JP2670292B2 - Method for producing aromatic amine resin - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel aromatic amine resin and a method for producing the same.

The aromatic amine resin may be used as a curing agent for a raw material of an epoxy resin or another epoxy compound, a curing agent for a raw material of a maleimide resin or another maleimide compound, a curing agent for a raw material of an isocyanate resin or another isocyanate compound, a chelating resin. , Ion-exchange resins, molding materials, insulating coatings, adhesives, rubber modifiers, additives for various resins, deoxidizers and raw materials for polyimide, polyamide, polyamide-imide, etc.

[Conventional technology]

Aromatic amine resins have hitherto been known as condensation products of aromatic amines and formalin. For example, from aniline and formalin, the following general formula (a) Aniline-formalin resin represented by the formula (Kay, Frey; Helvetica, Himmy Acta, Vol. 18, 48)
1 (1935)).

[Problems to be solved by the invention]

A conventional aromatic amine resin such as an aniline-formalin resin composed of a secondary amine represented by the general formula (a) is difficult to be maleimidized or isocyanated.
It is not suitable as a raw material for a maleimide resin or an isocyanate resin. Therefore, the conventional aromatic amine resin is widely used as a curing agent. However, when used as a matrix resin for a heat-resistant composite material or a curing agent such as a heat-resistant adhesive, the conventional aromatic amine resin has a weak point that it cannot meet recent high required performance.

Heat-resistant composite materials and adhesives are required to withstand instantaneous impacts such as stress concentration as external stress.
For this reason, elastically deforming like rubber ideally attracts attention as an important factor. As a criterion for determining such elastic deformation, the elongation at break of the matrix resin is particularly important. The greater the elongation of the matrix resin, the more the defects of the reinforcing agent such as glass fiber and carbon fiber required for the composite material can be compensated. That is, the strength of the entire composite material is improved.

Furthermore, in these matrix resins, in addition to heat resistance and dimensional stability, long-term storage stability is also important,
It is also required that degradation by light and oxygen in the air be small. This oxidation resistance is mainly derived from the structure of the resin, and it is difficult for conventional aromatic amine resins to overcome various drawbacks due to structural defects, together with the requirements for mechanical strength and the like. Was.

Further, the aniline-formalin resin has a crosslinked structure when the molar ratio of formalin at the time of condensation is increased for the purpose of increasing the degree of condensation and improving the mechanical properties and the like. Therefore, its molecular weight can generally only be increased to at most about 600 (Noda et al., 55
Volume 484-487 (1952)).

The present invention has been made in view of the above problems, and a purpose thereof is to provide a cured resin having excellent heat resistance, mechanical strength, dimensional stability, and stability against light and oxygen in air when used as a curing agent. A further object of the present invention is to provide an aromatic amine resin which can be used as a raw material for an isocyanate resin, a maleimide resin and the like having excellent properties, and a method for producing the aromatic amine resin.

[Means for solving the problem]

The present inventors have conducted intensive studies to achieve the above object, and as a result, completed the present invention.

That is, the present invention provides a compound of the formula (I) (Wherein, R ₁ represents a lower alkyl group having 4 or less carbon atoms;
Represents a halogen atom, a hydroxyl group, or a lower alkoxy group having 4 or less carbon atoms. ) Is self-condensed in the presence of an acid catalyst, an amino-α-alkylbenzyl derivative represented by the formula (II) (Wherein, R ₂ represents a halogen atom, a hydroxyl group, a lower alkoxy group having 4 or less carbon atoms or a lower alkyl group having 5 or less carbon atoms, and R ₂ may be the same or different and form a ring M may be an integer of 0 to 3), and the aniline derivative represented by
Formula (II) characterized in that the reaction is carried out at a temperature of 140 to 220 ° C.
I) (In the formula, R ₁ represents a lower alkyl group having 4 or less carbon atoms, R ₂
Represents a halogen atom, a hydroxyl group, a lower alkoxy group having 4 or less carbon atoms or a lower alkyl group having 5 or less carbon atoms, and
R _{2 s} may be the same or different and may form a ring. m represents an integer of 0 to 3, and n represents an integer of 0 to 50. The present invention relates to a method for producing an aromatic amine resin represented by the formula: and an aromatic amine resin having a softening point in the range of liquid to 150 ° C produced by the above method.

Since the aromatic amine resin of the present invention is a resin composed of a primary amine, isocyanate formation, maleimidization, epoxidation and the like are easy.

In addition, when the aromatic amine resin of the present invention is used as a curing agent for another resin (for example, an isocyanate compound, an epoxy compound, a bismaleimide compound, and the like), a resin having high performance can be obtained.

For example, when the resin of the present invention is used as a curing agent for a bismaleimide compound, the cured resin has excellent mechanical strength and dimensional stability, and has no problem with heat resistance, light, and stability against oxygen in air. To give a specific example,
When the resin of the present invention is used as a curing agent for bismaleimide derived from methylenedianiline, the bending strength of the cured resin, the bending elastic modulus, the thermal decomposition initiation temperature in air, the expansion coefficient, and the moisture absorption rate are Kelimide 1050 when using methylenedianiline as the agent (trade name: molding grade,
(Rhone Poulin Co.) resin, and the glass transition temperature and the heat distortion temperature are almost the same.

Further, the prepolymer using the resin of the present invention is soluble in low boiling point solvents (dioxane, methylene chloride, etc.).

Conventionally, a prepreg has been produced by dissolving a prepolymer such as kelimide in a high-boiling point aprotic polar solvent (N-methylpyrrolidone or the like) and impregnating the solution into glass cloth or carbon cloth. In contrast to such a conventional method, when the resin of the present invention is used as a prepolymer, it can be dissolved in a low boiling point solvent, so that the solvent can be easily volatilized and removed, and a very good prepreg can be obtained.

Next, a method for producing the aromatic amine resin of the present invention will be described.

The resin of the present invention is an amino-α represented by the general formula (I).
The condensation reaction of the alkylbenzyl derivative in the presence of an acid catalyst; At this time, it can be produced by using an aniline derivative represented by the general formula (II) as a terminal terminator and reacting at a temperature of 140 to 220 ° C. In the middle of the reaction, a resin containing a secondary amine is formed, and this secondary amine may be led to the primary amine resin of the present invention by a rearrangement reaction. The transfer reaction is carried out by means of (a) increasing the amount of catalyst, (b) increasing the reaction temperature, (c) increasing the reaction time, etc., compared with the reaction conditions under which the secondary amine resin is formed in the condensation reaction. It is performed by Especially (a) or (b)
The means of is effective.

In addition, conventionally known aniline-formalin resin,
As described above, while the molecular weight can be increased to about 600 at most, in the aromatic amine resin of the present invention, by changing the molar ratio of the amino-α-alkylbenzyl derivative and the aniline derivative, the formula ( III) n is 0
From a low molecular weight resin containing as a main component to a relatively high molecular weight resin with n up to about 50 can be arbitrarily selected. Therefore, the production method of the present invention is also characterized in that various forms of aromatic amine resins can be produced depending on the intended use, from those that are liquid at room temperature to those that are resinous with a high softening point.

The liquid to low softening point resin of the present invention can be obtained by increasing the molar ratio of the aniline derivative to the amino-α-alkylbenzyl derivative during the condensation reaction.
The liquid to low softening point resin thus obtained is excellent in workability such as melt blending, impregnation and coating, and is mainly used in the fields of adhesives, paints, urethanes and additives to other resins. You.

The resin of the present invention having a high softening point can be obtained by reducing the molar ratio of the aniline derivative to the amino-α-alkylbenzyl derivative during the condensation reaction. The resin having a high softening point thus obtained can be used in the fields of molding materials, ion exchange resins, laminating resins and the like.

The aromatic amine resin obtained by the production method of the present invention has a molecular weight range of about 200 to 6000, and a softening point range of the resin at room temperature to about liquid (about 150 in the ring and ball method according to JIS-K-2548). point).

Hereinafter, specific examples of the method for producing an aromatic amine resin of the present invention will be described in detail.

First, X in the amino-α-alkylbenzyl derivative represented by the formula (I) is a halogen atom such as a chlorine atom, a bromine atom, a fluorine atom and an iodine atom, a hydroxyl group, and a lower alkoxy group having 4 or less carbon atoms, The alkyl group represented by R ₁ at the α-position of the benzyl group is a lower alkyl group having 4 or less carbon atoms. The substitution position of the amino group is o for the benzyl group.
Position, m position and p position, and may be a mixture thereof.

Such an amino-α-alkylbenzyl derivative represented by the formula (I) can be produced by nitration reduction of the corresponding α-alkylbenzyl derivative. When X is a hydroxyl group, it can also be produced by reduction of nitroalkylophenone represented by the following formula (IV).

Amino-α-alkylbenzyl derivatives that can be produced by these methods include o-amino-α-methylbenzyl chloride, m-amino-α-methylbenzyl chloride,
p-amino-α-methylbenzyl chloride, o-amino-α-methylbenzyl bromide, m-amino-α-methylbenzyl bromide, p-amino-α-methylbenzyl bromide, o-amino-α-methylbenzyl iodide, p-amino-α-isopropylbenzyl fluoride, o-amino-α-methylbenzyl alcohol, m-
Amino-α-methylbenzyl alcohol, p-amino-
α-methylbenzyl alcohol, o-amino-α-ethylbenzyl alcohol, m-amino-α-isopropylbenzyl alcohol, o-amino-α-sec.butylbenzyl alcohol, m-amino-α-n-butylbenzyl alcohol, m-amino-α-methylbenzyl methyl ether, p-amino-α-methylbenzyl methyl ether, p-amino-α-isopropylbenzyl methyl ether, o-amino-α-methylbenzyl isopropyl ether, p-amino-α- Methylbenzyl-n-propyl ether, p-amino-α-ethylbenzyl-n-
Butyl ether and the like. Among them, the most preferred amino-α-alkylbenzyl compound of the present invention is o-, m- and / or p-amino-α-methylbenzyl alcohol.

The amino-α-alkylbenzyl derivative is self-condensed in the presence of an acid catalyst to produce an aromatic amine resin represented by the formula (III) of the present invention, which is represented by the formula (II). Aniline derivative is used as a terminal stopper.
The role of the aniline derivative as the terminal terminator is important in controlling the molecular weight of the aromatic amine resin of the present invention as well as in suppressing the change with time such as viscosity increase of the product. In applications that do not require these roles, there is no problem using the amino-α-alkylbenzyl derivative alone for self-condensation.

In the method using this aniline derivative, the amount used is 1 to 1 mol of the amino-α-alkylbenzyl derivative in the range of 0.02 to 20 mol, preferably 0.1 to 10 mol. These may be charged in the reactor at the same time as all the raw materials containing the amino-α-alkyl bezyl derivative and used, or may be added during the reaction.

R ₂ of the aniline derivative represented by the formula (II) is a halogen atom, a hydroxyl group, a lower alkoxy group having 4 or less carbon atoms, or a lower alkyl group having 5 or less carbon atoms, and 0 to 3 of them. May be the same or different, and may form a ring. Specifically, aniline, o-toluidine, m-toluidine, p-toluidine o-ethylaniline, m-ethylaniline, p-ethylaniline,
o-isopropylaniline, m-isopropylaniline, p-isopropylaniline, on-propylaniline, o-tert-butylaniline, p-tert-butylaniline, on-butylaniline, p-sec-butylaniline, 2,3-xylidine, 2,4-xylidine, 2,6-xylidine, 3,4-xylidine, 3,5-xylidine, 2-methyl-3-ethylaniline, 2-methyl-4-isopropylaniline, 2, 6-diethylaniline, 2-ethyl-
5-tert-butylaniline, 2,4-diisopropylaniline, 2,4,6-trimethylaniline, 4-chloroaniline, 4-bromoaniline, 4-fluoroaniline, 3-
Chloroaniline, 3-bromoaniline, 3,4-dichloroaniline, 3-chloro-o-toluidine, 3-chloro-
p-toluidine, 2,6-dimethyl-4-chloroaniline, o-aminophenol, m-aminophenol, p
-Aminophenol, 2-amino-4-cresol, 4
-Amino-2-tert-butylphenol, 2,6-dimethyl-4-aminophenol, 2,6-dichloro-4-aminophenol, 2-amino-1,3-resorcinol, 4-amino-1,3-resorcinol , 2-aminohydroquinone,
2-methoxyaniline, 3-methoxyaniline, 4-methoxyaniline, 2-isopropoxyaniline, 2,4-
Examples include dimethoxyaniline, 1-naphthylamine, 2-naphthylamine, 1,1-dimethyl-4-aminoindan and the like. Mao, the preferred compound is aniline,
Toluidine, xylidine, aminophenols,
Especially preferred is aniline.

Acid catalysts include inorganic or organic, especially mineral acids, such as hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid, or Friedel-Crafts catalysts such as zinc chloride, stannic chloride, aluminum chloride, ferric chloride, Organic sulfonic acids such as methane sulfonic acid or p-toluene sulfonic acid, and further super strong acids such as trifluoromethane sulfonic acid and Nafion H (trade name: manufactured by DuPont) may be used alone or in combination. . Industrially preferred is inexpensive hydrochloric acid. The amount of the catalyst used is in the range of 1 mol% to 100 mol%, preferably 3 to 50%, when the total amount of the raw material amino-α-alkylbenzyl derivative and aniline derivative is 1 mol. When X of the amino-α-alkylbenzyl compound represented by the formula (II) as a raw material is a halogen atom, the by-produced hydrogen halide can be used as an acid catalyst, and it is necessary to use a catalyst. There is no. The reaction temperature is in the range of 100 to 220 ° C, preferably 120 to 170 ° C.

The reaction time is until the reaction is substantially completed, and specifically, it is 3 to 20 hours.

In the method of the present invention, a solvent inert to the reaction may be used, or the reaction may be performed without a solvent. As the solvent, aromatic hydrocarbons such as benzene, toluene, monochlorobenzene and nitrobenzene, and ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether are often used. After completion of the reaction, the acid used as a catalyst is neutralized with a dilute alkaline aqueous solution such as an aqueous solution of caustic soda, an aqueous solution of potassium hydroxide and aqueous ammonia, and then separated.

In the following reaction, when unreacted aromatic amine compound remains, it is distilled off under vacuum or by steam distillation.

The aromatic amine resin of the present invention is obtained as described above.

〔Example〕

 Hereinafter, the present invention will be described in more detail with reference to examples.

Example 13 330.4 g of m-nitroacetophenone in the closed container of 3
(2 mol) 5% Pd / C catalyst 13.2g and methanol 2000m
l and hydrogen was introduced with vigorous stirring. When the reaction was continued for 12 hours while maintaining the reaction temperature at 50 to 55 ° C., 179
The hydrogen was absorbed and no more absorption was observed, so the reaction was terminated. Next, this reaction system was purged with nitrogen and then filtered to remove the catalyst. The filtrate was concentrated and then vacuum distilled to give 255.2 g of m-amino-α-methylbenzyl alcohol.
I got 93% yield.

Boiling point 135-136 ° C / 3mmHg, melting point 64-65 ° C Next, 68.6 g (0.5 mol) of this m-amino-α-methylbenzyl alcohol and 46.5 g (0.5 mol) of aniline were charged into a reactor, and 52 g (0.5 mol) of 35% hydrochloric acid aqueous solution was added to the catalyst, and nitrogen gas was added. The temperature was raised while introducing.

The temperature was raised to 150 ° C while removing distilled water out of the system, and the reaction was carried out at the same temperature for 8 hours. After completion of the reaction, 50 ml of water was added, 50 ml of toluene was further added, and the mixture was neutralized with 80 g of a 25% aqueous sodium hydroxide solution. After stirring at 70 to 80 ° C. for 1 hour, the mixture was allowed to stand and separated into two layers. After separating the lower aqueous layer by liquid separation,
An azeotropic dehydration was performed in a refluxing state of toluene, and this was filtered to remove a trace amount of an inorganic salt. The solution was concentrated in vacuo to completely remove toluene and some unreacted aniline to give the compound of formula (I)
66 g of a light reddish brown transparent aromatic amine resin corresponding to the case where R ₁ was a methyl group and no R ₂ (m = 0) was obtained.

The composition analysis by high performance liquid chromatography shows that n = 0 in the formula (1) is 12.5Area%, n = 1 is 27.5Area%, n = 2 is 32.9Area%, n ≧ 3 is 27.1Area%, and the average molecular weight is 460. Met.

Amine equivalent of this resin (perchloric acid-glacial acetic acid method)
Was equivalent / (100 g) = 0.662, and the softening point according to JIS-K-2548 was 95 ° C. ¹ H-NMR (CDCl ₃ , TMS) The results of infrared analysis are shown in FIG.

Examples 2 to 4 Using m-amino-α-methylbenzyl alcohol obtained in Example 1 and changing the type and amount of the aniline derivative and the type and amount of the catalyst, the same procedure as in Example 1 was carried out to obtain various Aromatic amine resin of

 The results are shown in FIG.

Example 5 To 34.3 g (0.25 mol) of m-amino-α-methylbenzyl alcohol obtained in Example 1, 5.4 g (0.05 mol) of o-toluidine as an aniline derivative, and 0.57 g of p-toluenesulfonic acid as a catalyst. (0.003 mol) and 10 ml of diethylene glycol dimethyl ether as a solvent were reacted at a temperature of 160 ° C. for 15 hours. After the reaction, the mixture was neutralized with dilute aqueous ammonia and then discharged into cold water, whereupon a precipitate was deposited. This was filtered, washed with water, and vacuum dried to obtain a yellowish brown resin.

The yield was 33 g, the softening point was 141 ° C., and the average molecular weight was 4,200.

Example 6 A reactor was charged with 122.2 g (1 mol) of 1-phenylethanol and 300 ml of 1,2-dichloroethane and cooled to -5 ° C. Next, a mixed acid consisting of 80 g of 95% nitric acid and 360 g of concentrated sulfuric acid was added dropwise over a period of 5 hours in the range of 0 to -5 ° C. after that,
After aging for 1 hour at the same temperature, the mixture was diluted with 500 g of ice water, and the lower waste acid layer was separated and removed. Next, 500 g of water was added and the mixture was washed with water and separated, and the organic layer was concentrated to give a pale yellow oil.
8 g were obtained. This is gas chromatography and ¹ H-NM
As a result of analysis by R, it was a composition containing 94.5% of 4-nitro-α-methylbenzyl alcohol. ¹ H-NMR (CDCl ₃ , TMS) (δ) 1.7 (3H, d CH (OH) CH ₃ ) 6.1 (1H, q CH (OH) CH ₃ ) 7.65 (2H, d 2,6H, J _{2-3 , 6-5 = 8.0Hz) 8.35 (2H} , d 3.5H, J 3-2, 5-6 = 8.0Hz) Next, the composition with methanol 500ml and 5% Pd / C catalyst 5g, autoclave Reduction with hydrogen in. The reaction temperature was 25 to 35 ° C., and hydrogen pressure was 5 to 10 kg / cm ² for 3 hours to complete the reaction. After the reaction, filtration was performed to remove the catalyst, and methanol as a solvent was distilled off. Since it crystallized when left unattended,
A small amount of methanol was added to this and filtered to give 4-amino-α.
97.5 g of methylbenzyl alcohol (total yield 71%) was obtained.

The melting point was 91 to 93 ° C, and the results of elemental analysis were as follows.

This 4-amino-α-methylbenzyl alcohol 68.6
g (0.5 mol) and aniline 186.2 g (2 mol) were charged into a reactor, and 25 g (0.25 mol) of sulfuric acid was charged in the catalyst to carry out the reaction.

The reaction temperature was 140-150 ° C, and the reaction time was 15 hours.
After the reaction, add a 15% caustic soda solution to the slightly viscous solution.
When 0 g was added, and the mixture was sufficiently stirred and allowed to stand, it was separated into two layers. The lower aqueous layer was removed, and 100 g of 20% saline was further added to wash and separate the layers. This was concentrated under reduced pressure to recover unreacted aniline to obtain a pale yellow oily aromatic amine resin.

 The yield was 60 g and the average molecular weight was 320.

Example 7 4-amino-α-methylbenzyl bromide 20.1 g
(0.1 mol) and 2,4-xylidine (60.6 g, 0.5 mol) were charged into the reactor, and the temperature was raised as it was to maintain the temperature at 50 to 70 ° C. for 3 hours. Next, the temperature was raised again and the reaction was carried out at a temperature of 140 to 150 ° C. for 8 hours to complete the reaction. Post-treatment after the reaction was carried out in the same manner as in Example 6 to obtain 20.5 g of a red-brown candy-like aromatic amine resin.

 The average molecular weight was 310.

Example 8 4-Amino-α-methylbenzyl methyl ether 15.1
g (0.1 mol), 107.2 g (1.0 mol) of p-toluidine, and 52 g of a 35% hydrochloric acid aqueous solution were added to the catalyst in the reactor, and the mixture was reacted under reflux of water for 7 hours. After that, the temperature was raised while distilling water off, and the reaction was carried out at a temperature of 160 ° C. for 8 hours. Post-treatment after the reaction was carried out in the same manner as in Example 6, to obtain 19.5 g of a red-brown oily aromatic amine resin.

 The average molecular weight was 270.

Example 9 m-amino-α-n-butylbenzyl alcohol 20.1
Using g (0.1 mol), aniline 18.6 g (0.2 mol) and 35% hydrochloric acid aqueous solution 20.8 g, a condensation reaction was performed in the same manner as in Example 1 to obtain 24.3 g of a reddish brown resinous aromatic amine resin.

 The softening point was 55 ° C.

Example 10 A reactor was charged with 120 g (1 mol) of acetophenone and 300 ml of 1,2-dichloroethane, and cooled to 0 ° C. Next, 95
A mixed acid consisting of 80 g of% nitric acid and 360 g of concentrated sulfuric acid was added dropwise in the range of 0 to 10 ° C over 5 hours to carry out a nitration reaction. The post-treatment was carried out in the same manner as in Example 6 to obtain 162 g of crude nitroacetophenone crystals.

 Yield 98%.

 The analysis results by gas chromatography were o-body 8.2Area% m-body 89.4Area% p-body 1.1Area% and other 1.3Area%.

Next, this crude nitroacetophenone was added to a 5% Pd / C catalyst.
The crude amino-α-methylbenzyl alcohol was reduced with 9 g and 1000 ml of methanol under the same conditions as in Example 1.
8 g were obtained. The total yield was 93.3%, and the analysis value by gas chromatography was almost the same as the analysis value with the nitro compound.

Based on this crude amino-α-methylbenzyl alcohol, 295 g (2.78 mol) of aniline and 194 g of 35% hydrochloric acid aqueous solution
(1.86 mol) in the same manner as in Example 1 to obtain 155 g of a red-brown candy-like aromatic amine resin.

 The average molecular weight was 310.

Use Example 1 33 parts by weight of the aromatic amine resin obtained in Example 1 and 100 parts by weight of bismaleimide-S (manufactured by Daiwa Kasei Kogyo Co., Ltd.) were mixed and heated and melted at 180 ° C. for 10 minutes to produce a prepolymer. did.

The solubility of this prepolymer in various solvents was measured. The results are shown in Table 2 as Experimental Example 1. Further, the appearance, softening temperature, gelation time and bulk specific gravity of this prepolymer are shown in Table 3 as Experimental Example 1. For comparison, Table 2 and Table 3 show, as Comparative Experimental Example 1, the same results as those of commercially available Kelimide-1050 (trade name: molding grade, manufactured by Nippon Polyimide Co., Ltd.).

Next, each of the prepolymer and Kelimide-1050 was compression-molded at a temperature of 200 ° C. under a pressure of 40 kg / cm ² for 1 hour, and then post-cured at 250 ° C. for 4 hours to obtain a cured test piece. Was prepared. The mechanical strength and thermophysical properties of this test piece were measured. The results are shown in Table 3 as Experimental Example 1 and Comparative Experimental Example, respectively.

Use Example 2 100 g of the aniline resin obtained in Example 10 was dissolved in 1400 g of dry orthochlorobenzene. Next, 270 g of phosgene was blown into the solution at a temperature of 5 to 10 ° C. for 3 hours. After that, slowly blow phosgene and raise the temperature to 120-1
It was aged at 40 ° C for 2 hours. Then, the ventilation of phosgene was stopped, and the ventilation was switched to the ventilation of nitrogen gas. The reaction solution was concentrated in vacuo to recover the solvent orthodichlorobenzene and 120 g of a light brown oily isocyanate resin was obtained.

9.8 g of the isocyanate resin obtained as described above was dissolved in 400 g of methylene chloride to obtain "solution A". Then, DE
TDA (Ethylene Corporation) 2.2g / JEFFAMINE T
-5000 (manufactured by Texaco Chemical) 10 g / methylene chloride 25
A good polyurea film can be obtained by mixing the “solution B” composed of 00 g and the “solution A”, casting the mixture on a glass plate, leaving it to stand overnight, and post-curing at 120 ° C. for 2 hours. Was.

〔The invention's effect〕

As described above, since the aromatic amine resin of the present invention is a resin composed of a primary amine, it can be easily converted to isocyanate, maleimidized, epoxy, etc., and can be used as a raw material for polyamide or the like.

Furthermore, when the aromatic amine resin of the present invention is used as a curing agent or as a raw material for other resins, the resulting cured resin has mechanical strength, dimensional stability, heat resistance, light and oxygen in the air. It has excellent stability and a fast curing speed.

Further, since the prepolermer using the aromatic amine resin of the present invention is soluble in a low melting point solvent, a good prepoler can be easily obtained.

Further, the aromatic amine resin of the present invention can be produced from inexpensive raw materials by a simple operation, and can be obtained by a pollution-free method without by-products.

Since the aromatic amine resin of the present invention has the above effects, it is added to a curing agent, a raw material of the curing resin, a chelate resin, an ion exchange resin, a molding material, an insulating paint, an adhesive, a rubber modifier, and various resins. It can be used in various fields such as agents, deoxidizers, and raw materials for polyimide, polyamide, and polyamideimide.

[Brief description of the drawings]

FIG. 1 is a graph showing the IR analysis result of the aromatic amine resin obtained in Example 1.

Claims (1)

(57) [Claims] (1) Formula (I) (Wherein, R ₁ represents a lower alkyl group having 4 or less carbon atoms;
Represents a halogen atom, a hydroxyl group, or a lower alkoxy group having 4 or less carbon atoms. ) Is self-condensed in the presence of an acid catalyst, an amino-α-alkylbenzyl derivative represented by the formula (II) (Wherein, R ₂ represents a halogen atom, a hydroxyl group, a lower alkoxy group having 4 or less carbon atoms or a lower alkyl group having 5 or less carbon atoms, and R ₂ may be the same or different and form a ring M may be an integer of 0 to 3), and the aniline derivative represented by
Formula (II) characterized in that the reaction is carried out at a temperature of 140 to 220 ° C.
I) (In the formula, R ₁ represents a lower alkyl group having 4 or less carbon atoms, R ₂
Represents a halogen atom, a hydroxyl group, a lower alkoxy group having 4 or less carbon atoms or a lower alkyl group having 5 or less carbon atoms, and
R _{2 s} may be the same or different and may form a ring. m represents an integer of 0 to 3, and n represents an integer of 0 to 50. ) A method for producing an aromatic amine resin represented by: