JPH0125510B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a curable composition with excellent heat resistance comprising an epoxy end group-containing aromatic imide or amide imide polymer and an aromatic imide or amide imide amine compound. Conventionally, in order to improve the heat resistance and rigidity of epoxy resins, attempts have been made to introduce imide rings into the intramolecular skeleton. However, there are many prepolymer types in which a general-purpose epoxy resin (e.g., diglycidyl ether of bisphenol A) is reacted with a curing agent having an imide skeleton, and there are almost no reports of imide or amide-imide polymers having direct epoxy ends. Katta. This is because the inherent imide skeleton is extremely weak and easily hydrolyzed by the base used for epoxidation, and a fully satisfactory product could not be obtained. In extreme cases, the epoxy groups painstakingly added by the carboxylic acid groups and amino groups produced by hydrolysis cause a curing reaction, resulting in gelation, resulting in a product that is completely unusable. As a result of intensive research on methods that do not cause hydrolysis, we have found that if the epoxidation reaction is carried out in the presence of an organic carboxylic acid and, if necessary, a quaternary ammonium salt, an imide or amide-imide polymer containing epoxy end groups can be produced without hydrolysis. The present invention was achieved by discovering that it can be manufactured. An object of the present invention is to provide a curable composition containing an aromatic imide or amide imide polymer containing epoxy end groups with no or very little hydrolysis. That is, the gist of the present invention is (In the formula, Ar is a divalent aromatic organic group,
Ar' is a tetravalent aromatic organic group, each of the four carbonyl groups is directly bonded to a different carbon atom, and each pair of carbonyl groups is bonded to an adjacent carbon atom in the Ar group, '' is a trivalent aromatic organic group, each of the three carbonyl groups is directly bonded to a different carbon atom, and the pair of carbonyl groups is
is bonded to the adjacent carbon atom in the Ar″ group,
and n and m are 0 or positive integers, provided that n+
m>0. ) and the general formula () [In the formula, Ar, Ar′, Ar″, n, m mean the above definitions, Y ¹ , Y ² , Y ³ and Y ⁴ are hydrogen,

[expression] or

[Formula] (R represents a hydrogen atom or an organic group, and X represents a halogen atom.) However, Y ¹ , Y ² , Y ³ and Y ⁴
at least one of

[IO-A]

0.45 mole of purified 2,4-diaminotoluene and 0.15 mole of purified 3,3,'4,4'-benzophenonetetracarboxylic dianhydride [hereinafter abbreviated as BTDA] in dry N-methylpyrrolidone solution during reflux. - After dropping the methylpyrrolidone solution and expelling the generated water from the system, the
An imide polymer containing an amine end group was obtained by imidization for a period of time. [IO-B] A solution of 0.125 mole of BTDA in N-methylpyrrolidone was added dropwise to a solution of 0.375 mole of 2,4-diaminotoluene and N-methylpyrrolidone at room temperature, and the mixture was kept at 30°C for 6 hours. Thereafter, the temperature was raised to expel generated water from the system, and the system was kept in a reflux state for 5.5 hours to obtain an imide polymer containing an amine end group. [IO-C] 3,3'-diaminobenzophenone 0.0094moleN
- during methylpyrrolidone solution reflux
A 0.0063 mole N-methylpyrrolidone solution of BTDA was added dropwise, and the system was kept in a reflux state for 6 hours while expelling the generated water from the system to obtain an imide polymer containing an amine end group. [IO-D] 3,3'-diaminodiphenylsulfone
An imide polymer containing an amine end group was obtained from 0.0081 mole and 0.0054 mole of BTDA in the same manner as IO-A. [IO-E] 3,3'-diaminodiphenylsulfone 0.15mole
and 4-acid chloride of trimellitic anhydride
An amide-imide polymer containing an amine end group was obtained from 0.1 mole by the same method as IO-B. Production of glycidylation reaction product [GAI-1] Amine end group-containing imide polymer IO-
After reacting 0.0369 mole of A (theoretical calculated amount), 1.476 mole of epichlorohydrin, and 0.0019 mole of tetraethylammonium bromide in glacial acetic acid at 60°C for 5 hours, NaOH (15% excess of the stoichiometric requirement) was added as a solid. The mixture was kept in a reflux state for 3 hours to obtain a glycidylated product. The NMR spectrum showed that the epoxidation rate due to ring closure was approximately 95%. [GAI-2] 0.0092 mole of IO-B (theoretical calculation amount) and 0.369 mole of β-methylepichlorohydrin in glacial acetic acid for 60
After reaction at 6.5 hours at 120 DEG C., 0.0425 mole of NaOH was reacted as a solid, and the mixture was kept in a reflux state at 120 to 130 DEG C. for 2 hours to obtain a β-methylglycidylated product. NMR showed that the epoxidation rate was approximately 98%. [GAI-3] IO-C0.0083mole (theoretical calculation amount), β-methylepichlorohydrin 0.416mole and LioH (IO-C
5mole%) was reacted in a mixed solvent of glacial acetic acid and N,N-dimethylformamide at 60°C for 6.5 hours.
Then, add 0.0318% mole of solid NaOH to 150
Reflux was performed at ℃ for 2 hours to obtain β-methylglycidylated product. NMR showed that the epoxidation rate was approximately 89%. [GAI-4] 0.0038 mole of IO-D (theoretical calculation amount), 0.152 mole of β-methylepichlorohydrin, and LiOH (the amount of IO-D
(4mole%) was reacted in a mixed solvent of glacial acetic acid and N,N-dimethylformamide at 70°C for 5 hours.
Thereafter, 0.0175 mole of solid NaOH was added, and the mixture was heated to 150°C and refluxed for 2 hours to obtain a β-methylglycidylated product. According to NMR, the epoxidation rate was approximately 92%. [GAI-5] Amine end group-containing amide-imide polymer IO-
E0.0095mole (theoretical calculation amount), β-methylepichlorohydrin 0.455mole and LiOH (IO-E)
5mole%) was reacted in a mixed solvent of glacial acetic acid and N,N-dimethylformamide at 50°C for 10 hours.
Then add 0.044mole of solid NaOH, 120~130℃
Stirring was continued for 3 hours in a reflux state to obtain a β-methylglycidylated product. NMR showed that the epoxidation rate was approximately 90%. Comparative example of preparation of cured product 1 Bisphenol A diglycidyl ether type epoxy (trade name: Ciel Co., Ltd., Epicoat 828)
[Epoxy equivalent: 1898 g/eq] 49.0 g of 4,4'-diaminodiphenylsulfone (DDS) was heated and mixed with 151 g, and heated in a mold at 150°C/3 hours + 170°C/2 hours +
A cured product was obtained by curing at 200°C for 17 hours. Vikatsu softening point temperature [TS] of this cured product, thermal decomposition start temperature (5% weight loss, Heating
Rate15℃/mm, in air) was measured. Comparative Example 2 Tetraglycidylamine type epoxy of 4,4'-diaminodiphenylmethane (trade name: Sumitomo Chemical Co., Ltd., ELM-434) [Epoxy equivalent: 110 to 130 g/
carbon fiber content
60% with mold heating press at 170℃/2 hours +200
C./17 hours to obtain a cured product. TS, TGA, and bending strength tests were conducted on these. (The bending strength test was carried out in accordance with JISK-6911.) Comparative Example 3 Polyfunctional epoxy of tetraglycidyl ether type of tetraphenylethane (trade name: Ciel Co., Ltd.)
Epicoat 1031) [Epoxy equivalent 200-220g/
eq] 21g and imide polymer containing amine end groups (IO
-A synthetic product) 15.4g was dissolved in N,N-dimethylformamide, impregnated and dried on a glass plate or carbon fiber, and heated at 180℃/2.
It was cured for 15 hours at +230°C to obtain a cured product. TS, TGA, and bending strength tests were conducted on these. Example 1 A varnish was prepared by dissolving 19.1 g of GAI-1 and 13.6 g of IO-A in a mixed solvent of methyl ethyl ketone and N,N-dimethylformamide. Carbon fiber is impregnated with varnish, dried and placed in a mold (carbon fiber content
After curing at 180°C for 3 hours using a heating press (60vo 1%), it was further cured at 230°C for 18 hours in an open environment to prepare a bending test piece. The samples for pyrolysis measurement were cured on a glass plate under the same curing conditions. Example 2 A varnish was prepared by dissolving 28.7 g of GAI-2, 4.6 g of diaminodiphenylsulfone, and 10.4 g of IO-B in methyl ethyl ketone. Thereafter, a cured product was produced in the same manner as in Example-1. Example 3 A varnish was prepared by dissolving 18.8 g of GAI-2 and 13.6 g of IO-B in a mixed solvent of methyl ethyl ketone and N,N-dimethylformamide. Then Example-1
A cured product was prepared in the same manner as above. Example 4 Example-1 from GAI-3 16.2g and IO-B6.8g
Samples for TGA and TS measurements were prepared under the same curing conditions. Example 5 Example-4 from 12.5g of GAI-4 and 3.4g of IO-B
A cured product was produced by the same method. Example 6 Example from GAI-5 13.7g and IO-E 12.5g-
4. A cured product was produced by the same method. Data regarding Comparative Examples 1 to 3 and Examples 1 to 6 are shown in Table-1. In addition, thermal decomposition comparison results for Comparative Examples 1 and 3 and Examples 3 and 5 (heating rate 15°C/min, air
Thermobalance data at 50 ml/min) are shown in Figure 1.

【table】 [Brief explanation of drawings]

FIG. 1 is a graph showing the relationship between heating temperature and weight coefficient retention when the thermal decomposition properties of an example of the resin composition of the present invention and a comparative product were measured using a thermobalance.

Claims (1)

[Claims] 1 General formula () (In the formula, Ar is a divalent aromatic organic group,
Ar' is a tetravalent aromatic organic group, each of the four carbonyl groups is directly bonded to a different carbon atom, and each pair of carbonyl groups is bonded to an adjacent carbon atom in the Ar' group, and Ar' is a trivalent aromatic organic group, each of the three carbonyl groups is directly bonded to a different carbon atom, and the pair of carbonyl groups is
is bonded to the adjacent carbon atom in the Ar″ group,
Further, n and m are 0 or positive integers. However, n
+m>0. ) and the general formula () (In the formula, Ar, Ar′, Ar″, nm mean the above definitions, Y ¹ , Y ² , Y ³ and Y ⁴ are hydrogen atoms, [Formula] or [Formula] (R is a hydrogen atom or an organic group, X represents a halogen atom).However, Y ¹ , Y ² , Y ³ and Y ⁴
A curable resin composition comprising an epoxy end group-containing aromatic imide or amide imide polymer, at least one of which is represented by the following formula: