JPS63264631A - Thermosetting imide compound - Google Patents

Abstract

PURPOSE:To obtain the title compound which can be dissolved in a low-boiling solvent in high concentrations, excels in compatibility with an epoxy resin and can give a cured product excellent in heat resistance, solvent resistance, mechanical properties, etc., when combined with said resin, having functional group-terminated structure of a specified structure. CONSTITUTION:A thermosetting, functional group-terminated imide compound of formula I (wherein X is NH2 or OH, Ar1 and Ar2 are each an aromatic group, R1 is H, a 1-10C alkyl, R2 is H, a 1-20C alkyl, or an alkoxy group or OH, and m and n are each 0-30). This compound can be dissolved in a low-boiling solvent such as acetone or ethyl cellosolve in a high concentration, excels in compatibility with an epoxy resin, can be heat-set when combined with said resin and can give a cured product excellent in heat resistance, solvent resistance, mechanical properties, etc. Said compound of formula I (wherein X is NH2) can be obtained by, for example, performing usual imidation of an aromatic diamine (e.g., 4,4'-diaminodiphenylmethane) with compounds of formulas II and/or III in conditions in which said aromatic diamine is excess.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a thermosetting imide compound having a terminal functional group.

<Prior art and problems> Aromatic imide compounds are generally produced using aromatic tetracarboxylic acid anhydride and aromatic diamine as raw materials.
Pyromellitic anhydride or benzophenone tetracarboxylic anhydride is well known as a typical aromatic tetracarboxylic acid. However, the aromatic imide compounds obtained using these acid anhydrides have extremely low solubility in ordinary low-boiling point organic solvents, and are commonly known as dimethylformamide, dimethylacetamide, N-
Special high-boiling solvents such as methylpyrrolidone, dimethylsulfoxide, and cresol must be used. Furthermore, the above-mentioned aromatic imide compounds have poor compatibility with epoxy resins, making it difficult to improve performance by combining them with epoxy resins.

In view of this, the present inventors have conducted intensive studies on imide compounds with excellent solubility and compatibility, and have found that the molecule contains a formula [wherein Rt is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms] R2 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, or a hydroxyl group. ] It was discovered that an imide compound having a tank-building unit represented by the following formula satisfies the above object, and the present invention was completed.

Means for Solving the Problems> That is, the present invention solves the following general formula (1) [wherein X is -
NHt group and q or -0) 1 group, Art, Ar
2 each independently represents an aromatic residue, R1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R2 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, or a hydroxyl group, m and n represent O ~3o represents the number. The present invention provides a thermosetting imide compound represented by

To explain Ar+ and Ar2 in more detail, A
rt and Ar2 are each independently mononuclear or polynuclear divalent aromatic residues, and the aromatic rings include those substituted with lower alkyl groups, halogens, lower alkoxy groups, etc., and those unsubstituted. It will be done. More specifically, Arl
and Art are both aromatic amine residues, and Ar
t represents the residue M of aromatic amine, and Arl represents the residue of aromatic monoamine or diamine. Examples of these aromatic amines include aromatic diamines such as 4,4
'-Diaminodiphenylmethane, 8,8'-Diaminodiphenylmethane, 4゜4'-Diaminodiphenyl ether, 8,4'-Diaminodiphenyl ether, 4
, 4'-diaminodiphenylpropane, 4.4'-diaminodiphenylsulfone, 8.8'-diaminodiphenylsulfone, 2.4-toluenediamine, 2゜6-
Toluene diamine, m-phenylene diamine, p-phenylene diamine, benzidine, 4゜4'-diaminodiphenylsulfide, 3,8'-dichloro-4,4'-
Diaminodiphenylsulfone, 8,8'-dichloro-
4,4'-diaminodiphenylpropane, 8.8'-dimethyl-4゜4'-diaminodiphenylmethane, 8.8
'-dimethoxy-4,4'-diaminobifer, 8,
8'-dimethyl-4,4'-diaminobiphenyl, l
.

8-bis(4-aminophenoxy)benzene, 1.8-
Bis(8-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4
-aminophenoxyphenyl)propane, 4,4'-bis(4-aminophenoxy)diphenylsulfone, 4
, 4'-bis(8-aminophenoxy)diphenylsulfone, 9,9'-bis(4-aminophenyl)anthracene, 9,9'-bis(4-aminophenyl)
Fluorene, 8,8'-dicarboxy-4゜4'-diaminodiphenylmethane, 2,4-diaminoanisole, bis(3-aminophenyl)methylphosphine oxide, 8,8'-diaminobenzophenone, o-toluidine Sulfone, 4,4'-methylene-bis-chloroaniline, tetrachlorodiaminodiphenylmethane,
m-xylylene diamine, p-xylylene diamine, 4
．． 4'-diaminostilbene, 5-amino-1-(4'
-aminophenyl-1,3,8-1-limethylindane, 6-amino-1-(4'-aminophenyl)-1,8
, 3-trimethylindane, 5-amino-6-methyl-
1-(8'-amino-4'-methylphenyl)-1,8
, 3-trimethylindane, 7-amino-6-methyl-
1-(3'-amino-4'-methylphenyl)-1,8
゜8-Trimethylindane, 6-amino-5-methyl-
1-(4'-amino-3'-methylphenyl)-1,8
, 8-1-limethylindane, 6-amino-two-methyl-
1-(4'-amino-8'-methylphenyl)-L,S
There are 184 or two or more types such as , 8-trimethylindan, etc.

On the other hand, regarding aromatic monoamines, 0-aminophenol, m-aminophenol, p-aminophenol,
6-amino-m-cresol, 4-amino-m-cresol, 2,2-(4-hydroxyphenyl-4-aminophenyl)-propane, 2,2-(4-hydroxyphenyl-21-methyl-4' -aminophenyl)-propane, 2,2-(8-methyl-4-hydroxyphenyl-
4'-aminophenyl)-propane, 8-amino-1-
There are one or more types of naphthol, 8-amino-2-naphthol, 5-amino-1-naphthol, 4-amino-2-methyl-1-naphthol, and the like.

R1 and R2 are as described above, but R1 is particularly preferably an alkyl group having 1-5-8 carbon atoms.

Furthermore, R2 is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

Further, m and n in the general formula (1) are as described above, but preferably m and n are numbers from 0 to 8, particularly preferably the number of ON5.

The method for producing the terminally functional imide compound of the present invention will be exemplified.

(1) For those of formula 12 in which X is -N, the above aromatic diamine and the formula % formula % [wherein R1 and R2 are the same as above. ] The compound (hereinafter referred to as B1, and its isomers are referred to as Y component or Z component, respectively) can be synthesized by carrying out a normal imidization reaction using an excess of aromatic diamine.

When X in the formula (1) is -(J)1, the above aromatic monoamine having a -〇H group and the above aromatic diamine are set as B, and the molar ratio of aromatic diamine/Bs is (
m + n ) / (m + n + 1 ) and the molar ratio of aromatic monoamine / B1 is 2 / (m + n + 1) (m and n are the same as above), and can be synthesized by performing a normal imidization reaction. can.

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

To illustrate the method of synthesizing B1, in the formula, R1,
R2 is the same as above. ] The compound represented by (hereinafter referred to as B8) and maleic anhydride are reacted at a molar ratio of 1/2 in the presence of a radical polymerization catalyst and in the presence or absence of a radical polymerization inhibitor. It will be done. For example, styrene, α-methylstyrene, α,
p-dimethylstyrene, a,m-dimethylstyrene, isopropylstyrene, vinyltoluene, p-t-butylstyrene, p-isopropenylphenol, m-isopropenylphenol, 1-methoxy-8-isopropenylbenzene, l-methoxy -4-isopropenylbenzene, vinylxylene, etc., or one or more of them.

Effect> The terminally functional imide compound of the present invention thus obtained is soluble at high concentrations in low boiling point solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, methylene chloride, and chloroform. It is.

The imide compound of the present invention also has excellent compatibility with epoxy resins. Therefore, the terminally functional imide compound of the present invention can be thermally cured in combination with an epoxy resin.

The resulting cured product exhibits excellent properties such as heat resistance, mechanical properties, and solvent resistance.

Typical epoxy resins are compounds having two or more epoxy groups in the molecule, and examples include bisphenol A1 bisphenol F1 hydroquinone, resorcinol, phloroglycine, tris-(4-hydroxyphenyl)methane, 1,1°2. Divalent or octavalent or higher phenol such as 2-tetrakis(4-hydroxyphenyl)xlin
Glycidyl ether compounds derived from halogenated bisphenols such as t- or tetrabromobisphenol A, phenol, novolak epoxy resins derived from novolak resins which are reaction products of phenols such as 0-cresol and formaldehyde, and aniline. , p
-aminophenol, m-aminephenol, 4-amino-m-cresol, 6-amino-m-cresol, 4
, 4'-diaminodiphenylmethane, 8,8'-diaminodiphenylmethane, 4゜4'-diaminodiphenyl ether, 8,4'-diaminodiphenyl ether,
1,4-bis(4-aminophenoxy)benzene, 1,
4-bis(8-aminophenoxy)benzene, 1.8-
Bis(4-aminophenoxy)benzene% 1#8-bis(8-aminophenoxy)benzene, 2.2-bis(
4-aminophenoxyphenyl)propane, p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 2,6-1-toluenediamine, p-xylylenediamine, m-xylylenediamine, 1,4-cyclohexane- Bis(methylamine), 1,8-cyclohexane-bis(methylamine), 5-amino-1-(
4'-'aminophenyl)-1゜8.8-)-limethylindane, 6-amino-1-(4'-aminophenyl)
-Amine-based epoxy resins derived from 1,8,8-trimethylindane, etc., glycidyl ester compounds derived from aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid, isophthalic acid, etc. , 5
, 5-dimethyl hydantoin, etc., 2,2'-bis(8,4-epoxycyclohexyl)propane, 2,2-bis[4-(
Alicyclic epoxy resins such as 2,8-epoxypropyl)cyclohexyl]propane, vinylcyclohexene dioxide, 8,4-epoxycyclohexylmethyl-8,4-epoxycyclohexanecarboxylate, others, triglycidyl isocyanurate, 2 .4.6-triglycidoxy-S-triazine, etc., or one or more of them can be mentioned.

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

The imide compound of the present invention is used in combination with an extender, a filler, a reinforcing agent, or a pigment, if necessary. For example, silica, calcium carbonate, antimony trioxide, kaolin,
One or two types of titanium dioxide, zinc oxide, metalloid, pallite, carbon black, polyethylene powder, polypropylene powder, aluminum powder, iron powder, copper powder, glass fiber, carbon fiber, alumina fiber, asbestos fiber, aramid anchor fiber, etc.
More than one species is used for applications such as molding, lamination, adhesives, and composite materials.

<Examples> The present invention will be explained in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited thereto.

Synthesis Example 1 500m with stirring device, thermometer, and cooling condenser
Anhydrous maleic iA110.3y (1
, 126 mol), N'-diphenyl-1,4-phenylenediamine 8.901) toluene 100 F and methyl isobutyl ketone 5 (1').
Raise the temperature to 20"C and keep it at the same temperature for 8 hours (
59.1 f (0.5 mol) of α-methylstyrene was added dropwise, and after the dropwise addition was completed, the mixture was kept at the same temperature for an additional 2 hours. After the reaction, 50 g of toluene and 259 g of methyl isobutyl ketone were added and cooled to precipitate crystals. The crystals were separated from P, washed several times with toluene, and then dried to obtain 55.7y of nearly white powder crystals.

The purity of B1 by GPC is 97.2%, the composition ratio of B1 isomers by GC is Y component/Z component 0.4510.55, and the melting point is 206-208"C.
Met.

Synthesis Example 2 500 with stirrer, thermometer, and cooling condenser
98.1 g (1 mol) of maleic anhydride, 8.90 f of N,N'-diphenyl-1,4-phenylenediamine, and 150 F of xylene are placed in a 4-m2 flask. Next, the temperature was raised to 145"C, and while maintaining the same temperature,
59.11 (0.5 mol) of α-methylstyrene was added dropwise over 8 hours, and after the addition was completed, the mixture was kept at the same temperature for an additional 2 hours. After the reaction, methyl isobutyl ketone 75y was added and the mixture was cooled to precipitate crystals. The crystals were separated from P, washed several times with toluene, and then dried to obtain nearly white powder crystals of 50.4F.

In this product, the purity of B1 by G)'C is 96.1%, and the composition ratio of B1 isomers by GC is Y component/Z
The component is 0.1710.88, and the melting point is 208-210
It was °C.

Synthesis Example 8 500 with stirring device, thermometer, and cooling condenser
t/In the fourth flask, add 98% maleic anhydride. II/(
1 mol), N-phenyl-N'-isobrobyl-1,4
- Charge 4.51 g of phenylene diamine, 120 f of toluene and 30 f of methyl isobutyl ketone. Subsequently, the temperature was raised to 120°C, and while maintaining the same temperature, α-methylstyrene (59.19 < 0.5 mol) was added over 2 hours.
was added dropwise, and after the completion of the dropwise addition, the mixture was kept at the same temperature for an additional 8 hours.

After reaction, toluene 60F and methyl isobutyl ketone 15y
was added and cooled, crystals precipitated. The crystals were separated from P, washed several times with toluene, and then dried to obtain 67.21 nearly white powder crystals.

In this product, the purity of B1 by GPC is 97.8%, the composition ratio of B1 isomers by GC is Y component/Z component 0.6610.84, and the melting point is 181-188°
It was C.

Example 1 In a flask equipped with a stirrer, a thermometer, and a cooling separation device, two
．． 4-Toluenediamine 26.2F (0,215 mol)
and m-cresol 117f and heated to 70°C to dissolve 2,4-toluenediamine, 45.0'i (0,148 mol) of the raw material obtained in Synthesis Example 1.
to form polyamic acid. Thereafter, 25.2 jF of toluene was charged, the temperature was raised to 150°C, and the dehydration reaction was continued at the same temperature for 10 hours.

After the reaction, the resulting resin liquid was precipitated with 7509 isopropanol, washed twice, and dried under reduced pressure to obtain an imide compound. The amine type of this product was 498 F/eq, and the melting point was about 260°C. Example 2 The raw material obtained in Synthesis Example 1 was placed in a flask equipped with a stirrer, a thermometer, and a cooling separation device. (0,148 mol),
m-cresol 161 f.

2.4-Toluenediamine 8.68 y (0,0714
15.5 moles of amine phenol (0,148 moles) were charged and the reaction was carried out for 1 hour at the same temperature.

After that, 82.2f of xylene was charged, and the dehydration reaction was continued at 170° for 6 hours.

After anti-IIS, the obtained resin liquid was precipitated in 5509 isopropanol, washed twice, and dried under reduced pressure to obtain an imide compound. The hydroxyl group of this product is 473 ft'/eq.
-Melting point was 270°C.

Example 3 In Example 1, 2,4-toluenediamine 26.2
yL0.215 mol) to 4,4'-diaminodiphenylmethane 19.8 f<0.0971 mol), and the raw material 45.yL obtained in Synthesis Example 1. OfI C0,148 mol) was added to 26.7y (0,085 mol) of the raw material obtained in Synthesis Example 2.
An imide compound was obtained in the same manner as in Example 1 except that the conditions were the same as in Example 1. The amine equivalent of this product is 1690y
/eqs melting point was higher than BOO-C.

Example 4 In Example 2, 44.8y of the raw material obtained in Synthesis Example 1
LO, 148 mol) as the raw material a obtained in Synthesis Example 2 2.
Of/ (0,102 mol), 8.689 (0,0714 mol) of 2゜4-toluenediamine was added to 4,4'-
12.9 mm (0,0639 mol) of diaminodiphenylmethane and 8.80 mm of m-7 minophenol! (0
, 0761 mol), but the other conditions were the same as in Example 2 to obtain an imide compound. What is the hydroxyl equivalent of this thing? 02'! /eC4, and the melting point was about 270''C.

Example 5 In Example 1, the raw material obtained by 9q in Synthesis Example 1 was added to the raw material obtained in Synthesis Example 3, and the other conditions were the same as in Example 1 to obtain an imide compound. The amine equivalent weight of this product was 506 no/eq, and the melting point was about 260°C.

Example 6 In Example 2, the raw materials obtained in Synthesis Example 1 were used in Synthesis Example 8.
An imide compound was obtained in the same manner as in Example 2 except for using the raw material obtained in Example 2. The hydroxyl equivalent of this product is 4
78 f/eq melting point was approximately 260°C.

Example 7 In Example 1, 2,4-toluenediamine 26.2
11.9 g (0,0971 mol) of N (0,215 mol) and 45.9 g (0,0971 mol) of the raw material obtained in Synthesis Example 1 were added. Of (0,1
48 mol) of the raw material obtained in Synthesis Example 8, 26.7 f
(0,085 mol) and other conditions were the same as in Example 1 to obtain an imide compound. The amine equivalent of this product was 1480 f/eq, and the melting point was above ao-c.

The imide compounds obtained in Examples 1 to 7 were acetone, ME
It was soluble in solvents such as K, methylene chloride, and methyl serotol, and had good compatibility with epoxy resins.

Claims (1)

[Claims] 1) The following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X represents -NH_2 group and/or -OH group, and Ar_1 and Ar_2 each independently represent an aromatic residue. group, R_1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R_2 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
It represents an alkoxy group or a hydroxyl group, and m and n represent numbers from 0 to 80. ] A thermosetting imide compound represented by: 2) The imide compound according to claim 1, wherein m and n represent numbers from 0 to 5. 3) The imide compound according to claim 1, wherein R_1 is an alkyl group having 1 to 8 carbon atoms. 4) The imide compound according to claim 1, wherein R_2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.