JPH06145352A - Polyimide and it production - Google Patents

Abstract

PURPOSE:To produce a new thermoplastic polyimide having an excellent moldability and a good chemical resistance in addition to the excellent heat resistance inherent in a polyimide. CONSTITUTION:A polyimide is produced which is represented by the formula wherein R is a tetravalent group selected from the group consisting of a 2-27C aliph. group, an alicyclic group, a monocyclic arom. group, a condensed polycyclic arom. group, and a noncondensed polycyclic arom. group formed by linking arom. groups to each other directly or through linking groups; and n is an integer of 1-1,000.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel thermoplastic polyimide. More specifically, it relates to a novel polyimide excellent in moldability and a method for producing the same.

[0002]

Polyimide is obtained by the reaction of tetracarboxylic dianhydride and diamine. Conventionally known polyimide is excellent in mechanical strength and dimensional stability in addition to high heat resistance peculiar to this polymer. It also has flame retardancy, electrical insulation, etc. Therefore, these polyimides
It has been used in the fields of electric and electronic devices, etc., and has already been widely used in the fields where heat resistance is required, and it is expected that the fields of use and the quantitative expansion will be further increased in the future.

Conventionally, various polyimides having excellent characteristics have been developed. However, conventionally known polyimide does not have a clear glass transition temperature even if it has excellent heat resistance, and therefore, when it is used as a molding material, it must be processed by a method such as sintering molding. Japanese Patent No. 31799631 discloses that it has excellent processability but is soluble in a halogenated hydrocarbon solvent and has a problem in terms of solvent resistance, and has advantages and disadvantages in performance. Recently, with the aim of expanding the fields of use of polyimides, there have been provided polyimides with improved polyimide defects and new properties.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel thermoplastic polyimide having excellent workability and excellent chemical resistance in addition to the excellent heat resistance originally possessed by polyimide, and a method for producing the same. Is to provide.

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the inventors have found that a polyimide containing an aromatic diamine having a specific structure as a monomer component does not impair the various properties peculiar to the polyimide. The inventors have found that the polyimide is a novel thermoplastic polyimide having excellent moldability and completed the present invention. That is, the present invention provides formula (1)
(Chemical formula 10)

[0006]

[Chemical 10] (In the formula, R represents an aliphatic group having 2 to 27 carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group which is directly or cross-linked to each other. Showing a tetravalent group selected from the group consisting of non-fused polycyclic aromatic groups, n is an integer of 1 to 1000), a polyimide having a repeating structural unit represented by A polyimide in which an end of a polymer molecule having a repeating structural unit is an aromatic ring which is essentially unsubstituted or substituted with a group having no reactivity with an amine or a dicarboxylic acid anhydride,
And their manufacturing methods. More specifically, the present invention relates to formula (1)

[0007]

[Chemical 11] (In the formula, R represents an aliphatic group having 2 to 27 carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group which is directly or cross-linked to each other. A tetravalent group selected from the group consisting of non-condensed polycyclic aromatic groups, n is an integer of 1 to 1000), and a polyimide having a repeating structural unit represented by the formula: 2) (Chemical formula 12)

[0008]

[Chemical 12] And an aromatic diamine containing at least one selected from bis (aminobenzoyloxy) naphthalene represented by the formula (3)

[0009]

[Chemical 13] (In the formula, R represents an aliphatic group having 2 to 27 carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group which is directly or cross-linked to each other. A tetracarboxylic acid dianhydride represented by the formula (4), which represents a tetravalent group selected from the group consisting of non-fused polycyclic aromatic groups, is reacted, and the resulting polyamic acid is thermally or chemically imidized. And a terminal of the repeating structural unit represented by the above formula (1) is an aromatic ring which is essentially unsubstituted or substituted with a group having no reactivity with amine or dicarboxylic acid anhydride. It is polyimide. Further, these polyimides are aromatic diamines mainly containing at least one selected from bis (aminobenzoyloxy) naphthalene represented by the above formula (2), and tetracarboxylic acid represented mainly by the above formula (3). The acid dianhydride is represented by the formula (4)

