precipitate a polyether resin, which was separated by filtration. After washing with hot methanol, it was dried under reduced pressure at 80 ° C. for 12 hours. The yield of the polyether resin was 78%. As a result of infrared absorption spectrum of this resin, it was confirmed that the resin had a structure represented by the following formula as a repeating unit.

[0085]

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Infrared absorption spectrum 1579 cm ^-1 (C
= N), 1250-1220 cm ^-1 (CF) The characteristics of this resin are shown below.

(1) Intrinsic viscosity: 0.33 dl / g (measured in tetrahydrofuran at 30 ° C. at a concentration of 0.5 g / dl) (2) Molecular weight Number average molecular weight (Mn): 25000 Weight average molecular weight (Mw): 50,000 Molecular weight distribution (Mw / Mn): 2.0 (3) Glass transition temperature (differential scanning calorimetry): 182 ° C (4) 10% weight loss temperature (thermobalance measurement): 405 ° C
(In air), 410 ° C. (in nitrogen) This polyether resin is an organic solvent such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, tetrahydrofuran, 1,4-dioxane, etc. And a colorless transparent cast film was prepared from a solution of the polyether resin in tetrahydrofuran.

Example 13 In a 100 ml eggplant-shaped flask, 0.506 g (2.5 mmol) of bis (4-hydroxyphenyl) ether and 0.27 g of cetyltrimethylammonium bromide (0.
(75 mmol) and 5.1 ml of a 1 molar aqueous solution of sodium hydroxide. To this solution, add 2- ｛4-
[2,2-bis (trifluoromethyl) -3,3,4
4,5,5,5-heptafluoropentyl] anilino
-4,6-dichloro-1,3,5-triazine 1.43
A solution of 3 g (2.5 mmol) in 5 ml of chloroform was added. The reaction was carried out with vigorous stirring at 20 ° C. for 12 hours. The reaction solution was poured into 400 ml of methanol to precipitate a polyether resin, which was separated by filtration. After washing with hot methanol, it was dried under reduced pressure at 80 ° C. for 12 hours. The yield of the polyether resin was 99%. As a result of infrared absorption spectrum and elemental analysis of this resin, it was confirmed that the resin had a structure represented by the following formula as a repeating unit.

[0089]

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Infrared absorption spectrum 1575 cm ^-1 (C
^{= N), 1250~1220cm -1 (C} -F) elemental analysis (as _{C 28 H 15 F 13 N 4} O 3) C H N calc (%) 47.88 2.15 7.98 Found (% ) 47.64 2.25 8.00 The properties of this resin are shown below.

(1) Intrinsic viscosity: 0.29 dl / g (N-
(Measured in methyl-2-pyrrolidone at a concentration of 0.5 g / dl at 30 ° C.) (2) Molecular weight Number average molecular weight (Mn): 27000 Weight average molecular weight (Mw): 51000 Molecular weight distribution (Mw / Mn): 1.9 (3) Glass transition temperature (differential scanning calorimetry): 156 ° C (4) 10% weight loss temperature (thermobalance measurement): 420 ° C
(In air), 420 ° C. (in nitrogen) This polyether resin is selected from N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, tetrahydrofuran, 1,4-dioxane, chloroform and the like. A colorless transparent cast film was produced from a solution of the polyether resin in tetrahydrofuran, which was soluble in an organic solvent.

Example 14 In a 100 ml eggplant flask, 0.285 g (1.25 mmol) of 2,2-bis (4-hydroxyphenyl) propane and 0.363 g of α, α-bis (4-hydroxyphenyl) ethylbenzene were added. 1.25 mmol) and 5.1 ml of a 1 molar aqueous solution of sodium hydroxide. To this solution was added 2- {4- [2,2-bis (trifluoromethyl) -3,3,4,4,5,5,5-heptafluoropentyl] anilino} -4,6-dichloro-
A solution of 1.433 g (2.5 mmol) of 1,3,5-triazine in 5 ml of chloroform was added. The reaction was carried out with vigorous stirring at 20 ° C. for 12 hours. The reaction solution was poured into 400 ml of methanol to precipitate a polyether resin, which was separated by filtration. After washing with hot methanol, 80
Dry under pressure at 12 ° C. for 12 hours. The yield of the polyether resin was 99%. As a result of infrared absorption spectrum and elemental analysis of this resin, it was confirmed that the resin had a structure represented by the following formula as a repeating unit.

[0093]

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Infrared absorption spectrum 1575 cm ^-1 (C
= N), 1250-1220 cm ^-1 (CF) The characteristics of this resin are shown below.

(1) Intrinsic viscosity: 0.83 dl / g (measured in tetrahydrofuran at 30 ° C. at a concentration of 0.5 g / dl) (2) Molecular weight Number average molecular weight (Mn): 50,000 Weight average molecular weight (Mw): 110,000 Molecular weight distribution (Mw / Mn): 2.2 (3) Glass transition temperature (differential scanning calorimetry): 192 ° C (4) 10% weight loss temperature (thermobalance measurement): 415 ° C
(In air), 420 ° C. (in nitrogen) This polyether resin is selected from N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, tetrahydrofuran, 1,4-dioxane, chloroform and the like. A colorless transparent cast film was produced from a solution of the polyether resin in tetrahydrofuran, which was soluble in an organic solvent. The tensile strength, elongation at break, and tensile modulus of the film were 42 MPa and 3.8, respectively.
%, 1.1 GPa. The contact angles of water and methylene iodide with this film were 93 degrees and 6 degrees, respectively.
At 0 degrees, the surface free energy calculated from these contact angles was 36 erg / cm ² .

Example 15 0.476 g of 2,2-bis (3-phenyl-4-hydroxyphenyl) propane was placed in a 100 ml eggplant flask.
(1.25 mmol), 1,1-bis (3-methyl-4)
-Hydroxyphenyl) cyclohexane 0.371 g
(1.25 mmol), 0.27 g (0.75 mmol) of cetyltrimethylammonium bromide and 5.1 ml of a 1 molar aqueous sodium hydroxide solution were added and dissolved. To this solution was added 2- {4- [2,2-bis (trifluoromethyl) -3,3,4,4,5,5,5-heptafluoropentyl] anilino} -4,6-dichloro-1,
A solution of 1.433 g (2.5 mmol) of 3,5-triazine in 5 ml of chloroform was added. 20
The mixture was reacted with vigorous stirring at 12 ° C. for 12 hours. Reaction solution 4
The mixture was poured into 00 ml of methanol to precipitate a polyether resin, which was separated by filtration. After washing with hot methanol, 12
It dried under reduced pressure for hours. 85% yield of polyether resin
Met. As a result of infrared absorption spectrum and elemental analysis of this resin, it was confirmed that the resin had a structure represented by the following formula as a repeating unit.

[0097]

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Infrared absorption spectrum 1575 cm ^-1 (C
= N), 1250-1220 cm ^-1 (CF) The characteristics of this resin are shown below.

(1) Intrinsic viscosity: 0.67 dl / g (measured in tetrahydrofuran at 30 ° C. at a concentration of 0.5 g / dl) (2) Molecular weight Number average molecular weight (Mn): 45000 Weight average molecular weight (Mw): 99000 Molecular weight distribution (Mw / Mn): 2.2 (3) Glass transition temperature (differential scanning calorimetry): 176 ° C (4) 10% weight loss temperature (thermobalance measurement): 410 ° C
(In air), 425 ° C. (in nitrogen) This polyether resin is selected from the group consisting of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, tetrahydrofuran, 1,4-dioxane, chloroform and the like. A colorless transparent cast film was produced from a solution of the polyether resin in tetrahydrofuran, which was soluble in an organic solvent. The contact angles of water and methylene iodide on this film were 93 degrees and 59 degrees, respectively.
The surface free energy calculated from these contact angles is 3
It was 6 erg / cm ² .

Comparative Example 1 1.296 g of bis (4-aminophenoxyphenyl) hexafluoropropane was placed in a 100 ml eggplant flask.
(2.5 mmol) and distilled and purified N-methyl-2-
5 ml of pyrrolidone was added and dissolved under a nitrogen stream. The temperature of the solution was raised to 80 ° C., 0.603 g (2.5 mmol) of 2-anilino-4,6-dichloro-1,3,5-triazine was added, and the temperature was maintained as it was for 24 hours under a nitrogen stream. And reacted. After the reaction, the reaction solution is
The mixture was poured into 0 ml of methanol to precipitate a polymer, which was separated by filtration. After washing with hot methanol, it was dried under reduced pressure at 80 ° C. for 12 hours. The yield was 99%. As a result of infrared absorption spectrum and elemental analysis of this polymer, it was confirmed that the polymer had a structure represented by the following formula as a repeating unit.

[0101]

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The characteristics of this polymer are shown below.

(1) Intrinsic viscosity: 0.74 dl / g (N-
(2) Glass transition temperature (differential scanning calorimetry): 197 ° C (3) 10% weight loss temperature (thermobalance measurement): 470 ° C in methyl-2-pyrrolidone at a concentration of 0.5 g / dl)
(In air), 470 ° C. (in nitrogen) The polyamine resin comprises N-methyl-2-pyrrolidone,
A colorless, transparent cast film was produced from a solution of the polyamine resin in N-methyl-2-pyrrolidone, which was soluble in organic solvents such as N, N-dimethylformamide and pyridine. The tensile strength, elongation at break, and tensile modulus of the film were 42 MPa, 7%, and 1.5 GPa, respectively. The contact angles of water and methylene iodide with this film were 80 degrees and 43 degrees, respectively, and the surface free energy was 44 erg / cm ² . Compared with the film made from the polyamine resin obtained in Example 2, the contact angle is small and the surface free energy is large.

Comparative Example 2 1.026 g (2.5 mmol) of bis (4-aminophenoxyphenyl) propane and 5 m of distilled and purified N-methyl-2-pyrrolidone were placed in a 100 ml eggplant flask.
and dissolved under a stream of nitrogen. 80 ° C
To 2-anilino-4,6-dichloro-1,3,
0.603 g (2.5 mmol) of 5-triazine was added, the temperature was kept as it was, and the mixture was reacted by stirring under a nitrogen stream for 24 hours. After the reaction, the reaction solution was poured into 400 ml of methanol to precipitate a polymer, which was separated by filtration. After washing with hot methanol, the resultant was dried under reduced pressure at 80 ° C. for 12 hours. The yield was 98%. As a result of infrared absorption spectrum and elemental analysis of this polymer, it was confirmed that the polymer had a structure represented by the following formula as a repeating unit.

[0105]

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The characteristics of this polymer are shown below.

(1) Intrinsic viscosity: 0.80 dl / g (N-
(2) Glass transition temperature (differential scanning calorimetry): 189 ° C. (3) 10% weight loss temperature (thermobalance measurement): 465 ° C. Methyl-2-pyrrolidone at 30 ° C., measured at a concentration of 0.5 g / dl)
(In air), 470 ° C. (in nitrogen) The polyamine resin comprises N-methyl-2-pyrrolidone,
A light yellow transparent cast film was produced from a solution of the polyamine resin in N-methyl-2-pyrrolidone, which was soluble in organic solvents such as N, N-dimethylformamide and pyridine. The tensile strength, elongation at break, and tensile modulus of the film were 93 MPa, 8%, and 1.5 GPa, respectively. The contact angles of water and methylene iodide with this film were 82 degrees and 36 degrees, respectively, and the surface free energy was 47 erg / cm ² . The contact angle was small and the surface free energy was large as compared with the film made from the polyamine resin obtained in Example 4.

Comparative Example 3 0.951 g of 2,2-bis (3-phenyl-4-hydroxyphenyl) propane was placed in a 100 ml eggplant-shaped flask.
(2.5 mmol), 0.27 g (0.75 mmol) of cetyltrimethylammonium bromide and 5.1 ml of a 1 molar aqueous sodium hydroxide solution were added and dissolved.
To this solution was added 2-anilino-4,6-dichloro-1,
A solution prepared by dissolving 0.603 g (2.5 mmol) of 3,5-triazine in 5 ml of chloroform was added. 20
The mixture was reacted with vigorous stirring at 12 ° C. for 12 hours. Reaction solution 4
The mixture was poured into 00 ml of methanol to precipitate a polyether resin, which was separated by filtration. This was washed with hot methanol and dried under reduced pressure at 80 ° C. for 12 hours. The yield of polyether resin is 9
9%. As a result of infrared absorption spectrum and elemental analysis of this resin, it was confirmed that the resin had a structure represented by the following formula as a repeating unit.

[0109]

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The characteristics of this resin are shown below.

(1) Intrinsic viscosity: 1.16 dl / g (N-
(2) Glass transition temperature (differential scanning calorimetry): 177 ° C (3) 10% weight loss temperature (thermobalance measurement): 400 ° C in methyl-2-pyrrolidone at a concentration of 0.5 g / dl)
(In air), 405 ° C. (in nitrogen) This polyether resin is soluble in an organic solvent such as N-methyl-2-pyrrolidone, tetrahydrofuran, chloroform and the like, and is a solution of the polyether resin in N-methyl-2-pyrrolidone. To produce a colorless transparent cast film. The contact angles of water and methylene iodide to this film were 67 ° and 22 °, respectively, and the surface free energy calculated from these contact angles was 51 erg / cm ² .
The contact angle was small and the surface free energy was large as compared with the film made from the polyether resin obtained in Example 9.

Comparative Example 4 In a 100 ml eggplant-shaped flask, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane 0.74
1 g (2.5 mmol), 0.27 g (0.75 mmol) of cetyltrimethylammonium bromide and 5.1 ml of a 1 molar aqueous sodium hydroxide solution were added and dissolved. To this solution was added 2-anilino-4,6-dichloro-
A solution of 0.603 g (2.5 mmol) of 1,3,5-triazine in 5 ml of chloroform was added. The reaction was carried out with vigorous stirring at 20 ° C. for 12 hours. The reaction solution was poured into 400 ml of methanol to precipitate a polyether resin, which was separated by filtration. This was washed with hot methanol and dried under reduced pressure at 80 ° C. for 12 hours. The yield of the polyether resin was 99%. As a result of infrared absorption spectrum and elemental analysis of this resin, it was confirmed that the resin had a structure represented by the following formula as a repeating unit.

[0113]

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The characteristics of this resin are shown below.

(1) Intrinsic viscosity: 1.20 dl / g (measured in tetrahydrofuran at 30 ° C. at a concentration of 0.5 g / dl) (2) Glass transition temperature (differential scanning calorimetry): 193 ° C. (3) 10% Weight loss temperature (measured by thermobalance): 390 ° C
(In air), 395 ° C (in nitrogen) This polyether resin is soluble in organic solvents such as metacresol, orthochlorophenol, and tetrahydrofuran, and forms a colorless transparent cast film from a tetrahydrofuran solution of the polyether resin. did. The surface free energy of this film was 51 erg / cm ² . The surface free energy was larger than that of the film made from the polyether resin obtained in Example 10.

Reference Example 1 2- {4- [2,2-bis (trifluoromethyl)-
Synthesis of 3,3,4,4,5,5,5-heptafluoropentyl] anilino {-4,6-dichloro-1,3,5-triazine 13.01 g (70.5 mmol) of cyanuric chloride was dehydrated and distilled Was dissolved in 70 ml of tetrahydrofuran. To this solution was added 4- [2,2-bis (trifluoromethyl)-
3,3,4,4,5,5,5-heptafluoropentyl] aniline (30.0 g, 70.5 mmol) in 35 m
A solution dissolved in 1 l of tetrahydrofuran was added dropwise at 0 to 5 ° C over 30 minutes. Thereafter, the reaction was performed for 2 hours while maintaining the temperature.

Next, 3.77 g of sodium carbonate (35.
(3 mmol) in 35 ml of distilled water was added dropwise, and the mixture was stirred for 2 hours while maintaining the reaction temperature at 0 to 5 ° C.
After the reaction, the tetrahydrofuran layer was separated. The organic layer was washed with a saturated aqueous solution of sodium chloride and then dried over anhydrous sodium sulfate. A crude product was obtained by removing the solvent from this solution. This was distilled under reduced pressure (190 ° C /
0.2 Torr). The yield is 30.7 g (76% yield).
Met. By recrystallizing twice with a mixed solvent of anhydrous hexane / toluene, colorless needle crystals were obtained.

Melting point: 129 to 130 ° C. Infrared absorption spectrum: 1576 cm ⁻¹ (C = N), 1
^{230~1213cm- 1 (C-F) 1} H- nuclear magnetic resonance spectrum (CDCl _3): 3.55p
pm (s, 2H, CH ₂ ), 7.34 ppm (d, J =
8.3 Hz, 2H, aromatic ring), 7.54 ppm (d, J
= 8.5 Hz, 2H, aromatic ring), 7.60 ppm (s,
IH, NH) Elemental analysis (C ₁₅ H ₅ Cl as _{2 F 11 N 4 O) C} H N calc (%) 33.53 1.23 9.78 Found (%) 33.56 1.17 9. 76

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-7-118382 (JP, A) JP-A 9-87385 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 73/00-73/06 C08G 65/00-65/48 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A compound of the general formula (1) [In the formula, Ar represents a divalent aromatic residue. Y is -NH -
It is shown. n shows the integer of 10-200. ] A fluorine-containing resin represented by the formula: