JPH0977870A - Polyimide copolymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a polyimide copolymer, having excellent heat resistance and mechanical characteristics and melt fluidity and useful for electrical and electronic appliances, etc., by reacting 1,3-bis[4-(4-aminophenoxy)-α,α- dimethylbenzyl]benzene and 4,4'-diaminodiphenyl ether as aromatic diamine components with pyromellitic dianhydride in the presence (absence) of a specific aromatic dicarboxylic acid anhydride and/or a specified aromatic monoamine. SOLUTION: This polyimide copolymer comprises 0.50-0.95mol% recurring structural unit of formula I and further 0.50-0.05mol% recurring structural unit of formula II. The copolymer is obtained by reacting 1,3-bis[4-(4- aminophenoxy)-α,α-dimethylbenzyl]benzene of formula IV and 4,4'- diaminodiphenyl ether of formula V as aromatic diamine components with pyromellitic dianhydride of formula V1 in the presence (absence) of an aromatic dicarboxylic acid anhydride of formula III (Z is a bivalent group which is a 6-15C monocyclic aromatic group, a condensed polycyclic aromatic group or a noncondensed polycyclic aromatic group in which an aromatic group is directly linked or mutually linked with a cross-linking member) and/or an aromatic monoamine of the formula, V-NH2 (V is a monovalent group same as Z) and further thermally or chemically imidating the resultant polyamic acid.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a device having excellent mechanical properties,
The present invention also relates to a polyimide copolymer having thermoplasticity and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, poiliimide obtained by the reaction of tetracarboxylic dianhydride and diamine has not only high heat resistance but also mechanical strength, chemical resistance, flame retardancy, and electrical insulation. It is used in fields such as electrical and electronic equipment, aerospace equipment, and transportation equipment, and is expected to be widely used in the fields where heat resistance is required in the future.

Conventionally, various polyimides having excellent properties have been developed. However, even if it has excellent heat resistance,
Since it does not have a clear glass transition temperature, it must be processed using a method such as sintering when used as a molding material, or it has excellent workability, but the glass transition temperature is low, and Soluble in halogenated hydrocarbons,
In terms of heat resistance and solvent resistance, it was not satisfactory, and there were merits and demerits in performance. For example, formula (2) [Formula 10]

[0004]

Embedded image Polyimide having a repeating structural unit represented by, in order to have its excellent heat resistance and mechanical and electrical properties,
It is widely used in the form of films and molding materials. However, since it does not have a clear glass transition temperature, when it is used as a molding material, a molded body can be obtained only by a method such as sinter molding or cutting. On the other hand, the present inventors have found that the formula (1)

[0005]

Embedded image A thermotropic liquid crystalline polyimide having a repeating structural unit represented by the following formula and having excellent melt fluidity was found (Japanese Patent Laid-Open No. 03-160024). Although this polyimide is a resin having excellent heat resistance and melt flowability, it was not yet satisfactory in mechanical properties and the like.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an injection moldable polyimide copolymer having melt flowability in addition to heat resistance and mechanical properties, and a method for producing the same.

[0007]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the inventors of the present invention found that formula (1)
2]

[0008]

[Chemical 12] And a repeating structural unit represented by the formula (2)

[0009]

Embedded image A polyimide copolymer containing a repeating structural unit represented in one molecule has excellent heat resistance and mechanical properties, and is a melt-flowable injection-moldable thermoplastic polyimide. Heading, completed the present invention. That is, the present invention provides a polymer having the formula (1)

[0010]

Embedded image Containing 0.50 to 0.95 mol% of a repeating structural unit represented by the formula (2)

[0011]

[Chemical 15] A polyimide copolymer containing 0.50 to 0.05 mol% of the repeating structural unit represented by the formula, a polyimide copolymer containing the copolymer having terminal ends sealed, a method for producing the same, and the present polyimide A polyimide resin composition containing a copolymer. More specifically, the present invention contains the repeating structural unit represented by the above formula (1) in an amount of 0.50 to 0.95 mol% in a polymer molecule, and the repeating structural unit represented by the above formula (2) is 0. A polyimide copolymer containing 50 to 0.05 mol% and / or a polyimide copolymer containing one whose ends are blocked, and 0.50
0.95 mol% of formula (5)

[0012]

Embedded image And 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, and 0.50 to 0.05 mol% of the formula (6) [ 17]

[0013]

Embedded image An aromatic diamine compound represented by, that is, 4,4′-
Diaminodiphenyl ether and a compound of formula (7)

[0014]

Embedded image When reacting with pyromellitic dianhydride represented by the general formula (3)

[0015]

Embedded image (In the formula, Z has 6 to 15 carbon atoms and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a crosslinking member. Is 2
Represents a valence group. ) And / or the general formula (4) [Chemical Formula 20]

[0016]

Embedded image V-NH ₂ (4) (wherein V has 6 to 15 carbon atoms, and a monocyclic aromatic group, a condensed polycyclic aromatic group or an aromatic group is directly or by a bridging member. A linked non-fused polycyclic aromatic group 1
Represents a valence group. ) Is reacted in the presence or absence of an aromatic monoamine, and the resulting polyamic acid is thermally or chemically imidized to produce a polyimide copolymer. Further, with respect to 100 parts by weight of the polyimide copolymer of the present invention, a polyimide resin containing 5 to 100 parts by weight of one or more reinforcing materials selected from carbon fiber, glass fiber, aromatic polyamide fiber and potassium titanate fiber. It is a composition.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The aromatic diamine compound and tetracarboxylic dianhydride used in the method for producing a polyimide copolymer of the present invention are represented by the formula (5):
Represented by 3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene and formula (6),
A diamine compound represented by 4,4′-diaminodiphenyl ether and a pyromellitic dianhydride represented by the formula (7), but other diamine compounds and tetracarboxylic acid dianhydrides within a range that does not impair the performance. It can also be used.

As the diamine compound which can be mixed and used, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, o-aminobenzylamine, 3-chloro-
1,2-phenylenediamine, 4-chloro-1,2-phenylenediamine, 2,3-diaminotoluene, 2,4
-Diaminotoluene, 2,5-diaminotoluene, 2,
6-diaminotoluene, 3,4-diaminotoluene,
3,5-diaminotoluene, 2-methoxy-1,4-phenylenediamine, 4-methoxy-1,2-phenylenediamine, 4-methoxy-1,3-phenylenediamine, benzidine, 3,3'-dichlorobenzidine, Three
3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 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'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,
3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone,
3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,1-bis [4- (4-aminophenoxy)
Phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4
-Aminophenoxy) phenyl] propane, 1,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis [4- (4-aminophenoxy) phenyl] propane, 1,1-bis [ 4- (4-aminophenoxy) phenyl] butane, 1,3-bis [4- (4-
Aminophenoxy) phenyl] butane, 1,4-bis [4- (4-aminophenoxy) phenyl] butane,
2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,3-bis [4- (4-aminophenoxy) phenyl] butane,

2- [4- (4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (4-aminophenoxy)] -3-Methylphenyl] propane, 2
-[4- (4-aminophenoxy) phenyl] -2-
[4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane,
1,4-bis (3-aminophenoxy) benzene, 1,
4-bis (4-aminophenoxy) benzene, 4,4 '
-Bis (2-aminophenoxy) biphenyl, 4,4 '
-Bis (3-aminophenoxy) biphenyl, 4,4 '
-Bis (4-aminophenoxy) biphenyl, 3,3 '
-Bis (2-aminophenoxy) biphenyl, 3,3 '
-Bis (3-aminophenoxy) biphenyl, 3,3 '
-Bis (4-aminophenoxy) biphenyl, 4,4 '
-Bis (4-aminophenoxy) diphenyl sulfide, 4,4'-bis (3-aminophenoxy) diphenyl sulfide, 4,4'-bis (2-aminophenoxy) diphenyl sulfide, 3,3'-bis (2- Aminophenoxy) diphenyl sulfide, 3,3′-bis (3-aminophenoxy) diphenyl sulfide, 3,
3'-bis (4-aminophenoxy) diphenyl sulfide, 4,4'-bis (2-aminophenoxy) benzophenone, 4,4'-bis (3-aminophenoxy) benzophenone, 4,4'-bis (4- Aminophenoxy) benzophenone, 3,3′-bis (2-aminophenoxy) benzophenone, 3,3′-bis (3-aminophenoxy) benzophenone, 3,3′-bis (4-aminophenoxy) benzophenone, 4,4 '-Bis (2
-Aminophenoxy) diphenyl ether, 4,4'-
Bis (3-aminophenoxy) diphenyl ether,
4,4'-bis (4-aminophenoxy) diphenyl ether, 3,3'-bis (2-aminophenoxy) diphenyl ether, 3,3'-bis (3-aminophenoxy) diphenyl ether 3,3'-bis (4-aminophenoxy) diphenyl ether, 4,4'-bis (2
-Aminophenoxy) diphenyl sulfone, 4,4'-
Bis (3-aminophenoxy) diphenyl sulfone,
4,4'-bis (4-aminophenoxy) diphenyl sulfone, 3,3'-bis (2-aminophenoxy) diphenyl sulfone, 3,3'-bis (3-aminophenoxy) diphenyl sulfone, 3,3'- Bis (4-aminophenoxy) diphenyl sulfone, 2,2-bis [4-
(2-Aminophenoxy) phenyl] propane, 2,2
-Bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (2-aminophenoxy) phenyl] propane , 2,2-bis [3-
(3-aminophenoxy) phenyl] propane, 2,2
-Bis [3- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (2-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2, 2-bis [4- (3-aminophenoxy)
Phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoro Propane, 2,2-bis [3- (2-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3- (3-aminophenoxy) phenyl ] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane ,

Bis [4- (4-aminophenoxy) phenyl] sulfoxide, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4
-(3-aminophenoxy) benzoyl] benzene,
1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, 4,4′-bis (3-aminophenoxy) -3 , 3'-dimethylbiphenyl,
4,4′-bis (3-aminophenoxy) -3,3 ′,
5,5'-tetramethylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,3 ', 5,5'-tetrachlorobiphenyl, 4,4'-bis (3-aminophenoxy) -3 , 3 ', 5,5'-Tetrabromobiphenyl, bis [4- (3-aminophenoxy) -3-methoxyphenyl] sulfide, [4- (3-aminophenoxy) phenyl] [4- (3-aminophenoxy) ) -3,
5-dimethoxyphenyl] sulfide, bis [4- (3
-Aminophenoxy) -3,5-dimethoxyphenyl]
Sulfide, 1,1-bis [4- (3-aminophenoxy) phenyl] propane, 1,3-bis [4- (3-aminophenoxy) phenyl] propane, 1,3-bis (3-aminophenoxy) benzene , 1,3-bis (4
-Aminophenoxy) benzene, 4,4'-bis (4-
Aminobenzoyl) biphenyl, 4,4'-bis (3-
Aminobenzoyl) biphenyl, 3,3′-bis (4-
Aminobenzoyl) biphenyl, 3,3'-bis (3-
Aminobenzoyl) biphenyl, 4,4'-bis (4-
Aminobenzoyl) diphenyl ether, 4,4′-bis (3-aminobenzoyl) diphenyl ether, 3,
3'-bis (4-aminobenzoyl) diphenyl ether, 3,3'-bis (3-aminobenzoyl) diphenyl ether, bis [4- (4-aminobenzoyl) phenyl] ketone, bis [4- (3-Aminobenzoyl) phenyl] ketone, bis [3- (4-aminobenzoyl)
Phenyl] ketone, bis [3- (3-aminobenzoyl) phenyl] ketone, bis [4- (4-aminobenzoyl) phenyl] sulfide, bis [4- (3-aminobenzoyl) phenyl] sulfide, bis [3- (4-
Aminobenzoyl) phenyl] sulfide, bis [3-
(3-aminobenzoyl) phenyl] sulfide, bis [4- (4-aminobenzoyl) phenyl] sulfone,
Bis [4- (3-aminobenzoyl) phenyl] sulfone, Bis [3- (4-aminobenzoyl) phenyl] sulfone, Bis [3- (3-aminobenzoyl) phenyl] sulfone, Bis [4- (4-amino) Benzoyl) phenyl] methane, bis [4- (3-aminobenzoyl)
Phenyl] methane, bis [3- (4-aminobenzoyl) phenyl] methane, bis [3- (3-aminobenzoyl) phenyl] methane, 2,2-bis [4- (4-aminobenzoyl) phenyl] propane, 2,2-bis [4- (3-aminobenzoyl) phenyl] propane,
2,2-bis [3- (4-aminobenzoyl) phenyl] propane, 2,2-bis [3- (3-aminobenzoyl) phenyl] propane, 2,2-bis [4- (4-
Aminobenzoyl) phenyl] -1,1,1,3,3,3
3-hexafluoropropane, 2,2-bis [4- (3
-Aminobenzoyl) phenyl] -1,1,1,3
3,3-hexafluoropropane, 2,2-bis [3-
(4-Aminobenzoyl) phenyl] -1,1,1,
3,3,3-hexafluoropropane, 2,2-bis [3- (3-aminobenzoyl) phenyl] -1,1,
1,3,3,3-hexafluoropropane,

4,4'-bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone, 4,4'-bis [4- (3-aminophenoxy) phenoxy] diphenylsulfone, 3,3'-bis [ 4- (4-aminophenoxy) phenoxy] diphenyl sulfone, 3,3′-
Bis [4- (3-aminophenoxy) phenoxy] diphenyl sulfone, 4,4'-bis [4- (4-aminocumyl) phenoxy] diphenyl sulfone, 4,4'-bis [4- (3-aminocumyl) phenoxy] Diphenyl sulfone, 3,3'-bis [4- (4-aminocumyl)
Phenoxy] diphenyl sulfone, 3,3′-bis [4
-(3-Aminocumyl) phenoxy] diphenylsulfone, 4,4'-bis [4- (4-aminophenoxy) benzoyl] diphenylether, 4,4'-bis [4-
(3-Aminophenoxy) benzoyl] diphenyl-
Ter, 3,3'-bis [4- (4-aminophenoxy)
Benzoyl] diphenyl ether, 3,3′-bis [4
-(3-Aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (4-aminophenoxy) phenoxy] biphenyl, 4,4'-bis [4-
(3-aminophenoxy) phenoxy] biphenyl,
3,3'-bis [4- (4-aminophenoxy) phenoxy] biphenyl, 3,3'-bis [4- (3-aminophenoxy) phenoxy] biphenyl, 4,4'-bis [4- (4- Aminocumyl) phenoxy] biphenyl,
4,4'-bis [4- (3-aminocumyl) phenoxy] biphenyl, 3,3'-bis [4- (4-aminocumyl) phenoxy] biphenyl, 3,3'-bis [4-
(3-aminocumyl) phenoxy] biphenyl, 4,
4'-bis [4- (4-aminophenoxy) benzoyl] biphenyl, 4,4'-bis [4- (3-aminophenoxy) benzoyl] biphenyl, 3,3'-bis [4- (4-aminophenoxy) ) Benzoyl] biphenyl, 3,3′-bis [4- (3-aminophenoxy) benzoyl] biphenyl, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene and the like. To be

The tetracarboxylic acid dianhydride which can be used within a range not impairing the performance includes ethylene tetracarboxylic acid dianhydride, butane tetracarboxylic acid dianhydride, cyclopentane tetracarboxylic acid dianhydride,
2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic Acid dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dianhydride, 3,3 ′, 4
4'-diphenylsulfone tetracarboxylic dianhydride,
3,3 ′, 4,4′-diphenylmethanetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) ) -1,1,1,3,3,3-hexafluoropropane dianhydride, 4,4 ′-(p-phenylenedioxy) diphthalic acid dianhydride, 2,2-bis [4-
(3,4-Dicarboxyphenyl) phenoxy] propane dianhydride, 2,2 ', 3,3'-diphenylmethanetetracarboxylic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride Anhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride,
1,2-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,2,3,4-benzenetetracarboxylic acid Dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride And 1,2,7,8-phenanthrenetetracarboxylic acid dianhydride.

In the method for producing a polyimide of the present invention, a dicarboxylic acid anhydride or a monoamine can be used for the purpose of blocking the polymer molecule ends. Specific examples of these compounds include phthalic anhydride, 2,
3-benzophenone dicarboxylic acid anhydride, 3,4-benzophenone dicarboxylic acid anhydride, 2,3-dicarboxyphenyl phenyl ether anhydride, 3,4-dicarboxyphenyl phenyl ether anhydride, 2,3-biphenyl dicarboxylic acid anhydride Substance, 3,4-biphenyldicarboxylic acid anhydride, 2,3-dicarboxyphenylphenyl sulfone anhydride, 3,4-dicarboxyphenylphenyl sulfone anhydride, 2,3-dicarboxyphenylphenyl sulfide anhydride, 3, 4-dicarboxyphenyl phenyl sulfide anhydride, 1,2-naphthalenedicarboxylic acid anhydride, 2,3-naphthalenedicarboxylic acid anhydride,
Examples thereof include 1,8-naphthalenedicarboxylic 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 a group having no reactivity with amines or dicarboxylic acid anhydrides. These can be used alone or 2
A mixture of two or more species can be used. Of these aromatic dicarboxylic acid anhydrides, phthalic anhydride is preferably used.

Examples of monoamines include the following. For example, 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,
p-nitroaniline, m-nitroaniline, o-aminophenol, p-aminophenol, m-aminophenol, o-anisidine, m-anisidine, p-anisidine, o-phenetidine, m-phenetidine, p-phenetidine, o -Aminobenzaldehyde, p-aminobenzaldehyde, m-aminobenzaldehyde, o-aminobenznitrile, p-aminobenznitrile, m-aminobenznitrile, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-amino Phenyl phenyl ether, 3-aminophenyl phenyl ether, 4-aminophenyl phenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-
Aminobenzophenone, 2-aminophenylphenyl sulfide, 3-aminophenylphenyl sulfide, 4
-Aminophenylphenyl sulfide, 2-aminophenylphenyl sulfone, 3-aminophenylphenyl sulfone, 4-aminophenylphenyl sulfone, α-naphthylamine, β-naphthylamine, 1-amino-2-
Naphthol, 5-amino-1-naphthol, 2-amino-1-naphthol, 4-amino-1-nafrole, 5-
Amino-2-naphthol, 7-amino-2-naphthol, 8-amino-1-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene and the like. Usually, of these aromatic monoamines, derivatives of aniline are preferably used. These can be used alone or in combination of two or more. These monoamines and / or dicarboxylic acid anhydrides may be used alone or in combination of two or more kinds without any problem. The amount of these compounds used is 1 to several times as much as the difference in the number of moles of the diamine and the tetracarboxylic dianhydride used (excess component is tetracarboxylic dianhydride), or dicarboxylic anhydride (excess component is Although it may be a diamine), it is generally used in an amount of about 0.01 mol times at least one component. Specifically, 0.001 to 1.0 mol of dicarboxylic acid anhydride and / or monoamine is used with respect to 1 mol of the total amount of the tetracarboxylic dianhydride. 0.
If the amount is less than 001 mol, the amount of clay is lowered during high temperature molding, which causes deterioration of moldability. On the other hand, if it exceeds 1.0 mol, the mechanical properties will deteriorate. Preferably 0.005 to 0.
70 mol, more preferably 0.01 to 0.5 mol.

The polymerization of the polyimide precursor, that is, the polyamic acid in the present invention is usually carried out in an organic solvent. As the organic solvent used in this reaction, any one can be used as long as it can dissolve the polyamic acid that is the precursor of the polyimide, and specifically, an amide solvent, an ether solvent, and a phenol solvent. Examples of the solvent include N, N-dimethylformamide and 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, pyridine, picoline, dimethyl sulfoxide,
Dimethyl sulfone, tetramethyl urea, hexamethyl phosphoramide, phenol, o-cresol, m-cresol, p-cresol, cresylic acid, o-chlorophenol, m-chlorophenol, p-chlorophenol, anisole and the like can be mentioned. These may be used alone or in combination of two or more. Particularly, an amide solvent is preferable from the viewpoint of solution stability and utilization as workability.

In the production of the polyimide of the present invention, it is possible to coexist with an organic base catalyst. As the organic base catalyst, tertiary amines such as pyridine, α-picoline, β-picoline, γ-picoline, quinoline, isoquinoline and triethylamine are used, and pyridine and γ-picoline are particularly preferable. The amount of these catalysts used is 0.001 to 0.50 mol per 1 mol of the total amount of tetracarboxylic dianhydride. It is particularly preferably 0.01 to 0.1 mol. The polymerization concentration (polymer concentration) in the production of the polyimide of the present invention is not particularly limited, but it is desirable to perform the polymerization at a high concentration in view of economical efficiency during production, 5 to 60 wt%, and more desirably 10 to 50 wt%. %.

Further, in a solvent, a diamine component, a tetracarboxylic dianhydride component and a dicarboxylic acid anhydride and /
Alternatively, a method of reacting a monoamine to obtain a polyamic acid that is a precursor of a polyimide includes: (a) reacting a tetracarboxylic acid dianhydride component with a diamine component, and then adding a dicarboxylic acid anhydride or monoamine to react How to continue. (B) A method in which a tetracarboxylic dianhydride component is reacted with a monoamine and then a diamine component is added to continue the reaction. (C) A method of reacting a diamine component and a dicarboxylic acid anhydride, and then adding a tetracarboxylic acid dianhydride component to continue the reaction. (D) tetracarboxylic dianhydride component, diamine component,
Examples thereof include a method in which a dicarboxylic acid anhydride or a monoamine is added and reacted at the same time, and any addition / reaction method may be used. In addition, the usual copolymer has various forms such as random copolymerization, block copolymerization, and alternating copolymerization. Since the copolymer of the present invention may take any form, depending on the intended form,
The order of addition of the monomers may be changed in various ways. The reaction temperature at the time of producing the polyamic acid which is a precursor of polyimide is -20 to 60 ° C, preferably 0 to 40 ° C. The reaction time depends on the diamine used, the tetracarboxylic dianhydride, the type of solvent, the reaction temperature, etc.
As a guide, it is 1 to 48 hours, and is usually several hours to ten and several hours. The polyamic acid thus obtained is then thermally dehydrated by heating to 150 to 400 ° C., or
The target polyimide is obtained by chemically imidizing using an organic base catalyst and an imidizing agent such as acetic anhydride.

The reaction temperature in the production of polyimide is 100 ° C. or higher, preferably 150 to 300 ° C. in the case of thermal imidization, and it is common to carry out withdrawing water generated by the reaction. . Prior to the imidization, it is possible to first synthesize the polyamic acid at a low temperature of 100 ° C. or lower and then raise the temperature to imidize, but simply by mixing the tetracarboxylic dianhydride component and the diamine component by the above method. After that, imidization can also be performed by immediately raising the temperature in the presence of an organic base. The reaction time varies depending on the type of tetracarboxylic dianhydride used, the type of solvent, the type and amount of organic base catalyst, the reaction temperature, etc., but as a guide, the amount of distilled water reaches the theoretical amount (usually Does not recover all, so the reaction rate is up to 70 to 90%. It is usually several hours to 10 hours. In this case, water generated by the imidization reaction is obtained by adding an azeotropic agent such as toluene to the reaction system,
The method of removing water by azeotropic distillation is general and effective.

Further, when chemically performing imidization using an imidizing agent such as acetic anhydride, the reaction can be performed at a lower temperature, and the temperature is 50 ° C. or higher, preferably 60 to 100 ° C. Since the imidizing agent (dehydrating agent) is used in this method, it is not necessary to remove the produced water out of the system. The reaction time is the same as in the case of the above-mentioned thermal imidization.
The polyimide copolymer of the present invention is produced by the above method.

Although the molecular weight of the polyimide copolymer obtained by the method of the present invention is not particularly limited,
The polyamic acid copolymer, which is a precursor of the present polyimide copolymer, is preferably dissolved in N, N-dimethylacetamide at a concentration of 0.5 g / dl, and then the logarithmic viscosity value measured at 35 ° C. is 0. 01-3.0 dl / g, and further contains 9 parts by weight of p-chlorophenol and 1 part of the present polyimide powder.
After dissolving by heating in a part by weight of a phenol mixed solvent at a concentration of 0.5 g / dl, the logarithmic viscosity value measured at 35 ° C. is 0.01 to 3.0 dl / g.

Further, as a method for producing a polyimide film in the present invention, a varnish of a polyamic acid copolymer which is a precursor of the present polyimide copolymer is applied on a smooth glass plate or a metal plate and then heated. A polyimide film can be obtained by the imidization method or by directly heating, pressing and stretching the polyimide powder. That is, a film-shaped or powder-shaped polyimide copolymer can be obtained by using a conventionally known technique.

When the polyimide copolymer of the present invention is subjected to melt molding, other thermoplastic resins such as polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, etc. may be used as long as the object of the present invention is not impaired.
Polyamide imide, polysulfone, polyether sulfone, polyether ketone, polyphenyl sulfide, polyether imide, modified polyphenylene oxide, polyimide other than the present invention and the like may be blended in appropriate amounts according to the purpose. Further, the following fillers and the like used in ordinary resin compositions may be used as long as the object of the invention is not impaired. That is, one or more solid lubricants such as molybdenum disulfide, graphite, boron nitride, lead monoxide, and lead powder can be added. Further, one or more reinforcing materials such as glass fiber, carbon fiber, aromatic polyamide fiber, potassium titanate fiber, and glass beads can be added. The amount of one or more reinforcing materials selected from carbon fiber, glass fiber, aromatic polyamide fiber, and potassium titanate fiber is the polyimide copolymer 1 of the present invention.
5 to 100 parts by weight, preferably 1 to 100 parts by weight
0 to 80 parts by weight.

An antioxidant, a heat stabilizer, an ultraviolet absorber, a flame retardant, a flame retardant auxiliary, and an antioxidant, as long as the object of the present invention is not impaired.
One or more usual additives such as antistatic agents, lubricants and colorants can be added. Further, the polyimide copolymer of the present invention, various molding materials, in addition to the form of the film,
A fiber form is also possible. Further, it is also used as a composite material in which a fiber cloth made of fibers such as carbon fiber is impregnated with the polyimide of the invention.

[0034]

The present invention will be described below in detail with reference to examples and comparative examples. The physical properties of the polyimide in the examples were measured by the following methods. 5% weight loss temperature: DTG in the air (Shimadzu DT-40
Series, DTG-40M). Melt viscosity, flow starting temperature: Measured using a Shimadzu Koka type flow tester (CFT500A) with a load of 100 kg, an orifice of 0.1 cm in diameter and 1 cm in length. Logarithmic viscosity Polyamic acid: N-methyl-2-pyrrolidone was used as a solvent and dissolved at a concentration of 0.5 g / 100 ml.
Measured at 35 ° C. Polyimide powder: 0.5 g / 100 using p-chlorophenol / phenol = 9/1 (weight ratio) as a solvent
Measured at 35 ° C after dissolution by heating at a concentration of ml. Film mechanical properties: Based on ASTM D-822.

Example 1 1,3-bis [4- (4-aminophenoxy)] was placed in a container equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet tube.
-Α, α-Dimethylbenzyl] benzene 16.911 g
(0.032 mol), 4,4'-diaminodiphenyl ether 1.602 g (0.008 mol), pyromellitic dianhydride 8.289 g (0.038 mol), phthalic anhydride 0.593 g (0.004 mol) Mol), 0.56 g (0.006 mol) of γ-picoline and m-cresol 1
07.21 g was inserted, and the temperature was raised to 150 ° C. with stirring under a nitrogen atmosphere. Then, the mixture was reacted at 150 ° C. for 4 hours. During this period, distillation of about 1.4 ml of water was confirmed. After completion of the reaction, the mixture was cooled to room temperature, discharged into 500 ml of methyl ethyl ketone, and then the polyimide powder was filtered.
After washing this polyimide powder with methyl ethyl ketone,
It was dried under a nitrogen atmosphere at 50 ° C. for 24 hours and under reduced pressure at 180 ° C. for 4 hours to obtain 25.29 g (yield 97.4%) of polyimide powder. The polyimide powder thus obtained had an inherent viscosity of 0.50 dl / g. The flow starting temperature is 2
The melt viscosity was 85 ° C., 340 ° C., and residence time 5 minutes, 2600 poise. The 5% weight loss temperature in air was 533 ° C.

Examples 2 and 3 The amounts of 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene and 4,4'-diaminodiphenyl ether used in Example 1 were changed. To synthesize polyimide powder. The polyimide production conditions are shown in Table 1, and the physical properties of the obtained polyimide powder are shown in Table 2 together with the results of Example 1.

Comparative Example 1 1,3-bis [4- (4-aminophenoxy) -α, α
-Dimethylbenzyl] benzene and 4,4'-diaminodiphenyl ether were used in the same manner as in Example 1 except that the amounts used were outside the range of the present application, to obtain a polyimide powder. Table 1 shows the polyimide production conditions, and Table 2 shows the physical properties of the obtained polyimide powder.

[0038]

[Table 1] * 1) 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene * 2) 4,4-diaminodiphenyl ether * 3) pyromellitic dianhydride * 4) phthalic anhydride

[0039]

[Table 2] * 1) Insoluble in η measurement solvent * 2) Does not melt and flow up to 450 ° C

From the results in Tables 1 and 2, 1,3-bis [4- (4-aminophenoxy) -based on all diamines was obtained.
α, α-Dimethylbenzyl] benzene (p-BAC-
The polyimide copolymer of the present application in which the proportion of M) is 50 mol% or more has thermoplasticity, whereas the polyimide in which the proportion of p-BAC-M, which is outside the scope of the present application, is less than 50 mol%. The copolymer does not melt and flow up to 450 ° C and is essentially non-thermoplastic.

Example 4 10.75 g (0.020 mol) of 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene was placed in a container equipped with a stirrer and a nitrogen introducing tube.
4,4'-diaminodiphenyl ether 4.005 g
(0.020 mol), N, N-dimethylformamide 9
2.5 g was charged, and 8.5550 g (0.0392 mol) of pyromellitic dianhydride was added in portions while stirring in a nitrogen atmosphere while paying attention to the rise of the solution temperature, and stirred at room temperature for 4 hours. After that, 0.237 g of phthalic anhydride
(0.0016 mol) was added, and the mixture was further stirred for 10 hours to obtain a uniform polyamic acid varnish. The polyamic acid varnish thus obtained had an inherent viscosity of 0.70 dl / g. The obtained polyamic acid varnish was coated on a glass plate and then heated at 250 ° C. for 4 hours under a nitrogen stream to obtain a polyimide film having a thickness of 35 μm. Table 3 shows the mechanical properties of the obtained polyimide film.

Example 5 20.082 g (0.038 mol) of 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene was placed in a container equipped with a stirrer and a nitrogen introducing tube.
0.44 g of 4,4'-diaminodiphenyl ether
(0.002 mol), N, N-dimethylformamide 1
Charge 16.1 g, and stir in a nitrogen atmosphere while stirring 8.550 g of pyromellitic dianhydride (0.0392
Mol) was added in portions while paying attention to the rise in solution temperature, and the mixture was stirred at room temperature for 4 hours, and then 0.237 g of phthalic anhydride was added.
(0.0016 mol) was added, and the mixture was further stirred for 10 hours to obtain a uniform polyamic acid varnish. The polyamic acid varnish thus obtained had an inherent viscosity of 0.68 dl / g. The obtained polyamic acid varnish was coated on a glass plate and then heated at 250 ° C. for 4 hours under a nitrogen stream to obtain a polyimide film having a thickness of 32 μm. Table 3 shows the mechanical properties of the obtained polyimide film.

Comparative Example 2 20.293 g (0.0384 mol) of 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene was placed in a container equipped with a stirrer and a nitrogen introducing tube. 4,4'-diaminodiphenyl ether 0.32
0 g (0.0016 mol) and 116.7 g of N, N-dimethylformamide were charged, and pyromellitic dianhydride 8.550 g (0.0
392 mol) was added in portions while paying attention to the rise in solution temperature, and the mixture was stirred at room temperature for 4 hours, and then phthalic anhydride 0.23
7 g (0.0016 mol) was added and further stirred for 10 hours to obtain a uniform polyamic acid varnish. The polyamic acid varnish thus obtained had an inherent viscosity of 0.67 dl / g. After coating the obtained polyamic acid varnish on a glass plate, it is heated at 250 ° C. for 4 hours under a nitrogen stream to give a thickness of 33 μm.
A polyimide film of m was obtained. Table 3 shows the mechanical properties of the obtained polyimide film.

[0044]

[Table 3] * 1) 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene / 4,4-diaminodiphenyl ether

1,3-bis [4- (4-aminophenoxy)-
α, α-Dimethylbenzyl] benzene (p-BAC-
Polyimide film having a copolymerization ratio of M) within the range of the present application has excellent mechanical properties, whereas p-BAC-M
The mechanical properties of the polyimide film of Comparative Example 2 in which the use amount of is outside the range of the present application are inferior.

From the above results, the polyimide copolymer of the present invention in which the amount of p-BAC-M used is 50 to 95 mol% based on all diamines has both excellent mechanical properties and thermoplasticity. On the other hand, a polyimide copolymer in which the amount of p-BAC-M used is less than 50 mol% has no thermoplasticity, and a polyimide copolymer in which the amount of p-BAC-M exceeds 95 mol% has poor mechanical properties.

[0047]

INDUSTRIAL APPLICABILITY The polyimide copolymer of the present invention is a thermoplastic polyimide copolymer which has excellent mechanical properties and can be injection-molded.

Claims (7)

[Claims] 1. A polymer of the formula (1) [Chemical formula 1] Containing 0.50 to 0.95 mol% of a repeating structural unit represented by the following formula, and having the formula (2) A polyimide copolymer containing 0.50 to 0.05 mol% of a repeating structural unit represented by: 2. When the above polyimide copolymer is produced, the compound represented by the general formula (3): [Chemical Formula 3] (In the formula, Z has 6 to 15 carbon atoms and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a crosslinking member. Is 2
Represents a valence group. ) And / or the general formula (4) [Chemical formula 4] V-NH ₂ (4) (wherein V has 6 to 15 carbon atoms and is a monocyclic ring). Formula Aromatic Group, Fused Polycyclic Aromatic Group, or Non-Fused Polycyclic Aromatic Group in which Aromatic Groups are Directly Connected to Each Other or by a Cross-Linking Member 1
Represents a valence group. The polyimide copolymer according to claim 1, comprising a polymer molecule obtained by allowing an aromatic monoamine represented by the formula (1) to coexist with the end of the polymer molecule blocked. 3. 0.50 to 0.95 mol% of the formula (5) [Chemical formula 5] And 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene represented by
0 to 0.05 mol% of the formula (6) [Chemical Formula 6] 4,4'-diaminodiphenyl ether represented by the formula (7) [Chemical Formula 7] [Chemical Formula 7] With pyromellitic dianhydride represented by the general formula (3)
[Chemical Formula 8] [Chemical Formula 8] (In the formula, Z has 6 to 15 carbon atoms and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a crosslinking member. Is 2
Represents a valence group. ) And / or a general formula (4) [Chemical formula 9] V-NH ₂ (4) (in the formula, V has 6 to 15 carbon atoms and is a monocyclic ring). Formula Aromatic Group, Fused Polycyclic Aromatic Group, or Non-Fused Polycyclic Aromatic Group in which Aromatic Groups are Directly Connected to Each Other or by a Cross-Linking Member 1
Represents a valence group. 3. The method for producing a polyimide copolymer according to claim 2, wherein the polyamic acid obtained is reacted in the presence or absence of an aromatic monoamine represented by the formula (1) to thermally or chemically imidize the polyamic acid. . 4. The amount of the aromatic dicarboxylic acid anhydride used is 0.001 to 1.0 mol based on 1 mol of the total amount of the aromatic diamine compounds represented by the formulas (5) and (6). The method for producing a polyimide copolymer according to claim 3, wherein 5. The use amount of the aromatic monoamine is 0.001 to 1.0 mol per 1 mol of the aromatic tetracarboxylic dianhydride represented by the formula (7). The method for producing the polyimide copolymer of. 6. A polyimide film containing the polyimide copolymer according to claim 1 or 2. 7. One or more reinforcing materials 5 to 100 selected from carbon fiber, glass fiber, aromatic polyamide fiber and potassium titanate fiber based on 100 parts by weight of the polyimide copolymer according to claim 1 or 2. Polyimide resin composition containing parts by weight.