JPS59166531A - Curable resin composition - Google Patents

Abstract

PURPOSE:To provide a curable resin composition having excellent heat resistance, by compounding an aromatic diamine with an aromatic imide or amide- imide polymer containing epoxy terminal groups having low degree of hydrolysis. CONSTITUTION:The objective composition is prepared by compounding (A) the diamine of formula I (Ar is bivalent aromatic organic group; Ar' is tetravalent aromatic organic group wherein four C=O groups are bonded directly to different C atoms and each pair of C=O groups are bonded to the adjacent C atoms in Ar' group; Ar'' is trivalent aromatic organic group wherein three C=O groups are bonded directly to different C atoms and the pair of C=O groups are bonded to the adjacent C atoms in Ar''; n and m are 0 or positive integer and n+m>0) with (B) an aromatic imide or amide-imide polymer of formula II [one or more Y<1>-Y<4> are group of formula III (R is H or organic group; X is halogen) and the others are H or group of formula IV] containing epoxy terminal groups having low degree of hydrolysis. The ratio of the active hydrogen of the amino group to the epoxy group is preferably selected to be 1.0-0.9.

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.

In order to improve the heat resistance and rigidity of conventional epoxy resins,
Attempts have been made to introduce an imide ring into the intramolecular skeleton. However, there are many prepolymer types in which general-purpose epoxy resins (e.g., diglycidyl ether of bisphenol A) are reacted with a curing agent having an imide skeleton, and there are few reports of imide or amide-imide polymers that directly cure epoxy resins. This is because the inherent imide skeleton was extremely weak and easily hydrolyzed by the base used for epoxidation, and a sufficiently satisfactory product could not be obtained.In extreme cases, the carbon dioxide produced by hydrolysis The epoxy groups that were painstakingly added by acid groups and amine groups caused a curing reaction, resulting in gelled L7 that could not be used for any purpose at all.

As a result of intensive research on methods that do not cause hydrolysis, we have found that if an epoxidation reaction is carried out in the presence of an organic carboxylic acid and, if necessary, a Hong Kong-grade ammonium salt, an imide or amide-imide polymer containing an epoxy end group 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 as follows: (wherein, Ar is a divalent aromatic organic group, A-r'
is a divalent aromatic organic group, each of the carbonyl groups is directly bonded to another carbon atom, and the six pairs of carbonyl groups are bonded to adjacent carbon atoms in the A/r group, Ar //1l-j is a trivalent aromatic organic group and each of the three carbonyl groups satisfies n+m>O. ] and the general formula (I[) [wherein, Ar 4 AI” b AN”% n9mkeH
Y', Y'', Y'' and Y4 represent hydrogen or an organic group, and X represents a halogen atom.

). However, the curable resin composition consists of y1%r5Y'' and Y4, which is a small amount of an epoxy end group-containing aromatic imide or amide-imide polymer.

To explain the present invention in detail, the diamine represented by the general formula (1) is prepared in a polar solvent such as dimethylformamide, methylpyrrolidone, m-cresol, etc. The number of moles of the aromatic acid anhydride and the acid anhydride represented by the general formula (V)N-Ar-NH2.1.
It can be obtained by reacting an aromatic diamine represented by . . . (V) (wherein Ar has the above definition).

Examples of acid anhydrides represented by the general formula (11) or (IV) include 3.3', tl, q'-benzophenone tetral)furopane dianhydride, bis(3,ll-dicarboxyphenyl)ether dianhydride 5.2..4-dichloronaphthalene-/, ta, s, g-te) lacalho 7e dianhydride, 7-enanthrene-/, za, ? , 10-tetras(3,'I-dicarboxyphenyl)sulpondi'
-,.

Anhydride, /, /, /, 3. J, ,? -hexafluoro-2,,2-j,・11 bis(3,II-dicarboxyphenyl)propane 2,
Examples include dianhydride and trimellitic anhydride.

sulfone, +, lI'-diaminodiphenylsulfone,
Ge, Ri'-diaminodiphenyl ether, 3.3'-dinyl ether, 3.3'-diethoxyg+lI'--
)'7'minodiphenylsulfone% 3+J V ethyl, ri, ri'-diaminodiphenylpropane 1. ? ,,
? '-dimethyl, +, lI'-diaminobenzophenone, 3. J 1- Monodiaminodiphenylmethane, 3.3'-diaminodiphenyl ether, u, lI-diaminotoluene, Tip 6
Examples include -diamittoluene, co-, ter-diaminoaniminophenoxy]benzene, and wauterbis(gef-aminophenyl)fluorene.

□゛ The reaction is carried out under known polymerization conditions to produce a diamine-terminated aromatic imide or amide-imide polymer.

The aromatic imide or amide imide polymer containing a terminal group such as epoxy with little hydrolysis represented by the general formula (II) is generally After reacting the diamine represented by formula (1) with an epoxy compound represented by the following formula (in the formula, X and R each have the above definitions), a base is added to perform a dehydrohalogenation reaction. It can be obtained by

The epoxy compounds used here include epichlorohydrin, β-methylepichlorohydrin, β-ethylepichlorohydrin, and the β-ammonium salts include, for example, tetramethylammonium chloride, tetraethylammonium chloride, triethylmethylammonium chloride, and tetramethylammonium bromine).
Examples of the lithium compound include sodium hydroxide, potassium hydroxide, and the like.
Alkali metal hydroxides such as lithium hydroxide and alkali metal carbonates such as sodium carbonate and potassium carbonate,
The reaction of calcium hydroxide, MAG hydroxide, and the compound epoxidizes 7 to 9 hydrogen atoms of the diamine base. Although it is possible to epoxidize only 7 parts of the amine aqueous solution, it is preferable to epoxidize all parts, ie, the entire amount, for the stability of the product. Generally diamine-compound 1
The epoxy compound is reacted in an amount of 1 mole or more per mole, preferably in a ratio of damole or more.

The amount of organic carboxylic acid used is diamined, if necessary the 4'M ammonium salt used or the amount of lithium compound used is rOl, 0
! ~/0.03iii% preferably (1),
5~x, oz! , 藷°chi is used.

Although the reaction can be carried out without a solvent, it is preferable to carry out the reaction in a solvent from the viewpoint of smoothness and uniformity of the reaction.

Examples of solvents that can be used include N,N-dimethylformamide, N-methylcaprolactam, N,N-dimethylacetamide, dimethylsulfoxide, N-methylcopyrrolidone, hexamethylphosphoramide, tetramethylenesulfone, butyrolactone, and the like. However, benzene, xylene, toluene, phenol, benzonitrile, acetonitrile, cyclohexane, etc. can also be used depending on the case. Mixed solvents of these can also be used.

The amount of solvent is not particularly limited, but is generally θ~20 (weight) times the amount of the diamine compound, preferably 0-10
(9 times the weight is fully used.

First, an addition reaction is carried out as a one-step reaction, and the amount of base used is generally 2 to 3 moles per 1 mole of diamine compound.

The base can be added as is or as a solution in a solvent (water etc.). It is preferable that the reaction temperature be below 0.degree. C. or less. When water is produced in the reaction, it is also possible to dehydrate it by azeotropy or the like.

If it is obtained in solid form after the reaction, it can be used as is as an epoxy end group-containing resin, but if it is obtained in solution form, it can be isolated in solid form by evaporating the solvent or using a precipitation solvent. can do. As the precipitation solvent, methanol, ethanol, acetone, ethyl acetate, methyl cellosolve, benzene, toluene, xylene, cyclohexane, water, etc. can be used.

The aromatic imide or amide imide polymer containing epoxy end groups thus obtained does not undergo hydrolysis and is therefore stable, and also does not undergo self-polymerization. This is achieved by blending an aromatic diamine represented by: Curing accelerators and/or common curing agents may also be used in combination. Curing accelerators and general curing agents include imidogusols, BF, amine complex dicyandiamide, diaminodiphenylmethane,
Examples include diaminodiphenylsulfone and benzophenonetetracarboxylic dianhydride.

These epoxy end group-containing aromatic imide or amide imide polymers represented by the above formula (II) and the above formula (I)
The blending ratio of the aromatic diamine represented by is such that the ratio of amino group active hydrogen to epoxy group/amount is /0.2 to 0.
7 equivalent ratio, preferably /, 0 to θ0 g equivalent ratio. Further, the blending ratio of the curing accelerator is not particularly limited, and is the same as the blending amount in conventional resin compositions such as epoxy.

Therefore, it has excellent heat resistance and is extremely useful.

1. Pami i: ,...i ``Next, the present invention will be explained in more detail with reference to Examples111'', but the present invention is not limited thereto in any way. Manufacture [Step 0-A] Purified diaminotoluene 0. smol and dry N-methylpyrrolidone solution during reflux, v'iI
? A dry N-methylpyrrolidone solution of 3,3ζp, An imide polymer containing an amine end group was obtained by imidization for a certain period of time.

[Work 0-B] Diaminotoluene θ, 3 & mO] -θ and N -
B T D A O, / in methylpyrrolidone solution at room temperature.
2! ;Drop the N-methylpyrrolidone solution of mobθ,
It was kept at 30°C for 6 hours. The water produced by the gradual temperature rise was expelled from the system, and the mixture was kept in a 7 lux state for S and S hours to obtain an imide polymer containing an amine end group.

[Work o-a]

15- [Work 0-D], 7. ,? '-diaminodiphenyl sulpone. ,00g
/mole (!: B T D AO,00!r'
From I mole. An imide polymer containing an amine end group was obtained in the same manner as in -A.

[Engineering 0-E] 3.3'-diaminodiphenylsulpone □, / jm
ol, e and trimellitic anhydride gooic acid chloride 0
, /mo]J to obtain an amide-imide polymer containing an amine end group in the same manner as in Process 0-B.

Manufacture of glycidylation reaction products [GA-nee/] Imide polymerization woodworking containing amine end groups. -AO, 0349m
ole (theoretical calculation amount) and shrimp chlorhito - Masuse 1 so 9
g(li"'Qa')1・1 [':'a A-ko], San, side work 0-BO, θO?, 2 mole (theoretical calculation amount) and β-,, /,)," Tile epichlorohydrin 0.3
After reacting 49 moles in glacial acetic acid at 60°C for 1.3 hours, NaOH0,0'l was added as a solid, and the β-
A methylglycidylated product was obtained. According to NMR, the epoxidation rate was approximately 9 g.

CGAI-3] Engineering O-00,00g,? mole (theoretical weight 1 and β
-Methyl epichlorohydrin θ, II/A mo'
lθ and Li0H (IO-C jm○1θ relationship) in a mixed solvent of glacial acetic acid and N,N-dimethylformamide at 60°C.
A,! The reaction was carried out for r hours. Thereafter, 0.03/g mole of solid NaOH was added and co-time reflux was performed at 750°C to obtain a β-methylglycidylated product. According to NMR, the epoxidation rate was approximately gqoir16-.

(GA kneader) -11;
, lacing the β-methylglycidylated product to 1
.

Ha was accompanied. According to NMR, the epoxidation rate was approximately that of octopus.

[GA Any] Amine end group-containing amide-imide j° combination process 〇-wo, o
oq left mole (theoretical calculation amount) and β-methylepichlorohydrin o, qs left mo:te and Li0H (technical amount)
-B in a mixed solvent of glacial acetic acid and N,N-dimethylformamide at 56°C for 10 hours. Thereafter, 1 mole of solid NaOHO, OII' was added, and stirring was continued for 3 hours in a reflux state of 7.20° C. and 70° C. to obtain a β-methylglycidylated product. According to NMR, the epoxidation rate was approximately 90.

Comparative example of preparation of cured product - / Bisphenol A diglycidyl ether type epoxy (Part name: Shell Co., Ltd., Epicoat 1; Hardness (&1 weight reduction, Heating Rate / !r'C/ mms
Comparative Example - Co+, lI'-diaminodiphenylmethane tetraglycidylamine type epoxy (trade name: Sumitomo Chemical Co., Ltd.)
liiLM-+jlI) [epoxy equivalent weight/10~/30
1//eq]/3.111 and g, p'-diaminodiphenylsulfone A L,2F are dissolved in methyl ethyl 19-ketone and placed on a glass plate or on carbon fiber (trade name Toshisha, Torayka T-300). The impregnated and dried material is heated and pressed into a mold as carbon fiber containing 0%.
C./2 hours+SOO.degree. C.//7 hours to obtain a cured product. These were subjected to TS, TGA, and bending strength tests. (The bending strength test was carried out in accordance with J Engineering SK-/, 9//.) Comparative Example-3 Tetraglycidyle T of tetraphenylethane, ii
; Dissolved in NwN-dimethylformamide, impregnated and dried on a glass plate or carbon fiber, and cured with a die-cast hot press at /gO℃/hour+230'C// to obtain a cured product. . T S % for these
A T G Ab bending strength test was conducted.

20-Example-/GA knee//ri,/17 and process 3.6 g of AI was dissolved in a mixed solvent of methyl ethyl ketone and N,N-dimethylborumamide to prepare a face. Carbon fiber is impregnated with Fes, and after drying, it is placed in a mold (carbon fiber content Ovol
%) Curing was performed at 230° C.//g for hours in a hot press at 230° C.//g for 3 hours and then cured for 3 hours to prepare a bending test piece. The samples for pyrolysis measurement were cured on a glass plate under the same curing conditions.

Example-2 GA eny 2g, 7g and diaminodiphenylsulfone +
. Thereafter, a cured product was prepared in the same manner as ★Male Side-7.

Example-3 Ta.

Example - Samples for TGA and TS measurements were prepared from gGA Any/A, KoI and Work0-BB, g under the same curing conditions as in Example-/.

Example-5 GA kneader/2. ! ;l! and 0-B 3. A cured product was prepared from DaI in the same manner as in Example-Hiroshi.

Example 6 A cured product was prepared from GA Eta/3.7g and Process 0/YJg in the same manner as in Example-G.

Data for Comparative Examples/~3 and Examples/~B are shown in Table-/.

In addition, the thermal decomposition comparison results for Comparative Example/3 and Example 3 (left) (thermal balance data at heating rate is° C./min, air !0d37 min) are shown in the figure.

[Brief explanation of the drawing]

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

Claims (1)

[Claims] , (1) General formula (1) (wherein, Ar is a co-valent aromatic organic group, Ar' is a g-valent aromatic organic group, and each of the carbonyl groups is A carbonyl group that is directly bonded to another carbon atom and has six pairs of carbonyl groups is A
It is bonded to the adjacent carbon atom in the r' group, and Ar1
is a trivalent aromatic organic group, each of the three carbonyl groups is directly bonded to another carbon atom, and a pair of carbonyl groups is bonded to adjacent carbon atoms in the Ar" group, and n , m is O or a positive integer, provided that n 10 m > 0] and the general formula (
II) (wherein Ar, Ar', Ar', nm mean the above definitions, Y", Y' and Y4 represent a hydrogen atom, a child or an organic group, and X represents a halogen atom.) A curable resin composition comprising an aromatic imide or amide imide polymer containing an epoxy end group.