JPH06122745A - Polyamine and imide compound - Google Patents

Abstract

PURPOSE:To obtain a polyamine which has a low melting point, is soluble in a high concentration even in a low-boiling solvent and excellent in workability, can give a cured product of excellent heat resistance, and is useful as an intermediate for an imide compound by selecting a specified polyamine. CONSTITUTION:A polyamine of formula I (wherein R<1> and R<2> are each halogen, hydroxyl, phenyl, 1-4 C alkoxyl, phenoxy, 1-10 C substituted phenoxy, 1-6 C alkyl or 1-6 C alkenyl; R<3> is H, phenyl-or 1-6 C alkyl; (k) is 0-3; (l) is 0-4; (m) is 1-5; and (n) is 0-10) is selected. A compound of formula II (wherein D is a 2-24 C group having a polymerizable unsaturated double bond) is selected as an imide compound derived from the above polyamine.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to novel polyamine and imide compounds.

[0002]

2. Description of the Related Art In recent years, in the fields of electric / electronics, transportation equipment such as airplanes / vehicles, etc., materials having higher heat resistance have been demanded as the performance of the equipment has been improved and the size and weight have been reduced.
Conventionally, epoxy resins, maleimide resins and polyimide resins have been used in this field. However, although the epoxy resin has excellent mechanical properties and electrical properties, it does not necessarily have sufficient heat resistance. Further, although the polyimide resin has excellent heat resistance, it is often insoluble and infusible so that molding is often difficult. Addition-type bismaleimide resins are known as polyimides having improved moldability, but N, N '
Known bismaleimides typified by -4,4'-diphenylmethane bismaleimide have a high melting point and a low solubility in a low boiling point solvent such as acetone, and thus DMF.
(N, N-Dimethylformamide), NMP (N-methyl-2-pyrrolidone) and other high-boiling polar solvents dissolve only at low concentrations, resulting in poor workability. Also, the formula (c)

[Chemical 3] The bismaleimide represented by is also known, but its solubility in a low boiling point solvent is still insufficient.

[0003]

The present invention overcomes the drawbacks of conventional bismaleimide compounds, has a low melting point and is soluble in a low boiling point solvent at a high concentration, and has excellent workability and excellent heat resistance. It is intended to provide an imide compound that gives a cured product and a polyamine as a raw material thereof.

[0004]

The present invention comprises the following inventions. (1) General formula (a)

[Chemical 4] (In the formula, R ¹ and R ² are a halogen atom, a hydroxyl group, a phenyl group, an alkoxy group having 4 or less carbon atoms, a phenoxy group,
It represents a substituted phenoxy group having 10 or less carbon atoms, an alkyl group having 6 or less carbon atoms or an alkenyl group having 6 or less carbon atoms, and R ¹ and R ² may be the same or different from each other. R ³ represents a hydrogen atom, a phenyl group or an alkyl group having 6 or less carbon atoms. K is an integer of 0 to 3, L is 0 to 4
, M is an integer of 1 to 5, and n is a number of 0 to 10. ) The polyamine represented by.

(2) General formula (b)

[Chemical 5] (In the formula, R ¹ and R ² are a halogen atom, a hydroxyl group, a phenyl group, an alkoxy group having 4 or less carbon atoms, a phenoxy group,
It represents a substituted phenoxy group having 10 or less carbon atoms, an alkyl group having 6 or less carbon atoms or an alkenyl group having 6 or less carbon atoms, and R ¹ and R ² may be the same or different from each other. R ³ represents a hydrogen atom, a phenyl group or an alkyl group having 6 or less carbon atoms. K is an integer of 0 to 3, L is 0 to 4
, M is an integer of 1 to 5, and n is a number of 0 to 10. D represents a group having a polymerizable unsaturated double bond having 2 to 24 carbon atoms. ) An imide compound represented by:

The polyamine of the first invention is obtained by a condensation reaction between anilines and a carbonyl compound. The anilines used in the present invention include aniline, toluidine, ethylaniline, propylaniline, butylaniline, xylidine, diethylaniline, ethylmethylaniline, ethylpropylaniline, ethylbutylaniline, methylpropylaniline, dipropylaniline, trimethylaniline. , Cyclohexylaniline, phenylaniline, chloroaniline, dichloroaniline, bromoaniline, dibromoaniline, fluoroaniline, chlorotoluidine, chloroxylidine, aminophenol,
Examples include various isomers such as aminocresol, methoxyaniline, dimethoxyaniline, methoxymethylaniline, hydroxymethoxyaniline, phenoxyaniline, methylphenoxyaniline, vinylaniline and allylaniline. These anilines can be used not only alone but also as a mixture of two or more kinds.

The carbonyl compound used in the present invention has at least one substituent R ² in the general formula (a).
A compound in which one carbonyl group is directly bonded to each benzene nucleus, specifically, tolualdehyde, ethylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde,
Phenylbenzaldehyde, phenoxybenzaldehyde, methylphenoxybenzaldehyde, vinylbenzaldehyde, allylbenzaldehyde, methylacetophenone, benzophenone, chlorobenzaldehyde, dichlorobenzaldehyde, bromobenzaldehyde, dibromobenzaldehyde, fluorobenzaldehyde,
Various isomers and derivatives such as difluorobenzaldehyde may be mentioned.

These carbonyl compounds can be used not only alone but also as a mixture of two or more kinds, and
Other carbonyl compounds may be mixed with the carbonyl compound of the present invention to the extent that the effects of the present invention are not impaired. Other carbonyl compounds include formaldehyde, acetaldehyde, acetone, benzaldehyde,
Examples include various isomers and derivatives such as acetophenone, aminobenzaldehyde, acrolein, crotonaldehyde, cinnamic aldehyde, glyoxal, and 2,3-naphthalenedialdehyde.

Condensation reactions of these anilines and carbonyl compounds are carried out by using inorganic acids such as HCl and H ₂ SO ₄ , acetic acid, p
-Toluenesulfonic acid, organic acids such as thioglycolic acid,
In the presence of an acidic catalyst such as Lewis acid, or an ion exchange resin,
It can be obtained by a well-known method of post-treatment such as condensation at a temperature of 40 to 150 ° C., neutralization, washing with water, distillation of unreacted aniline and the like. When the target substance precipitates as crystals, the crystals may be filtered off, washed and dried.

The n in the general formula (a) can be adjusted by the synthesis conditions such as the charged molar ratio of the aniline and the carbonyl compound and the amount of catalyst. Although n is appropriately adjusted depending on the purpose, it is generally 0 to 10 and preferably 0 to 3.

The imide compound of the second invention can be obtained by imidizing the polyamine of the first invention and the unsaturated dicarboxylic acid anhydride by a known method. For example, a known method of imidization using a conventional dehydrating agent such as acetic anhydride or a method described in Japanese Patent Publication No. 2-58267 can be applied.

Specifically, 1 to 1. 1 of unsaturated dicarboxylic acid anhydride is added to 1 equivalent of the amino group in the polyamine compound.
Using 3 moles, an addition reaction is carried out in a mixed solvent of an aromatic hydrocarbon solvent or a halogenated hydrocarbon solvent and an aprotic polar solvent, and dehydration is performed in the temperature range of 80 to 200 ° C. for 0.5 to 10 hours in the presence of an acidic catalyst. Carry out the ring closure reaction.

As the aromatic hydrocarbon solvent, for example, benzene, toluene, xylene, etc. are used, and as the halogenated hydrocarbon solvent, for example, chloroform, 1,2-dichloroethane, chlorobenzene, etc. are used. As the aprotic polar solvent, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone and the like can be used. The mixing ratio of the aromatic hydrocarbon solvent or halogenated hydrocarbon solvent and the aprotic polar solvent in the mixed solvent is 50: 5.
It is about 0 to 99: 1. This mixed solvent is usually used in an amount of 1 to 10 times the weight of the raw materials.

After completion of the reaction, the reaction solution is added dropwise to a poor solvent to precipitate the desired product, and then the product is obtained by filtering, washing and drying.

The unsaturated dicarboxylic acid anhydrides used in the present invention include maleic anhydride, itaconic anhydride, citraconic anhydride, dichloromaleic anhydride, and Diels-Alder reaction products of these unsaturated dicarboxylic anhydrides and dienes. Examples thereof include Diels-Alder reaction products of maleic anhydride with cyclopentadiene, furan and terpinene. In general formula (b), n is generally suitable from 0 to 10, preferably 0.
~ 3.

The imide compound of the second invention can be cured by a known method. For example, the imide compound of the present invention has a low melting point, and by heating and melting alone, a tough cured product is obtained. Also, since it dissolves in a low boiling point solvent at a high concentration, it is easy to form a varnish and after impregnating the glass cloth,
The solvent is distilled off in a short time to obtain a prepreg. A cured plate is obtained by stacking several of the obtained prepregs and press-molding them.

The imide compound can be used alone, but various polymerization initiators and catalysts can be added for the purpose of promoting the crosslinking reaction. It is also possible to add other types of imide compounds or polyimides,
In addition, curing by addition reaction with amines (including polyamines) and allylphenols, and combination with epoxy resin, phenol resin, vinyl compound, acrylate, methacrylate, cyanate ester, silicone resin, etc. It is also possible to carry out denaturation.
Further, depending on the application, filler such as silica or glass fiber,
A reinforcing material such as carbon fiber or aramid fiber can be used.

[0018]

INDUSTRIAL APPLICABILITY The imide compound of the present invention has a lower melting point than conventional bismaleimide compounds, and since it dissolves at a high concentration in a solvent having a low boiling point, it is excellent in workability and can be used as an adhesive, a paint, a prepreg, or a laminate. It can be used in a wide range of fields such as plates, molding materials, casting materials, and composite materials. Further, the polyamine of the present invention is important as an intermediate of the imide compound having the above characteristics.

[0019]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. Example 1 Synthesis of Polyamine 595.2 g (6.40 mol) of aniline in a 2 liter four-necked flask equipped with a stirrer, thermometer and condenser,
3-Phenoxybenzaldehyde 158.4 g (0.8
0 mol) and 32.4 g (0.32 mol) of concentrated hydrochloric acid were charged, the internal temperature was raised to 110 ° C., and the temperature was kept for 7 hours. After completion of the reaction, 48% sodium hydroxide aqueous solution at an internal temperature of 60 ° C. 3
2.0 g (0.38 mol) was added while paying attention to the heat of neutralization, and the mixture was stirred for 1.5 hours to precipitate crystals. After cooling to room temperature and separating the crystals by filtration, the crystals were washed twice with 300 g of water and then twice with 500 g of toluene, and then at 70 ° C.
By drying under reduced pressure at 232 g, 232 g of white crystals (referred to as ANPA) was obtained. The average number of repeating units n (see general formula (a)) by GPC analysis was 0. FD-M
368 corresponding to the molecular weight of the target substance by S spectrum
Fragments were detected. ANPA is a compound of the general formula (a) in which L = 0, R ² : phenoxy group (3
Position), M = 1, R ³ : H, n = 0.

Example 2 Synthesis of Polymaleimide A maleic anhydride of 10.8 g (0. 0) was added to a 300 ml four-necked flask equipped with a stirrer, a thermometer and a condenser.
11 mol) and 67.9 g of acetone were charged and dissolved with stirring. To this solution, 18.4 g (0.05 mol) of ANPA was dividedly charged at an internal temperature of 5 ° C. over 2 hours, stirred for 1 hour, and left overnight. Nickel acetate tetrahydrate 0.107
g (0.00043 mol), triethylamine 3.04
g (0.03 mol) was charged, and subsequently, 13.3 g (0.13 mol) of acetic anhydride was added dropwise at an internal temperature of 40 ° C over 30 minutes.
The temperature was kept at 10 ° C for 10 hours. After completion of the reaction, the reaction solution was dropped into 390 g of a water-methanol (1: 1) mixed solvent which was stirred at a high speed, and stirred for 1 hour to crystallize. The crystals are separated by filtration, washed twice with 320 g of methanol and then dried under reduced pressure at 60 ° C. to obtain the objective yellow crystals (designated ANPA-M).
0 g was obtained. The melting point of this product was 132 ° C. ¹ H
-NMR (chloroform d ₃₎ δ (ppm) is 5.5
6 (s1H), 6.79 (s1H), 6.83 to 7.3.
It was 5 (m17H). In the IR (KBr tablet) absorption spectrum, characteristic absorption was observed at 1710 cm ^-1 (derived from the imide ring). ANPA-M is a compound in which L, R ² , M, R ³ and n in the general formula (a) are the same as those in the above ANPA, and D has an unsaturated double bond having 2 carbon atoms.

Example 3 Synthesis of Polyamine 390.6 g (4.20 mol) of aniline was placed in a 2 liter four-necked flask equipped with a stirrer, thermometer and condenser.
4-isobutylbenzaldehyde 113.4 g (0.7
(0 mol) and 21.7 g (0.26 mol) of concentrated hydrochloric acid were charged, the internal temperature was raised to 110 ° C., and the temperature was kept for 4 hours. After completion of the reaction, 48% sodium hydroxide aqueous solution at an internal temperature of 60 ° C. 3
3.6 g (0.27 mol) was charged and neutralized. Chloroform (537 g) was charged, and the mixture was washed 3 times with ion-exchanged water (300 g) and liquid separation was repeated, and the organic layer was concentrated to obtain 203.4 g of a target resinous material (referred to as ANIB). The average number of repeating units n by GPC analysis was 0.17. FD
-MS spectrum shows 3 corresponding to the molecular weight of the target compound.
30 (n = 0), 567 (n = 1), 804 (n = 2)
Fragments were detected. ANIB is represented by the formula (a) in which L = 0, R ² : isobutyl group (4
Position), M = 1, R ³ : H, n = 0.17 (average value).

Example 4 Synthesis of Polymaleimide Maleic anhydride 1 in a 500 ml four necked flask.
0.8 g (0.11 mol) and 108 g of toluene were charged and dissolved. A solution prepared by previously dissolving 16.5 g (0.01 equivalent) of ANIB in 16.5 g of NMP and 16.5 g of toluene was added dropwise to the solution at an internal temperature of 25 ° C. over 1 hour, and the mixture was stirred for 4 hours after the addition. p-toluenesulfonic acid
2.85 g (0.015 mol) of monohydrate was charged, the internal temperature was raised to the toluene reflux temperature, and an azeotropic dehydration cyclization reaction was carried out at 120 ° C. for 4 hours. During this period, toluene was returned to the reaction system by the azeotropic dehydration tube, and the produced water was continuously distilled out of the reaction system. After cooling, wash 4 times with 400 g of deionized water.
Separation was repeated. After washing with water, the organic layer was concentrated under reduced pressure at 80 ° C. to obtain a solid. After crushing this solid, it was further dried under reduced pressure at 80 ° C. In this way, the target yellow powder (ANIB
-M). The softening point of this product was 120 ° C. ¹ H-NMR (chloroform d ₃ ) δ (ppm)
Is 0.90 (d6H), 1.84 (m1H), 2.4
5 (d2H), 5.56 (s1H), 6.79 (s4
H), 7.05 (d4H) and 7.25 (d8H). IR (KBr tablet) absorption spectrum is 1710 cm
^-1 (derived from imide ring) showed characteristic absorption. ANIB
In the general formula (a), —M is a compound in which L, R ² , M, R ³ and n are the same as those in the above ANIB, and D is a compound having an unsaturated double bond having 2 carbon atoms.

Comparative Example 1 Formula

[Chemical 6] Synthesis of polyamine represented by. In Example 1, 3-
Except for changing 158.4 g (0.80 mol) of phenoxybenzaldehyde to 84.8 g (0.80 mol) of benzaldehyde, the same reaction and post-treatment were carried out to obtain 180 g of white crystals (referred to as ANBA). The average number of repeating units n of this product by GPC treatment analysis was 0. The FD-MS spectrum detected 274 fragments corresponding to the molecular weight of the target substance.

Comparative Example 2 Synthesis of bismaleimide represented by the formula (C). In Example 2, 18.4 g (0.05 mol) of ANPA was added to AN.
The same reaction and post-treatment were carried out except that BA was changed to 13.7 g (0.05 mol) to obtain 16.3 g of yellow crystals (designated ANBA-M). The melting point of this product was 210 ° C. ¹ H-NMR (chloroform d ₃ ) δ (pp
m) is 5.56 (s1H), 6.79 (s4H),
The values were 7.05 (t5H) and 7.25 (d8H). I
As for R (KBr tablet), the absorption spectrum showed a characteristic absorption at 1710 cm ^-1 (derived from the imide ring).

Table 1 shows Example 2, Example 4 and Comparative Example 2.
And the conventional N, N'-4,
4 shows the solubility of 4′-diphenylmethane bismaleimide (referred to as Comparative Example A). As is clear from this table, the polymaleimide of the present invention is more soluble in low boiling point solvents than conventional ones, and can be used in a wide range of fields.

[0026]

[Table 1]

Application Example 1 20 parts by weight of ANPA-M obtained in Example 2 and 0.2 parts by weight of triphenylphosphine were dissolved in 80 parts by weight of N, N-dimethylformamide with stirring at room temperature to obtain a uniform varnish. . Use this varnish with glass cloth (Kanebo Corporation)
KS-1600 manufactured by K.K., and dried in an oven at 160 ° C. for 10 minutes to obtain a prepreg. The resin powder was rubbed off from the obtained prepreg, and the resin powder was press-molded at 200 ° C. for 5 hours to obtain a uniform cured product. The glass transition temperature of this cured product was 205 ° C.

Application Example 2 A uniform cured product was obtained by the same procedure as in Application Example 1 except that ANIB-M obtained in Example 4 was used instead of ANPA-M. The glass transition temperature of this cured product was 196 ° C. Comparative Application Example 1 In Application Example 1, instead of ANPA-M, N, N'-
An attempt was made to varnish using 4,4′-diphenylmethane bismaleimide under the same conditions, but crystals were not completely dissolved and a uniform varnish could not be obtained. Comparative Application Example 2 Instead of ANPA-M in Application Example 1, ANBA-M
An attempt was made to make a varnish under the same conditions, but the crystals were not completely dissolved and a uniform varnish could not be obtained.

Claims (4)

[Claims] 1. A compound represented by the general formula (a): (In the formula, R ¹ and R ² are a halogen atom, a hydroxyl group, a phenyl group, an alkoxy group having 4 or less carbon atoms, a phenoxy group,
It represents a substituted phenoxy group having 10 or less carbon atoms, an alkyl group having 6 or less carbon atoms or an alkenyl group having 6 or less carbon atoms, and R ¹ and R ² may be the same or different from each other. R ³ represents a hydrogen atom, a phenyl group or an alkyl group having 6 or less carbon atoms. K is an integer of 0 to 3, L is 0 to 4
, M is an integer of 1 to 5, and n is a number of 0 to 10. ) The polyamine represented by. 2. In the general formula (a), R ² is a phenoxy group or an alkyl group having 6 or less carbon atoms, R ³ is a hydrogen atom,
The polyamine according to claim 1, wherein L = 0, M = 1, and n = 0-3. 3. A compound represented by the general formula (b): (In the formula, R ¹ and R ² are a halogen atom, a hydroxyl group, a phenyl group, an alkoxy group having 4 or less carbon atoms, a phenoxy group,
It represents a substituted phenoxy group having 10 or less carbon atoms, an alkyl group having 6 or less carbon atoms or an alkenyl group having 6 or less carbon atoms, and R ¹ and R ² may be the same or different from each other. R ³ represents a hydrogen atom, a phenyl group or an alkyl group having 6 or less carbon atoms. K is an integer of 0 to 3, L is 0 to 4
, M is an integer from 1 to 5, and n is a number from 0 to 10.
D represents a group having a polymerizable unsaturated double bond having 2 to 24 carbon atoms. ) An imide compound represented by: 4. In the general formula (b), R ² is a phenoxy group or an alkyl group having 6 or less carbon atoms, R ³ is a hydrogen atom,
The imide compound according to claim 3, wherein L = 0, M = 1, n = 0 to 3, and D is a group represented by the formula —CH═CH—.