[0010]

[Chemical 14] (In the formula, Z is a monocyclic aromatic group having 6 to 15 carbon atoms, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are directly or cross-linked to each other. An aromatic dicarboxylic acid anhydride represented by a divalent group selected from the group consisting of: or a formula (5) Z—NH ₂ (5) (wherein Z is a monocyclic ring having 6 to 15 carbon atoms). Formula Aromatic Group, Condensed Polycyclic Aromatic Group, Monovalent Group Selected from the Group consisting of Non-condensed Polycyclic Aromatic Groups in which Aromatic Groups are Directly Connected to Each Other or by Cross-Linking Members) A method for producing a polyimide, which comprises reacting in the presence of an aromatic monoamine represented to thermally and chemically imidize the resulting polyamic acid. The polyimide of the present invention has the formula (1)
5)

[0011]

[Chemical 15] (Wherein R is as described above) having a repeating structural unit, and the polyimide is a polyimide in which the terminal of the polyimide is an aromatic ring group containing no reactive group.

The polyimide of this repeating structural unit uses the bis (aminobenzoyloxy) naphthalene represented by the above formula (2) as the aromatic diamine component.
These are shown in Japanese Patent Application No. 04-003875, and specifically, 2,7-bis (4-aminobenzoyloxy) naphthalene, 2,7-bis (3-aminobenzoyloxy) naphthalene, 2 , 6-bis (4-
Aminobenzoyloxy) naphthalene, 2,6-bis (3-aminobenzoyloxy) naphthalene, 1,5-
Bis (4-aminobenzoyloxy) naphthalene, 1,
5-bis (3-aminobenzoyloxy) naphthalene,
1,6-bis (4-aminobenzoyloxy) naphthalene, 1,6-bis (3-aminobenzoyloxy) naphthalene, 2,5-bis (4-aminobenzoyloxy)
Naphthalene, 2,5-bis (3-aminobenzoyloxy) naphthalene, 1,4-bis (4-aminobenzoyloxy) naphthalene, 1,4-bis (3-aminobenzoyloxy) naphthalene, 1,7-bis ( 4-Aminobenzoyloxy) naphthalene and 1,7-bis (3-aminobenzoyloxy) naphthalene can be used. Further, as an aromatic tetracarboxylic dianhydride, the compound represented by the formula (3)
6)

[0013]

[Chemical 16] The tetracarboxylic dianhydride represented by In formula (3), R is an aliphatic group having 2 to 27 or more carbon atoms,
Cyclic aliphatic group, monocyclic aromatic group, condensed polycyclic aromatic group,
A tetravalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are connected to each other directly or by a cross-linking member is shown. Specifically, R in the formula (1) is a carbon atom. Aliphatic group having 2 to 10 carbon atoms, cycloaliphatic group having 4 to 10 carbon atoms, and formula (a)
(Chemical 17)

[0014]

[Chemical 17] A monocyclic aromatic group represented by the formula (b)

[0015]

[Chemical 18] And a condensed polycyclic aromatic group represented by the formula (c)
9)

[0016]

[Chemical 19] {In the formula, X is a direct bond, -CO-, -O-, -S-,-
_{SO 2 -, - CH 2 -} , - C (CH 3) 2 -, - C (C
F ₃ ) ₂ −,

[0017]

[Chemical 20] (Where Y is a direct bond, -CO-, -O-, -S-,
_{-SO 2 -, - CH 2 -} , - C (CH 3) 2 - or -
C (CF ₃ ) _2- )), and a tetravalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups represented by The tetracarboxylic dianhydride is used.

That is, the polyimide of the present invention is obtained by further dehydrating and cyclizing a polyamic acid obtained by polymerizing the diamine and at least one kind of the aromatic tetracarboxylic dianhydride. Therefore, the polyimide of the present invention uses at least one diamine selected from the above-mentioned bis (aminobenzoyloxy) naphthalene as an essential monomer raw material, but other aromatic diamine within the range not impairing good physical properties of the polyimide. It can also be used as a mixture.

Examples of diamines which can be mixed and used include m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 4,4'-diaminodiphenyl ether, 3, 3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,
3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide,
4,4'-diaminodiphenyl sulfoxide, 3,3 '
-Diaminodiphenyl sulfone, 3,4'-diaminophenyl sulfone, 4,4'-diaminophenyl sulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3 '-Diaminodiphenylmethane, 3,4'
-Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy)
Phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4
-Aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane,
1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) Phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane,
2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane , 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3 -Bis (4-aminophenoxy)
Benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4 -Aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl]
Ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy)
Phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4-
(3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone,
Bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis [4- (3-aminophenoxy)
Benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3- (3-Aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4
-Amino-α, α-dimethylbenzyl) phenoxy] diphenyl sulfone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [{4- (4-aminophenoxy) phenoxy }-
α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene and the like can be mentioned, and these can be used alone or in admixture of two or more. used.

Examples of the tetracarboxylic acid dianhydride represented by the above formula (3) used in the present invention include ethylene tetracarboxylic acid dianhydride, cyclopentane tetracarboxylic acid dianhydride and pyromellitic acid dianhydride. Anhydrous 3,
3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride , 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (2,3-
Dicarboxyphenyl) propane dianhydride, bis (3,3
4-dicarboxyphenyl) sulfone dianhydride, 1,1
-Bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2- Bis (3,4-dicarboxylphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4 5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9, Examples thereof include 10-perylene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, and 1,2,7,8-phenanthrene tetracarboxylic dianhydride. These may be used alone or in combination of two or more.

The polyimide of the present invention obtained by using these aromatic diamine component and aromatic tetracarboxylic dianhydride as monomer components is mainly a polyimide having a repeating structural unit of the formula (1), and mainly of the formula (1) )
Polyimide having a repeating structural unit of, the polymer molecule terminal is also unsubstituted or a polyimide having an aromatic ring substituted with a group having no reactivity with amine or dicarboxylic acid anhydride or a composition containing these polyimides included.

The polyimide having an aromatic ring which is unsubstituted or substituted with a group having no reactivity with amines or dicarboxylic acid anhydrides at the terminal is selected from the bis (aminobenzoyloxy) naphthalenes of the above formula (2). An aromatic diamine mainly composed of at least one diamine
The tetracarboxylic acid dianhydride compound mainly represented by the formula (3) is replaced by the compound represented by the formula (4)

[0023]

[Chemical 21] (In the formula, Z is a monocyclic aromatic group having 6 to 15 carbon atoms, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are directly or cross-linked to each other. An aromatic dicarboxylic acid anhydride represented by a divalent group selected from the group consisting of: or a formula (5) Z-NH ₂ (5) (wherein Z is a monocyclic group having 6 to 15 carbon atoms) A monovalent group selected from the group consisting of aromatic groups, condensed polycyclic aromatic groups, and non-condensed polycyclic aromatic groups in which aromatic groups are connected directly or by crosslinkers) It is obtained by reacting in the presence of the aromatic monoamine described above, and thermally or chemically imidizing the resulting polyamic acid. Examples of the dicarboxylic acid anhydride used in these methods include 2,3-benzophenone dicarboxylic acid anhydride, 3,4-benzophenone dicarboxylic acid anhydride, 2,3-dicarboxyphenylphenyl ether anhydride and 3,4-dicarboxylic acid anhydride. Carboxyphenyl phenyl ether anhydride, 2,3-biphenyldicarboxylic acid anhydride, 3,4-biphenyldicarboxylic acid anhydride, 2,3-dicarboxylic acid phenylphenylsulfone anhydride, 3,4-dicarboxyphenylphenylsulfone anhydride 2,3-dicarboxyphenyl phenyl sulfide anhydride, 3,4-dicarboxyphenyl phenyl sulfide anhydride, 1,2-naphthalene dicarboxylic acid anhydride, 2,3-naphthalene dicarboxylic acid anhydride, 1,8-
Examples thereof include naphthalene dicarboxylic acid anhydride, 1,2-anthracene dicarboxylic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, and 1,9-anthracene dicarboxylic acid anhydride. These dicarboxylic acid anhydrides may be substituted with groups that do not react with amines or dicarboxylic acid anhydrides.

Of these dicarboxylic acid anhydrides, phthalic anhydride is most preferable from the viewpoint of performance and practical use of the obtained polyimide. That is, it is a polyimide having excellent molding stability during high-temperature molding, has excellent chemical resistance, and when considering the excellent processability described above,
A polyimide that is extremely useful as a base material for aircraft and a base material for electric and electronic parts. Further, when phthalic anhydride is used, it may be used by substituting a part thereof with another dicarboxylic acid anhydride as long as the good physical properties of the polyimide are not impaired. The amount of the dicarboxylic acid anhydride used is 0.001 to 1.0 mol per mol of the aromatic diamine represented by the above formula (2). 0.001
If it is less than the molar amount, the viscosity is increased during high temperature molding, which causes deterioration of moldability. Further, if it exceeds 1.0 mol, the mechanical properties are deteriorated. The preferred amount used is 0.01 to 0.5
It is a molar ratio.

When an aromatic monoamine is used,
Examples of aromatic monoamines include aniline, o-toluidine, m-toluidine p-toluidine, 2,3-xylidine, 2,6-xylidine, 3,4-xylidine,
3,5-xylidine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline,
m-bromoaniline, p-bromoaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline,
o-aminophenol, m-aminophenol, p-aminophenol, o-anisidine, m-anisidine, p
-Anisidine, o-phenetidine, m-phenetidine,
p-phenetidine, o-aminobenzaldehyde m-aminobenzaldehyde, p-aminobenzaldehyde,
o-aminobenzonitrile, m-aminobenzonitrile, p-aminobenzonitrile, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2
-Aminophenyl phenyl ether, 3-aminophenyl phenyl ether, 4-aminophenyl phenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminophenylphenyl sulfide, 3-aminophenylphenyl sulfide, 4 -Aminophenyl phenyl sulfide, 2
-Aminophenylphenyl sulfone, 3-aminophenylphenyl sulfone, 4-aminophenylphenyl sulfone, α-naphthylamine, β-naphthylamine, 1-
Amino-2-naphthol, 2-amino-1-naphthol, 4-amino-1-naphthol, 5-amino-1-naphthol, 5-amino-2-naphthol, 7-amino-
2-naphthol, 8-amino-1-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-
Examples thereof include aminoanthracene and 9-aminoanthracene. These aromatic monoamines may be substituted with groups that are not reactive with amines or dicarboxylic acid anhydrides.

The amount of the aromatic monoamine used is 0.001 to 0.1 mol per mol of the tetracarboxylic dianhydride represented by the formula (3). 0.001
If it is less than the molar amount, the viscosity is increased during high temperature molding, which causes deterioration of molding processability. On the other hand, if it exceeds 1.0 mol, the mechanical properties will deteriorate. The preferred amount used is 0.01-0.
It is a ratio of 5 mol. Therefore, in the case of producing a polyimide in which the terminal of the polyimide of the present invention is an unsubstituted or substituted aromatic ring in this way, the molar ratio of tetracarboxylic dianhydride, aromatic diamine, and dicarboxylic anhydride or aromatic monoamine. The aromatic diamine is 0.9 to 1.0 mol, and the dicarboxylic acid anhydride or aromatic monoamine is 0.001 to 1 mol per 1 mol of the tetracarboxylic dianhydride.
It is 1.0 mol.

In the production of polyimide, it is usual to adjust the ratio of tetracarboxylic dianhydride and aromatic diamine in order to adjust the molecular weight of the produced polyimide. In the method of the present invention, the molar ratio of aromatic diamine to tetracarboxylic dianhydride, which is suitable for obtaining a polyimide having good melt flowability, is 0.9 to 1.0.
Is the range.

The method for producing the polyimide of the present invention includes:
Any method including a known method that can produce a polyimide can be applied, but among them, the reaction is preferably performed in an organic solvent. Examples of the organic solvent used in such a reaction include N, N-dimethylformamide,
N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N
-Methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-
Dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis {2- (2-methoxyethoxy) ethyl} ether,
Tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyrroline, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethylurea, hexamethylphosphoramide, phenol, o-cresol, m-
Cresol, p-cresol, m-cresylic acid, p-
Examples include chlorophenol and anisole. Also,
These organic solvents may be used alone or in combination of two or more.

The method of adding bis (aminobenzoyloxy) naphthalene, tetracarboxylic dianhydride, aromatic dicarboxylic acid anhydride or aromatic monoamine to an organic solvent by the method of the present invention includes (i) tetracarboxylic acid A method of reacting an acid dianhydride with bis (aminobenzoyloxy) naphthalene and then continuing the reaction by adding an aromatic dicarboxylic acid anhydride or an aromatic monoamine,
(B) A method in which an aromatic dicarboxylic acid anhydride is added to bis (aminobenzoyloxy) naphthalene to cause a reaction, and then a tetracarboxylic acid dianhydride is added, and the reaction is continued, (c) a tetracarboxylic acid dianhydride A method of adding an aromatic monoamine to a product to cause a reaction, then adding bis (aminobenzoyloxy) naphthalene, and continuing the reaction,
(D) Tetracarboxylic acid dianhydride, bis (aminobenzoyloxy) naphthalene, aromatic dicarboxylic acid anhydride or aromatic monoamine are added at the same time and reacted, and any addition method may be used. Absent. The reaction temperature is usually 250 ° C. or lower, preferably 5
It is 0 ° C or lower. The reaction pressure is not particularly limited, and it can be carried out at normal pressure. The reaction time varies depending on the type of tetracarboxylic dianhydride, the type of solvent and the reaction temperature, and is usually 4
~ 24 hours is sufficient. Further, the obtained polyamic acid is heated to 100 to 400 ° C. for imidization, or is chemically imidized with an imidizing agent such as acetic anhydride to obtain a polyimide having a repeating unit corresponding to the polyamic acid. To be

Further, bis (aminobenzoyloxy) naphthalene and tetracarboxylic dianhydride, and further, when the terminal of the polyimide is an aromatic ring, aromatic dicarboxylic acid anhydride or aromatic monoamine is added to an organic solvent. It is also possible to obtain the desired polyimide by suspending or dissolving it and then heating it to carry out imidization at the same time as the generation of the polyamic acid which is the precursor of the polyimide. That is, a film-form or powder-form polyimide can be obtained by using a conventionally known method.

When the polyimide of the present invention is subjected to melt molding, other thermoplastic resins such as polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, polysulfone, and polyethersulfone are used as long as the object of the present invention is not impaired. , Polyetherketone,
It is also possible to blend polyphenyl sulfide, polyamide imide, polyether imide, modified polyphenylene oxide and the like in appropriate amounts according to the purpose.

Further, the following fillers and the like used in ordinary resin compositions may be used to such an extent that the object of the invention is not impaired. That is, graphite, carborundum, silica powder, molybdenum disulfide, wear resistance improving materials such as fluororesin, glass fibers, reinforcing materials such as carbon fibers,
Flame retardant improvers such as antimony trioxide, magnesium carbonate, calcium carbonate, electrical property improvers such as clay and mica, tracking resistance improvers such as asbestos, silica and graphite, barium sulfate, silica, calcium metasilicate etc. Acid resistance improver, thermoelectric conductivity improver such as iron powder, zinc powder, aluminum powder, copper powder, other glass beads, glass spheres, talc, diatomaceous earth, alumina, silasbaln,
Hydrated alumina, metal oxides, colorants and the like.

The present invention will be described in detail below with reference to examples. The physical properties of the polyimide in the examples were measured by the following methods. Tg, Tc, Tm; (Shimadzu DT-40 series, DSC
-41M). 5% weight loss temperature: DTG in the air (Shimadzu DT-40
Series, DTG-40M). Melt viscosity: Shimadzu Koka type flow tester (CFT500
Measured with a load of 100 kg according to A).

Synthesis Example 1 40.0 g of 2,7-dihydroxynaphthalene was placed in a glass reaction vessel equipped with a stirrer, a thermometer and a reflux condenser.
(0.25 mol), 41.5 g (0.53 mol) of pyridine and 500 g of N, N-dimethylformamide were charged, and the internal temperature was kept at 25 ° C and stirred. Then 97.5 g
(0.53 mol) of 4-nitrobenzoyl chloride was added to 3
Gradually added in 0 minutes. During this time, the internal temperature was 25 to 40 ° C. Further, stirring was continued at the same temperature for 3 hours. After the reaction was completed, 50 g of water was added, the internal temperature was cooled to 25 ° C., and the precipitated crystals were filtered. This is washed and dried to a coarse 2,7
-Bis (4-nitrobenzoyloxy) naphthalene 9
7.6 g was obtained. This was recrystallized from 240 g of N, N-dimethylformamide to give 93.2 g of pure 2,7-bis (4-nitrobenzoyloxy) naphthalene (yield 81.
3%) was obtained. The purity measured by high performance liquid chromatography was 99.3% (Area%). Melting point 235.5-236.2 [deg.] C.

Next, in a glass closed container equipped with a stirrer, a thermometer and a reflux condenser, the above 2,7-bis (4-
Nitrobenzoyloxy) naphthalene 64.2 g (0.
14 mol), 1.3% of 5% palladium / alumina catalyst (NE Chemcat) and 650 g of N, N-dimethylformamide are charged, and hydrogen is introduced while stirring at a temperature of 15 to 25 ° C. 1 in 9 hours
Absorbed 8.5 L of hydrogen. After the reaction was completed, the reaction solution was filtered at the same temperature to remove the catalyst. Next, set the solution temperature to 8
When the temperature was raised to 0 ° C., 280 g of water was added, and the mixture was gradually cooled to 25 ° C., crystals were precipitated. This was filtered, washed and then dried to obtain 47.1 g of crude 2,7-bis (4-aminobenzoyloxy) naphthalene. It was recrystallized from 700 g of 2-methoxyethanol to give pure 2,7-bis (4-aminobenzoyloxy) naphthalene 42.1 g (yield 75.5%).
Got Purity by high performance liquid chromatography is 9
It was 9.0%. Melting point 266.8-267.2 [deg.] C.

Synthesis Example 2 2,7-Dihydroxynaphthalene and 3-nitrobenzoyl chloride were used in the same manner as in Synthesis Example 1 to obtain 2,7.
-Bis (3-nitrobenzoyloxy) naphthalene was obtained. Yield 81.2% Purity 99.6% Melting point 164.7 to 165.4 ° C Next, the obtained 2,7-bis (3-nitrobenzoyloxy) naphthalene was reduced in the same manner as in Synthesis Example 1. Then, 2,7-bis (3-aminobenzoyloxy) naphthalene was obtained.

Yield 83.3% Purity 99.2% Melting point 160.1-161.4 ° C Example 1 2,7-bis (in a container equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet pipe. 4-aminobenzoyloxy)
Naphthalene 12.0g (0.03mol), 3,3 ',
4,4'-Diphenyl ether tetracarboxylic dianhydride 8.75 g (0.028 mol), phthalic anhydride 0.5
3 g (3.6 × 10 ⁻³ mol), γ-picoline 0.42
g, m-cresol 67.8 g were charged, and the mixture was heated to 140 ° C. while stirring under a nitrogen atmosphere. The reaction was continued for another 4 hours. Then cool to room temperature, about 30
After discharging into 0 ml of methyl ethyl ketone, it was filtered off.
After washing this polyimide powder with methyl ethyl ketone,
After drying under reduced pressure at 180 ° C. for 24 hours, 20.1 g (yield 9
(6.2%) of polyimide powder was obtained.

Logarithmic viscosity of the polyimide powder thus obtained
Was 0.43 dl / g. The logarithmic viscosity is
0.50 g of p-chlorophenol / phenol
(Weight ratio 9/1) Heat-dissolved in 100 ml of mixed solvent
After that, the value is measured at 35 ° C. This polyimide
Had a glass transition temperature (Tg) of 222 ° C. Again sky
The 5% weight loss temperature in air was 451 ° C. This port
The infrared spectrum of the Liimide powder is shown in FIG. This
In the spectrum diagram, the characteristic absorption band of imide is 1780 cm.
^-1And 1720 cm^-1Absorption in the vicinity was noticeable.
The elemental analysis values of the obtained polyimide powder are as follows.
Met. Elemental analysis value C H N Calculated value (%) 71.43 3.00 4.17 Measured value (%) 72.50 3.98 3.65 Further, the melt viscosity of this polyimide is high flow tester.
With a load of 100 kg and a diameter of 0.1 cm
It measured using the orifice. Melt viscosity at 410 ° C
The degree was 8825 poise.

Example 2 In a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube,
2.7-Bis (4-aminobenzoyloxy) naphthalene (5.98 g, 0.015 mol) and N, N-dimethylacetamide (52.40 g) were charged, and pyromellitic dianhydride was added under a nitrogen atmosphere. 272 g (0.15 mol) was added in portions while paying attention to the rise in solution temperature, and the mixture was stirred at room temperature for about 20 hours. The polyamic acid thus obtained had an inherent viscosity of 1.6 dl / g. The logarithmic viscosity of the polyamic acid is a value measured with N, N-dimethylacetamide as a solvent at a solution of 0.5 g / 100 ml at 35 ° C. A part of this polyamic acid solution was cast on a glass plate and then heated at 100 ° C., 200 ° C., and 300 ° C. for 1 hour, respectively, to obtain a polyimide film having a thickness of about 50 μm. The tensile strength of this polyimide film is 1
3.0 Kg / mm ² , tensile elastic modulus is 242 Kg / m
m ² and the tensile elongation were 32%.

Examples 3 to 7 Polyamic acids were polymerized in the same manner as in Example 2 except that the tetracarboxylic dianhydrides shown in Table 1 were used in the amounts shown in Table 1. Also, using these polyamic acid solutions, in the same manner as in Example 2, corresponding polyimide films were obtained. Table 1 shows the logarithmic viscosity of the polyamic acid and the physical properties of the obtained polyimide film.

Examples 6 to 13 By the same method as in Example 2, the diamine compounds shown in Tables 2 and 3 were each polymerized with a polycarboxylic acid using tetracarboxylic acid to obtain a corresponding polyimide film. The logarithmic viscosity of these polyamic acids and the physical properties of the obtained polyimide film are summarized in Tables 2 and 3.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

Industrial Applicability The present invention provides a novel thermoplastic polyimide having excellent workability and chemical resistance in addition to the excellent heat resistance originally possessed by polyimide, and a method for producing the same. This is a very useful invention.

[Brief description of drawings]

FIG. 1 is an IR spectrum of the polyimide compound of Example 1 measured by a KBr tablet method.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshiyuki Kataoka 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Chemical Within the corporation

Claims (11)

[Claims] 1. Formula (1) (Formula 1) (In the formula, R represents an aliphatic group having 2 to 27 carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group which is directly or cross-linked to each other. And a tetravalent group selected from the group consisting of non-fused polycyclic aromatic groups, wherein n represents an integer of 1 to 1000). 2. Formula (1) (Formula 2) [Formula 2] (In the formula, R represents an aliphatic group having 2 to 27 carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group which is directly or cross-linked to each other. A tetravalent group selected from the group consisting of non-fused polycyclic aromatic groups, n is an integer of 1 to 1000), and the polymer molecule has a terminal end A polyimide that is an aromatic ring that is essentially unsubstituted or substituted with a group that is not reactive with amines or dicarboxylic acid anhydrides. 3. Formula (2) (Formula 3) [Formula 3] An aromatic diamine mainly containing at least one selected from bis (aminobenzoyloxy) naphthalene represented by the formula: and mainly represented by the formula (3) (formula 4) (In the formula, R represents an aliphatic group having 2 to 27 carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group which is directly or cross-linked to each other. A tetracarboxylic acid dianhydride represented by the formula (4) which represents a tetravalent group selected from the group consisting of non-condensed polycyclic aromatic groups), and thermally or chemically imidize the resulting polyamic acid. The method for producing a polyimide according to claim 1, wherein 4. Formula (2) (Formula 5) [Formula 5] And an aromatic diamine mainly containing at least one selected from bis (aminobenzoyloxy) naphthalene represented by the following formula (3) (In the formula, R represents an aliphatic group having 2 to 27 carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group which is directly or cross-linked to each other. A tetracarboxylic acid dianhydride represented by the formula (4) is a tetravalent group selected from the group consisting of non-fused polycyclic aromatic groups. (In the formula, Z is a monocyclic aromatic group having 6 to 15 carbon atoms, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are directly or cross-linked to each other. A divalent group selected from the group consisting of) is reacted in the presence of an aromatic dicarboxylic acid anhydride represented by the formula, and the resulting polyamic acid is thermally or chemically imidized. Item 2
A method for producing the described polyimide. 5. Formula (2) (Formula 8) Bis (aminobenzoyloxy) naphthalene represented by the formula (3) and the formula (3) (In the formula, R represents an aliphatic group having 2 to 27 carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group which is directly or cross-linked to each other. and unfused expression _{(5) Z-NH 2 (} 5) ( wherein the tetracarboxylic dianhydride represented by polycyclic selected from the group consisting of aromatic groups represents a tetravalent group), Z Is selected from the group consisting of monocyclic aromatic groups having 6 to 15 carbon atoms, condensed polycyclic aromatic groups, and non-condensed polycyclic aromatic groups in which aromatic groups are connected to each other directly or by cross-linking members. A monovalent group), which is reacted in the presence of an aromatic monoamine to thermally or chemically imidize the resulting polyamic acid. . 6. The method for producing a polyimide according to claim 4, wherein the aromatic dicarboxylic acid anhydride is phthalic anhydride. 7. The method for producing a polyimide according to claim 5, wherein the aromatic monoamine is aniline. 8. The amount of the aromatic dicarboxylic acid anhydride used is
0. 1 to 1 mol of the aromatic diamine represented by the formula (2).
The method for producing a polyimide according to claim 4, wherein the ratio is 001 to 1.0 mol. 9. The amount of phthalic anhydride used is 0.001 to 0. 0 per 1 mol of the aromatic diamine represented by the formula (2).
The method for producing a polyimide according to claim 6, wherein the ratio is 1 mol. 10. The use amount of the aromatic monoamine is 0.001 to 1.0 mol with respect to 1 mol of the tetracarboxylic dianhydride represented by the formula (3). Method for producing polyimide. 11. The amount of aniline used is 0.0 with respect to 1 mol of the tetracarboxylic dianhydride represented by the formula (3).
The method for producing a polyimide according to claim 7, wherein the ratio is 01 to 0.1 mol.