JP3169440B2 - Polyimide and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polyimide. More specifically, the present invention relates to a novel thermoplastic polyimide and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, polyimide has excellent properties such as mechanical properties, chemical resistance, flame retardancy, and electrical properties in addition to its excellent heat resistance.
It is widely used in the fields of composite materials, electric / electronic parts and the like. However, even if it is excellent in heat resistance, it does not have a clear glass transition temperature, so when it is used as a molding material, it must be processed using a method such as sinter molding, and the workability is excellent. Has low and high glass transition temperatures, is soluble in halogenated hydrocarbon solvents, and is not satisfactory in terms of heat resistance and solvent resistance. For example, the formula (7) (Formula 1)
3)

[0003]

Embedded image Is a polyimide having a basic skeleton represented by (Dupont: Kapton, Vespel).
It is a polyimide with excellent heat resistance, but it does not have a clear glass transition point, is difficult to process when used as a molding material, and must be molded using techniques such as sinter molding (supervised by Toshiaki Hirai, Engineering plastics,
(Plastics Age, 1984). On the other hand, various kinds of aromatic polyethers having crystallinity have been developed. For example, the formula (8)

[0004]

Embedded image An aromatic polyether represented by the following formula (manufactured by ICI; trade name <VICTREX> PEEK) shows crystallinity,
Although it has excellent low water absorption and chemical resistance, it has a low glass transition temperature of 143 ° C., and cannot be said to have sufficient heat resistance. Further, in the production method, there is a problem that a high boiling point solvent such as diphenyl sulfone must be used (the above-mentioned engineering plastics). Furthermore, some crystalline polyethers having a benzonitrile skeleton are also known (for example, Proceedings of the Society of Polymer Science, 37 , 306, 1).
988 and JP-A-59-206433), and the glass transition temperature is 200 ° C. or less, and it is hard to say that it is still sufficiently high.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermoplastic polyimide having good moldability in addition to the excellent heat resistance inherent to polyimide.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, a polyimide containing an aromatic diamine having a specific structure as a monomer component impairs various properties inherent to the polyimide. Without any problem, they found that they were thermoplastic polyimides having excellent moldability and completed the present invention. That is, the present invention relates to general formula (1)
(Formula 15)

[0007]

Embedded image (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 are directly or mutually linked by a bridge member. A tetravalent group selected from the group consisting of non-fused polycyclic aromatic groups), a polyimide having a repeating structural unit represented by the formula: A polyimide which is an aromatic ring essentially having no substituent or substituted with a group having no reactivity with an amine or a dicarboxylic anhydride, and a polyamic acid which is a precursor of the present polyimide is converted into dimethylacetamide. After dissolving at a concentration of 0.5 g / dl, a polyimide having a logarithmic viscosity at 35 ° C. of 0.01 to 3.0 dl / g, or 9 parts by weight of the polyimide powder and 1 part by weight of p-chlorophenol In a mixed solvent of phenol 0.5
A polyimide having a logarithmic viscosity of 0.01 to 3.0 dl / g measured at 35 ° C. after heating and dissolving at a concentration of g / dl, and a method for producing them. More specifically, the present invention relates to a compound represented by the general formula (1):

[0008]

Embedded image (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 are directly or mutually linked by a bridge member. A tetravalent group selected from the group consisting of non-fused polycyclic aromatic groups) and a polyimide having a repeating structural unit represented by the formula (3):

[0009]

Embedded image And an aromatic diamine represented by general formula (4)
(Formula 18)

[0010]

Embedded image (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 are directly or mutually linked by a bridge member. And a tetracarboxylic dianhydride represented by the formula (1), wherein the resulting polyamic acid is thermally or chemically imidized. It is a method of manufacturing. Further, an aromatic ring in which the terminal of the repeating structural unit represented by the general formula (1) has essentially no substituent or is substituted by a group having no reactivity with an amine or a dicarboxylic anhydride. Polyimide,
Further, these polyimides are converted into an aromatic diamine represented by the above formula (3) and a tetracarboxylic dianhydride mainly represented by the above general formula (4) by the following formula (5).

[0011]

Embedded image (In the formula, Z ₁ is an aliphatic group having 6 to 15 carbon atoms, a cyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group connected directly or by a crosslinking member. An aromatic dicarboxylic anhydride represented by the formula (6): Z ₂ —NH ₂ (6) (showing a divalent group selected from the group consisting of a non-fused polycyclic aromatic group) In the formula, Z ₂ represents an aliphatic group having 6 to 15 carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group connected directly or by a crosslinking member. A monovalent group selected from the group consisting of non-condensed polycyclic aromatic groups) in the presence of an aromatic monoamine represented by the formula (I) to thermally or chemically imidize the resulting polyamic acid. This is a method for producing a polyimide. The polyimide of the present invention has the general formula (1)

[0012]

Embedded image (Wherein, R is as defined above), and a polyimide having a repeating structural unit represented by the formula: Polyimide of this repeating structural unit as an aromatic diamine component,
The above formula (3)

[0013]

Embedded image Is used.

The above formula (3) used as a raw material of the present invention
Of 1,3-bis [4- (4-amino-6-cyanophenoxy) -α, α-dimethylbenzyl] benzene, the method of producing 1,3-bis [4- (4-nitro- 6-cyanophenoxy) -α, α-dimethylbenzyl] benzene. This nitro compound
For example, by reacting 1,3-bis [(4-hydroxy) -α, α-dimethylbenzyl] benzene with 2-chloro-5-nitrocyanobenzene in the presence of a base in an aprotic polar solvent. Each is manufactured. The method for reducing the dinitro compound is not particularly limited, and a method for reducing a nitro group to an amino group, for example, a method described in Shin-Jikken Kagaku Koza, Vol. 15, Oxidation and Reduction, Maruzen (1977) can be applied. Specifically, it can be produced by a catalytic reduction method using a metal catalyst such as a palladium catalyst.

The polyimide of the present invention has the formula (3): 1,3-bis [4- (4-amino-6-cyanophenoxy)-
α, α-Dimethylbenzyl] benzene is used as an essential monomer raw material of an aromatic diamine. Furthermore, other aromatic diamines can be mixed and used within a range that does not impair the good physical properties of the polyimide.

Examples of the diamines which can be used as a mixture include, for example, m-phenylenediamine, o-phenylenediamine, p-
Phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, bis (3-aminophenyl) sulfide, bis ( 4-aminophenyl) sulfide, (3-aminophenyl) (4-aminophenyl) sulfide, bis (3
-Aminophenyl) sulfoxide, bis (4-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, (3- Aminophenyl) (4-aminophenyl) sulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone,
4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4 -Aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [ 4- (4-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 [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, 1,3-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- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-amino Phenoxy) 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-amino) Phenoxy) 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-dimethyl) Benzyl) 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) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-
Bis [4- (4-amino-6-fluorophenoxy) -α, α-
Dimethylbenzyl] benzene, 1,3-bis [4- (4-amino
-6-methylphenoxy) -α, α-dimethylbenzyl] benzene and the like, and these are used alone or in combination of two or more. Further, as the aromatic tetracarboxylic dianhydride, a compound represented by the general formula (4)

[0017]

Embedded image The tetracarboxylic dianhydride represented by is used. In the general formula (4), R is an aliphatic group having 2 to 27 carbon atoms,
Cyclic aliphatic group, monocyclic aromatic group, fused polycyclic aromatic group,
And a tetravalent group selected from the group consisting of non-fused polycyclic aromatic groups in which the aromatic groups are connected to each other directly or by a bridging member. Specifically, R in the general formula (4) is 2 to 1 carbon atoms
0 aliphatic group, cycloaliphatic group having 4 to 10 carbon atoms, formula (a)

[0018]

Embedded image A monocyclic aromatic group represented by the formula (b):

[0019]

Embedded image A fused polycyclic aromatic group represented by the formula (c)
5)

[0020]

Embedded image (Wherein X is a direct bond, -CO-, -O-, -S-,-
_{SO 2 -, - CH 2 -} , - C (CH 3) 2 -, - C (CF
₃ ) _2- , Formula (d) (Formula 26), Formula (e) (Formula 26)

[0021]

Embedded image Or the formula (f)

[0022]

Embedded image (Where Y is a direct bond, -CO-, -O-, -S-,
_{-SO 2 -, - CH 2 -} , - C (CH 3) 2 -, - C (C
Tetracarboxylic acid, which is a tetravalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which the aromatic groups represented by F ₃ ) ₂ — are interconnected directly or by a bridging member Dianhydride is used.

The tetracarboxylic dianhydride represented by the general formula (4) used in the present invention includes, for example, ethylene tetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride and pyromellitic dianhydride. Anhydride, 3,
3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,
2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2',
3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (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-dicarboxyphenyl) -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, 10-perylenetetracarboxylic dianhydride, 2,
3,6,7,-anthracenetetracarboxylic dianhydride, 1,2,
7,8-phenanthrenetetracarboxylic dianhydride and the like. These may be used alone or in combination of two or more.

The polyimide obtained by using the aromatic diamine component and the aromatic tetracarboxylic dianhydride component as monomer components is mainly a polyimide having a repeating structural unit represented by the general formula (1), and is mainly a polyimide having the general formula (1) A) a polyimide having an aromatic ring substituted with a group having no substituent at the terminal of the polymer molecule or having no reactivity with an amine or a dicarboxylic anhydride, or a polyimide having the same. A composition containing a polyimide is also included.

The polyimide having an aromatic ring having no substituent at its terminal or substituted with a group having no reactivity with an amine or a dicarboxylic anhydride can be obtained by preparing an aromatic amine represented by the formula (3): The tetracarboxylic dianhydride mainly represented by the general formula (4) is converted into a compound represented by the formula (5)
8)

[0026]

Embedded image (In the formula, Z ₁ is an aliphatic group having 6 to 15 carbon atoms, a cyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group connected directly or by a crosslinking member. An aromatic dicarboxylic anhydride represented by the formula (6): Z ₂ —NH ₂ (6) (showing a divalent group selected from the group consisting of a non-fused polycyclic aromatic group) In the formula, Z ₂ represents an aliphatic group having 6 to 15 carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group connected directly or by a crosslinking member. A monovalent group selected from the group consisting of non-condensed polycyclic aromatic groups) in the presence of an aromatic monoamine represented by the formula (I) to thermally or chemically imidize the resulting polyamic acid. It can be obtained by:

Here, Z ₁ and Z ₂ in the formulas (5) and (6) include those having the same definition as R in the polyimide formula represented by the formula (1). The dicarboxylic anhydrides used in these methods include phthalic anhydride, 2,3-
Benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride, 2,3-dicarboxyphenyl phenyl ether anhydride, 3,4-dicarboxyphenyl phenyl ether anhydride, 2,3-biphenyl dicarboxylic anhydride, 3,4-biphenyldicarboxylic anhydride, 2,3-dicarboxyphenylphenylsulfone anhydride, 3,4-dicarboxyphenylphenylsulfone anhydride, 2,3-dicarboxyphenylphenylsulfide anhydride, 3,4- Dicarboxyphenylphenyl sulfide anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, 1,2-anthracenedicarboxylic anhydride, 2, 3-anthracene dicarboxylic anhydride, 1,9-anthracene dicarboxylic anhydride and the like. These dicarboxylic anhydrides may be substituted with a group having no reactivity with amine or dicarboxylic anhydride.

Of these dicarboxylic anhydrides, phthalic anhydride is most preferred from the viewpoint of properties and practicality of the polyimide obtained. That is, it is a polyimide excellent in molding stability at the time of high-temperature molding, has excellent chemical resistance, and considering the excellent workability, for example,
Polyimide is extremely useful as a base material for spacecraft and as an electric / electronic component.

When phthalic anhydride is used, there is no problem in using a part of it with another dicarboxylic anhydride as long as the good physical properties of polyimide are not impaired. The amount of the dicarboxylic anhydride used is 0.001 per mole of the aromatic diamine represented by the formula (3).
１．０1.0 molar ratio. If the amount is less than 0.001 mol, the viscosity is increased during high-temperature molding, which causes a reduction in molding processability. On the other hand, if it exceeds 1.0 mol, the mechanical properties deteriorate. The preferred amount is 0.01 to 0.5 mol.

