JP3025071B2 - Polyimide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a novel thermoplastic polyimide. More specifically, the present invention relates to a novel polyimide having excellent moldability.

[0002]

2. Description of the Related Art Polyimides are obtained by the reaction of tetracarboxylic dianhydride with diamines. Conventionally known polyimides have a high heat resistance characteristic of this polymer,
It has excellent mechanical strength and dimensional stability, and also has flame retardancy and electrical insulation. Therefore, these polyimides are used in the fields of electric and electronic equipment, etc., and are already widely used in fields where heat resistance is required. is there.

Hitherto, various polyimides exhibiting excellent characteristics have been developed. However, conventional polyimides do not have a clear glass transition temperature even if they have excellent heat resistance, so if they are used as a molding material, they must be processed using techniques such as sinter molding, In addition, they have excellent processability, but are soluble in halogenated hydrocarbon solvents and have problems in terms of solvent resistance and have advantages and disadvantages in performance. In recent years, polyimides which have improved the disadvantages of polyimides and have been given new performances have been provided with the aim of expanding the application fields of polyimides.

[0004]

An object of the present invention is to provide a novel thermoplastic polyimide having excellent processability and good chemical resistance in addition to the excellent heat resistance inherent to polyimide. is there.

[0005]

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. The present invention was found to be a novel thermoplastic polyimide having excellent moldability without any problems, and completed the present invention. That is, the present invention relates to a compound of the formula (2)

Embedded image And an aromatic diamine mainly composed of 2,7-bis (4-aminophenoxy) naphthalene represented by the following formula:

Embedded image (Wherein, R represents the general formula (4)

Embedded image And a tetravalent group selected from the group consisting of: ) Is reacted with an anhydride, and the resulting polyamic acid is thermally or chemically imidized to obtain a general formula (1) (formula 8)

Embedded image (Wherein, R represents the above-described group).

That is, the polyimide of the present invention is obtained by further dehydrating a polyamic acid obtained by polymerizing the diamine and the at least one aromatic tetracarboxylic dianhydride. Accordingly, the polyimide of the present invention uses the above 2,7-bis (4-aminophenoxy) naphthalene as an aromatic diamine as an essential monomer material, but other aromatic diamines within a range that does not impair the good physical properties of the polyimide. May be used in combination.

As diamines which can be used in combination, 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, (3-aminophenyl) (4-aminophenyl) sulfide, bis (4-
Aminophenyl) sulfide, bis (3-aminophenyl) sulfide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (3-aminophenyl)
Sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenyl) 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 [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
-(3-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] diphenylsulfone, 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. They are used alone or in combination of two or more.

The above-mentioned general formula (4) used in the present invention
As the tetracarboxylic dianhydride represented by, for example, ethylene tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetraanhydride Carboxylic 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) -1,1,1,1 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, 1,2,2
7,8-phenanthrenetetracarboxylic dianhydride and the like can be mentioned. These may be used alone or in combination of two or more.

In the production of polyimide, it is customary to control the ratio of tetracarboxylic dianhydride to aromatic diamine in order to control the molecular weight of the resulting polyimide. 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 0.9 to 1.0.
Range.

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 solution. 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-methylcaplactam, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxy Ethoxy) ethane, bis {2- (2-methoxyethoxy) ethyl} ether,
Tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyrroline, picoline, dimethylsulfoxide, dimethylsulfone, tetramethylurea, hexamethylphosphoramide, phenol, o-cresol, m-
Cresol, p-cresol, m-cresylic acid, p-
Chlorophenol, anisole and the like can be mentioned. Also,
These organic solvents may be used alone or in combination of two or more.

According to the method of the present invention, 2,7-bis (4-aminophenoxy) naphthalenetetracarboxylic dianhydride, aromatic dicarboxylic anhydride or aromatic monoamine is added to an organic solvent for reaction. ) Tetracarboxylic dianhydride and 2,7-bis (4
-Aminophenoxy) naphthalene, followed by addition of an aromatic dicarboxylic anhydride or an aromatic monoamine to continue the reaction; (b) 2,7-bis (4-aminophenoxy) naphthalene to aromatic dicarboxylic acid After reacting by adding an anhydride,
(C) reacting tetracarboxylic dianhydride with an aromatic monoamine and then adding 2,7-bis (4-aminophenoxy) naphthalene (D) tetracarboxylic dianhydride, 2,7-bis (4-
Examples thereof include a method of simultaneously adding and reacting (aminophenoxy) naphthalene, an aromatic dicarboxylic anhydride or an aromatic monoamine, and any addition method may be used.

The reaction temperature is usually not higher than 250 ° C., preferably not higher than 50 ° C. 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, the obtained polyamic acid is heated to 100 to 400 ° C. for imidization, or chemically imidized using an imidizing agent such as acetic anhydride to obtain a polyimide having a repeating unit corresponding to the polyamic acid. Can be Also, 2,7-bis (4-aminophenoxy) naphthalene and tetracarboxylic dianhydride,
Furthermore, when the terminal of the polyimide is an aromatic ring, an aromatic dicarboxylic anhydride or an aromatic monoamine is suspended or dissolved in an organic solvent, and then heated to produce a polyamic acid which is a precursor of the polyimide. Simultaneously, the target polyimide can be obtained by imidization. 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, and polyethersulfone may be used as long as the object of the present invention is not impaired. , Polyetherketone,
An appropriate amount of polyphenyl sulfide, polyamide imide, polyether imide, modified polyphenylene oxide or the like can be blended according to the purpose. In addition, the following fillers and the like used in ordinary resin compositions may be used to the extent that the object of the invention is not impaired. That is, graphite, carborundum, silica stone powder, molybdenum disulfide, abrasion resistance improver such as fluorine resin, glass fiber,
Reinforcing material such as carbon fiber, flame retardant improver such as antimony trioxide, magnesium carbonate, calcium carbonate, clay,
Electrical property improver such as mica, tracking resistance improver such as asbestos, silica, graphite, barium sulfate,
Acid resistance improvers such as silica and calcium metasilicate, thermal conductivity improvers such as iron powder, zinc powder, aluminum powder and copper powder, and other glass beads, glass spheres, talc, diatomaceous earth, alumina, silica balun, hydration Alumina, metal oxides, coloring agents and the like.

[0014]

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; (Shimadzu DT-40 series, DSC
-41M). 5% weight loss temperature: DTG (Shimadzu DT-40) in the air
Series, DTG-40-M). Melt viscosity: Shimadzu Koka type flow tester (CFT500
Measured with a load of 100 kg according to A). Example 1 In a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube,
2,7-bis (4-aminophenoxy) naphthalene 3
4.2 g (0.1 mol) and 375 g of N, N-dimethylacetamide were charged, and under nitrogen atmosphere,
31.88 g (0.099 mol) of 3 ', 4,4'-benzophenonetetracarboxylic dianhydride was added in portions, paying attention to the rise in solution temperature, and the mixture was stirred at room temperature for about 20 hours. The logarithmic viscosity of the polyamic acid thus obtained is 1.
It was 9 dl / g. Note that the logarithmic viscosity of polyamic acid is 0.5, using N, N-dimethylacetamide as a solvent.
g / 100 ml solution, measured at 35 ° C. A part of this polyamic acid solution was cast on a glass plate and heated at 100 ° C., 200 ° C., and 300 ° C. for 1 hour each to obtain a polyimide film having a thickness of about 50 μm. The tensile strength of this polyimide film is 15.2 kg / m
m ² , tensile modulus was 340 kg / mm ² , and tensile elongation was 45%.

Examples 2 to 4 Polyamic acids were polymerized in the same manner as in Example 1 using the tetracarboxylic dianhydrides shown in Table 1 in amounts shown in Table 1. Moreover, the corresponding polyimide films were obtained in the same manner as in Example 1 using these polyamic acid solutions. Table 1 shows the logarithmic viscosity of these polyamic acids and the dielectric constant of the obtained polyimide film.

[0016]

[Table 1]

[0017]

The polyimide of the present invention is a novel polyimide having excellent processability and heat resistance, characterized by using 1,7-bis (4-aminophenoxy) naphthalene as an aromatic diamine component. This polyimide is a thermoplastic polyimide with good moldability while having the same heat resistance as conventional polyimides. Among the polyimides in the present invention, there is a high elastic modulus and flexibility with excellent elongation. It also contains high-elasticity polyimide, which has excellent properties.

[Brief description of the drawings]

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

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

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemicals Co., Ltd. (56) References JP-A-2-279726 (JP, A) JP-A-64 -29431 (JP, A) JP-A-1-131240 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 73/10

Claims (1)

(57) [Claims] 1. A compound represented by the general formula (2): And an aromatic diamine mainly composed of 2,7-bis (4-aminophenoxy) naphthalene represented by the general formula (3): (Wherein, R represents the general formula (4)) And a tetravalent group selected from the group consisting of: )) Is reacted with an anhydride, and the resulting polyamic acid is thermally or chemically imidized to obtain a compound represented by the general formula (1). (Wherein R represents the above-mentioned group) A polyimide having a repeating structural unit represented by the following formula: