JPH05320339A - Polyimide having excellent thermal stability and its production - Google Patents

Abstract

PURPOSE:To obtain a polyamide having excellent thermal stability, especially stability to thermal-oxidative stability and improved moldability and processability by reacting a specific diaminobenzene with a specific tetracarboxylic acid anhydride in the presence of an aromatic dicarboxylic acid anhydride. CONSTITUTION:1mol diaminobenzene of formula I (R is H, 1-3C alkyl, etc.) (e.g. p-phenylenediamine) is reacted with 0.8-1 mol tetracarboxylic acid anhydride of formula II (C is CO, 0, etc.) [e.g. 4,4'-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride] in the presence of 0.3-3 times 2Xm mol aromatic dicarboxylic acid anhydride of formula III (Z is bifunctional group such as 1-6C monocyclic aromatic group or condensed polycyclic aromatic group) (preferably phthalic anhydride) when difference in the number of mols between the compound of formula I and the compound of formula II is m to give the objective polymer having a repeating unit of formula IV, containing polymer ends hindered with the compound of formula III.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a melt-molding polyimide having excellent thermal stability. More specifically, heat resistance, thermal stability, especially thermal oxidation stability, dimensional stability, excellent in mechanical strength, also excellent in moldability polyimide and its manufacturing method, and a resin composition containing these polyimide as a main component. And a heat resistant polyimide film.

[0002]

2. Description of the Related Art Conventionally, a polyimide obtained by the reaction of a tetracarboxylic dianhydride and a diamine has not only high heat resistance but also excellent mechanical strength and dimensional stability, flame retardancy, electrical insulation and the like. It is used in the fields of electrical and electronic equipment, aerospace equipment, transportation equipment, etc. to have both performances, and is expected to be widely used in the fields where heat resistance is required in the future.

Many of the polyimides developed so far have excellent properties, but they have excellent heat resistance but poor workability, and resins developed for the purpose of improving workability have heat resistance, There are merits and demerits in performance, such as poor solvent resistance. For example, formula (7)

[0004]

[Chemical formula 12] Polyimide consisting of a basic skeleton represented by (DuPont: trade name Kapton, Vespel) does not have a clear glass transition temperature and is a polyimide with excellent heat resistance, but when used as a molding material It is difficult to work and must be processed using a technique such as sinter molding. Further, when used as a material for electric / electronic parts, it has a property of high moisture absorption which affects dimensional stability, insulation and solder heat resistance. In addition, formula (8) [Chemical formula 13]

[0005]

[Chemical 13] Polyetherimide having a basic skeleton as represented by (General Electric Co .: trade name Ultem) is
Although it is a resin with excellent processability, it has a glass transition temperature of 216
It is as low as ℃ and soluble in halogenated hydrocarbons such as methylene chloride, so it is not a satisfactory resin in terms of heat resistance and solvent resistance. Furthermore, the following formula (9) [Chemical formula 14] recently found by General Electric Co.

[0006]

[Chemical 14] The fused crystalline polyimide containing a repeating unit structure represented by the formula (wherein R ₁ is a residue of a linear aromatic diamine) (JP-A-3-68629) has a glass transition temperature of 2
The temperature is 25 ° C or higher, which is an improvement over the Ultem of the above formula (8), but since the end capping is incomplete, heat resistance, especially thermal oxidation stability, etc. remains a problem, and if it is kept at high temperature for a long time (For example, during injection molding, if the material is allowed to stay in the cylinder at a high temperature for a long time, etc.), the fluidity gradually decreases, and the moldability decreases.

[0007]

DISCLOSURE OF THE INVENTION The object of the present invention is that, in addition to the excellent properties inherent to polyimide, it also has good thermal stability, especially thermal oxidative stability, and is moldable even when kept at high temperature for a long time. It is to provide an excellent polyimide that does not deteriorate.

[0008]

[Means for Solving the Problems] The present inventors completed the present invention by conducting intensive research to solve the above problems. That is, the present invention provides a compound represented by the general formula (2)

[0009]

[Chemical 15] (In the formula, X is a direct bond, -CO-, -O-, -S-,-.
SO ₂ —, R is —H, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, —F, —Cl, —B.
Indicates r. ) Is a polyimide having a repeating unit structure represented by the formula) as a basic skeleton, and the molecular end of the polyimide is represented by the general formula (1)

[0010]

[Chemical 16] (In the formula, Z is a monocyclic aromatic group having 6 to 15 carbon atoms or a condensed polycyclic ring, which has essentially no substituent or is substituted with a group having no reactivity with an amine or a dicarboxylic acid anhydride. Aromatic dicarboxylic acid represented by the formula: Aromatic group, divalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are directly or cross-linked by a crosslinking member. Anhydrous or general formula (3)

[0011]

Embedded image Y—NH ₂ (3) (In the formula, Y has 6 to 15 carbon atoms, which has essentially no substituent or is substituted with a group having no reactivity with amine or dicarboxylic acid anhydride. A monovalent group selected from the group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which aromatic groups are linked to each other directly or by a bridging member. And a method for producing the same, which is sealed with an aromatic monoamine and has good thermal stability. More specifically, the general formula (4)

[0012]

[Chemical 18] (Wherein R is the same as above), and the diaminobenzenes represented by the general formula (5) [Chem.

[0013]

[Chemical 19] (Wherein X is the same as above), when the difference in the number of moles between the diamine compound and the tetracarboxylic acid dianhydride is m, 2 × m is 0. 0.5 to 3.0 times amount of formula (1)

[0014]

[Chemical 20] (Wherein Z is the same as above), and the above formula (2) is obtained by reacting in the presence of an aromatic dicarboxylic acid anhydride.
The polyimide having good thermal stability represented by the formula, a method for producing the same, and the general formula (5)

[0015]

[Chemical 21] (In the formula, X is the same as above.), And a general formula (4) [of a tetracarboxylic acid dianhydride of 0.8 to 1.0 mol ratio per 1 mol of the tetracarboxylic acid dianhydride]. 22]

[0016]

[Chemical formula 22] (Wherein R is the same as above), when the difference in mole between the tetracarboxylic dianhydride and the diamine is n, 2 × n of 0.5 to 3 .0
Double amount of formula (3)

[0017]

Embedded image Y—NH ₂ (3) (wherein Y is the same as described above), which is obtained by reacting in the presence of an aromatic monoamine represented by the above formula (2). It is a good polyimide and its manufacturing method. That is, the polyimide of the present invention is characterized in that the molecular end of the polymer is completely sealed with an aromatic dicarboxylic acid anhydride or an aromatic monoamine, and the thermal stability is improved. The diamine compound used in the production method of the present invention has the formula (4)

[0018]

[Chemical formula 24] (In the formula, R is the same as above), specifically, p-phenylenediamine, m
-Phenylenediamine, o-phenylenediamine, methyl-phenyldiamines, ethyl-phenyldiamines, propyl-phenyldiamines, isopropyl-phenyldiamines, methoxy-phenyldiamines, ethoxy-phenyldiamines, propoxy-phenyldiamines , Isopropoxy-phenyldiamines, fluoro-phenyldiamines, chloro-phenyldiamines, and bromo-phenyldiamines, and these diamine compounds may be used alone or in combination of two or more kinds. Further, although the above-mentioned aromatic diaminobenzenes are used as an essential monomer raw material in the polyimide of the present invention, other aromatic diamines can be mixed and used within a range that does not impair the good physical properties.

Examples of diamines that can be mixed and used include 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, and 2,4 '. -Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone,
2,3'-diaminobenzophenone, 2,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, m-aminobenzylamine, p-aminobenzylamine, bis (3
-Aminophenyl) sulfide, (3-aminophenyl) (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) Sulfoxide, bis (4-aminophenoxy) sulfoxide, bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenoxy) sulfone, 4,4 ′
-Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis [4
-(3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 1,
1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] Ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 2,2-bis [4- (3
-Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane,
2,2-bis [4- (3-aminophenoxy) phenyl]
Butane, 2,2-bis [4- (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] diphenyl sulfone,
Bis [4- {4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethyl] benzene, 1,3-bis [4-
(4-aminophenoxy) -α, α-dimethyl] benzene and the like can be mentioned, and these can be used alone or in admixture of two or more. The tetracarboxylic dianhydride used in the production method of the present invention has the formula (5)

[0020]

[Chemical 25] (X in the formula is the same as above.), Specifically, 4,4'-bis (3,4-
Dicarboxyphenoxy) biphenyl dianhydride, 4,4'-
Bis (3,4-dicarboxyphenoxy) benzophenone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl ether dianhydride, 4,4′-bis (3,3
4-dicarboxyphenoxy) diphenyl sulfide dianhydride and 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride, and these tetracarboxylic acid dianhydrides may be used alone or You may mix and use a kind or more.

Further, although the polyimide of the present invention uses the aromatic tetracarboxylic dianhydride represented by the above formula (5) as an essential monomer raw material, other aromatic tetracarboxylic acid dianhydrides can be used as long as the good physical properties are not impaired. It is also possible to use a mixture of carboxylic acid dianhydrides. The tetracarboxylic dianhydride that can be used as a mixture, for example, ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, 2, 2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride Substance, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2'-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2'-bis (2,3 -Dicarboxyphenyl) propane dianhydride, 2,2'-bis (3,4
-Dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2'-bis (2,3-dicarboxyphenyl) -1,1,1,3,3 , 3-Hexafluoropropane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) Sulfone dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane Dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 4,4 '-(p-phenylenedioxy) diphthalic dianhydride, 4,4'-(m-
(Phenylenedioxy) diphthalic 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-anthracene tetra Examples thereof include carboxylic acid dianhydride and 1,2,7,8-phenanthrenetetracarboxylic acid dianhydride. These may be used alone or in admixture of two or more. The method of the present invention comprises the steps of reacting a diamine compound of the formula (1)

[0022]

[Chemical formula 26] (Wherein Z is as described above), or an aromatic dicarboxylic acid dianhydride represented by the formula (3)

[0023]

Embedded image An aromatic monoamine represented by Y—NH ₂ (3) (wherein Y is as described above) is present.

The aromatic dicarboxylic acid anhydride represented by the formula (1) is preferably phthalic anhydride, and the dicarboxylic acid anhydride which can be substituted with phthalic anhydride is, for example, 2,3-benzophenone. Dicarboxylic acid anhydride, 3,4-benzophenone dicarboxylic acid anhydride, 2,3-dicarboxyphenylphenyl ether acid anhydride, 3,4-dicarboxyphenylphenyl ether acid anhydride, 2,3-biphenylcarboxylic acid anhydride , 3,4-biphenylcarboxylic acid anhydride, 2,3-
Dicarboxyphenyl phenyl sulfone anhydride, 3,4-dicarboxyphenyl phenyl sulfone anhydride, 2,3-dicarboxyphenyl phenyl sulfide anhydride, 3,4-dicarboxyphenyl phenyl sulfide anhydride, 1,2-naphthalenedicarboxylic Acid anhydride, 2,3-naphthalene dicarboxylic acid anhydride, 1,8-naphthalene dicarboxylic acid anhydride, 1,2-anthracene dicarboxylic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, 1,9-anthracene dicarboxylic acid Examples thereof include acid anhydrides, which may be used alone or in combination of two or more. These aromatic dicarboxylic acid anhydrides may be substituted with groups that are not reactive with amines or dicarboxylic acid anhydrides.

Further, the aromatic monoamine represented by the formula (3) is preferably aniline, and the monoamines which can be substituted for aniline are, for example, o-toluidine, m-toluidine, p-toluidine, 2, 3-xylidine, 2,6-xylidine, 3,4-xylidine, 3,
5-xylidine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-
Bromoaniline, p-bromoaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline, o-
Aminophenol, m-aminophenol, p-aminophenol, o-anisidine, m-anisidine, p-anisidine, o-phenidine, m-phenidine, p-phenidine, 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-aminophenyl phenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-
Aminobenzophenone, 2-aminophenylphenyl sulfide, 3-aminophenylphenyl sulfide, 4
-Aminophenyl phenyl sulfide, 2-aminophenyl phenyl sulfone, 3-aminophenyl phenyl sulfone, 4-aminophenyl phenyl 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 can be mentioned. May be used alone or in combination of two or more. These aromatic monoamines can be substituted with groups that are not reactive with amines or dicarboxylic acid anhydrides.

The molar ratio of the diamine compound and the tetracarboxylic dianhydride used in the method of the present invention is 1 mol of the diamine compound represented by the formula (4) when sealed with an aromatic dicarboxylic acid anhydride. Therefore, when the tetracarboxylic dianhydride represented by the formula (5) is sealed with an aromatic diamine in a molar ratio of 0.8 to 1.0, the tetracarboxylic dianhydride represented by the formula (5) is used. The ratio is 0.8 to 1.0 mole ratio of the diamine compound represented by the formula (4) per mole. However, from the viewpoint of the balance between thermal oxidation stability and molding processability of the obtained polyimide, both are preferably 0.90 to 0.99.
It is a molar ratio.

Further, the formula (1) used in the present invention
The amount of the dicarboxylic acid anhydride represented by or the amount of the monoamine represented by the formula (3) is the same as that of the diamine compound and the tetracarboxylic dianhydride per 1 mol of the diamine compound represented by the formula (4). 2m, where m is the difference in the number of moles of
0.5 to 3.0 times the amount of the above, the latter is the difference in the number of moles of the tetracarboxylic acid dianhydride and the diamine compound per mole of the tetracarboxylic acid dianhydride represented by the formula (5). n
Is 0.5 to 3.0 times the amount of 2n. In both cases, when 2m or 2n is less than 0.5 times, the viscosity at the time of high temperature molding is increased, which causes deterioration of molding processability. On the other hand, if the amount exceeds 3.0 times, the mechanical properties will deteriorate. The preferred amount used is 1.0 to 1.5 times.

In the method of the present invention, the reaction medium is not particularly limited, but it is particularly preferable to carry out the reaction in an organic solvent. Examples of the organic solvent used in this reaction include N,
N-dimethylformamide, N, N-dimethylacetamide,
N, N-diethylacetamide, N, N-dimethylethoxyacetamide, 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, tetramethylurea, hexamethylphosphoramide, phenol, o-cresol, m-cresol, p
-Cresol, m-cresylic acid, p-chlorophenol, anisole, benzene, toluene, xylene and the like. You may use these individually or in mixture of 2 or more types.

In the organic solvent according to the method of the present invention, a compound represented by the general formula (4)
A diamine compound represented by formula (1), a tetracarboxylic dianhydride represented by formula (5), a dicarboxylic acid anhydride represented by formula (1), or a monoamine represented by formula (3) is added. As a method of reacting, for example, (a)
After reacting a tetracarboxylic dianhydride and a diamine, a method of continuing the reaction by adding a dicarboxylic acid anhydride, or a monoamine, (b) after reacting by adding a dicarboxylic acid anhydride, or a monoamine to the diamine, A method of adding tetracarboxylic dianhydride and continuing the reaction,
(C) A method in which tetracarboxylic dianhydride, diamine, dicarboxylic acid anhydride, or 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 can be carried out at normal pressure. The reaction time varies depending on the type of diamine compound and the reaction temperature, and usually 4 to 24 hours is sufficient.

Further, the obtained polyamic acid is added to 100 to 400
A polyimide corresponding to a polyamic acid can be obtained by heating at 0 ° C. for imidization or by chemical imidization using an imidizing agent such as acetic anhydride. Also, tetracarboxylic dianhydride and diamine, dicarboxylic acid anhydride,
Alternatively, it is also possible to obtain a polyimide by suspending or dissolving a monoamine in an organic solvent and then heating the mixture to perform imidization at the same time as the generation of a polyamic acid as a precursor of the polyimide. That is, a conventionally known method can be used to obtain a film-shaped or powder-shaped polyimide.

The polyimide of the present invention is obtained by using each raw material as described above, obtaining a polyamic acid by the above reaction method and reaction conditions, and then imidizing the polyamic acid. A certain polyamic acid is, for example, N, N-dimethylacetamide as a solvent,
Concentration 0.5 g / 100 ml, logarithmic viscosity of 0.01 measured at 35 ℃
~ 3.0 dl / g. Furthermore, the logarithmic viscosity of the finally obtained polyimide powder was 0.5 g / 100 m in a mixed solvent of 9 parts by weight of p-chlorophenol and 1 part by weight of phenol.
Melt at a concentration of 1 and measure at 35 ℃, 0.01-3.0 dl
/ G.

The polyimide of the present invention obtained by the above-mentioned production method, when subjected to melt molding, is not limited to other thermoplastic resins such as polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, as long as the object of the present invention is not impaired. Polysulfones, polyether sulfones, polyether ketones, polyether ether ketones, polyphenylene sulfides, polyamideimides, polyetherimides, modified polyphenylene oxides, polyimides other than the present invention and the like can be blended in appropriate amounts according to the purpose.

The following fillers used in ordinary resin compositions such as graphite, carborundum,
Abrasion resistance improver such as silica powder, molybdenum disulfide, fluororesin, glass fiber, carbon fiber, boron fiber, silicon carbide fiber, carbon whiskers, asbestos, metal fiber, ceramic fiber and other reinforcing materials, antimony trioxide, carbonic acid Flame retardant improver such as magnesium, electrical property improver such as clay and mica, tracking resistance improver such as asbestos, silica and graphite, acid resistance improver such as barium sulfate, silica and calcium metasilicate, iron powder, Zinc powder, aluminum powder, thermal conductivity improver such as copper powder, other glass beads, glass spheres, talc, diatomaceous earth, alumina, silas balun, hydrated alumina, metal oxides, colorants, etc. You may use it in the range which does not exist.

The polyimide of the present invention may be in the form of fibers in addition to various molding materials and films.
Further, it is also used as a composite material in which a polyimide of the present invention is impregnated into a fiber cloth made of fibers such as carbon fiber. Further, it is also used as a substrate for a copper clad circuit coated with a metal foil such as copper or a metal plate, and can be used in a wide variety of applications.

[0035]

EXAMPLES The present invention will be described in detail below with reference to examples. The physical properties of the polyimide in the examples were measured by the following methods. Tg, Tc, Tm; DSC (Shimadzu DT-40 series,
Measured by DSC-41M). Melt viscosity; Shimadzu Koka type flow tester (CFT500
Measured with a load of 100 kg according to A). Logarithmic viscosity; polyamic acid in N, N-dimethylacetamide, polyimide in p-chlorophenol / phenol (weight ratio 9/1) mixed solvent, 0.5 g / 10 each
After dissolution at a concentration of 0 ml, measurement was performed at 35 ° C.

Example 1 10.82 g of m-phenylenediamine was placed in a container equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen introducing tube.
(0.1 mol), 4,4'-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride 45.93 g (0.09)
6 mol), phthalic anhydride 1.19 g (0.008 mol), γ-picoline 1.40 g, m-cresol 22
7.0 g was charged and the temperature was raised to 150 ° C. with stirring under a nitrogen atmosphere. Then, when the reaction was carried out at 150 ° C. for 4 hours, it was confirmed that about 3.5 ml of water was distilled off.

After the reaction is completed, the temperature is cooled to room temperature and about 2.0 L is obtained.
After discharging into the methyl ethyl ketone, the polyimide powder was filtered off. After washing this polyimide powder with methyl ethyl ketone, it was heated in air at 50 ° C for 24 hours and then in nitrogen at 250 ° C for 4 hours.
After drying for 53 hours, 53.77 g (yield 99.0%) of polyimide powder was obtained. The polyimide powder thus obtained had an inherent viscosity of 0.53 dl / g. The glass transition temperature of this polyimide powder was 235 ° C.

The infrared absorption spectrum of this polyimide powder is shown in FIG. From this spectrum diagram, the absorptions near the imide characteristic absorption bands 1780 and 1720 cm ⁻¹ were remarkably observed. The elemental analysis values of this polyimide were as follows. Elemental analysis value C H N Calculated value 74.17 3.30 5.09 Analytical value 73.91 3.36 5.14 Further, the molding stability of the obtained polyimide was evaluated by using a high flow tester of 100 kg. Load and diameter 0.1
The measurement was performed using an orifice having a cm and a length of 1 cm. 35
The results of measurement at 0 ° C. while changing the residence time in the cylinder are shown in FIG. It can be seen that the melt viscosity hardly changes even when the residence time in the cylinder becomes long, and the molding processing stability is good. Further, the thermal oxidative stability of the polyimide powder obtained in this example was measured from its weight loss rate while changing the holding time in air at 350 ° C. The result is shown in Figure 3.
Shown in.

Example 2 In a reactor similar to Example 1, 4,4'-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride 47.84
g (0.1 mol), m-phenylenediamine 10.38
g (0.096 mol), aniline 0.75 g (0.00
8 mol), γ-picoline 1.40 g, m-cresol 2
32.9 g was charged, and the temperature was raised to 150 ° C. with stirring under a nitrogen atmosphere. After reacting for 4 hours, it was confirmed that about 3.5 ml of water was distilled during this period.

After completion of the reaction, the mixture was cooled to room temperature, discharged into about 2.0 L of methyl ethyl ketone, and then the polyimide powder was filtered off. The polyimide powder was washed with methyl ethyl ketone and then dried in air at 50 ° C. for 24 hours and in nitrogen at 250 ° C. for 4 hours to obtain 53.48 g (yield 96.6%) of polyimide powder. The polyimide thus obtained had an inherent viscosity of 0.51 dl / g and a glass transition temperature of 233 ° C. The infrared absorption spectrum of this polyimide powder is shown in FIG. From this spectrum diagram, the absorptions near 1780 and 1720 cm ^-1, which are the imide characteristic absorption bands, were remarkably observed. Further, with respect to the present polyimide powder, the molding processing stability and the thermal oxidation stability were measured in the same manner as in Example 1.
The results are shown in FIGS. 2 and 3 together with the results of Example 1.

Comparative Example 1 In a reactor similar to Example 1, 50 g of 4,4'-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride was added.
(0.105 mol), m-phenylenediamine 11.8
2 g (0.109 mol), phthalic anhydride 0.62 g
(0.00419 mol), sodium phenylphosphinate 0.010 g, o-dichlorobenzene 300 m
1 of which is charged and stirred under a nitrogen atmosphere at 150
The temperature was raised to 0 ° C., and then the mixture was reacted at 150 ° C. for 4 hours.
The polyimide powder after the reaction was filtered, washed and dried in the same manner as in Example 1. The polyimide powder thus obtained had an inherent viscosity of 0.46 dl / g and a glass transition temperature of 233 ° C.

Example 1 of the polyimide powder of this comparative example
The molding processing stability and the thermal oxidation stability were measured in the same manner as in. The results are shown in FIGS. 2 and 3 together with the results of Example 1. From the results of FIG. 2, it is found that the melt viscosity increases as the residence time becomes longer, so that the molding processing stability is inferior to the polyimides obtained in Examples 1 and 2, and the results of FIG. It can be seen from the results that the weight reduction rate increases as the holding time becomes longer, and thus the thermal oxidation stability is poorer than that of the polyimides obtained in Examples 1 and 2.

Comparative Example 2 A polyimide powder was obtained in exactly the same manner as in Example 1 except that phthalic anhydride was not used. The polyimide powder had an inherent viscosity of 0.52 dl / g and a glass transition temperature of 232 ° C.

Example 1 of the polyimide powder of this comparative example
The molding processing stability and the thermal oxidation stability were measured in the same manner as in. The results are shown in FIGS. 2 and 3 together with the results of Example 1. From the results of FIG. 2, it is found that the melt viscosity increases as the residence time becomes longer, so that the molding processing stability is inferior to the polyimides obtained in Examples 1 and 2, and the results of FIG. It can be seen from the results that the weight reduction rate increases as the holding time becomes longer, and thus the thermal oxidation stability is poorer than that of the polyimides obtained in Examples 1 and 2.

Examples 3 to 10 Comparative Examples 3 to 5 Polyimide powder was obtained in the same manner as in Example 1, except that the acid anhydride component, the diamine component and the terminal blocking agent were changed as shown in Table 1. Molding stability and thermal oxidation stability of each polyimide were examined in the same manner as in Example 1, and the results are shown in FIG.
Table 1 also shows logarithmic viscosity, glass transition temperature, and presence / absence of thickening. Furthermore, the infrared absorption spectrum of the polyimide powder of Example 5 is also shown.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

EFFECT OF THE INVENTION The polyimide obtained according to the present invention is excellent in melt fluidity as compared with the conventionally known polyimide and has greatly improved molding processability. Further, since it has excellent thermal oxidative stability, it is a useful material for electric / electronic parts, automobile parts, and precision machine parts that require heat resistance. That is, the present invention is extremely useful industrially.

[Brief description of drawings]

1 is an infrared absorption spectrum diagram of the polyimide powder obtained in Example 1. FIG.

FIG. 2 compares the molding stability of the polyimide powders obtained in Examples 1 and 2 with that of the polyimide powders obtained in Comparative Examples 1 and 2 at a temperature of 400 ° C., a load of 100 kg, and a residence time in a cylinder of a flow tester. The results of measurement with different values are shown.

FIG. 3 shows the thermal oxidative stability of the polyimide powders obtained in Examples 1 and 2 as compared with the polyimide powders obtained in Comparative Examples 1 and 2 at 350 ° C. and weight reduction by changing the holding time in air. It is a figure which shows the result of having measured the rate.

4 is an infrared absorption spectrum diagram of the polyimide powder obtained in Example 2. FIG.

5 compares the molding stability of the polyimide powders obtained in Examples 3 and 4 with that of the polyimide powder obtained in Comparative Example 3, and changes the residence time in the cylinder of the flow tester at a temperature of 400 ° C. and a load of 100 kg. The results of measurement are shown below.

FIG. 6 compares the thermo-oxidative stability of the polyimide powders obtained in Examples 3 and 4 with that of the polyimide powder obtained in Comparative Example 3 at 350 ° C. and the holding time in air to change the weight loss rate. It is a figure which shows the measured result.

FIG. 7 is a comparison of the molding stability of the polyimide powders obtained in Examples 5 and 6 with that of the polyimide powder obtained in Comparative Example 4, and the residence time in the cylinder of the flow tester was changed at a temperature of 400 ° C. and a load of 100 kg. The results of measurement are shown below.

FIG. 8 shows the thermal oxidation stability of the polyimide powders obtained in Examples 5 and 6 as compared with the polyimide powder obtained in Comparative Example 4 at 350 ° C. and the holding time in air to change the weight loss rate. It is a figure which shows the measured result.

9 compares the molding stability of the polyimide powders obtained in Examples 7 and 8 with the polyimide powder obtained in Comparative Example 5, and changes the residence time in the cylinder of the flow tester at a temperature of 400 ° C. and a load of 100 kg. The results of measurement are shown below.

FIG. 10 compares the thermo-oxidative stability of the polyimide powders obtained in Examples 7 and 8 with the polyimide powder obtained in Comparative Example 5 at 350 ° C. and the holding time in air to change the weight loss rate. It is a figure which shows the measured result.

11 is an infrared absorption spectrum diagram of the polyimide powder obtained in Example 5. FIG.

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

Claims (10)

[Claims] 1. A polymer molecule having a terminal represented by the general formula (1) [Chemical Formula 1] (In the formula, Z is a monocyclic aromatic group having 6 to 15 carbon atoms or a condensed polycyclic ring, which has essentially no substituent or is substituted with a group having no reactivity with an amine or a dicarboxylic acid anhydride. Aromatic dicarboxylic acid represented by the formula: Aromatic group, divalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which aromatic groups are directly or cross-linked by a crosslinking member. General formula (2) [Chemical Formula 2], which is sealed with an anhydride, (In the formula, X is a direct bond, -CO-, -O-, -S-,-.
SO ₂ —, R is —H, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, —F, —Cl, —B.
Indicates r. ) A polyimide having good thermal stability and having a repeating structural unit represented by 2. The polymer terminal has a general formula (3):
[Chemical Formula 3] Y-NH ₂ (3) (wherein Y is a carbon which has essentially no substituent or is substituted with a group having no reactivity with an amine or a dicarboxylic acid anhydride). 1 selected from the group consisting of monocyclic aromatic groups of the formulas 6 to 15, condensed polycyclic aromatic groups, and non-condensed polycyclic aromatic groups in which aromatic groups are connected to each other directly or by a bridging member. (Showing a valent group), which is sealed with an aromatic monoamine represented by the general formula (2) [Chemical Formula 4] A polyimide having a repeating structural unit represented by the formula (X and R are the same as above) and having good thermal stability. 3. A polyimide having good thermal stability according to claim 1, wherein the aromatic dicarboxylic acid anhydride is phthalic anhydride. 4. The polyimide having good thermal stability according to claim 2, wherein the aromatic monoamine is aniline. 5. A compound represented by the general formula (4): [Chemical Formula 5] (In the formula, R represents —H, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, —F, —Cl, and —Br), and the diamine. 0.8 to 1.0 mol ratio of the formula (5) per mol of the compound
[Chemical Formula 6] [Chemical Formula 6] When the tetracarboxylic dianhydride represented by the formula (X is the same as above) is the difference in the number of moles between the diamine compound and the tetracarboxylic dianhydride, m is 2 × m. 0.5 to 3.0 times the amount of the formula (1) [Chemical formula 7] The method for producing a polyimide having good thermal stability according to claim 1, which is obtained by reacting in the presence of an aromatic dicarboxylic acid anhydride represented by the formula (Z is the same as above). 6. General formula (5) [Chemical formula 8] [Chemical formula 8] (In the formula, X is the same as above.), And a formula (4) [of a molar ratio of 0.8 to 1.0 per 1 mol of this tetracarboxylic dianhydride]. [Chemical 9] [Chemical 9] (Wherein R is the same as above), when the difference in the number of moles of the tetracarboxylic dianhydride and the diamine is n, 2 × n of 0.5 to 3.
It is obtained by reacting in the presence of an aromatic monoamine represented by the formula (3) [Chemical formula 10] Y-NH ₂ (3) (wherein Y is the same as above) in an amount 0 times. The method for producing a polyimide having good thermal stability according to claim 2. 7. A compound represented by the following formula (6), which is a precursor of a polyimide having a repeating unit structure represented by the formula (2):
1] (Wherein X and R are the same as above), the polyamic acid was dissolved in dimethylacetamide at a concentration of 0.5 g / dl, and then the logarithmic viscosity measured at 35 ° C. was 0.01 to 3. The polyimide having good thermal stability according to claim 1 or 2, having a content of 0.0 dl / g. 8. A mixed solvent of 9 parts by weight of p-chlorophenol and 1 part by weight of phenol is added with 0.5 g of a polyimide having a repeating unit structure represented by the formula (2) in an amount of 100 m.
The polyimide having good heat stability according to claim 1 or 2, wherein the polyimide has a logarithmic viscosity value of 0.01 to 3.0 dl / g measured at 35 ° C after dissolution in 1. 9. A composition containing the polyimide according to claim 1 or 2. 10. A heat-resistant polyimide film containing the polyimide according to claim 1.