When an aromatic monoamine is used,
As the aromatic monoamine, for example, aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-xylysine,
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-phenezine, m-phenezine, p-phenezine, o-aminobenzaldehyde, m-aminobenzaldehyde, p-aminobenzaldehyde, o-aminobenzonitrile, m-aminobenzonitrile, p-aminobenzonitrile, 2-aminobiphenyl, 3-aminobiphenyl,
4-aminobiphenyl, 2-aminophenylphenyl ether, 3-aminophenylphenyl ether, 4-aminophenylphenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminophenylphenyl sulfide, 3-aminophenyl Aminophenylphenyl sulfide, 4-aminophenylphenyl 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-aminoanthracene, 9-aminoanthracene and the like. These aromatic monoamines may be substituted with a group having no reactivity with amine or dicarboxylic anhydride.

The amount of the aromatic monoamine used is 0.001 to 1.0 mole ratio per mole of the tetracarboxylic dianhydride represented by the general formula (4). If the amount is less than 0.001 mol, the viscosity is increased at the time of high-temperature molding, which causes a reduction in moldability. If the molar ratio exceeds 1.0, the mechanical properties deteriorate. The preferred amount is 0.01 to 0.1.
5 mole ratio. Thus, when producing a polyimide having no substituent at the terminal of the polyimide of the present invention or a substituted aromatic ring, tetracarboxylic dianhydride, aromatic diamine, and dicarboxylic anhydride or aromatic monoamine The mole ratio of the aromatic diamine is 0.9 to 1.0 mole per mole of the tetracarboxylic dianhydride,
Dicarboxylic anhydride or aromatic monoamine is 0.00
1 to 1.0 mol. In producing polyimide,
In order to adjust the molecular weight of the resulting polyimide, it is common practice to adjust the ratio of tetracarboxylic dianhydride to aromatic diamine. In the method of the present invention, an appropriate molar ratio of aromatic diamine to tetracarboxylic dianhydride to obtain a polyimide having good melt flowability is 0.1.
It is in the range of 9 to 1.0.

The method for producing the polyimide of the present invention includes:
Although all methods capable of producing polyimide can be applied including known methods, it is particularly preferable to carry out the reaction in an organic solvent. The solvent used in such a reaction is preferably N, N-dimethylacetamide, but other usable solvents include, for example, N,
N-dimethylformamide, N, N-diethylacetamide,
N, N-dimethoxyacetamide, 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, tetra Examples include methylurea, hexamethylphosphoramide, phenol, o-cresol, m-cresol, p-cresol, m-cresylic acid, p-chlorophenol, anisole, benzene, toluene, xylene and the like. These organic solvents may be used alone or as a mixture of two or more.

In the method of the present invention, an aromatic diamine, a tetracarboxylic dianhydride, an aromatic dicarboxylic anhydride or an aromatic monoamine of the formula (3) is added to an organic solvent and reacted with the organic solvent as described in (a). A method in which a tetracarboxylic dianhydride is reacted with an aromatic diamine, followed by adding an aromatic dicarboxylic anhydride or an aromatic monoamine to continue the reaction. (B) adding an aromatic dicarboxylic anhydride to the aromatic diamine; After the reaction, a tetracarboxylic dianhydride is added, and the reaction is further continued. (C) After the aromatic monoamine is added to the tetracarboxylic dianhydride and reacted,
A method of adding an aromatic diamine and continuing the reaction further,
(D) A method in which a tetracarboxylic dianhydride, an aromatic diamine, an aromatic dicarboxylic anhydride or an aromatic monoamine is simultaneously added and reacted, and the like, and any addition method may be used.

The reaction temperature is usually 250 ° C. or lower, preferably 50 ° C. or lower. The reaction pressure is not particularly limited, and the reaction can be sufficiently performed at normal pressure. The reaction time varies depending on the type of tetracarboxylic dianhydride, the type of solvent and the reaction temperature, and usually 4 to 24 hours is sufficient. Further, by heating the obtained polyamic acid to 100 to 400 ° C. to imidize or chemically imidizing using an imidizing agent such as acetic anhydride, a polyimide having a repeating structural unit corresponding to the polyamic acid is obtained. can get.

After dissolving polyamic acid as a precursor of the present polyimide in N, N-dimethylacetamide at a concentration of 0.5 g / dl, the logarithmic viscosity measured at 35 ° C. is 0.01.
After further dissolving the polyimide powder by heating in a mixed solvent of 9 parts by weight of p-chlorophenol and 1 part by weight of phenol at a concentration of 0.5 g / dl, 35
The value of the logarithmic viscosity measured in ° C is 0.01 to 3.0 d.
1 / g. In addition, the aromatic diamine of the formula (3) and tetracarboxylic dianhydride, and further, when the terminal of the polyimide is an aromatic ring, an aromatic dicarboxylic anhydride or an aromatic monoamine is suspended or suspended in an organic solvent. It is also possible to obtain the target polyimide by heating after dissolving and performing imidation simultaneously with the generation of the polyamic acid which is a precursor of the polyimide.

Further, as a method for producing a polyimide film in the present patent, a varnish of a polyamic acid, which is a precursor of the present polyimide, is applied on a glass plate and then heated to imidize, or a polyimide powder is directly used. A method of forming a film by heating and pressing is possible. That is, a film-like or powder-like polyimide can be obtained by using a conventionally known technique.

When the polyimide of the present invention is subjected to melt molding, other thermoplastic resins such as polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, polysulfone, polyethersulfone, and the like can be used without impairing the object of the present invention. It is also possible to mix appropriate amounts of polyether ketone, polyphenyl sulfide, polyamide imide, polyether imide, modified polyphenylene oxide, polyimide other than the present invention, etc. 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, graphite, carborundum,
Abrasion resistance improvers such as silica stone powder, molybdenum disulfide, and fluororesin; reinforcing agents such as glass fiber and carbon fiber; flame retardant improvers such as antimony trioxide, magnesium carbonate and calcium carbonate; clays and mica Electric property improver, tracking resistance improver such as asbestos, silica, graphite, etc., acid resistance improver such as barium sulfate, silica, calcium metasilicate, etc., heat conductivity improvement of iron powder, zinc powder, aluminum powder, copper powder, etc. Agent, other glass beads, glass spheres, talc, diatomaceous, alumina, shirasubarun,
Hydrated alumina, metal oxides, coloring agents and the like. In addition, the polyimide of the present invention may be in the form of fibers in addition to various molding materials and films. Furthermore, the present invention is also used as a composite material in which a fiber cloth made of fibers such as carbon fiber is impregnated with polyimide.

[0038]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. In addition, the physical property of the polyimide in an Example was measured by the following methods. Tg, Tc, Tm; DSC (Shimadzu DT-40 series,
DSC-41M). 5% weight loss temperature; DTG (Shimadzu DT-40) in air
Series, DTG-40M). Melt viscosity; Shimadzu Koka type flow tester (CFT500
Measured with a load of 100 kg according to A). Logarithmic viscosity; polyimide powder in p-chlorophenol / phenol (weight ratio 9/1) mixed solvent, polyamic acid in N,
Measured at 35 ° C. after dissolving in N-dimethylacetamide at a concentration of 0.5 g / 100 ml.

Synthesis Example 1 (1,3-bis [4- (4-nitro-6-cyanophenoxy) -α, α
-Synthesis of [dimethylbenzyl] benzene) In a vessel equipped with a thermometer, a reflux condenser and a stirrer, 130 g of N, N-dimethylformamide (DMF) and 20 g of toluene
g, 2-chloro-5-nitrobenzonitrile 55 g (0.3
01 mol), 50.6 g (0.149 mol) of 1,3-bis (4-hydroxycumyl) benzene, potassium carbonate 2
4.5 g (0.177 mol) of each was charged, and the mixture was heated to 120 ° C. with stirring, and then aged at 120 ° C. for 6 hours.

After completion of the reaction, the mixture was cooled to 90 ° C. and filtered to remove inorganic salts. 525 ml of water was added to the filtrate, and the mixture was cooled to room temperature to crystallize the desired product. The precipitated crystals were separated by filtration and sludged with isopropyl alcohol to give 1,3-bis [4- (4-nitro-6-cyanophenoxy) -α, α-dimethylbenzyl] benzene, which was the target substance. Obtained. Melting point 209.4-210.5 ° C. Yield 89.0 g Yield 95% Elemental analysis (C ₃₈ H ₃₀ N ₄ O ₆ ) CH N ──────────────────計算 Calculated value (%) 71.46 4.73 8.77 Actual value (%) 71.81 4.71 8.70８ ──────────

Synthesis Example 2 (1,3-bis [4- (4-amino-6-cyanophenoxy) -α,
Synthesis of α-dimethylbenzyl] benzene) In a reduction device equipped with a thermometer, reflux condenser, and stirrer,
1,3-bis [4- (4-nitro-6-cyanophenoxy) -α, α
-Dimethylbenzyl] benzene 68 g (0.106 mol
l), 200 g of methyl cellosolve and 5% -Pd / C
3.0 g (50% water-containing product) was charged, and 70
The reaction was carried out at ８０80 ° C. for 4 hours. After the completion of the reaction, the catalyst was filtered off, and the filtrate was concentrated under reduced pressure to give 1,3-bis [4- (4
-Amino-6-cyanophenoxy) -α, α-dimethylbenzyl] benzene was obtained. Melting point 191.4-192.4 ° C Yield 51.8 g Yield 84% Note: * s; singlet, D; doublet, m; multi Elemental analysis (C ₃₈ H ₃₄ N ₄ O ₂ ) CH N ───────────────────────── Calculated value (%) 78.87 5. 92 9.68 Actual value (%) 78.90 5.94 9.73

Example 1 1,3-bis [4- (4-amino-6-cyanophenoxy) -α, α-dimethyl was placed in a vessel equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube. Benzyl] benzene 57.88
g (0.1 mol), pyromellitic dianhydride 21.38
g (0.098 mol), phthalic anhydride 0.592 g
(0.004 mol), 1.40 g of γ-picoline, and 317.0 g of m-cresol, and heated to 150 ° C. while stirring under a nitrogen atmosphere. Then 15
The reaction was performed at 0 ° C. for 4 hours. During this time, distillation of about 3.6 ml of water was confirmed.

After the completion of the reaction, cool to room temperature
After discharge into methyl ethyl ketone, the polyimide powder was separated by filtration. After washing the polyimide powder with methyl ethyl ketone, the powder was dried in air at 50 ° C for 24 hours and under reduced pressure at 180 ° C for 4 hours.
It was dried for 74 hours to obtain 74.38 g (yield 97.5%) of polyimide powder. The logarithmic viscosity of the polyimide powder thus obtained is 0.59 dl / g, and the glass transition temperature (Tg) is 21.
The crystallization temperature (Tc) was 278 ° C, and the melting point (Tm) was 383 ° C. The 5% weight loss temperature is 500 ° C
Met.

FIG. 1 shows the infrared absorption spectrum of this polyimide powder. From this spectrum diagram, absorption around 1780 and 1720 cm ^-1 which is an imide characteristic absorption band was remarkably recognized. The elemental analysis values of the polyimide powder were as follows.

(Elemental analysis value) CH N Ｃ calculated value (%) 75.77 4.25 7. 37 Measured value (%) 75.24 4.36 7.51 ────────────────────────── Furthermore, molding processing stability of this polyimide Using a Koka type flow tester, a load of 100 kg, and a diameter of 0.1 kg.
The measurement was performed using an orifice having a length of 1 cm and a length of 1 cm. The melt flow starting temperature was 390 ° C., 400 ° C., and the melt viscosity at a residence time of 5 minutes was 5,420 poise. Also, 37
The result of measuring the melt viscosity at 0 ° C. while changing the residence time in the cylinder is shown in FIG. Even if the residence time in the cylinder becomes longer, the melt viscosity hardly changes, indicating that the thermal stability is good.

Example 2 73.22 g of polyimide powder (96.7% yield) in the same manner as in Example 1 except that phthalic anhydride was not used.
I got The logarithmic viscosity of the polyimide powder thus obtained is 0.60 dl / g, and the glass transition temperature (Tg) is 218.
° C, crystallization temperature (Tc) 278 ° C, melting point (Tm) 3
85 ° C. The molding processing stability of this polyimide was measured in the same manner as in Example 1 using a flow tester.
The results are shown in FIG. 2 together with the results of Example 1. Polyimide obtained in this embodiment is a melt-molding, the melt viscosity is increased as the residence time in the cylinder is increased,
It can be seen that the molding stability is lower than that of the polyimide obtained in Example 1.

Example 3 In a vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube, 1,3-bis [4- (4-amino-6-cyanophenoxy)-
α, α-dimethylbenzyl] benzene 57.88 g
(0.1 mol), N, N-dimethylacetamide 318.8
g, and under a nitrogen atmosphere, 21.81 g (0.1 mol) of pyromellitic dianhydride were added in portions while paying attention to the rise in solution temperature, and the mixture was stirred at room temperature for about 30 hours. The logarithmic viscosity of the polyamic acid thus obtained is 0.8.
It was 7 dl / g. Take a part of this polyamic acid,
After casting on glass plate, 100 ℃, 200 ℃, 30 ℃
Each was heated at 0 ° C. for 1 hour to obtain a polyimide film.

The glass transition temperature (Tg) of this polyimide film is 228 ° C., the crystallization temperature (Tc) is 286 ° C.,
Melting point (Tm) was 384 ° C. The film had a tensile strength of 8.71 kg / mm ² and a tensile modulus of 24.
It was 8 kg / mm ² and the elongation was 5.3% (the measuring method was based on ASTM D-822).

Examples 4 and 5 Various polyimide powders were obtained in exactly the same manner as in Example 1 using the diamine components and acid anhydride components as shown in Table 1. Table 1 shows logarithmic viscosity, glass transition temperature (Tg),
The melt flow start temperature and melt viscosity of the polyimide powder are also shown. In this embodiment, the crystallization temperature (T
c), no melting point (Tm) was observed.

[0050]

[Table 1]

Examples 6 and 7 In the same manner as in Example 3 , various polyimide films were obtained using the diamine component and the acid anhydride component as shown in Table 2. Table 2 also shows the logarithmic viscosity of the polyamic acid, the glass transition temperature (Tg), the tensile strength (TS), the tensile modulus (TM), and the elongation (EL) of the polyimide film. In this embodiment, the crystallization temperature (T
c), no melting point (Tm) was observed.

[0052]

[Table 2]

[0053]

The polyimide of the present invention comprises 1,3-bis [4- (4
-Amino-6-cyanophenoxy) -α, α-dimethylbenzyl] benzene as an aromatic diamine component, and has excellent processability and heat resistance. This polyimide has the same heat resistance as the conventional polyimide, but also has good thermoplasticity and good moldability, so it is industrially particularly useful in the field of molding materials, and in the field of electric and
It can be greatly expected to be used in the field of electronic materials.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of a polyimide powder obtained in Example 1 of the present invention.

FIG. 2 shows the results of measuring the relationship between the residence time of a polyimide powder obtained in Examples 1 and 2 in a cylinder of a flow tester and a change in melt viscosity.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Examiner, Mitsui Toatsu Chemicals Co., Ltd. Tamotsu Fujimoto (58) Field surveyed (Int.Cl. ⁷ , DB name) C08G 73/10 CA (STN)

Claims (17)

(57) [Claims] 1. A compound represented by the general 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 are directly or mutually linked by a bridge member. A tetravalent group selected from the group consisting of non-fused polycyclic aromatic groups). 2. A compound represented by the general 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 are directly or mutually linked by a bridge member. Represents a tetravalent group selected from the group consisting of non-condensed polycyclic aromatic groups), and whether the terminal of the polymer molecule has essentially no substituent, Alternatively, a polyimide which is an aromatic ring substituted with a group having no reactivity with an amine or dicarboxylic anhydride. 3. A compound of the general formula (1) 3. The polyimide according to claim 1, wherein R is a benzene ring in the polyimide having a repeating structural unit represented by the formula: 4. The following formula (2), which is a precursor of a polyimide having a repeating structural unit represented by the formula (1): (Wherein R is the same as described above).
After dissolving in N, N-dimethylacetamide at a concentration of 0.5 g / dl, the value of the logarithmic viscosity measured at 35 ° C. is 0.
The polyimide according to claim 1, 2 or 3, wherein the amount is from 01 to 3.0 dl / g. 5. A mixed solvent of 0.5 g of a polyimide having a repeating structural unit represented by the formula (1) and 9 parts by weight of p-chlorophenol and 1 part by weight of phenol.
The value of the logarithmic viscosity measured at 35 ° C. after dissolution is 0.01 to 3.0 dl / g.
The polyimide as described. 6. A compound of the formula (3) And an aromatic diamine represented by general formula (4)
(Chemical formula 6) (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 are directly or mutually linked by a bridge member. A tetravalent dianhydride selected from the group consisting of non-condensed polycyclic aromatic groups), and thermally or chemically imidizing the resulting polyamic acid. The method for producing a polyimide according to claim 1, wherein 7. A compound of the formula (3) And an aromatic diamine represented by general formula (4)
(Formula 8) (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 are directly or mutually linked by a bridge member. A tetravalent dianhydride selected from the group consisting of non-condensed polycyclic aromatic groups) represented by the formula (5): (In the formula, Z ₁ is an aliphatic group having 6 to 15 carbon atoms, a cyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group connected directly or by a crosslinking member. Represents a divalent group selected from the group consisting of a non-fused polycyclic aromatic group), is reacted in the presence of an aromatic dicarboxylic anhydride represented by
The method for producing a polyimide according to claim 2, wherein the obtained polyamic acid is thermally or chemically imidized. 8. A compound of the formula (3) And an aromatic diamine represented by general formula (4)
(Formula 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 are directly or mutually linked by a bridge member. A tetracarboxylic dianhydride represented by the following formula (6): Z ₂ —NH ₂ (6) , Z ₂ represent an aliphatic group having 6 to 15 carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-cyclic group in which aromatic groups are connected to each other directly or by a bridge member. A monovalent group selected from the group consisting of condensed polycyclic aromatic groups), and thermally or chemically imidizing the resulting polyamic acid. The method for producing a polyimide according to claim 2, wherein: 9. A compound of the general formula (1) The method for producing a polyimide according to claim 6 , wherein R is a benzene ring in the polyimide having a repeating structural unit represented by the formula: 10. The process for producing a polyimide according to claim 7 , wherein the aromatic dicarboxylic anhydride is phthalic anhydride. 11. The method for producing a polyimide according to claim 8 , wherein the aromatic monoamine is aniline. 12. The amount of the aromatic dicarboxylic anhydride used is:
0.1 mole per 1 mole of the aromatic diamine represented by the formula (3).
The method for producing a polyimide according to claim 7 , wherein the ratio is from 001 to 1.0 mol. 13. The amount of phthalic anhydride to be used ranges from 0.001 to 1 mol per mol of the aromatic diamine represented by the formula (3).
The method for producing a polyimide according to claim 10 , wherein the proportion is 0 mol. 14. The use amount of the aromatic monoamine is represented by the formula (4)
0.1 mol per mol of the tetracarboxylic anhydride represented by
The method for producing a polyimide according to claim 8 , wherein the ratio is from 001 to 1.0 mol. 15. The amount of aniline used is 0.001 to 1 mol per mol of the tetracarboxylic anhydride represented by the formula (4).
The method for producing a polyimide according to claim 11 , wherein the ratio is 1.0 mol. 16. A composition containing the polyimide according to claim 1 or 2. 17. A polyimide film containing the polyimide according to claim 1.