JP2890646B2 - Method for producing fluorine-containing benzoxazole-based polymer - Google Patents

Description

The present invention relates to a method for producing a novel fluorine-containing polybenzoxazole-based polymer.

[Conventional technology]

Conventionally, it has been known that polybenzoxazole has excellent properties such as mechanical strength such as tensile strength, bending strength and impact strength, and thermal properties such as thermal deformation temperature and thermal decomposition. The polybenzoxazole and its production method are described in, for example, Macromolecule Chemie.
ol Chem., 83, 167 (1965), and JP-B-42-19271.

In particular, JP-A-62-207332 discloses a compound represented by the general formula (A)
The polybenzoxazole containing a fluorine atom represented by the following formula is known.

(In the formula, R represents a divalent aromatic group.) [Problems to be Solved by the Invention] However, the above-mentioned polybenzoxazole has a high water absorption rate and is insufficient in water resistance and moisture resistance. .

In order to improve these points, a polymer containing more fluorine atoms is considered to be effective.

Thus, the present inventors have invented a novel method for producing a benzoxazole-based polymer.

[Means for solving the problem]

The method for producing a fluorinated benzoxazole-based polymer in the present invention is represented by the general formula (I) [In the formula, Rf is (here n is a integer from 6-12) -C _n F _2n-1 is represented by hydrogen of the benzene ring is substituted with a lower alkyl group, a lower alkoxy group or a halogen And an acid component containing an aromatic dicarboxylic acid or an amide-forming derivative thereof represented by the general formula (II): (Wherein, R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen or a trialkylsilyl group, X represents a tetravalent organic group containing an aromatic ring, and —NH—R ¹ and -OR ³ and -NH-
R ² and —O—R ⁴ are each bonded to the aromatic ring in X at the ortho position.
It is characterized by reacting an aminophenol component containing a compound. Here, the “lower” refers to “1-5 carbon atoms”.
It is used in the meaning of "no" (the same applies hereinafter).

In this method, an aromatic dicarboxylic acid represented by the general formula (I) or an amide-forming derivative thereof is used as an acid component, and a bis (aminophenol) compound represented by the general formula (II) is reacted with a reaction partner (aminophenol component). ), And these are subjected to a condensation or condensation / ring-closure reaction. As the acid component, besides the aromatic dicarboxylic acid or the amide-forming derivative thereof, a dicarboxylic acid or an amide-forming derivative thereof reactive with the aminophenol component is used. You may use together.

Examples of the dicarboxylic acid compound represented by the general formula (I) include 5- (perfluorononenyloxy) isophthalic acid, 4- (perfluorononenyloxy) phthalic acid,
-(Perfluorononenyloxy) terephthalic acid, 4-
Methyl-5- (perfluorononenyloxy) isophthalic acid, 4-methoxy-5- (perfluorononenyloxy) isophthalic acid, 2,4,6-trifluoro-5- (perfluorononenyloxy) isophthalic acid , 4-chloro-
5- (perfluorononenyloxy) isophthalic acid, 4
-Bromo-5- (perfluorononenyloxy) isophthalic acid, 4-methyl-5- (perfluorononenyloxy) phthalic acid, 4-methoxy-5- (perfluorononenyl) phthalic acid, 3,4, 6-trifluoro-5- (perfluorononenyloxy) phthalic acid, 4-chloro-5
(Perfluorononenyloxy) phthalic acid, 4-bromo-5- (perfluorononenyloxy) phthalic acid, 2-
Methyl-5- (perfluorononenyloxy) terephthalic acid, 4-methoxy-5- (perfluorononenyloxy) terephthalic acid, 2,3,6-trifluoro-5- (perfluorononenyloxy) terephthalic acid , 2-chloro-
5- (perfluorononenyloxy) terephthalic acid, 2
-Bromo-5- (perfluorononenyloxy) terephthalic acid, 5- (perfluorohexenyloxy) isophthalic acid, 4- (perfluorohexenyloxy) phthalic acid, 2- (perfluorohexenyloxy) terephthalic acid, 4- Methyl-5- (perfluorohexenyloxy) isophthalic acid, 4-methoxy-5- (perfluorohexenyloxy) isophthalic acid, 2,4,6-trifluoro-5- (perfluorohexenyloxy) isophthalic acid, 4- Chloro-5- (perfluorohexenyloxy) isophthalic acid, 4-bromo-5- (perfluorohexenyloxy) isophthalic acid, 4-methyl-5- (perfluorohexenyloxy) phthalic acid, 4-methoxy-5- ( Perfluorohexenyloxy) phthalic acid, 3,
4,6-trifluoro-5- (perfluorohexenyloxy) phthalic acid, 4-chloro-5- (perfluorohexenyloxy) phthalic acid, 4-bromo-5- (perfluorohexenyloxy) phthalic acid, 2- Methyl-5
(Perfluorohexenyloxy) terephthalic acid, 4-
Methoxy-5- (perfluorohexenyloxy) terephthalic acid, 2,3,6-trifluoro-5- (perfluorohexenyloxy) terephthalic acid, 2-fluoro-5-
(Perfluorohexenyloxy) terephthalic acid, 2-
Bromo-5- (perfluorohexenyloxy) terephthalic acid and the like.

