JPH0653797B2 - Aromatic polyimide resin - Google Patents

Description

TECHNICAL FIELD The present invention relates to an aromatic polyimide resin.

(Prior Art) Conventionally, aromatic polyimide resins have excellent heat resistance,
It has excellent electrical and mechanical properties and has been widely used as an industrial material. However, many of these polyimide resins are
Since it is insoluble in any of various organic solvents and mineral acids, and is also thermally infusible, it was extremely difficult to carry out its molding process.

(Problems to be Solved by the Invention) Among the above-mentioned conventional aromatic polyimide resins, there are few that have a high glass transition temperature and excellent heat resistance, and at the same time have good solubility in an organic solvent. ,
The lack of an aromatic polyimide resin having both such heat resistance and moldability has been a major problem in the commercial use of this resin. Therefore, an object of the present invention is to provide a novel polyimide resin that is soluble in various organic solvents and has a high glass transition temperature.

(Means for Solving the Problems) The present inventors have made diligent efforts to produce a polyimide resin that is soluble in various organic solvents and mineral acids and has a high glass transition point, and completed the present invention.

The present invention has the general formula (In the formula, R is 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride or 3,4,3
A tetravalent aromatic group derived from 3 ', 4'-biphenyltetracarboxylic dianhydride, Ar is 1,1-bis (4-
Aminophenyl) -2,2-diphenylethylene-derived divalent tetraphenylethylene group, n is 22 to 48
Is a novel aromatic polyimide resin.

Novel aromatic polyimide resin of the present invention have the general formula _{H 2 N -Ar-NH 2 ......} (II) ( wherein, Ar is 1,1-bis (4-aminophenyl) -
A diamine represented by a divalent tetraphenylethylene group derived from 2,2-diphenylethylene), and a general formula (In the formula, R is 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride or 3,4,3
It is produced by reacting a tetracarboxylic acid dianhydride represented by 3 ′, 4′-biphenyltetracarboxylic acid dianhydride, which represents a tetravalent aromatic group derived from 3 ′, 4′-biphenyltetracarboxylic acid dianhydride, in an organic solvent.

The polyimide resin represented by the general formula (I) is produced from the diamine represented by the general formula (II) and the tetracarboxylic dianhydride represented by the general formula (III). The diamine containing the phenylethylene group may be used alone, or the diamine containing one or more divalent aromatic groups may be mixed and used.

The diamine having a divalent tetraphenylethylene group represented by the general formula (II) means 1,1-bis (4-aminophenyl) -2,2-diphenylethylene. This diamine can be easily produced from tetraphenylethylene as a starting material through a two-step synthetic route.

Examples of the tetracarboxylic dianhydride derivative represented by the general formula (III) used in the present invention include, for example, pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 3,4 , 3'4, '-biphenyltetracarboxylic dianhydride, 2,3,2', 3'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2, 2-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl)
Ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,3 ', 4'-benzophenone tetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxy) (Phenyl) hexafluoropropane dianhydride and the like.

The diamine represented by the general formula (II) and the general formula (III)
The method for producing the polyimide resin represented by the general formula (I) from the tetracarboxylic dianhydride represented by
A diamine represented by the general formula (II) and a tetracarboxylic acid dianhydride derivative represented by the general formula (III) are mixed in an organic solvent under substantially anhydrous conditions at 0 to 100 ° C. for several tens of minutes. The reaction is carried out at 80 to 400 ° C. for several tens of minutes to several days.

The degree of polymerization (average degree of polymerization) n of the polyimide resin represented by the general formula (I) is the charged amount of the diamine represented by the general formula (II) and the tetracarboxylic dianhydride derivative represented by the general formula (III). The use of these reaction components in equimolar amounts makes it possible to produce a polyimide resin represented by the general formula (I) having a high degree of polymerization. The reason why n of the polyimide resin of the general formula (I) is limited to an integer of 22 to 48 is that when n is less than 22, the mechanical properties and heat resistance of the molded article molded into a film are not sufficient. n is
If it exceeds 48, the solubility in organic solvents and the moldability will deteriorate.

The organic solvent that can be used in the production method according to the present invention,
For example, N, N-dimethylformamide, N, N-dimethylacetamide, amide solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfur solvents such as tetramethylene sulfone, anisole, diphenyl ether, nitrobenzene, benzonitrile, Examples include benzene-based solvents such as cresol and phenol. In particular, when a solvent capable of azeotroping with water, such as cresol or nitrobenzene, is used, the latter stage reaction is carried out at the boiling point of these solvents, and at the same time, the solvent is removed by distillation, and the like. The reaction can proceed with high efficiency. At this time, it does not matter if the reaction is carried out by adding an additive such as isoquinoline.

In the present invention, a diamine represented by the general formula (II) is reacted with a tetracarboxylic acid dianhydride derivative represented by the general formula (III) to give a compound represented by the general formula: (Wherein R represents the above-mentioned tetravalent aromatic group, Ar represents the above-mentioned divalent tetraphenylethylene group, and n represents an integer of 22 to 48), and a polyamic acid derivative represented by Existing cyclodehydration methods (eg CESroog, Mac
romolecular Syntheses Collective Volume Volume 1, Volume 2
The polyimide resin of the present invention represented by the general formula (I) can also be produced by the method described on page 95 (1977). The polyamic acid derivative represented by the general formula (V) includes a diamine represented by the general formula (II) and a tetracarboxylic acid dianhydride derivative represented by the general formula (III) under substantially anhydrous conditions. It can be easily obtained by reacting. The degree of polymerization of the polyamic acid derivative represented by the general formula (V) is limited by the charged amounts of the diamine represented by the general formula (II) and the tetracarboxylic dianhydride derivative represented by the general formula (III). When the reaction components are used in an equimolar amount, a high degree of polymerization of the general formula (V)
A polyamic acid derivative represented by can be produced. The reaction temperature at the time of producing the polyamic acid derivative represented by the general formula (V) can be selected from 0 to 300 ° C., but the reaction product at a high temperature may contain a polyimide structure in which the reaction is further advanced. It is preferable that the reaction temperature be controlled to 60 ° C. or lower. Examples of the organic solvent that can be used in this reaction include the same organic solvents as in the above case in which the polyimide resin is produced without passing through the polyamic acid derivative represented by the general formula (V).

One of the methods for converting the thus obtained polyamic acid derivative represented by the general formula (V) into the polyimide resin represented by the general formula (I) is to convert the polyamic acid derivative represented by the general formula (V) to 150 to 400. This is a method of heating to a temperature of ℃. This heating time varies depending on the heating temperature, but is usually from several minutes to several tens hours. Alternatively, the polyamic acid derivative represented by the general formula (V) can be easily treated by a chemical treatment such as treatment with an acid anhydride such as acetic acid, propionic acid, butyric acid, benzoic acid, etc. Cyclization to Here, pyridine or the like can be used in combination as the substance that promotes the cyclization reaction.

Furthermore, as an alternative to the method for producing the polyimide resin represented by the general formula (I), the reaction is allowed to proceed by the same method as the method for producing the polyamic acid derivative represented by the general formula (V). There is a method in which an additive such as acetic anhydride is added without isolation of the polyamic acid derivative represented by the formula (V), and the reaction is further performed at a temperature of 0 to 300 ° C. for several minutes to several tens hours. As the additive used in this reaction, it is preferable to use the same additive as used in the production of the polyimide resin represented by the general formula (I) by the chemical treatment of the polyamic acid derivative represented by the general formula (V). it can.

The amount of the organic solvent used may be an amount sufficient to dissolve one of the reaction components. Generally, a polyimide having a high degree of polymerization can be obtained by using the reaction components in an amount of 0.05 to 50%.

The polymerization reaction may proceed in a solution state, or the polymer may precipitate from the reaction system. A molded product such as a film of a polyimide resin can be molded directly from this polymerization solution.

The polyimide resin represented by the general formula (I) thus produced has the same production method as the general formula (III) used.
The solubility of the polyimide resin varies depending on the type of the tetracarboxylic dianhydride derivative represented by, but many polyimide resins are soluble in mineral acids such as sulfuric acid. Further, some polyimide resins are soluble in all or part of solvents such as N-methyl-2-pyrrolidone, dimethylimidazolidinone, dimethyl sulfoxide, metacresol, orthochlorophenol, and pyridine. Most of the polyimide resins represented by the general formula (I) have a high glass transition point of 300 ° C. or higher, are thermally stable and show no thermal decomposition even when heated to around 500 ° C.

(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 0.31 g (1 mmol) of 1,1 bis (4-aminophenyl) -2,2-diphenylethylene and 0.4 g of isoquinoline were dissolved in 5 ml of purified meta-cresol and heated to 40 ° C. under a nitrogen stream. Heated. To this solution was added 0.322 g (1 mmol) of 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride. The solution was reacted at 45 ° C. for 3 hours and at 150 ° C. for 3 hours with stirring. A distillation device was attached to the reactor, and the solvent metacresol was distilled off under a nitrogen stream at an oil bath temperature of 240 ° C. At this time, meta-cresol containing 0.5% of isoquinoline was added so as to keep the liquid volume in the reactor at about 4 ml. After performing this operation for 5 hours, it was cooled to room temperature under a nitrogen stream to obtain a yellow polyimide resin solution. A portion of this solution was poured into 300 ml of methanol,
A polyimide resin precipitate was obtained, which was filtered off and dried in vacuum at 100 ° C. The remaining polymerization solution was cast on a glass plate, which was vacuum dried at 100 ° C. and then at 180 ° C. to obtain a polyimide film.

Intrinsic viscosity: 0.54 dl / g (measured in N-methyl-2-pyrrolidone at a concentration of 0.5 g / dl at 30 ° C) Infrared absorption spectrum (film): 1780, 1720, 1365,
720 cm _-1 (both are characteristic absorption of imide bond) Glass transition temperature: 300 ° C. Degree of polymerization n: 26 10% weight loss temperature: 535 ° C in air and 560 ° C in nitrogen.

Solubility: It was soluble in sulfuric acid, metacresol, orthochlorophenol, pyridine, dimethylimidazolidinone, N-methyl-2-pyrrolidone and the like.

Example 2 3.51 ml of 0.217 g (0.6 mmol) of 1,1-bis (4-aminophenyl) -2,2-diphenylethylene was purified.
It was dissolved in N, N-dimethylacetamide. Add 0.
131 g (0.6 mmol) of pyromellitic dianhydride was added under a nitrogen stream and reacted at 20 ° C for 3 hours. A part of the obtained polymerization solution was added to 300 ml of methanol to precipitate a polyamic acid, which was filtered and dried under vacuum at room temperature (intrinsic viscosity 0.51 d
1 / g, in dimethylacetamide, concentration 0.5 g / dl, measured at 30 ° C). On the other hand, the remaining polymerization solution was cast into a glass plate and dried at 80 ° C. to obtain a polyamic acid film. The film was heat-treated at 100 ° C., 200 ° C. and 280 ° C. for 1 hour in sequence to obtain a polyimide film.

Infrared absorption spectrum (film): 1780, 1730, 1355,
720 cm _-1 (both are characteristic absorption of imide bond) Intrinsic viscosity: 0.45 dl / g (in sulfuric acid, concentration 0.5 g / dl, 30 ° C)
Measured by) Glass transition temperature: 396 ° C. Degree of polymerization n: 25 10% weight loss temperature: 550 ° C. in air, 560 ° C. in nitrogen.

Solubility: Only soluble in sulfuric acid.

Example 3 0.217 g (0.6 mmol) of 1,1-bis (4-aminophenyl) -2,2-diphenylethylene was purified to 3.5 ml.
It was dissolved in N, N-dimethylacetamide. Add 0.
Add 193 g (0.6 mmol) of 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride under a nitrogen stream at 20 ° C.
And reacted for 3 hours. 300 ml of a part of the obtained polymerization solution
Of methanol to precipitate polyamic acid, and after filtration, vacuum dried at room temperature (intrinsic viscosity 0.50 dl / g, concentration in dimethylacetamide 0.5 g / dl, measured at 30 ° C.). on the other hand,
The rest of the polymerization solution was cast into a glass plate, which was then
And dried to obtain a polyamic acid film. This film was heat-treated at 100 ° C., 200 ° C. and 280 ° C. for 1 hour in sequence to obtain a polyimide film.

Intrinsic viscosity: 0.45 dl / g (measured in N-methyl-2-pyrrolidone at a concentration of 0.5 g / dl at 30 ° C) Glass transition temperature: 300 ° C. Degree of polymerization n: 22 10% weight loss temperature: 535 ° C in air, 560 ° C in nitrogen.

Solubility: Soluble in sulfuric acid and N-methyl-2-pyrrolidone.

Example 4 0.217 g (0.6 mmol) of 1,1-bis (4-aminophenyl) -2,2-diphenylethylene was purified to 3.5 ml.
It was dissolved in N, N-dimethylacetamide. Add 0.
177 g (0.6 mmol) of 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride was added under a nitrogen stream and the mixture was stirred at 20 ° C for 3 hours.
Reacted for hours. A part of the obtained polymerization solution was poured into 300 ml of methanol to precipitate the polyamic acid, which was then vacuum dried at room temperature after filtration (intrinsic viscosity 0.93 dl / g, in dimethylacetamide, concentration 0.5 g / dl, at 30 ° C.). Measurement). On the other hand, the remaining polymerization solution was cast into a glass plate and dried at 80 ° C. to obtain a polyamic acid film. This film
Heat treatment at 100 ℃, 200 ℃, 280 ℃ for 1 hour each,
A polyimide film was obtained.

Intrinsic viscosity: 0.88 dl / g (measured in sulfuric acid at a concentration of 0.5 g / dl at 30 ° C) Glass transition temperature: 295 ° C. Degree of polymerization n: 40 10% weight loss temperature: 540 ° C. in air, 560 ° C. in nitrogen.

Solubility: Soluble in sulfuric acid and orthochlorophenol.

Example 5 0.180 g (0.5 mmol) of 1,1 bis (4-aminophenyl) -2,2-diphenylethylene and 0.100 g (0.5 mmol) of 4,4'-oxydianiline in 3.5 ml of purified N,
Dissolved in N-dimethylacetamide. 0.29 in this solution
4 g (1.0 mmol) of 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride was added under a nitrogen stream and reacted at 20 ° C for 3 hours. A part of the obtained polymerization solution was poured into 300 ml of methanol to precipitate a polyamic acid, which was filtered and vacuum dried at room temperature (intrinsic viscosity 1.47 dl / g, in dimethylacetamide, concentration 0.5 g / dl, at 30 ° C.). Measurement).

On the other hand, the remaining polymerization solution was cast into a glass plate and dried at 80 ° C. to obtain a polyamic acid film. The film was heat-treated at 100 ° C., 200 ° C. and 280 ° C. for 1 hour in sequence to obtain a polyimide film.

Intrinsic viscosity: 1.03 dl / g (measured in ortho-chlorophenol at a concentration of 0.5 g / dl at 30 ° C) Glass transition temperature: 293 ° C. Degree of polymerization n: 48 10% weight loss temperature: 550 ° C. in air, 560 ° C. in nitrogen.

Solubility: Soluble in sulfuric acid, metacresol, orthochlorophenol, dimethylimidazolidinone, and N-methyl-2-pyrrolidone.

The mechanical properties of the film were a tensile strength of 64 MPa, an elongation at break of 3% and a tensile elastic modulus of 2.4 GPa.

(Effects of the Invention) The present invention provides a polyimide resin represented by the general formula (I) and an advantageous production method thereof. Many of the conventional polyimide resins were difficult to mold because they have low solubility in organic solvents, whereas the polyimide resin of the present invention is soluble in organic solvents, and is related to the present invention. It has a characteristic that it can be obtained as an organic solvent solution by the manufacturing method, and can mold a molded product such as a film of a polyimide resin more easily than this solution, and since it has excellent heat resistance, it is extremely valuable as an industrial material. large.

Although the present invention has been described with reference to specific examples and numerical values, the present invention is not limited to these, and various changes and modifications can be made without departing from the broad spirit and scope of the present invention. Of course.

Claims (1)

[Claims] 1. A general formula (In the formula, R is 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride or 3,4,3
A tetravalent aromatic group derived from 3 ', 4'-biphenyltetracarboxylic dianhydride, Ar is 1,1-bis (4-
Aminophenyl) -2,2-diphenylethylene-derived divalent tetraphenylethylene group, n is 22 to
An aromatic polyimide resin represented by the formula: