JPH1149754A - Quinoline compound, its production and heat-resistant resin using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a quinoline compound for producing a heat-resistant resin capable of improving workability and solubility of a polyquinoline and lowering its hygroscopic property, by reacting a ketomethylene compound with a specific ether. SOLUTION: This compound is shown by formula I (R is H, a 1-8C alkyl, a 6-18C aryl, etc.; R' is H, a 1-8C alkyl, a 6-18C aryl, a 1-20C alkoxy, etc.); X is F, Cl, Br or I; (l) is 1-5; (m) is 0-4 and (l+m) is 5). The compound is preferably obtained by reacting a ketomethylene compound of formula II with 4,4'- diamino-3,3'-dibenzoyldiphenyl ether in a solvent such as benzene in the presence of an acid catalyst such as hydrochloric acid at -20 to 250 deg.C for about 30 minutes to 24 hours.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a quinoline compound,
The present invention relates to a method for producing the same and a heat-resistant resin using the same.

[0002]

2. Description of the Related Art Conventionally, among various organic polymers, polyimides have been widely used in the fields of space and aviation to electronic communication because of their excellent heat resistance. In particular, recently, it is expected not only to have excellent heat resistance, but also to have various performances according to applications. For example, a printed circuit board, an interlayer insulating film for LSI, a passivation film, and the like are required to have a small coefficient of thermal expansion and a small dielectric constant. However, since polyimide has a highly polar imide structure, it has been difficult to develop a low dielectric type and low moisture absorption type. In addition, it is expected that the refractive index of the optical communication, especially the cladding material of the optical waveguide is small. However, a polyimide which sufficiently satisfies these characteristics has not been obtained at present. On the other hand, as a resin having excellent heat resistance, Macromolecules, published in 1981, Vol. 14, pages 870 to 880 (macr.
omolecules, 14, 870-881 (198
The polyquinoline described in 1)) is an excellent heat-resistant resin having a high glass transition temperature and a high thermal decomposition temperature.

However, the method for synthesizing polyquinoline reported in the above literature uses m-cresol as a solvent and synthesizes a polymer under extremely dangerous and severe conditions using phosphoric acid or polyphosphoric acid as a catalyst. . Therefore, a method for synthesizing polyquinoline having excellent heat resistance without using m-cresol and phosphoric acid or polyphosphoric acid is required.

Further, the synthesized polyquinoline has a problem of poor workability due to low solubility in general-purpose solvents (DMF, xylene, etc.), and it is also required to improve the solubility and workability of polyquinoline at the same time. Have been.

[0005] In order to satisfy these requirements, it can be used in a method for synthesizing polyquinoline without using m-cresol and phosphoric acid or polyphosphoric acid, and improves the solubility and workability of the synthesized polyquinoline. There is a need for quinoline compounds that can be used.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a quinoline compound which improves the workability and solubility of polyquinoline.

Another object of the present invention is to provide a method for producing a quinoline compound which improves the workability and solubility of polyquinoline.

[0008] Another object of the present invention is to provide a heat-resistant resin which can reduce the hygroscopicity.

[0009]

The present invention provides a compound represented by the general formula (I):

[0010]

Embedded image (Wherein, R represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. R ′ represents a hydrogen atom, 1 to 8 carbon atoms. An alkyl group, an aryl group having 6 to 18 carbon atoms,
It represents 20 alkoxy groups, arylalkyl groups having 7 to 20 carbon atoms, hydroxyl groups, amino groups or nitro groups.
X represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Here, l is an integer of 1 to 5, m is an integer of 0 to 4, and 1 + m = 5. When l and m are 2 or more, X and R 'may be the same or different. )).

Further, the present invention provides a compound represented by the general formula (II):

[0012]

Embedded image (Wherein, R represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. R ′ represents a hydrogen atom, 1 to 8 carbon atoms. An alkyl group, an aryl group having 6 to 18 carbon atoms,
It represents 20 alkoxy groups, arylalkyl groups having 7 to 20 carbon atoms, hydroxyl groups, amino groups or nitro groups.
X represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Here, l is an integer of 1 to 5, m is an integer of 0 to 4, and 1 + m = 5. When l and m are 2 or more, X and R 'may be the same or different. ) And the following formula

[0013]

Embedded image And 4,4'-diamino-3,3'-dibenzoyldiaryl ether represented by the following formula:

[0014] The present invention also relates to a heat-resistant resin obtained by reacting the quinoline compound with a diol monomer.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The quinoline compound of the present invention is represented by the above general formula (I).
Wherein, as R, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms, for example, methyl, ethyl, propyl, butyl, pentyl, Hexyl, heptyl, octyl, phenyl, benzyl and the like are mentioned, and among them, a hydrogen atom, methyl, ethyl and phenyl are more preferable.

In the general formula (I), a hydrogen atom represented by R ', an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkoxy group having 7 to 20 carbon atoms. As the arylalkyl group, hydroxyl group, amino group or nitro group, for example, methyl, ethyl, propyl,
Butyl, pentyl, hexyl, heptyl, octyl, phenyl, benzyl, methoxy, ethoxy, propoxy,
Butoxy, hydroxy, amino, nitro and the like,
Among them, a hydrogen atom, methyl, ethyl, phenyl, methoxy, ethoxy, and hydroxy are more preferred.

In the general formula (I), X represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, of which a fluorine atom and a chlorine atom are more preferred.

In the general formula (I), it is necessary that l = 1 to 5, and preferably 1 or 2.

In the general formula (I), m needs to be 0 to 4, and preferably 3 to 4.

Examples of the quinoline compound represented by the above general formula (I) of the present invention include the following compounds.

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image Among them, exemplified compounds (1), (2), (5),
(6), (9), (10), (15), (16), (2
3), (24), (27), (28), (35), and (36) are preferred, and exemplary compounds (1), (2),
(5), (6), (9) and (10) are more preferred.

The process for producing the quinoline compound of the present invention is represented by the general formula (II):

[0025]

Embedded image (Wherein, R represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. R ′ represents a hydrogen atom, 1 to 8 carbon atoms. An alkyl group, an aryl group having 6 to 18 carbon atoms,
It represents 20 alkoxy groups, arylalkyl groups having 7 to 20 carbon atoms, hydroxyl groups, amino groups or nitro groups.
X represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Here, l is an integer of 1 to 5, m is an integer of 0 to 4, and 1 + m = 5. When l and m are 2 or more, X and R 'may be the same or different. ) And the following formula

[0026]

Embedded image And 4,4'-diamino-3,3'-dibenzoyldiphenyl ether.

The general formula (II) which is a raw material of the above general formula (I) of the present invention

[0028]

Embedded image As the ketomethylene compound represented by, for example,
2'-fluoroacetophenone, 3'-fluoroacetophenone, 4'-fluoroacetophenone, 2'-chloroacetophenone, 3'-chloroacetophenone, 4 '
-Chloroacetophenone, 2'-bromoacetophenone, 3'-bromoacetophenone, 4'-bromoacetophenone, 2'-iodoacetophenone, 3'-iodoacetophenone, 4'-iodoacetophenone, 2'-
Fluoro-2-phenylacetophenone, 3'-fluoro-2-phenylacetophenone, 4'-fluoro-2
-Phenylacetophenone, 2'-chloro-2-phenylacetophenone, 3'-chloro-2-phenylacetophenone, 4'-chloro-2-phenylacetophenone, 2'-bromo-2-phenylacetophenone, 3 '
-Bromo-2-phenylacetophenone, 4'-bromo-2-phenylacetophenone, 2'-iodo-2-phenylacetophenone, 3'-iodo-2-phenylacetophenone, 4'-iodo-2-phenylacetophenone, 2 ' -Fluoropropiophenone, 3'-fluoropropiophenone, 4'-fluoropropiophenone, 2'chloropropiophenone, 3'-chloropropiophenone, 4'-chloropropiophenone, 2'-bromopro Piophenone, 3'-bromopropiophenone, 4'-bromopropiophenone, 2'-iodopropiophenone, 3'-iodopropiophenone, 4 '
-Iodopropiophenone, 2'-fluorobutyrophenone, 3'-fluorobutyrophenone, 4'-fluorobutyrophenone, 2'-chlorobutyrophenone, 3'-
Chlorobutyrophenone, 4'-chlorobutyrophenone,
2'-bromobutyrophenone, 3'-bromobutyrophenone, 4'-bromobutyrophenone, 2'-iodobutyrophenone, 3'-iodobutyrophenone, 4'-iodobutyrophenone, 2'-fluorovalerophenone,
3'-fluorovalerophenone, 4'-fluorovalerophenone, 2'-chlorovalerophenone, 3'-chlorovalerophenone, 4'-chlorovalerophenone, 2'-
Bromovalerophenone, 3'-bromovalerophenone,
4'-Bovavalerophenone, 2'-Iodovalerophenone, 3'-Iodovalerophenone, 4'-Iodovalerophenone, 2'-Fluorohexanophenone, 3'-Fluorohexanophenone, 4'-Fluorohexano Phenone, 2'-chlorohexanophenone, 3'-chlorohexanophenone, 4'-chlorohexanophenone, 2 '
-Bromohexanophenone, 3'-bromohexanophenone, 4'-bromohexanophenone, 2'-iodohexanophenone, 3'-iodohexanophenone, 4 '
-Iodohexanophenone, 2'-fluoroheptanophenone, 3'-fluoroheptanophenone, 4'-fluoroheptanophenone, 2'-chloroheptanophenone, 3'-chloroheptanophenone, 4'-chloro Heptanophenone, 2'-bromoheptanophenone, 3'-
Bromoheptanophenone, 4'-bromoheptanophenone, 2'-iodoheptanophenone, 3'-iodoheptanophenone, 4'-iodoheptanophenone, 2'-
Fluorooctanophenone, 3'-fluorooctanophenone, 4'-fluorooctanophenone, 2'-chlorooctanophenone, 3'-chlorooctanophenone,
4'-chlorooctanophenone, 2'-bromooctanophenone, 3'-bromooctanophenone, 4'-bromooctanophenone, 2'-iodooctanophenone,
3'-iodooctanophenone, 4'-iodooctanophenone, 2 ', 4'-difluoroacetophenone,
2 ', 5'-difluoroacetophenone, 3', 4'-
Difluoroacetophenone, 2 ', 4'-chloroacetophenone, 2', 5'-dichloroacetophenone,
3 ', 4'-dichloroacetophenone, 2', 4'-dibromoacetophenone, 2 ', 5'-dibromoacetophenone, 3', 4'-dibromoacetophenone, 2 ',
4'-diiodoacetophenone, 2 ', 5'-diiodoacetophenone, 3', 4'-diiodoacetophenone, 2 ', 3', 4 ', 5', 6'-pentafluoroacetophenone, 2 ', 3 ', 4', 5 ', 6'-pentachloroacetophenone, 2', 3 ', 4', 5 ', 6'
-Pentabromoacetophenone, 2 ', 3', 4 ',
5 ', 6'-pentaiodoacetophenone, 2', 4 '
-Difluoro-2-phenylacetophenone, 2 ',
5'-difluoro-2-phenylacetophenone,
3 ', 4'-difluoro-2-phenylacetophenone, 2', 4'-dichloro-2-phenylacetophenone, 2 ', 5'-dichloro-2-phenylacetophenone, 3', 4'-dichloro-2-phenyl Acetophenone, 2 ', 4'-dibromo-2-phenylacetophenone, 2', 5'-dibromo-2-phenylacetophenone, 3 ', 4'-dibromo-2-phenylacetophenone, 2', 4'-diiodo-2 -Phenylacetophenone, 2 ', 5'-diiodo-2-phenylacetophenone, 3', 4'-diiodo-2-phenylacetophenone, 2 ', 3', 4 ', 5', 6'-pentafluoro-
2-phenylacetophenone, 2 ', 3', 4 ',
5 ', 6'-pentachloro-2-phenylacetophenone, 2', 3 ', 4', 5 ', 6'-pentabromo-2
-Phenylacetophenone, 2 ', 3', 4 ', 5',
6'-pentaiodo-2-phenylacetophenone,
2 ', 4'-difluoropropiophenone, 2', 5 '
-Difluoropropiophenone, 3 ', 4'-difluoropropiophenone, 2', 4'-dichloropropiophenone, 2 ', 5'-dichloropropiophenone,
3 ', 4'-dichloropropiophenone, 2', 4'-
Dibromopropiophenone, 2 ', 5'-dibromopropiophenone, 3', 4'-dibromopropiophenone, 2 ', 4'-diiodopropiophenone, 2',
5'-diiodopropiophenone, 3 ', 4'-diiodopropiophenone, 2', 3 ', 4', 5 ', 6'-
Pentafluoropropiophenone, 2 ', 3', 4 ',
5 ', 6'-pentachloropropiophenone, 2',
3 ', 4', 5 ', 6'-pentabromopropiophenone, 2', 3 ', 4', 5 ', 6'-pentaiodopropiophenone, 2', 4'-difluorobutyrophenone, 2 ' , 5'-Difluorobutyrophenone, 3 ',
4'-difluorobutyrophenone, 2 ', 4'-dichlorobutyrophenone, 2', 5'dichlorobutyrophenone, 3 ', 4'-dichlorobutyrophenone, 2', 4 '
-Dibromobutyrophenone, 2 ', 5'-dibromobutyrophenone, 3', 4'-dibromobutyrophenone,
2 ', 4'-diiodobutyrophenone, 2', 5'-diiodobutyrophenone, 3 ', 4'-diiodobutyrophenone, 2', 3 ', 4', 5 ', 6'-pentafluorobutyrophenone, ', 3', 4 ', 5', 6'-pentachlorobutyrophenone, 2 ', 3', 4 ', 5',
6'-pentabromobutyrophenone, 2 ', 3',
4 ', 5', 6'-pentaiodobutyrophenone, 3 '
-Fluoro-2'-methylacetophenone, 3'-fluoro-4'-methylacetophenone, 5'-fluoro-
2'-methylacetophenone, 3'-chloro-2'-methylacetophenone, 3'-chloro-4'-methylacetophenone, 5'-chloro-2'-methylacetophenone, 3'-bromo-2'-methylacetophenone, 3 '
-Bromo-4'-methylacetophenone, 5'-bromo-2'-methylacetophenone, 3'-iodo-2'-
Methylacetophenone, 3'-iodo-4'-methylacetophenone, 5'-iodo-2'-methylacetophenone, 2 ', 6'-difluoro-3-methylacetophenone, 2', 6'-dichloro-3-methylacetophenone 2,2 ', 6'-dibromo-3-methylacetophenone, 2', 6'-diiodo-3-methylacetophenone, 3'-fluoro-2'-methyl-2-phenylacetophenone, 3'-fluoro-4'- Methyl-2-phenylacetophenone, 5'-fluoro-2'-methyl-
2-phenylacetophenone, 3'-chloro-2'-methyl-2-phenylacetophenone, 3'-chloro-
4'-methyl-2-phenylacetophenone, 5'-chloro-2'-methyl-2-phenylacetophenone,
3'-bromo-2'-methyl-2-phenylacetophenone, 3'-bromo-4'-methyl-2-phenylacetophenone, 5'-bromo-2'-methyl-2-phenylacetophenone, 3'-iodo- 2'-methyl-2-
Phenylacetophenone, 3'-iodo-4'-methyl-2-phenylacetophenone, 5'-iodo-2'-
Methyl-2-phenylacetophenone, 2 ', 6'-difluoro-3-methyl-2-phenylacetophenone,
2 ', 6'-dichloro-3-methyl-2-phenylacetophenone, 2', 6'-dibromo-3-methyl-2-
Phenylacetophenone, 2 ', 6'-diiodo-3-
Methyl-2-phenylacetophenone, 3'-fluoro-2'-methylpropiophenone, 3'-fluoro-
4'-methylpropiophenone, 5'-fluoro-2 '
-Methylpropiophenone, 3'-chloro-2'-methylpropiophenone, 3'-chloro-4'-methylpropiophenone, 5'-chloro-2'-methylpropiophenone, 3'-bromo- 2'-methylpropiophenone, 3'-bromo-4'-methylpropiophenone,
5'-bromo-2'-methylpropiophenone, 3'-
Iodo-2'-methylpropiophenone, 3'-iodo-4'-methylpropiophenone, 5'-iodo-2 '
-Methylpropiophenone, 2 ', 6'-difluoro-
3-methylpropiophenone, 2 ', 6'-dichloro-
3-methylpropiophenone, 2 ', 6'-dibromo-
3-methylpropiophenone, 2 ', 6'-diiodo-
3-methylpropiophenone, 3'-fluoro-2'-
Methylpropiophenone, 3'-fluoro-4'-methylpropiophenone, 5'-fluoro-2'-methylbutyrophenone, 3'-chloro-2'-methylbutyrophenone, 3'-chloro-4'-methylbutyrophenone ,
5'-chloro-2'-methylbutyrophenone, 3'-bromo-2'-methylbutyrophenone, 3'-bromo-
4'-methylbutyrophenone, 5'-bromo-2'-methylbutyrophenone, 3'-iodo-2'-methylbutyrophenone, 3'-iodo-4'-methylbutyrophenone, 5'-iodo-2'-methylbutyrophenone,
2 ', 6'-difluoro-3-methylbutyrophenone,
2 ', 6'-dichloro-3-methylbutyrophenone,
2 ', 6'-dibromo-3-methylbutyrophenone,
2 ', 6'-diiodo-3-methylbutyrophenone,
2'-fluoro-4 ', 6'-dimethylacetophenone, 2'-chloro-4', 6'-dimethylacetophenone, 2'-bromo-4 ', 6'-dimethylacetophenone, 2'-iodo-4', 6'-dimethylacetophenone, 2'-fluoro-4 ', 6'-dimethyl-2-phenylacetophenone, 2'-chloro-4', 6'-dimethyl-2-phenylacetophenone, 2'-bromo-
4 ', 6'-dimethyl-2-phenylacetophenone,
2'-iodo-4 ', 6'-dimethyl-2-phenylacetophenone, 2'-fluoro-4', 6'-dimethylpropiophenone, 2'-chloro-4 ', 6'-dimethylpropiophenone, 2'-bromo-4 ', 6'-dimethylpropiophenone, 2'-iodo-4', 6'-dimethylpropiophenone, 2'-fluoro-4 ', 6'
-Dimethylbutyrophenone, 2'-chloro-4 ', 6'
-Dimethylbutyrophenone, 2'-bromo-4 ', 6'
-Dimethylbutyrophenone, 2'-iodo-4 ', 6'
-Dimethylbutyrophenone and the like. Among these, 2'-fluoroacetophenone, 3'-fluoroacetophenone, 4'-fluoroacetophenone, 2 '
-Chloroacetophenone, 3'-chloroacetophenone, 4'-chloroacetophenone, 2'-bromoacetophenone, 3'-bromoacetophenone, 4'-bromoacetophenone, 2'-iodoacetophenone, 3'-
Iodoacetophenone, 4'-iodoacetophenone,
2'-fluorophenylacetophenone, 3'-fluorophenylacetophenone, 4'-fluorophenylacetophenone, 2'-chlorophenylacetophenone,
3'-chlorophenylacetophenone, 4'-chlorophenylacetophenone, 2'-bromophenylacetophenone, 3'-bromophenylacetophenone, 4'-
Bromophenylacetophenone, 2'-iodophenylacetophenone, 3'-iodophenylacetophenone, 4'-iodophenylacetophenone are preferred,
2'-fluoroacetophenone, 3'-fluoroacetophenone, 4'-fluoroacetophenone, 2'-chloroacetophenone, 3'-chloroacetophenone, 4 '
-Chloroacetophenone, 2'-fluorophenylacetophenone, 3'-fluorophenylacetophenone,
4'-Fluorophenylacetophenone, 2'-chlorophenylacetophenone, 3'-chlorophenylacetophenone, 4'-chlorophenylacetophenone are more preferred.

The following formula, which is a raw material of the quinoline compound represented by the above general formula (I) of the present invention,

[0030]

Embedded image The 4,4'-diamino-3,3'-dibenzoyldiphenyl ether represented by the formula can be synthesized by any known method for synthesizing o-aminobenzophenone.

The synthesis conditions for synthesizing the quinoline compound of the present invention by reacting 4,4'-diamino-3,3'-dibenzoyldiphenyl ether with the ketomethylene compound represented by the general formula (II) are described below. I do.

The amount of the ketomethylene compound reacted with 1 mol of 4,4'-diamino-3,3'-dibenzoyldiphenyl ether is preferably 2 to 20 times, particularly preferably 2 to 5 times. It is.

This reaction is carried out in a solvent, and the solvent is not particularly limited as long as it is an organic solvent inert to the reaction. For example, aromatic solvents such as benzene, toluene, xylene, cresol, and phenol; Methanol, ethanol, propanol, alcohol solvents such as butanol, quinoline, heterocyclic solvents containing nitrogen atoms such as pyridine, ether solvents such as tetrahydrofuran, 1,4-dioxane, diethyl ether, dipropyl ether,
Methyl acetate, ethyl acetate, propyl acetate, ester solvents such as butyl acetate, dimethyl ketone, diethyl ketone,
Ketone solvents such as methyl ethyl ketone and ethyl butyl ketone, basic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and 2-methylpyrrolidone, and sulfoxide solvents such as dimethyl sulfoxide are used. Particularly, benzene, toluene, xylene, cresol, and phenol are preferred.

The catalyst is usually an alkali compound such as sodium hydroxide, potassium hydroxide, calcium hydrogen carbonate, potassium carbonate or the like, or a salt such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, polyphosphoric acid or p-toluenesulfonic acid which is usually used. It is possible to use acids. Particularly preferred are acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, polyphosphoric acid and p-toluenesulfonic acid.

The amount of the catalyst is 4,4'-diamino-3,3 '
-The catalyst can be used in an amount of 0.001 to 20 times by mole to 1 mole of dibenzoyldiphenyl ether. Particularly preferably, it is 0.01 to 2 moles.

The reaction can be carried out in a wide temperature range from -20 to 250 ° C., particularly preferably 20 to 250 ° C.
２０５205 ° C.

The reaction time is from 30 minutes to 24 hours to obtain the desired product. In carrying out this reaction, liquid chromatography,
The progress of the reaction is checked by gas chromatography, thin-layer chromatography, GPC or the like, and the stage at which the raw material 4,4'-diamino-3,3'-dibenzoyldiphenyl ether is consumed is determined as the end point of the reaction.

The quinoline compound of the present invention described above can be used, for example, as a raw material of a heat-resistant resin (polyquinoline) that can be used for an interlayer insulating film for semiconductors, a passivation film, and the like.

The heat-resistant resin of the present invention can be obtained by reacting the quinoline compound of the present invention with a diol monomer. Details of the reaction conditions are described below.

The diol monomer is not particularly limited, and for example, hydroquinone derivatives and bisphenol derivatives are preferably used. Specific examples of suitable hydroquinone derivatives and bisphenol derivatives are shown below.

[0041]

Embedded image Above all, in order to improve the solubility of the heat-resistant resin and to lower the dielectric constant,

[0042]

Embedded image Is preferred.

The amount of the diol monomer to be reacted with respect to 1 mol of the quinoline compound is preferably 0.95 to 1.1 times mol, particularly preferably 0.97 to 1.03 mol.

This reaction is carried out in a solvent. The solvent that can be used is not particularly limited as long as it is an organic solvent inert to the reaction. For example, alcohol solvents such as methanol, ethanol, propanol and butanol, quinoline, Heterocyclic solvents containing a nitrogen atom such as pyridine, ether solvents such as tetrahydrofuran, 1,4-dioxane, diethyl ether and dipropyl ether; ester solvents such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate;
Ketone solvents such as dimethyl ketone, diethyl ketone, methyl ethyl ketone and ethyl butyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide,
A basic solvent such as 2-methylpyrrolidone, a sulfoxide-based solvent such as dimethyl sulfoxide, and the like are used.

As the catalyst, an alkali compound such as sodium hydroxide, potassium hydroxide, calcium hydrogen carbonate, potassium carbonate or the like can be usually used.

The amount of the catalyst is preferably from 0.001 to 20 times, more preferably from 0.5 to 2 times, the mole of the catalyst based on 1 mole of the quinoline compound.

The reaction can be carried out in a wide temperature range from 100 to 250 ° C., particularly preferably 15 to 250 ° C.
0 ° C to 230 ° C.

The desired heat-resistant resin can be obtained by reacting for 30 minutes to 24 hours. When performing this reaction, the progress of the reaction is checked using GPC, and the reaction is stopped when the desired molecular weight is reached.

[0049]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Synthesis Example 1 Synthesis of 4,4'-dinitrodiphenyl ether In a 300 ml eggplant-shaped flask, 59.262 g (0.42 mol) of p-fluoronitrobenzene, 58.422 g (0.42 mol) of p-nitrophenol and potassium fluoride Add 51.626 g (0.889 mol)
A cooling tube was attached, and the mixture was refluxed at an oil bath temperature of 205 ° C. for 25 minutes with good stirring with a magnetic stirrer. After cooling in an ice bath, the reaction solution was poured into 750 ml of purified water, and the reaction solution was left at room temperature for one day. The precipitated yellow needle crystals were filtered by suction, and the filtered crystals were washed with toluene 7
The mixture was dissolved while heating to 00 ml and recrystallized. Further, it was dried in a dryer at 110 ° C. for 3 hours to obtain yellow crystals 9
6.5 g (yield: 88.3%) was obtained.

Melting point: 141 to 144 ° C. ¹ H-NMR: Shown in FIG.

Synthesis Example 2 Synthesis of 5,5'-oxybis (3-phenyl-2,1-benzoisoxazole) 20 equipped with a cooling tube, a thermometer and a mechanical stirrer
Sodium hydroxide 147.3 in a 00 ml four-necked flask
2 g and 736 g of methanol were added, and the mixture was stirred at 20 to 25 ° C. for 2 hours. Then, phenylacetonitrile 8
6.82 g were added dropwise over 40 minutes. After the dropwise addition, the mixture was allowed to stand at room temperature for 30 minutes to obtain 4,4'-dinitrodiphenyl ether 9
When 5.96 g (powder) was added over 10 minutes, the color of the solution changed from yellow to black. After heating at 70 ° C. for 6 hours, the reaction solution was cooled to room temperature, and 736 g of methanol was added. Transfer the reaction solution to a beaker and place it in a freezer (-15 ° C)
And left overnight. A black solid was obtained by suction filtration. This solid was dissolved in 1600 ml of toluene while heating, dust was removed by suction filtration, and the filtrate was allowed to stand overnight. The precipitated crystals were separated by filtration, recrystallized with 800 ml of toluene, and dried in a dryer at 110 ° C. for 3 hours.
After drying for an hour, 32.87 g (yield: 22.0%) of brown crystals were obtained.

Melting point: 201-205 ° C. ¹ H-NMR: shown in FIG.

Synthesis Example 3 Synthesis of 4,4'-diamino-3,3'-dibenzoyldiphenyl ether 34.5 g of 5,5'-oxybis (3-phenyl-2,1-benzoisoxazole) and 2.40 g of palladium carbon. 8 g, 9.3 ml of triethylamine and 320 ml of tetrahydrofuran are charged into a 500 ml autoclave. After heating and heating to 70 ° C., hydrogen gas was added for 20 hours.
kg / m ² . Upon stirring, hydrogen gas was consumed and the pressure decreased. The reaction is terminated when the consumed hydrogen amount reaches the theoretical amount, and the reaction vessel of the autoclave is cooled.

After cooling, the catalyst was filtered off from the reaction solution, and the solvent was distilled off from the filtrate using a rotary evaporator. When toluene was added to the obtained viscous liquid, crystals precipitated. By suction filtration, a yellow powder crystal was obtained.
05 g (yield = 94.9%) was obtained.

Melting point: 151-154 ° C. ¹ H-NMR: Shown in FIG.

Example 1 Synthesis of a quinoline compound (exemplary compound (1)) 4,4'-diamino-3,4
2.042 g of 3'-dibenzoyldiphenyl ether,
1.416 g of 4'-fluoroacetophenone, 38.0 mg of p-toluenesulfonic acid monohydrate and xylene 5
0 ml was added, and the mixture was reacted at xylene reflux temperature for 6 hours. After completion of the reaction, the xylene solvent was distilled off, and chloroform was added to obtain a homogeneous solution. After washing the chloroform solution with an aqueous sodium hydroxide solution, the organic phase was recovered using a separating funnel, and sodium sulfate was further added to dehydrate. After the sodium sulfate was filtered off, the solvent was distilled off under reduced pressure. The obtained solid was recrystallized using toluene to obtain 1.89 g of crystals (yield = 67.2%).

Melting point: 204-207 ° C. ¹ H-NMR: Shown in FIG.

Example 2 Nine-methylpyrrolidone 99.4 g, toluene 27.5 g, Example 1 in a 300 ml 4-neck flask equipped with a mechanical stirrer, a water content receiver, a condenser tube and a thermometer.
14. the quinoline compound (exemplified compound (1)) obtained in
31 g (2.5 mmol), 1,1,1,3,3,3-
8.40 g (25 mmol) of hexafluoro-2,220-bis (4-hydroxyphenyl) propane and 5.18 g (37.5 mmol) of potassium carbonate are added. Then, after heating at 160 ° C. for 3 hours, the reaction temperature was increased to 210 ° C.
The temperature is raised to 0 ° C. and the reaction is carried out while dehydrating for 6 hours. After completion of the reaction, the reaction solution was poured into an aqueous solution to reprecipitate the polymer, and the polymer was recovered. The number average molecular weight of the obtained polymer was 22,000. (The number average molecular weight is measured using GPC and is in terms of standard polystyrene.) FIG.
The elution curve by GPC of the obtained polymer is shown.

Next, this polymer was dissolved in xylene,
After coating on a glass plate, the film was cured at 100 ° C. for 5 minutes (using a hot plate), at 200 ° C. for 5 minutes (using a hot plate), and at 300 ° C. for 60 minutes (using a dryer). . The properties were evaluated using this film.

Comparative Example 1 A mechanical stirrer, a cooling pipe and a thermometer were mounted.
In a 00 ml four-neck separable flask, 2.00 g of 4,4'-diaminodiphenyl ether and 28 g of N-methylpyrrolidone are added and stirred. After dissolution of the diamine, 2.18 g of pyromellitic dianhydride and NMP4.
By adding 0 g and stirring for 1 hour, a polyamic acid varnish was synthesized.

Next, this polyamic acid varnish was applied on a glass plate, and was dried at 100 ° C. for 60 minutes (using a drier).
The film was cured at 0 ° C. for 60 minutes (using a dryer) and further cured at 400 ° C. for 60 minutes (using a dryer) to produce a film. The properties were evaluated using this film.

Comparative Example 2 4,4'-Diamino-3,3'-dibenzoyldiphenyl ether 2 was placed in a 300 ml four-necked flask equipped with a mechanical stirrer, a water content receiver, a condenser and a thermometer.
0.42 g, 8.11 g of 1,4-diacetylbenzene,
347 g of m-cresol and 99.3 g of polyphosphoric acid were added and reacted at 135 ° C. for 48 hours. The polymer was recovered by filtration, and triethylamine and ethanol (10/90
(Volume ratio). The polymer was recovered by suction filtration again, washed with a mixed solvent of triethylamine and ethanol (volume ratio of 10/90), recovered by filtration, and dried at 105 ° C. for 24 hours.

In the evaluation of the characteristics, measurement was performed with the following analytical instrument.

The thermal decomposition temperature and the water absorption were measured using TGA.

The glass transition temperature was measured using TMA.

The solubility of the polymer in the solvent is as follows:
200 mg of the resin was added to 1.8 g of the solvent (nonvolatile component = 1).
(0% by weight solution) It was visually observed whether the polymer was dissolved.

The properties of the obtained polymer are shown in Table 1.

The results of examining the solubility of the polymer are shown in Table 2.

[0070]

[Table 1] From this result, it can be seen that the heat-resistant resin (polyquinoline) synthesized in Example 1 has a lower water absorption of the polymer than the polyimide synthesized in Comparative Example 1 and is excellent in water resistance.

[0071]

[Table 2] From Table 2, it can be seen that the solubility of the polyquinoline synthesized in Example 2 was remarkably improved as compared with the polymer synthesized in Comparative Example 2.

[0072]

Industrial Applicability According to the present invention, a quinoline compound which improves the workability and solubility of polyquinoline, and a preferable method for producing the same can be obtained.

Further, according to the present invention, a heat-resistant resin excellent in solubility, low in moisture absorption and excellent in moisture resistance was obtained.

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR chart of 4,4′-dinitrodiphenyl ether synthesized in Synthesis Example 1.

FIG. 2 shows 5,5′-oxybis (3
- phenyl-2,1-benzisoxazole) of the ¹ H
-NMR chart.

FIG. 3 shows 4,4′-diamino-3, synthesized in Synthesis Example 3.
¹ H-NMR of 3'-dibenzoyldiphenyl ether
chart.

FIG. 4 shows ¹ H—N of the quinoline compound synthesized in Example 1.
MR chart.

FIG. 5 is a graph showing an elution curve by GPC of a polymer synthesized in Example 2.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Yasuhiro Kuwana 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside the Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd.

Claims (3)

[Claims] 1. A compound of the general formula (I) (Wherein, R represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. R ′ represents a hydrogen atom, 1 to 8 carbon atoms. An alkyl group, an aryl group having 6 to 18 carbon atoms,
It represents 20 alkoxy groups, arylalkyl groups having 7 to 20 carbon atoms, hydroxyl groups, amino groups or nitro groups.
X represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Here, l is an integer of 1 to 5, m is an integer of 0 to 4, and 1 + m = 5. When l and m are 2 or more, X and R 'may be the same or different. A quinoline compound represented by the formula: 2. A compound of the general formula (II) (Wherein, R represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. R ′ represents a hydrogen atom, 1 to 8 carbon atoms. An alkyl group, an aryl group having 6 to 18 carbon atoms,
It represents 20 alkoxy groups, arylalkyl groups having 7 to 20 carbon atoms, hydroxyl groups, amino groups or nitro groups.
X represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Here, l is an integer of 1 to 5, m is an integer of 0 to 4, and 1 + m = 5. When l and m are 2 or more, X and R 'may be the same or different. And a ketomethylene compound represented by the following formula: The method for producing a quinoline compound according to claim 1, wherein the reaction is carried out with 4,4'-diamino-3,3'-dibenzoyldiphenyl ether represented by the following formula: 3. A heat-resistant resin obtained by reacting the quinoline compound according to claim 1 with a diol monomer.