The perfluorononenyloxyisophthalic acid and perfluorohexenyloxyisophthalic acid are, for example,
According to the method disclosed in JP-A-60-51146, a trimer or dimer of hexafluoropropene is reacted with hydroxyisophthalic acid in an aprotic polar solvent at room temperature or lower in the presence of a base catalyst. Can be manufactured.

Examples of the perfluorononenyl group include, for example, those represented by the formula (A) And the perfluorohexenyl group includes, for example, a compound represented by the formula (B) There is a group.

Among the aromatic dicarboxylic acids represented by the general formula (I), perfluoroalkenyloxyisophthalic acid is based on, for example, the method for producing p-perfluoroalkenyloxybenzoic acid described in JP-A-60-51146. Can be adjusted. For example, they can be prepared by reacting 5-hydroxyisophthalic acid with a hexafluoropropene dimer or trimer in the presence of an excess of an amine, and others can likewise be prepared with a dicarboxylic acid. It can be produced using perfluoroalkenes.

The dicarboxylic acid represented by the above general formula (I) can be prepared, for example, according to the method described in JP-A-50-121243, by esterification such as diphenyl ester and dibenzyl ester of hydroxy-dicarboxybenzene. And a fluoroalkene oligomer, such as fluoropropene trimer and tetrafluoroethylene pentamer, in the presence of a proton acceptor in an aprotic organic solvent at or near room temperature in the presence of a base catalyst The reaction product can be produced by isolating the reaction product, hydrolyzing the reaction product in the presence of a basic compound such as sodium hydroxide, potassium hydroxide or the like, and further appropriately treating the reaction product with an acid such as hydrochloric acid.
The reaction product and the final product are appropriately purified by means such as washing and recrystallization.

The amide-forming derivative of the aromatic dicarboxylic acid represented by the general formula (I) is a derivative capable of forming an amide bond by reacting with the bis (aminophenol) represented by the general formula (II). Examples thereof include acid halides such as dichloride and dibromide of aromatic dicarboxylic acid, and dialkyl esters such as dimethyl ester and diethyl ester of the acid.

The above dichloride can be obtained in high yield by reacting, for example, an aromatic dicarboxylic acid represented by the general formula (I) with thionyl chloride.

The above dialkyl esters such as dimethyl ester and diethyl ester can be obtained by reacting an alcohol such as methanol and ethanol with an aromatic dicarboxylic acid represented by the general formula (I) in the presence of an acid.

The dicarboxylic acid or amide-forming derivative which may be used in combination with the aromatic dicarboxylic acid or amide-forming derivative thereof represented by the general formula (I) includes the general formula (II)
I) [However, in the formula, Z is (Where Rf is a divalent organic group other than the same as in the general formula (I))], and Z in the general formula (III) is an aromatic ring Dicarboxylic acid which is a divalent organic group containing amide or an amide-forming derivative thereof is preferable in view of heat resistance of the obtained polymer.

As the divalent organic group containing an aromatic ring, a compound represented by the general formula (a) A group represented by the general formula (b) (Wherein, Z 'is a bond, -O -, - S -, - SO 2 -, And a group represented by the general formula (c) (Where Z 'is the same as above, and two Z's
May be the same or different), a group represented by the general formula (d) (Where Z 'is the same as above and three Z's
May be the same or different), and these groups may be appropriately substituted with a lower alkyl group, a lower alkoxy group, or a halogen such as chlorine, bromine, or fluorine. .

Examples of the dicarboxylic acids represented by the general formula (III) include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and other aliphatic dicarboxylic acids, and phthalic acid. Acid, isophthalic acid, phthalic acid, 3,3'-dicarboxylic diphenyl ether, 3,4'-dicarboxylic diphenyl ether, 4,
4'-dicarboxyl diphenyl ether, 3,3'-dicarboxyl diphenyl methane, 3,4'-dicarboxyl diphenyl methane, 4,4'-dicarboxyl diphenyl methane, 3,3'-dicarboxyl diphenyl Enyldifluoromethane, 3,4'-dicarboxydiphenyldifluoromethane, 4,4'-dicarboxydiphenyldifluoromethane, 3,3'-dicarboxydiphenylsulfone,
3,4'-dicarboxyldiphenylsulfone, 4,4'-dicarboxyldiphenylsulfone, 3,3'-dicarboxyldiphenylsulfide, 3,4'-dicarboxyldiphenylsulfide, 4, 4'-dicarboxyl diphenyl sulfide, 3,3'-dicarboxyl diphenyl ketone, 3,4'-dicarboxyl diphenyl ketone, 4,4'-
Dicarboxyldiphenyl ketone, 2,2-bis (3-carboxylphenyl) propane, 2,2- (3,4'-dicarboxylphenyl) propane, 2,2-bis (4-carboxylphenyl) propane , 2,2-bis (3-carboxylphenyl) hexafluoropropane, 2,2- (3,
4'-dicarboxyldiphenyl) hexafluoropropane, 2,2-bis (4-carboxylphenyl) hexafluoropropane, 1,3-bis (3-carboxylphenoxy) benzene, 1,4-bis (3 -Carboxylphenoxy) benzene, 1,4-bis (4-carboxylphenoxy) benzene, 3,3 '-(1,4-phenylenebis (1
-Methylethylidene)) bisbenzoic acid, 3,4 '-(1,4-
Phenylenebis (1-methylethylidene)) bisbenzoic acid, 4,4 '-(1,4-phenylenebis (1-methylethylidene)) bisbenzoic acid, 2,2-bis (4- (3-carboxylphenoxy) Phenyl) propane, 2,2-bis (4- (4-carboxylphenoxy) phenyl) propane, 2,2-bis (4- (3-carboxylphenoxy) phenyl) hexafluoropropane, 2,2- Bis (4- (4-carboxylphenoxy) phenyl) hexafluoropropane, bis (4- (3-carboxylphenoxy) phenyl) sulfide, bis (4- (4-carboxylphenoxy) phenyl) sulfide, Aromatic dicarboxylic acids such as bis (4- (3-carboxylphenoxy) phenyl) sulfone and bis (4- (4-carboxylphenoxy) phenyl) sulfone There is.

Examples of the amide-forming derivative of the dicarboxylic acid represented by the general formula (III) include acid halides of the dicarboxylic acid such as dichloride and dibromide, and dialkyl esters of the dicarboxylic acid such as dimethyl ester and diethyl ester.

As the acid component in the present invention, it is preferable to use an aromatic dicarboxylic acid represented by the general formula (I) or an amide-forming derivative thereof in the acid component in an amount of 1 to 100 mol%, particularly 10 to 100 mol%. If the content of such an acid component is too small, the obtained fluorinated benzoxazole-based polymer tends to have low moisture absorption resistance.

Bis (aminophenol) represented by the general formula (II)
Among the compounds, trialkylsilylated diamines in which R ¹ , R ² , R ³ , and R ⁴ are represented by trialkylsilyl groups are described in Macromolecules, Vol. 21, p. 2305 (1988).
It can be adjusted according to the production method of 3,3'-bis (trimethylsiloxy) -4,4'-bis (trimethylsilylamino) biphenyl as shown below. For example,
In a solution of 4,4'-diamino-3,3'-dihydroxybiphenyl in tetrahydrofuran, in the presence of triethylamino,
Reacting a trialkylsilyl chloride to give 3,3′-
Bis (trialkylsiloxy) -4,4'-bis (trialkylsilylamino) biphenyl can be obtained.

Bis (aminophenol) represented by the general formula (II)
The compound is preferably a compound in which at least R ¹ and R ² are a trialkylsilyl group in order to obtain a higher-molecular-weight benzoxazole-based polymer. Examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a tripropylsilyl group.

In the general formula (II), X represents the general formula (a ′) A group represented by the general formula (b ') [Wherein, Z 'is a bond, -O -, - S -, - SO 2 -, -Rf'ORf _'m (wherein, Rf' is a divalent fluorocarbon, m is an integer from 1 to 5, a plurality of Rf '
May be the same or different)], a group represented by the formula (c ') (Where Z 'is the same as above, and two Z's
May be the same or different), a group represented by the general formula (d ') (Where Z 'is the same as above and three Z's
May be the same or different), and the benzene ring in these groups is appropriately substituted with a lower alkyl group, a lower alkoxy group, halogen, such as chlorine, bromine, and fluorine. You may.

Bis (aminophenol) represented by the general formula (II)
The compounds are 3,4-diamino-1,5-benzenediol, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-diamino-4,4'-dihydroxybiphenyl, 2,2 '-Bis (3-amino-4-hydroxyphenyl) ketone, 2,2-bis (3-amino-4-hydroxyphenyl)
Sulfide, 2,2-bis (3-amino-4-hydroxyphenyl)
Ether, 2,2-bis (3-amino-4-aminophenyl) sulfone, 2,2-bis (3-amino-4-hydroxyphenyl)
Propane, 2,2-bis (3-hydroxy-4-aminophenyl)
Propane, 2,2-bis (3-hydroxy-4-aminophenyl)
Methane, 2,2-bis (3-amino-4-hydroxyphenyl)
Hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl)
Hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl)
Difluoromethane, And their trialkylsilyl compounds.

By reacting the acid component and the aminophenol component at an appropriate temperature, a fluorine-containing benzoxazole-based polymer can be produced. In this reaction, the degree of ring closure can be appropriately adjusted by selecting appropriate conditions. For example, a method in which the acid component and the aminophenol component are melted (preferably at a temperature of 200 ° C. or higher) and reacted without a solvent, the acid component and the aminophenol component are dissolved in an organic solvent or polyphosphoric acid,
Almost or completely closed-ring polybenzoxazole can be produced by a method in which the reaction is carried out at a temperature of not lower than 80 ° C., and the acid component (particularly dihalide) and the aminophenol component are reacted in an organic solvent at 80 ° C. or lower, particularly 50 ° C. or lower. By doing so, a polyhydroxyamide which is a precursor of polybenzoxazole and has little or no ring closure (the hydroxyl group may be trialkylsilylated as described above) can be produced.

Further, the polybenzoxazole precursor (the above-mentioned polyhydroxyamide or polyhydroxyamide in which the ring closure is partially advanced) may be further subjected to acetic anhydride, propionic anhydride, benzoic anhydride and the like at 100 ° C. or higher, particularly at 150 ° C. or higher as required. An acid anhydride, a ring-closing agent such as carbodiimide such as dicyclohexylcarbodiimide, and further, if necessary, a ring-closing catalyst such as pyridine, isoquinoline, trimethylamine, aminopyridine, imidazole and the like are added to chemically close the ring (the ring-closing agent and the ring-closing catalyst are 1 to 1 mole of each acid component
It is preferred to use within a range of 8 moles), so that polybenzoxazoles with almost or completely completed ring closure can be prepared. These reactions are preferably performed in the presence of an organic solvent.

Organic solvents that can be used in the above include N, N-dimethylformamide, N, N-dimethylacetamide, N
There are organic polar solvents such as -methyl-2-pyrrolidone, dimethylsulfoxide, hexamethylphosphoramide, phenol, m-cresol, and chlorobenzene, and two or more kinds thereof may be used as a mixture as long as they are compatible with each other. Also,
Along with these organic polar solvents, toluene, xylene,
General-purpose solvents such as cellosolve acetate and methyl cellosolve can be used in combination as long as the solubility of polybenzoxazole or its precursor is not reduced.

In any of the above-mentioned reactions, when dihalide is used as the acidic component, the reaction can be appropriately performed in the presence of a hydrogen halide trapping agent. Examples of the hydrogen halide trapping agent include tertiary amines such as pyridine, triethylamine and dimethylaniline.

The reaction between the acid component and the bis (aminophenol) component is preferably carried out in an equimolar or almost equimolar manner, and the order of addition of each component is arbitrary.

In the above reaction, -NH-R ¹ and -NH-R ² in the general formula (VI) is reacted with the acid component in preference to -OR ³ or -OR ^4.

Fluorinated benzoxazole-based polymer (polybenzoxazole and its precursor) obtained in this manner
Is soluble in dimethylacetamide (DMAc)
It is preferably dissolved in the solvent at a concentration of 0.1 g / dl and has a reduced viscosity measured at 30 ° C. of 0.01 dl / g or more, particularly preferably 0.3 dl / g or more. Polyhydroxyamide dissolves in DMAc.

Further, the fluorine-containing benzoxazole-based polymer,
Those having a thermal decomposition temperature of 400 ° C. or higher are preferred.

The fluorine-containing benzoxazole-based polymer obtained by the present invention can be used in the form of a varnish dissolved in an organic solvent or in the form of a powder. In particular, polyhydroxyamide and a precursor of polybenzoxazole having a low degree of ring closure are soluble in an organic solvent and can be used in a varnish form.However, a polyimide resin whose ring closure is almost completed can be treated with an organic solvent. There are soluble and poorly soluble ones, and the latter is preferably used in powder form.

In addition, in order to prevent voids due to the generation of condensation by-products due to the ring closure reaction, it is preferable to use polybenzoxazole which is almost completely closed.

The varnish of the fluorinated benzoxazole-based polymer is applied to the surface of glass, silicon wafer, enameled wire, etc. by a commonly used method such as spin coating, spraying, brush coating, impregnation, and then heated to form a polybenzoxazole film. Can be. In this case, when a polybenzoxazole precursor is used, the ring is closed during the heat treatment.

The polybenzoxazole or its precursor obtained in the present invention is particularly useful as an insulating material for enameled wires, an insulating film or a molding material.

Among the fluorine-containing benzoxazole-based polymers obtained in the present invention, polybenzoxazole is represented by the general formula (IV) [Wherein, Rf and X are the same as those in the general formulas (I) and (II), respectively, and two sets of N and O each represent an aromatic ring in X so as to form a five-membered ring. And the hydrogen of the benzene ring may be substituted with a lower alkyl group, a lower alkoxy group or a halogen]. The polyhydroxyamide has a general formula (V ) Wherein Rf and X are the same as those in formulas (I) and (II), and R ′ and R ″ each independently represent hydrogen or a trialkylsilyl group;
And -OR 'and -NH- and -OR "are respectively bonded to the aromatic ring in X at the ortho position, and the hydrogen of the benzene ring is substituted with a lower alkyl group, a lower alkoxy group or a halogen. May be included in the formula).

In the general formula (V), a polymer containing a structural unit in which R ′ and R ″ are a tolalkylsilyl group is a polymer containing a bis (amino) in which R ³ or R ⁴ is a trialkylsilyl group in the general formula (II). A phenol) compound is produced when the compound is used. In this case, after completion of the above-described reaction, the reaction solution is left as it is, or the polymer is isolated and added to methanol or water to obtain R ′ or R ′ in the general formula (V). It may be a polymer containing a structural unit in which R ″ is hydrogen.

〔Example〕

Hereinafter, the present invention will be described with reference to examples, but the present invention is not particularly limited by these examples.

Example 1 3,3'-Dihydroxy-4,4'-diaminobiphenyl was placed in a reaction vessel equipped with a stirring device, a nitrogen introducing tube, and a drying tube.
2.16 g (0.01 mol), 1.74 g (0.022 mol) of pyridine, and 12.3 g of dimethylacetamide were added and cooled in an ice water bath. 3,3 ′
When the dihydroxy-4,4'-diaminobiphenyl is dissolved, 6.49 g (0.01 mol) of 5-perfluorononenyloxyisophthalic dichloride are added in small portions. After stirring for 5 hours, the reaction solution was poured into a large amount of methanol to precipitate the polymer. The precipitated polymer was separated by filtration, washed with methanol, and dried to obtain polyhydroxyamide.

Example 2 3.66 g (0.01 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 1.74 g (0.022 g of pyridine) were placed in a reaction vessel equipped with a stirring device, a nitrogen inlet tube, and a drying tube. mol) and 15.2 g of dimethylacetamide were cooled in an ice-water bath. When 2,2-bis (3-amino-4-hydroxy) hexafluoropropane is dissolved, 5-
Perfluorononenyloxyisophthalic dichloride
6.49 g (0.01 mol) are added in small portions. After stirring for 5 hours, the reaction solution was poured into a large amount of methanol to precipitate the polymer. The precipitated polymer was separated by filtration, washed with methanol, and dried to obtain polyhydroxyamide.

Example 3 3,3'-Dihydroxy-4,4'-diaminobiphenyl was placed in a reaction vessel equipped with a stirring device, a nitrogen inlet tube, and a drying tube.
2.16 g (0.01 mol), 1.74 g (0.022 mol) of pyridine, and 9.65 g of dimethylacetamide were added and cooled in an ice water bath. 3,3 ′
When the dihydroxy-4,4'diaminobiphenyl is dissolved, 3.25 g (0.005 mol) of 5-perfluorononenyloxyisophthalic acid dichloride and 1.02 g (0.005 mol) of isophthalic acid dichloride are added little by little. After stirring for 5 hours, the reaction solution was poured into a large amount of methanol to precipitate the polymer. Filtration of the precipitated polymer,
After washing with methanol, drying was performed to obtain polyhydroxyamide.

Example 4 3.66 g (0.01 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 1.74 g (0.022 g of pyridine) were placed in a reaction vessel equipped with a stirring device, a nitrogen inlet tube, and a drying tube. mol) and dimethylacetamide (9.2 g) were cooled in an ice water bath. 2,2-bis (3-amino-4-
When (hydroxyphenyl) hexafluoroparopan is dissolved, 0.65 g (0.001 mol) of 5-perfluorononenyloxyisophthalic acid dichloride and 1.83 g (0.009 mol) of isophthalic acid dichloride are added little by little. After stirring for 5 hours, the reaction solution was poured into a large amount of methanol to precipitate the polymer. The precipitated polymer was separated by filtration, washed with methanol, and dried to obtain polyhydroxyamide.

Example 5 2.16 g (0.01 mol) of 3,3'-dihydroxy-4,4'-diaminobiphenyl and 100 g of polyphosphoric acid were placed in a reaction vessel equipped with a stirring device, a nitrogen inlet tube, and a cooling tube containing balls.
Heat to 6.12 g (0.01 mol) of 5-perfluorononenyloxyisophthalic acid is added and reacted at 200 ° C. for 4 hours. The reaction solution was poured into water to precipitate the polymer. The precipitated polymer was separated by filtration, washed with water, a dilute aqueous solution of sodium hydrogen carbonate, water and methanol, and dried to obtain polybenzoxazole.

Example 6 A reaction vessel equipped with a stirring device, a nitrogen inlet tube, and a drying tube was charged with 5.03 g (0.01 m3) of 3,3'-bis (trimethylsiloxy) -4,4'-bis (trimethylsilylamino) -biphenyl.
ol) and 17.3 g of dimethylacetamide, and cooled in an ice-water bath. 6.49 g (0.01 mol) of 5-perfluorononenyloxyisophthalic dichloride are added little by little. After stirring for 5 hours, the reaction solution was poured into a large amount of methanol to precipitate the polymer. The precipitated polymer was separated by filtration and washed with methanol to obtain a dried polyhydroxyamide.

Example 7 6.55 g of 2,2-bis (4- (trimethylsiloxy) -3 (trimethylsilylamino) hexafluoropropane was placed in a reaction vessel equipped with a stirring device, a nitrogen inlet tube, and a drying tube.
(0.01 mol) and 19.5 g of dimethylacetamide, and cooled in an ice-water bath. 6.49 g (0.01 mol) of 5-perfluorononenyl oisisophthalic acid dichloride are added little by little. After stirring for 5 hours, the reaction solution was poured into a large amount of methanol to precipitate the polymer. The precipitated polymer was separated by filtration, washed with methanol, and dried to obtain polyhydroxyamide.

Comparative Example 1 Instead of 6.49 g of 5-perfluorononenyloxyisophthalic acid dichloride shown in Example 1, 2.03 g (0.01 mol) of isophthalic acid dichloride was used to obtain polyhydroxyamide in the same manner as in Example 1.

Comparative Example 2 Instead of 6.49 g of 5-perfluorononenyloxyisophthalic acid dichloride of Example 7, 2.03 g (0.01 mol) of isophthalic acid dichloride was used to obtain a polyhydroxyamide in the same manner as in Example 7.

The 5-perfluorononenyloxyisophthalic acid used above has the structural formula Is a compound of

The polymers obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were made into a solution of about 20% of dimethylacetamide, and the solution was coated on a glass plate, and sequentially heated at 150 ° C, 200 ° C and 250 ° C for 30 minutes. The mixture was heated to obtain a polybenzoxazole film. At this time, the polyhydroxyamides obtained in Examples 1 to 4, 6, and 7 and Comparative Examples 1 and 2 were dehydrated and ring-closed by heating to produce polybenzoxazole.

Table 1 shows the properties of the obtained polybenzoxazole.

In Table 1, PFIP is 5-perfluorononenyloxyisophthalic acid dichloride, IP is isophthalic acid dichloride, HAB is 3,3'dihydroxy-4,4-diaminophenyl, Bis-AP-AF is 2,2- Bis (3-amino-4-hydroxyphenyl) hexafluoropropane, TMSHAB is 3,
3'-bis (trimethylsiloxy) -4,4'-bis (trimethylsilylamino) -vinphenyl is shown.

Physical property measurement method IR absorption spectrum Measured by the KBr tablet method.

Thermal decomposition temperature The weight loss under heating was measured using a thermobalance at a heating rate of 10 ° C./min, and the temperature at which the weight loss started was read.

Reduced viscosity at a concentration of 0.1 g / dl in DMAc solvent at a temperature of 30
Measured at ° C. Water Absorption A polybenzoxazole film was immersed in water at room temperature for 24 hours, and calculated from the weight change before and after.

The fluorine-containing polyhydroxyamide obtained in Examples 1 and 6 has the formula (1) Wherein the fluorine-containing polybenzoxazole obtained from the fluorine-containing polyhydroxyamide and the fluorine-containing polybenzoxazole obtained in Example 5 are represented by the formula (2) Is a polymer having a repeating unit of

The fluorine-containing polyhydroxyamide obtained in Examples 2 and 7 has the formula (3) And a fluorine-containing polybenzoxazole obtained from this polymer has the formula (4) Is a polymer having a repeating unit of

The fluorine-containing polyhydroxyamide obtained in Example 3 was obtained by adding 50 mol% of the repeating unit of the above formula (1) to the compound of the formula (5) Is a polymer having a repeating unit of 50 mol%, and a fluorine-containing polybenzoxazole obtained therefrom is a polymer having a repeating unit of the above formula (2) of 50 mol% and a compound of the formula (6) Is a polymer having a repeating unit of 50 mol%.

The fluorine-containing polyhydroxyamide obtained in Example 4 was obtained by adding 10 mol% of the repeating unit of the above formula (3) to the compound of the formula (7). Is a polymer having a repeating unit of 90 mol%, and the fluorine-containing polybenzoxazole obtained from the polymer comprises 10 mol% of the repeating unit of the above formula (4) and 10 mol% of the formula (8) Is a polymer having a repeating unit of 90 mol%.

FIG. 1 shows the IR absorption spectrum of the fluorine-containing polyhydroxyamide obtained in Example 1, and FIG. 2 shows the IR absorption spectrum of the fluorine-containing polybenzoxazole obtained from the fluorine-containing polyhydroxyamide. FIG. 3 shows the IR absorption spectrum of the fluorine-containing polyhydroxyamide obtained in Example 2, FIG. 4 shows the IR absorption spectrum of the fluorine-containing polybenzoxazole obtained from the fluorine-containing polyhydroxyamide, and FIG. FIG. 6 shows the IR absorption spectrum of the fluorine-containing polyhydroxyamide obtained in Example 3, FIG. 6 shows the IR absorption spectrum of the fluorine-containing polybenzoxazole obtained from the fluorine-containing polyhydroxyamide, and FIG. IR absorption spectrum of the fluorine-containing polyhydroxyamide obtained in Example 4,
FIG. 8 shows an IR absorption spectrum of the fluorine-containing polybenzoxazole obtained from the fluorine-containing polyhydroxyamide,
FIG. 9 shows the IR absorption spectrum of the fluorine-containing polybenzoxazole obtained in Example 5, FIG. 10 shows the IR absorption spectrum of the fluorine-containing polyhydroxyamide obtained in Example 6,
FIG. 11 shows an IR absorption spectrum of the fluorine-containing polybenzoxazole obtained from the fluorine-containing polyhydroxyamide.

〔The invention's effect〕

The fluorinated benzoxazole-based polymer obtained by the method according to any one of claims 1 to 3 is a novel fluorinated polybenzoxazole and has a low water absorption rate and is excellent in water resistance and moisture resistance in the form of fluorinated polybenzoxazole.

[Brief description of the drawings]

FIG. 1 is an IR absorption spectrum of the fluorine-containing polyhydroxyamide obtained in Example 1, FIG. 2 is an IR absorption spectrum of a fluorine-containing polybenzoxazole obtained from the fluorine-containing polyhydroxyamide, and FIG. The figure shows the IR absorption spectrum of the fluorine-containing polyhydroxyamide obtained in Example 2, FIG. 4 shows the IR absorption spectrum of the fluorine-containing polybenzoxazole obtained from the fluorine-containing polyhydroxyamide, and FIG. IR absorption spectrum of the fluorine-containing polyhydroxyamide obtained in Example 3, FIG. 6 shows the IR absorption spectrum of the fluorine-containing polybenzoxazole obtained from the fluorine-containing polyhydroxyamide, and FIG. 7 shows the Example. IR absorption spectrum of fluorine-containing polyhydroxyamide obtained in 4
FIG. 9 shows the IR absorption spectrum of the fluorine-containing polybenzoxazole obtained from the fluorine-containing polyhydroxyamide, FIG. 9 shows the IR absorption spectrum of the fluorine-containing polybenzoxazole obtained in Example 5, and FIG. Is an IR absorption spectrum of the fluorine-containing polyhydroxyamide obtained in Example 6,
FIG. 11 is an IR absorption spectrum of fluorine-containing polybenzoxazole obtained from the fluorine-containing polyhydroxyamide.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08G 73/22 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. The compound of the general formula (I) [Wherein, Rf is represented by -CnF _2n-1 (where n is an integer of 6 to 12), and hydrogen of the benzene ring has 1 carbon atom.
Or an aromatic dicarboxylic acid or an amide-forming derivative thereof represented by the formula (II): (Wherein, R ¹ , R ² , R ³ and R ⁴ are each independently
Represents hydrogen or a trialkylsilyl group, X represents a tetravalent organic group containing an aromatic ring, -NH-R ¹ and -O-R ³ and -NH
—R ² and —O—R ⁴ are each bonded to the aromatic ring in X at the ortho position.) An aminophenol component containing a bis (aminophenol) compound represented by the formula: General formula (V), characterized by reacting with [Wherein, Rf and X have the same meanings as in general formulas (I) and (II), and R ′ and R ″ each independently represent hydrogen or a trialkylsilyl group, and —NH— and —O—
-R 'and -NH- and -OR "are respectively bonded to the aromatic ring in X at the ortho position, and hydrogen of the benzene ring is an alkyl group having 1 to 5 carbon atoms, and 1 to 5 carbon atoms. May be substituted with an alkoxy group or a halogen). 2. A compound represented by the formula (IV), wherein the fluorine-containing polyhydroxyamide of the formula (V) according to claim 1 is ring-closed. [Wherein, Rf and X have the same meanings as in general formulas (I) and (II)]. A process for producing a fluorine-containing benzoxazole-based polymer represented by the following formula: 3. An acid component containing an aromatic dicabonic acid or an amide-forming derivative thereof represented by the general formula (I) according to claim 1, and a bis (aminophenol) represented by the general formula (II) A general formula (IV) characterized by reacting an aminophenol component containing a compound by any one of the following methods (1) to (3): [Wherein, Rf and X have the same meanings as in formulas (I) and (II)]. A process for producing a fluorine-containing benzoxazole-based polymer represented by the formula: (1) Both components are reacted in polyphosphoric acid at 150 ° C. or higher. (2) Both components are reacted in an organic solvent at 150 ° C. or higher. (3) Dissolve both components and react without solvent.