JPS6131432A - Polyamide-imide resin and preparation thereof - Google Patents

Abstract

PURPOSE:A resin, obtained by reacting a specific diamine with an anhydrotrimellitic acid halide in an organic solvent, and soluble in organic solvents, and having a high glass transition point and improved heat resistance. CONSTITUTION:A polyamide-imide resin, expressed by formula II (n is an integer 10-200), and obtained by reacting a diamine expressed by the formula H2N-Ar-NH2 (Ar is bifunctional tetraphenylthiophene if Ar is of one kind, and one is bifunctional tetraphenylthiophene and the rest are bifunctional aromatic groups if Ar is of two or more kinds) with an anhydrotrimellitic acid halide expressed by formula II (X is halogen) in an organic solvent. Preferably, pyridine, triethylamine, etc. may be present with the organic solvent to carry out the reaction.

Description

Detailed Description of the Invention (Field of Industrial Application) This invention relates to a novel polyamide-imide resin and a method for producing the same, particularly a novel polyamide resin that is soluble in organic solvents, has a high glass transition point, and has excellent heat resistance. This invention relates to an imide resin and a method for producing the same.

(Prior Art) Conventionally, wholly aromatic polyamideimide resins have excellent mechanical properties and have been used as industrial materials.

These polyamideimide resins exhibit relatively good solubility in organic solvents. For such polyamide-imide resin, for example, Double KM Alpino (W
, M., Alvino) has been reported (Journ
al of Applied Polymer 5ci
ence Vol. 19, p. 678, 1975) (Problems to be Solved by the Invention) However, the above three conventional wholly aromatic polyamideimide resins have a low glass transition point and have a problem in heat resistance.

Therefore, an object of the present invention is to provide a novel polyamide-imide resin which is soluble in organic solvents, has a high glass transition point, and has improved heat resistance.

Another object of the present invention is to provide a method for producing the novel polyamideimide resin.

(Means for Solving the Problems) As a result of extensive research into solving the above problems, the present inventors found that a tetraphenylthiophene group of this value is used as the aromatic residue or at least a part thereof in the aromatic diamine moiety. By using this method, it was confirmed that it was suitable for the above purpose, and the present invention was achieved.

The first invention of the present invention is based on the general formula (wherein, Ar is a divalent tetraphenylthiophene group when there is one type of Ar, and one of them when there are two or more types of Ar).
m is a tetraphenylthiophene group having this valence, the other species is a divalent aromatic group, and n is an integer of 10 to 200.

The second invention of the present invention is based on the general formula (wherein, Ar is a divalent tetraphenylthiophene group when Ar is lFJ, and when Ar'b'' is two or more types, one of them is a divalent tetraphenylthiophene group. valent tetraphenylthiophene group,
Another species is a divalent aromatic group, n is an integer of 10 to 200. In the case of a species, a divalent tetraphenylthiophene group, in the case of two or more types of Ar, one of them
One or more diamines represented by a divalent tetraphenylthiophene group as a species and a divalent aromatic group as another species, and the general formula (wherein, X represents a halogen atom) This is a method for producing a polyamide-imide resin, which involves reacting trimellitic anhydride halide represented by the following in an organic solvent.

The polyamide-imide resin represented by the above general formula (Il) is a diamine represented by the above general formula (■) and the above general formula (II
It is produced from trimellitic anhydride represented by [1], but as the diamine, a diamine of the above formula (Ill in which Ar is a divalent tetraphenylthiophene group) can be used alone, Alternatively, 20 to 99 mol% of the above diamine consisting of Ar catetraphenylthiophene groups is mixed with 80 to 1 mol% of the above diamine consisting of one or more divalent aromatic groups of Ar. It is also possible to use a diamine compound consisting of a divalent tetraphenylthiophene group.
If it is less than mol %, the increase in glass transition point, which is a feature of this invention, will not be fully satisfied.

Among the diamines represented by the above general formula in), the diamine in which Ar is a divalent tetraphenylthiophene group refers to 2,5-bis(4-aminophenyl)-8,4-diphenylthiophene. It is known that this diamine can be produced from benzyl chloride and sulfur, which are industrially available at low cost.

For example, Ba Dilthey et al.
By Journal Practical Hemy (J,
Prakt, Ohem, Volume 2, pages 151 and 857 (1988).

Among the diamines represented by the above general formula in), diamines consisting of a divalent aromatic group include metaphenylenediamine, paraphenylenediamine, 8.8'-diaminobiphenyl, 4.4'-diaminobiphenyl, 8 .8
'-methylene dianiline, 4.4'-methylene dianiline, 4.4'-ethylene dianiline, 4.4'-isopropylidene dianiline, 8, B'-oxydianiline, 4.4'-oxydianiline Aniline, 8.4'-oxydianiline, 8.8'-thiodianiline, 4.4'-
Thiodianiline, 8,8'-carbonyldianiline,
4.4'-carbonyldianiline, 8. B'-sulfonyl dianiline, 4.4'-sulfonyl dianiline,
Examples include 1.4-naphthalenediamine, 1.5-naphthalenediamine, and 2.6-naphthalenediamine.

Trimellitic anhydride represented by the above general formula ([r)]
Examples of the halogen atom of the ride include fluorine, chlorine, and bromine.

The method for producing a polyamide-imide resin represented by the above general formula (Il) includes a method for producing a polyamide-imide resin represented by the above general formula (II) in an organic solvent, and a diamine compound expressed by the above general formula (II) and trimellitic anhydride represented by the above general formula (Il). By reacting the compound with Ride at -20 to 100°C for several minutes to several days, the general formula (where Ar is a divalent tetraphenylthiophene group when there is one type of Ar, and when there is two or more types of Ar) One of them is a divalent tetraphenylthiophene group, the other is a divalent aromatic group, n is an integer of 10 to 200).
Next, the intermediate is subjected to a dehydration cyclization method conventionally used in the production of polyimide resins, such as C.E. Sloop (0
, E., Sroog) Macromolecular 5ynthesis
a) Collective Volume Volume 1, page 295 (1
The polyamide-imide resin represented by the general formula (I) is produced by the method described in 1997).

In this method, the molecule I of the polyamideimide resin represented by the general formula (I) is limited by the amount of the diamine compound represented by the general formula (u) and the trimellitic anhydride halide represented by the general formula (II). When these reaction components are used in equimolar amounts, a polymeric polyamide-imide resin represented by the above general formula (I) can be produced. In the polyamideimide resin represented by general formula (I), n
The reason why is limited to an integer between 10 and 200 is that if n is smaller than 10, the mechanical properties and heat resistance of the molded product, such as a film, will not be sufficient. This is because the solubility of

Organic solvents that can be used in this method include N,N-dimethylborumamide, N,N-dimethylacetamide, N
-methyl-2-pyrrolidone, etc.)”, l1m, be/
Aromatic solvents such as zene, anisole, diphenyl ether, nitrobenzene, benzonitrile, chloroform, dichloromethane, 1.2-dichloroethane, 1.1
, 2,2-tetrachloroethane, and other heliogen-based solvents. It is effective to carry out the reaction in the presence of an acid acceptor such as pyridine or triethylamine together with such an organic solvent. In particular, when amide solvents such as N,N-dimethylacetamide and N-methyl-2-pyrrolidone are used, these solvents themselves become acid acceptors, making it possible to obtain a high polymer polyamide-imide resin.

The solubility of the thus produced polyamideimide resin represented by the general formula (r) changes depending on the type of diamine used (expressed in ml),
- It becomes soluble in all or part of solvents such as dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, m-cresol, and pyridine. The polyamideimide resin represented by the above general formula (tl) is 80
The glass transition point was not observed until around 0°C, and at 400″C
No significant weight change is observed even when heated to a temperature close to that level.

(Example) The present invention will be explained in more detail below with reference to Examples.

Example 1 2.090 g (5 mmol) of 2.5-di(4-aminophenyl)-8,4-diphenylthiophene and 0.505 g (5 mmol) of triethylamine were dissolved in 18.28 mj of dimethylacetamide. The solution was cooled to 0°C and at this temperature 1.052 g (5 mmoJ) of trimellitic anhydride chloride was added in one portion. After stirring for 8 hours at room temperature under a nitrogen stream, the floating liquid was
The mixture was diluted with dimethylacetamide of n/m and poured into methanol at 500 mA' to obtain a precipitate of polyamideamic acid.

Yield 2.89.9 (98%) The intrinsic viscosity of the polyamide amic acid was 0.44 (measured at 80° C. in dimethylacetamide at a concentration of OJ 11/d1).

The obtained polyamideamic acid was cast onto a glass plate from a dimethylacetamide solution to obtain a film. This film was heated at 180 to 2120°C under a silicon air stream to obtain a polyamide-imide film.

10% weight loss temperature change by thermogravimetry: 600°C under nitrogen flow, 580°C in air.

The glass transition point determined by thermomechanical analysis was 880°C. The polyamide-imide film was easily soluble in concentrated sulfuric acid, m-cresol, n-methyl-2-pyrrolidone, and the like.

Example 2 By the same operation as in Example 1, 2. F)-di(4-aminophenyl)-34-diphenylthiophene 1.045
g (2.5 mmol), 4,4'-oxydianiline 0.490 g (2.5 mmol) and trimellitic anhydride 1.052 g (5 mmol)
Polyamic acid 2.40II (99%) was obtained from The intrinsic viscosity was 0.49 (measured at 80° C. in dimethylacetamide at a concentration of 0.5 y/dJ). Further, this product was heat-treated to obtain a polyamideimide film. 10% weight loss temperature change by thermogravimetry, 560°C in nitrogen
℃, and 540 ℃ in air.

(IS) The glass transition point determined by thermomechanical analysis was 300°C.

The obtained polyamide-imide film was easily soluble in concentrated sulfuric acid, m-cresol, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and pyridine.

Reference Example 1 By the same operation as in Example 1, 1.81s of polyamideamic acid, ? (99%). The intrinsic viscosity was 0.51 (measured at 80° C. in dimethylacetamide at a concentration of 0.5 l/dl).

Further, a polyamideimide film was obtained by heat treatment. The lO% weight loss temperature by M gravimetry was 495° C. in 510″C1 air in nitrogen.

What is the glass transition point determined by thermomechanical analysis? It was 60'C. The obtained polyamide-imide film was easily soluble in concentrated sulfuric acid, m-cresol, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and the like.

(Effects of the Invention) The present invention provides a novel polyamideimide resin represented by the general formula (Il) and an advantageous method for producing the same.

While conventional polyamide-imide resins are soluble in organic solvents but have a relatively low glass transition point, the polyamide-imide resin of this invention is soluble in organic solvents, easy to mold, and has a high glass transition point. Since it has excellent heat resistance due to the presence of dots, it has great value as an industrial material.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. A polyamide-imide resin represented by a divalent tetraphenylthiophene group as one type, a divalent aromatic group as the other type, and n being an integer of 10 to 200. 2. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ In producing a polyamideimide resin represented by the general formula H_2N-Ar-NH_2 (formula H_2N-Ar-NH_2 Among them, Ar is a divalent tetraphenylthiophene group when there is one type of Ar, a divalent tetraphenylthiophene group as one type when there are two or more types of Ar, and a divalent aromatic group as the other type. One or more types of diamines represented by (indicates a group) and trimellitic anhydride halide represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (in the formula, X represents a halogen atom) 1. A method for producing a polyamideimide resin, which comprises reacting in an organic solvent.