JPH068295B2 - Heat-curable imide compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting imide compound having a terminal functional group.

Aromatic imide compounds are generally produced from aromatic tetracarboxylic acid anhydrides and aromatic diamines as raw materials,
Pyromellitic dianhydride or benzophenone tetracarboxylic dianhydride is well known as a typical aromatic tetracarboxylic acid. However, an aromatic imide compound obtained by using these acid anhydrides has extremely low solubility in an ordinary low-boiling point organic solvent, and when dissolved, dimethylformamide, dimethylacetamide, N
-It is necessary to use special high boiling solvents such as methylpyrrolidone, dimethylsulfoxide, cresol and the like. On the other hand, the above aromatic imide compounds have poor compatibility with epoxy resins, phenolic resins, amines, acid anhydrides, unsaturated group-containing compounds, etc., and are said to be used in combination with them to improve performance. Is difficult.

From these facts, the present inventors diligently studied the imide compound having excellent solubility and compatibility, and as a result, the formula in the molecule was [In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ₂ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, or a hydroxyl group. The present invention was completed by finding that an imide compound having a structural unit represented by the following] satisfies the above object.

That is, the present invention, the following general formula (1) [In the formula, X represents a terminal functional group, Ar ₁ and Ar ₂ are each independently an aromatic residue, R ₁ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ₂ is a hydrogen atom and 1 carbon atom. ~ 2
0 represents an alkyl group, an alkoxy group or a hydroxyl group, and n represents an integer of 0 to 80. ] The thermosetting imide compound shown by these is provided.

[In the formula, R ₃ , R ₅ , and R ₆ independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ₄ represents an alkylene group having 1 to 20 carbon atoms or an aralkylene group. ] There is what is shown by the formula.

Ar ₁ and Ar ₂ will be described in more detail when Ar ₁
And Ar ₂ are each independently a mononuclear or polynuclear divalent aromatic residue, and aromatic rings include those substituted with a lower alkyl group, halogen, lower alkoxy group and the like, and unsubstituted ones. Be done. More specifically, Ar ₁ and Ar ₂ are both aromatic amine residues, Ar ₂ is an aromatic diamine residue, and Ar ₁ is an aromatic monoamine or diamine residue. Examples of these aromatic amines include 4,4'-
Diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether,
3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,4-toluenediamine, 2,6-toluenediamine, m -Phenylenediamine, p-phenylenediamine, benzidine, 4,4'-diaminodiphenylsulfide, 3,3'-dichloro-4,4'-diaminodiphenylsulfone, 3,3'-dichloro-4,4'-
Diaminodiphenylpropane, 3,3'-dimethyl-
4,4'diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3
-Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4'-bis (4-
Aminophenoxy) diphenyl sulfone, 4,4'-
Bis (3-aminophenoxy) diphenyl sulfone,
9,9'-bis (4-aminophenyl) anthracene,
9,9'-bis (4-aminophenyl) fluorene,
3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 2,4-diaminoanisole, bis (3-aminophenyl) methylphosphine oxide, 3,3 '
-Diaminobenzophenone, o-toluidine sulfone, 4,4'-methylene-bis-o-chloroaniline,
Tetrachlorodiaminodiphenylmethane, m-xylylenediamine, p-xylylenediamine, 4,4'-diaminostilbene, 5-amino-1- (4'-aminophenyl-1,3,8-trimethylindane, 6-amino −
1- (4'-aminophenyl) -1,3,3-trimethylindane, 5-amino-6-methyl-1- (3'-amino-4'-methylphenyl) -1,3,3-trimethylindane , 7-amino-6-methyl-1- (3'-amino-4'-methylphenyl) -1,3,3-trimethylindane, 6-amino-5-methyl-1- (4'-amino-3) 1-type such as'-methylphenyl) -1,3,3-trimethylindane, 6-amino-7-methyl-1- (4'-amino-3'-methylphenyl) -1,3,3-trimethylindane Or there are two or more types.

On the other hand, regarding aromatic monoamines, o-aminophenol, m-aminophenol, p-aminophenol,
6-amino-m-cresol, 4-amino-m-cresol, 2,2- (4-hydroxyphenyl-4-aminophenyl) -propane, 2,2- (4-hydroxyphenyl-2'-methyl-4) ′ -Aminophenyl) -propane, 2,2- (3-methyl-4-hydroxyphenyl-
4'-aminophenyl) -propane, 3-amino-1-
Naphthol, 8-amino-2-naphthol, 5-amino-1-naphthol, 4-amino-2-methyl-1-naphthol, o-aminobenzoic acid, m-aminobenzoic acid, p
-Aminobenzoic acid, o-aminothiophenol, m-aminothiophenol, p-aminothiophenol, m-
Aminostyrene, p-aminostyrene, m-amino-α
-Methylstyrene, p-amino-α-methylstyrene,
1-isopropenyl-3- (2-aminoisopropyl)
-Benzene, 1-isopropenyl-4- (2-aminoisopropyl) -benzene, and the like.

Although R ₁ and R ₂ are as described above, R ₁ is particularly preferably an alkyl group having 1 to 10 carbon atoms.

The method for producing the terminal functional imide compound of the present invention will be illustrated.

When X in the formula (1) is —NH ₂ , the above aromatic diamine and the formula [In the formula, R ₁ and R ₂ are the same as described above. Compounds represented by] a (. To not more than B _1), and an excess of aromatic diamine, can be synthesized by usual imidization reaction. The synthesized compound is designated as B ₂ .

X in the formula (1) is -COOH, -OH, -SH or [In the formula, R ³ , R ⁵ and R ⁶ are the same as described above. ], The above-mentioned aromatic monoamine having each functional group and the above-mentioned aromatic diamine are added to B ₁ and aromatic diamine /
The molar ratio of B ₁ is n / (n + 1) and the molar ratio of aromatic monoamine / B ₁ is 2 / (n + 1) (n is the same as above).
In addition to the above, an ordinary imide compound can be used for the synthesis. The synthesized compounds are referred to as B ₃ , B ₄ , B ₅ , and B ₆ according to the order of X described above.

Also, X in equation (1) is (R ₃ , R ₅ , and R ₆ are the same as described above)
For example, it is possible to synthesize by subjecting B ₂ , B ₃ , B ₄ or B ₅ to a β-alkyl substituted or unsubstituted epihalohydrin to carry out a usual epoxidation reaction. Let the synthesized compounds be B ₇ , B ₈ , B ₉ , and B ₁₀ , respectively.

Examples of the above epihalohydrin include one or two or more of epichlorohydrin, epibromohydrin, β-methyl-epibromohydrin and the like.

In addition, X in formula (1) is [In the formula, R ₃ , R ₄ , R ₅ and R ₆ are the same as described above. Can be synthesized, for example, by subjecting B ₂ , B ₄ or B ₅ and a halogenated hydrocarbon containing an unsaturated group to a dehydrochlorination reaction in the presence of an alkali or an amine compound. The synthesized compounds are represented by B ₁₁ , B ₁₂ , and
B ₁₃ Exemplifying the above unsaturated group-containing halogenated hydrocarbon, allyl chloride, allyl bromide,
Allyl fluoride, 1-propenyl chloride, 1-
Propenyl bromide, 1-propenyl fluoride,
CH ₃ CH = CHCH ₂ C, CH ₂ = CH (CH ₂ ) ₂ C, CH ₂ = CH (CH ₂ ) ₃ C
, CH ₃ CH = CH (CH ₂ ) ₂ C, CH ₂ = C (CH ₃ ) (CH ₂ ) ₂ C, CH ₂
= CH (CH ₂ ) ₄ C, vinylbenzyl chloride, vinylbenzyl bromide, vinylbenzyl fluoride, There are one kind or two or more kinds.

Also, X in equation (1) is [In the formula, R ₃ , R ₄ , R ₅ , and R ₆ are the same as described above. The compound of [] can be synthesized, for example, by subjecting B ₈ to an esterification reaction with an unsaturated group-containing alcohol. The synthesized compound is designated as B ₁₄ . Examples of the above unsaturated group-containing alcohol include allyl alcohol, CH ₃ CH = CHOH, CH ₃ CH =
CHCH ₂ OH, CH ₂ = CH (CH ₂ ) ₂ OH, CH ₂ = CH (CH ₂ ) ₃ OH, CH ₃ CH =
_{CH (CH 2) 2 OH,} CH 2 = C (CH 3) (CH 2) 2 OH, CH 2 = CH (CH 2) 4 OH,
Vinyl benzyl alcohol And the like.

In addition, X in formula (1) is [In the formula, R ₅ and R ₆ are the same as described above. ]]
For example, B ₂ can be synthesized by subjecting an acid anhydride containing an unsaturated group to an imidization reaction. The synthesized compounds are referred to as B ₁₅ , B ₁₆ , B ₁₇ , and B ₁₈ , respectively. Examples of the unsaturated group-containing acid anhydride, maleic anhydride, dimethyl maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic acid anhydride, methyl nadic acid anhydride, oxy nadic acid anhydride, methyloxy There is one kind or two or more kinds such as nadic acid anhydride and dimethyloxy nadic acid anhydride.

Although the method for synthesizing the terminal functional imide compound of the present invention has been exemplified above, it is not limited thereto.

Illustrating the synthesis method of B ₁ , the formula is [In the formula, R ₁ and R ₂ are the same as described above. ] The compound (hereinafter, referred to as B ₁₉ ) and maleic anhydride have a molar ratio of 1 /.
It is obtained by reacting in 2 in the absence of a radical polymerization catalyst and in the presence or absence of a radical polymerization inhibitor. B
Examples of ₁₉ are styrene, α-methylstyrene, α, p-dimethylstyrene, α, m-dimethylstyrene, isopropylstyrene, vinyltoluene and p-t.
-Butylstyrene, p-isopropenylphenol, m
There are one or more of isopropenylphenol, 1-methoxy-3-isopropenylbenzene, 1-methoxy-4-isopropenylbenzene, vinylxylene and the like.

The terminally functionalized imide compound of the present invention thus obtained is soluble in a low boiling point solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, methylene chloride and chloroform at a high concentration. Further, the imide compound of the present invention is an epoxy resin,
Excellent compatibility with phenolic resins, amines, acid anhydrides, unsaturated group-containing compounds, etc. Therefore, the terminal functional type imide compound of the present invention can be heat-cured alone or in a mixed system with the above compound depending on the kind of the functional group. The obtained cured product exhibits excellent properties such as heat resistance, mechanical properties and solvent resistance.

To illustrate how a _{thermosetting,} B _2, B 3, for _{B 4} or _{B 5} are possible cure in combination with a conventional epoxy resin or _{B 7, B 8, B 9} or _{B 10.} Ordinary epoxy resin is a compound having two or more epoxy groups in the molecule, and exemplified are bisphenol A, bisphenol F, hydroquinone, resorcin, phloroglysin, tris- (4-hydroxyphenyl) methane, 1,1,2. , 2-tetrakis (4-hydroxyphenyl) ethane and other divalent or trivalent phenols or tetrabromobisphenol A and other halogenated bisphenols derived glycidyl ether compounds, phenol, o-cresol and other phenols Novolak-based epoxy resin derived from a novolak resin which is a reaction product of aldehyde and formaldehyde, aniline, p-aminophenol, m-aminophenol,
4-amino-m-cresol, 6-amino-m-cresol, 4,4'-diaminodiphenylmethane, 3,3 '
-Diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene,
1,4-bis (3-aminophenoxy) benzene, 1,
3-bis (4-aminophenoxy) benzene, 1,3-
Bis (3-aminophenoxy) benzene, 2,2-bis (4-aminophenoxyphenyl) propane, p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, p-xylyl Diamine, m-xylylenediamine, 1,4-cyclohexane-bis (methylamine), 1,3-cyclohexane-bis (methylamine), 5-amino-1-
(4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl)-
Amine-based epoxy resins derived from 1,3,3-trimethylindane and the like, glycidyl ester-based compounds derived from aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid and isophthalic acid, 5,
Hydantoin-based epoxy resin derived from 5 dimethyl hydantoin, 2,2'-bis (3,4-epoxycyclohexyl) propane, 2,2-bis [4- (2,2
3-epoxypropyl) cyclohexyl] propane, vinylcyclohexenedioxide, alicyclic epoxy resin such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and others, triglycidyl isocyanurate, 2,4,6 -Triglycidoxy-S-triazine and the like may be used alone or in combination of two or more.

If necessary, conventionally known tertiary amines, phenol compounds, imidazoles and other Lewis acids may be added as curing accelerators.

The imide compound of B ₇ , B ₈ , B ₉ or B ₁₀ can be combined with a usual epoxy curing agent in addition to the combination with the imide compound of B ₂ , B ₃ , B ₄ or B ₅ . Examples of such known curing agents include dicyandiamide, tetramethylguanidine, aromatic amines, phenol novolac resins, cresol novolac resins, acid anhydrides, and one or more of various aliphatic and alicyclic amines. Used. As the aromatic amine, the above-mentioned aromatic diamine is typical.

_{B 6, B 11, B 12} , B 13, B 14, B 15, B
₁₆ , B ₁₇ or B ₁₈ alone or in combination with an unsaturated compound containing at least one unsaturated group in the molecule, can be heat-cured in the presence or absence of a radical polymerization catalyst. It is possible. Examples of the above unsaturated compounds include styrene, α-methylstyrene,
Divinylbenzene, acrylic acid ester, methacrylic acid ester, acrylonitrile, N-phenylmaleimide, diaminodiphenylmethane-bis (N-phenylmaleimide), diallyl phthalate resin, triallyl isocyanurate, 3,3′-diallyl-bisphenol A, bisphenol A Diallyl ether, allyl ether of phenol novolac or cresol novolac, unsaturated polyester resin having maleic acid or fumaric acid unit, epoxy acrylate resin or epoxy methacrylate resin derived from acrylic acid or methacrylic acid and epoxy resin, or the like, or There are two or more types.

The imide compound of the present invention may be used in combination with a filler, a filler, a reinforcing agent, a pigment or the like, if necessary. For example, silica, calcium carbonate, antimony trioxide, kaolin, titanium dioxide, zinc oxide, mica, barite, carbon black, polyethylene powder, polypropylene powder, aluminum powder, iron powder, copper powder, glass fiber, carbon fiber, alumina fiber, asbestos. One kind or two or more kinds of fibers, aramid fibers and the like are used, and are used for molding, lamination, adhesives, composite materials and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to these.

Example 1 29.7 g (0.15 g) of 4,4'-diaminodiphenylmethane was added to a flask equipped with a stirrer, a thermometer, and a cooling separator.
Mol) and 242 g of m-cresol to dissolve diaminodiphenylmethane, 48.5 g of xylene is added, and the temperature is raised to 120 ° C. 1-methyl-at this temperature
3,4-Dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic anhydride 31.4 g (0.1 mol)
Was added and the temperature was raised to 175 ° C. and the dehydration reaction was continued for 5 hours. After the reaction, the solution was precipitated in a hexane / isopropanol mixed solution, washed twice with the same solution, and dried under reduced pressure to obtain an imide compound. This product had a melting point of 241 ° C. and an amine equivalent of 643 g / eq.

Example 2 4,4′-diaminodiphenylmethane of Example 1 29.7
g (0.15 mol) to m-aminophenol 24.0 g (0.10 mol).
22 mol) and the same reaction was carried out to obtain an imide compound. This product has a melting point of about 210 ° C and a hydroxyl equivalent of 249.
It was g / eq.

Example 3 In a flask equipped with a stirrer, a thermometer, and a reflux condenser, 19.9 g (0.04 mol) of the imide compound obtained in Example 2, 185 g (2 mol) of epichlorohydrin and triethylamine were added. 182 g was charged, the temperature was raised to 105 ° C., and the temperature was kept at the same temperature for 2 hours. Then, the mixture was cooled to 70 ° C., 16.0 g (0.0832 mol) of 28% sodium methoxide was charged, and the mixture was kept at the same temperature for 2 hours. After keeping warm, pass the generated salt, distill off the residual epichlorohydrin and wash with water,
It was dried under reduced pressure to obtain an epoxidized product.

This product has an epoxy equivalent of 348 g / eq and a melting point of about 120.
It was ℃.

Example 4 19.9 g of the imide compound obtained in Example 2 was placed in a flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel.
(0.04 mol), 168 g of dimethyl sulfoxide,
28% sodium methoxide 17.7 g (0.092 mol)
Was charged, the temperature was raised to 40 ° C., and allyl bromide 14.
5 g (0.12 mol) was added dropwise over 30 minutes, and then the mixture was kept warm for 5 hours. After the reaction, the product was extracted with methyl isobutyl ketone, washed 3 times with water, and dried under reduced pressure to obtain an allyl ether compound.

This product had an allyl etherification rate of 100% as determined from infrared spectrum and a melting point of about 170 ° C.

Example 5 4,4′-diaminodiphenylmethane of Example 1 29.7
g (0.15 mol) of 2,4-toluenediamine 24.4 g
The same reaction was carried out in place of (0.2 mol) to obtain an imide compound. The melting point of this product is about 220 ° C and the amine equivalent is 358.
It was g / eq.

Stirrer, thermometer and reflux condenser marked with the above imide compound into a flask 17.7 g (-NH ₂ per 0.05 moles),
150 g of acetone was charged and dissolved at 50 ° C. Then 3
The mixture was cooled to 0 ° C. or lower, and 5.39 g (0.055 mol) of maleic anhydride was gradually added so that the temperature did not exceed 30 ° C. After the addition, the mixture was kept warm for 1 hour. Then acetic anhydride 5.61g (0.05
5 mol) anhydrous sodium acetate 2.30 g (0.023 mol)
Was added and reacted at 30 ° C. for 4 hours. After the reaction, acetone was distilled off, the residue was precipitated in water, washed with water, and dried under reduced pressure to obtain a maleimide compound.

This product had a melting point of about 180 ° C., and it was confirmed from the infrared spectrum that no amino group remained.

The imide compounds obtained in Examples 1 to 5 were acetone, M
It is soluble in solvents such as EK, methylene chloride and methyl cellosolve.

Claims (2)

[Claims] 1. The following general formula [Where X is the following formula (Wherein R ₃ , R ₅ , and R ₆ independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ₄ represents an alkylene group having 1 to 20 carbon atoms or an aralkylene group). Represents a functional group, Ar ₁ and Ar ₂ are each independently an aromatic residue, R ₁ is a hydrogen atom or a carbon number of 1
-10 alkyl group, R ₂ is hydrogen atom or carbon number 1
~ 20 represents an alkyl group, an alkoxy group or a hydroxyl group, and n represents an integer of 0-30. ] The thermosetting imide compound shown by these. 2. The imide compound according to claim 1, wherein R ₁ is an alkyl group having 1 to 10 carbon atoms.