JPH01123828A - Method for producing aromatic amine resin - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing an aromatic amine resin.

The aromatic amine resin obtained by the method of the present invention is a curing agent for epoxy resin raw materials or other epoxy compounds, a curing agent for maleimide resin raw materials or other maleimide compounds, an isocyanate resin raw material or other isocyanate compounds. curing agent, chelate resin,
It can be used in many ways, including ion exchange resins, molding materials, insulating paints, adhesives, rubber modifiers, additives for various resins, deoxidizing agents, and raw materials for polyimide, polyamide, and polyamideimide.

[Conventional technology]

Aromatic amine resins have been known as condensates of aromatic amines and formalin. For example, an aniline-formalin resin represented by the following formula (d) is produced from aniline and formalin.
81 (1935)).

[Problem that the invention seeks to solve]

Conventional aromatic amine resins such as aniline-formalin resins consisting of secondary amines, as represented by general formula (d), are difficult to maleimide or incyanate.
It is not suitable as a raw material for maleimide resin or incyanato resin. Therefore, conventional aromatic amino resins have been frequently used as curing agents. However, when used as a curing agent for matrix resins for heat-resistant composite materials, heat-resistant adhesives, and the like, conventional aromatic amine resins are no longer able to meet the advanced performance requirements of recent years.

Heat-resistant composite materials, heat-resistant adhesives, and the like are required to withstand instantaneous shocks such as stress concentration as external stress. For this reason, ideally, elastic deformation like rubber is attracting attention as an important element. As a criterion for determining such elastic deformation, elongation of the matrix resin at break is especially important. The greater the elongation of the matrix resin, the more it can compensate for the drawbacks of reinforcing agents such as glass fiber and carbon fiber required for composite materials. In other words, the strength of the composite material as a whole is improved.

Furthermore, in addition to heat resistance and dimensional stability, long-term storage stability is also important for these matrix resins.
It is also required that there is little deterioration due to light and oxygen in the air. This oxidation resistance is mainly derived from the structure of the resin, and in addition to the above-mentioned requirements for mechanical strength, it is difficult for conventional aromatic amino resins to overcome various drawbacks caused by structural defects. there were.

Further, when the molar ratio of formalin is increased in the aniline-formalin resin during condensation for the purpose of increasing the degree of condensation and improving mechanical properties, etc., the aniline-formalin resin becomes a crosslinked structure.

Therefore, in general, its molecular weight can only be increased to about 600 (Noda et al., Industrial Chemistry Journal 55
Volumes 484-487 (1952)).

The inventors of the present invention have discovered a new aromatic amine resin capable of improving these drawbacks, and the applicant has filed an application for the same (Japanese Patent Application No. 1987-230987). However, since this resin consists of a secondary amine, it is difficult to convert it into isocyanate or maleimide. Furthermore, when used as a curing agent, there still remain problems such as the need to use a relatively large amount and the curing speed being relatively slow.

Therefore, the present inventors further investigated to solve these remaining problems, and as a result, the novel primary amine resin, which is the object of the production method of the present invention obtained by subjecting the above-mentioned amine resin to a transfer reaction, Having found that the various problems mentioned above could be solved, the applicant filed an application (Patent Application No. 62
-252517). In addition, the applicant has proposed the above-mentioned primary amine resin as well as a method for producing the same. The method for producing the same comprises an aromatic amine compound and the following: This is a production method based on reacting an aralkyl alcohol derivative represented by (wherein R2 represents a hydrogen atom, an acyl group, or a lower alkyl group having 4 or less carbon atoms) in the presence of an acid catalyst.

The main object of the present invention is to further improve the above-mentioned production method, and to provide a method for producing the primary amine resin that is cheaper and causes fewer side reactions.

[Means for solving problems]

The present inventors have completed the present invention as a result of extensive studies to achieve the above object.

That is, the present invention is based on the general formula (a) (wherein R 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 the R's are the same) may be different,
It may form a ring. 2 indicates 1 or 2, m is 0~
Indicates an integer of 3. ), and an aromatic amine compound represented by the general formula (b) (wherein A is a phenylene group, an alkyl-substituted phenylene group, a diphenylene group, Represents a diphenyl ether group or a naphthylenyl group, R is a halogen atom, a hydroxyl group, and has 4 carbon atoms.
It represents the following lower alkoxy group or lower alkyl group having 5 or less carbon atoms, and R may be the same or different from each other, and may form a ring. l represents 1 or 2,
m represents an integer of 0 to 3, and n represents an integer of 0 to 300. ) is a method for producing an aromatic amine resin represented by:

Hereinafter, the method for producing aromatic amine resin of the present invention will be explained in detail.

The method of the present invention can be carried out in a two-step reaction between an aromatic amine compound represented by the general formula (a) and a shalogenomethyl derivative represented by the general formula (b) without using a catalyst. In the first stage of the reaction, a resin containing a secondary amine is produced, and this secondary amine may be introduced into the primary amine resin by a rearrangement reaction (second stage reaction). The rearrangement reaction is achieved using hydrogen halide generated when the primary amine resin is produced as a catalyst. In order to speed up this rearrangement reaction, measures such as (a) increasing the amount of the same or different catalyst, (b) raising the reaction temperature, and (c) lengthening the reaction time, are better than the reaction conditions under which the secondary amine resin is produced. This is done by In particular, increasing the amount of catalyst is effective.

In addition, while the conventionally known aniline-formalin resin can only increase the molecular weight to about 600 as mentioned above, the aromatic amine resin of the present invention has an aromatic amine compound and a bishalogenomethyl By changing the molar ratio of the derivatives, it is possible to arbitrarily produce resins ranging from low molecular weight resins whose main component is those in general formula (e) where n is O to high molecular weight resins where n is up to about 300. Therefore, the production method of the present invention is characterized in that it can produce aromatic amine resins in various forms, from those in liquid form at room temperature to those in the form of resins with high softening points, depending on the intended use.

A liquid to low softening point aromatic amine resin can be obtained by increasing the molar ratio of the aromatic amine compound to the bishalogenomethyl derivative during the condensation reaction. The liquid to low softening point resin thus obtained has excellent workability in melt compounding, impregnation, coating, etc., and is mainly used in fields such as adhesives, paints, urethanes, and additives to other resins. Ru.

Aromatic amine resins with high softening points, during their condensation reactions,
It can be obtained by keeping the molar ratio of the bishalogenomethyl derivative and the aromatic amine close to the theoretical amount. The high softening point resin thus obtained can be used in fields such as molding materials, ion exchange resins, and lamination resins.

The molecular weight range of the aromatic amine resin obtained by the production method of the present invention is about 300 to 60,000, and the softening point range of the resin is from liquid at room temperature to about 250°C (
Ring and ball softening point according to JIS-2548).

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

First, 1 to 15 moles, preferably 1.1 to 10 moles, of an aromatic amine compound represented by the general formula (a) is added to 1 mole of the bishalogenomethyl derivative represented by the formula (b), and as it is. The temperature is raised and the reaction is carried out at the temperature described below. At this time, for the purpose of speeding up the reaction, a suitable acid catalyst may be added in advance or during the reaction.

In addition, A of the bishalogenomethyl derivative represented by the general formula (b) used in the present invention is an alkyl-substituted phenylene group, =6 now-1 (D- diphenylene group, -@-0+
diphenyl ether group, -@@=-, naphthylenyl group, etc., and X is a chlorine atom, bromine atom, fluorine atom, or iodine atom. Therefore, the substances used in the present invention include α, α°-dichloro〇-xylene, α, α°
-dichloro m-xylene, α, α゛-dichloro p-
Xylene, α, α°-dibromo〇-xylene, α, α
°-dibromo m-xylene, α, α°-dibromo p
-xylene, α, α°-difluoro-xylene, α
, α゛-difluoro m-xylene, α, α′-difluoro p-xylene, α, α°-shorto-xylene, α, α゛-shorto m-xylene, α, α゛-shorto p-xylene, 4 .4°-bis(chloromethyl)diphenyl ether, 4.4'-bis(chloromethyl)diphenyl, 2.6-bis(chloromethyl)naphthalene, 4.4-bis(bromomethyl)diphenyl ether, 4,4'-bis (bromomethyl)diphenyl,
2,6-bis(bromomethyl)naphthalene, 4.4-
Bis(fluoromethyl)diphenyl ether, 4,4
°-bis(fluoromethyl)diphenyl, 4,4°-bis(iodomethyl)diphenyl ether, 4,4゛-
Bis(iodomethyl)diphenyl, α,α゛-dichloro2-methyl-p-xylene, α,α°-dichloro3
-Methyl-■-xylene, α, α°-dichloro2.5
-dimethyl-p-xylene, α, α°-dibromo2.
5-dimethyl-p-xylene, α,α°-dichloro2
, 4-dimethyl-1,3-xylene, α, α°-dichloro-2,4-dimethyl-1,5-xylene, and the like. Among them, more preferable compounds are α,
α°-dichlorop-xylene.

R of the aromatic amine compound represented by the general formula (a) used in the present invention 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 these are 0 to There are three, and they may be the same or different from each other, and may form a ring. The number of amino groups is 1 or 2.

Specifically, aniline, o-toluidine, m-toluidine, p-toluidine, 0-ethylaniline, river-ethylaniline, p-ditylaniline, 0-isopropylaniline, ■-isoprotoluaniline, p-isopropylaniline, o-n-propylaniline, o-tert-butylaniline, p-tert-butylaniline, o-n
-butylaniline, p-5ec-butylaniline, 2.
3-xylidine, 2.4-xylidine, 2,6-xylidine, 3゜4-xylidine, 3.5-xylidine, 2-
Methyl-3ethylaniline, 2-methyl-4-isopropylaniline, 2,6-dichloroaniline, 2-ethyl-3-tert-butylaniline, 2.4-diisopropylaniline, 2゜4.6-drimethylaniline, 4-
Chloroaniline, 4-bromoaniline, 4-fluoroaniline, 3-chloroaniline, 3-bromoaniline, 3
, 4-dichloroaniline, 3-chloro-〇-toluidine, 3-chloro-p-toluidine, 2,6-cymethyl-4
-chloroaniline, 0-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-resorcin, 4-amino-1,3-resorcin,
2-aminohydroquinone, 2-methoxyaniline, 3
-Methoxyaniline, 4-methoxyaniline, 2-isopropoxyaniline, 2,4-dimethoxyaniline, 0
-phenylenediamine, m-phenylenediamine, p-
phenylenediamine, 2.4-diaminotoluene, 2.
6-diaminotoluene, 2,4-diaminoethylbenzene, 2,6-diaminoethylbenzene, 2,4-diaminoisopropylbenzene, 2,4-diamino-tert
-butylbenzene, 2.6-cyamitsu-tert-butylbenzene, 2.4-diamino-1,3-dimethylbenzene, 1.1-dimethyl-4-aminoindan, 1.1
-dimethyl-4,6-cyamitindane and the like. In addition, suitable compounds are aniline, toluidines, xylidines, aminophenols and diamines, and particularly preferred is aniline.

In the method of the present invention, an acid catalyst may be used for the purpose of accelerating the reaction as described above. The acid catalyst is
inorganic or organic acids, especially mineral acids, such as hydrochloric acid, phosphoric acid,
sulfuric acid or nitric acid, or free sol fluorocarbon catalysts such as zinc chloride, stannic chloride, aluminum chloride, ferric chloride, organic sulfonic acids such as methanesulfonic acid or p-toluenesulfonic acid, and A super strong acid such as trifluoromethanesulfonic acid or 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 that may be added in addition to the hydrogen halide generated during the reaction is 100 mol % or less based on the aromatic amine compound. Above this range, there is no problem with the reaction, but it is not economical.

The reaction temperature is 0 to 240°C for the entire reaction, but
In the first stage reaction, 0 to 130°C, preferably 2
0 to 100°C, and 130°C in the second stage reaction.
-240°C, and a temperature range of about 170-240°C is desirable in order to shorten the reaction time of the second stage as much as possible. The reaction time is 1 to 10 hours for the first stage reaction and 5 to 40 hours for the second stage reaction.

Although an inert solvent may be used in the reaction in the method of the present invention, the reaction is usually carried out without a solvent. After the reaction is complete,
The acid produced in the reaction or the acid used as a catalyst is neutralized with a dilute alkali aqueous solution such as a caustic soda aqueous solution, a potassium hydroxide aqueous solution, or an aqueous ammonia solution, and then separated.

If unreacted aromatic amine compounds remain in the above reaction, they are distilled off under vacuum or by steam distillation.

By the manufacturing method of the present invention as described above, - Formula (C)
An aromatic amine resin represented by is obtained.

Since the aromatic amine resin obtained by the method of the present invention is a resin consisting of a primary amine, it can be easily converted into isocyanate, maleimid, and epoxidized.

Furthermore, when the aromatic amine resin obtained by the method of the present invention is used as a curing agent for other resins (for example, isocyanate compounds, epoxy compounds, bismaleimide compounds, etc.), resins with high performance can be obtained. .

For example, when the resin obtained by the method of the present invention is used as a curing agent for bismaleimide compounds, the cured resin has excellent mechanical strength and dimensional stability, and also has excellent heat resistance and stability against light and oxygen in the air. There is no problem. To give a specific example, when the resin obtained by the method of the present invention is used as a curing agent for bismaleimide derived from methylene dianiline, the flexural strength, flexural modulus, The decomposition onset temperature, expansion coefficient, and water absorption rate are superior to those of Kelimide 1050 (trade name: molding grade, manufactured by Rhone-Poulenc) resin when methylene dianiline is used as a hardening agent, and the glass transition temperature and thermal The deformation temperatures are almost the same.

Further, a prepolymer using a resin obtained by the method of the present invention is soluble in a low boiling point solvent (dioxane, methylene chloride, etc.).

Conventionally, prepregs have been produced by dissolving a prepolymer such as kelimide in a high boiling point aprotic polar solvent (such as N-methylpyrrolidone) and impregnating glass cloth or carbon cloth with the solution. In contrast to such conventional methods, if the resin obtained by the method of the present invention is used as a prepolymer, it can be dissolved in a low boiling point solvent, so the solvent can be easily removed by volatilization, and an extremely good prepreg can be obtained. can get.

Furthermore, the resin obtained by the method of the present invention has a faster curing speed than the resin proposed by the applicant in Japanese Patent Application No. 62-230987, and is particularly suitable for use in semiconductor encapsulation resins.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 Aniline l11. as an aromatic amine compound represented by formula (a) was placed in a reaction vessel equipped with a stirrer and a thermometer.
6 g (1,2 mol), α,α°-dichloro p- as a bishalogenomethyl derivative of the formula (b)
70.0 g (0.4 mol) of xylene was charged, and the temperature was raised while nitrogen gas was passed through the reactor. Although heat generation was observed from an internal temperature of about 30°C, the temperature was raised and kept constant at 85 to 100°C for 3 hours (first stage reaction). Thereafter, the temperature was raised continuously and the reaction was carried out at 190 to 200°C for 20 hours (second stage reaction).

Next, the mixture was cooled to lower the internal temperature to 95° C., and 230 g of a 15% aqueous solution of caustic soda was added thereto for neutralization with stirring. After standing still, the lower aqueous layer was separated and removed, and 300% saturated saline solution was added.
g was added to perform washing and liquid separation. Next, the mixture was heated and hydrophilized under a nitrogen stream, and then filtered under pressure to remove inorganic salts and the like.

This was vacuum concentrated under a vacuum of 2 to 3 mmHg to recover 48.5 g of unreacted aniline. The residue was discharged to obtain 100 g of a pale yellowish brown aniline resin.

As a result of compositional analysis of the aromatic amine resin obtained by the method of the present invention as described above by high performance liquid chromatography, n=0 in formula (C) is 27.8, n=1 is 19.
2, n=2 is 14.0, n=3 is 11.8, n=4 is 2
It was 7.2 (area%).

In addition, the amine equivalent of this resin (perchloric acid-glacial acetic acid method) is 0.65 equivalent/(100 g), and it is -2 in JIS-2.
The softening point measured using a ring and ball softening point measuring device manufactured by No. 548 was 64°C. Moreover, the average molecular weight was 880.

Example 2 As an aromatic amine compound represented by general formula (a), 2.
Using 61.1 g (0.5 mol) of 4-diaminotoluene, α,α°-dibromo-2,5-dimethyl-p-
Example 1 was repeated except that 29.2 g (0.1 mol) of xylene was used and the reaction time of the second stage was 30 hours, to obtain 32.5 g of diaminotoluene resin.

As a result of compositional analysis of the aromatic amine resin obtained by the method of the present invention as described above by high performance liquid chromatography, n=o in formula (C) is 41.8, n=1 is 21.
2, n=2 is 13.1% n≧3 is 23.9 (area%)
Met.

Further, the amine equivalent of this resin was 1.212, the softening point was 46°C, and the average molecular weight was 520.

Example 3 As an aromatic amine compound represented by general formula (a), o
-19%, m-53%, p-28% mixed toluidine 5
Using 3.6 g (0.5 mol), 4.4-bis(
chloromethyl) diphenyl ether 106.9 g (
Example 1 was repeated except that 0.4 mol) was used, and 116 g of toluidine resin was obtained.

The amine equivalent of the aromatic amine resin obtained by the method of the present invention as described above is 0.35, and is rated according to JIS-2548.
The softening point measured by a ring and ball softening point measuring device is 136
℃, and the average molecular weight was 13,200.

Example 4 In a reaction vessel similar to Example 1, 93.1 g of aniline as an aromatic amine compound represented by formula (a) (1
mol), α,α°-dichloro-m-xylene 17 as a bishalogenomethyl derivative represented by general formula (b)
．． 5 g (0.1 mol) was charged, and the temperature was raised while nitrogen gas was passed through the reactor. Although heat generation was observed from an internal temperature of about 30°C, the temperature was raised and kept constant at 70 to 80°C for 5 hours (first stage reaction). Next, in this reaction solution, 35%
31.3 g (0.3 mol) of an aqueous hydrochloric acid solution was added, and the temperature was raised as it was. Note that water distilled out during the process was distilled out of the system. The reaction was carried out at a temperature of 180 to 190°C for 16 hours (second stage reaction). Next, in the same manner as in Example 1, cooling, stirring neutralization, liquid separation removal, washing liquid separation, heating dehydration, pressure filtration, and vacuum concentration were performed to obtain 25 g of a pale brown oily aniline resin.

As a result of compositional analysis of the aromatic amine resin obtained by the method of the present invention as described above by high performance liquid chromatography, n=0 in general formula (C) is 79.0, n=1 is 17
．． 7, n=2 was 2.7, n=3 was 0.6 (area%).

Moreover, the amine equivalent of this resin was 0.674, and the average molecular weight was 330.

Example 5 As a bishalogenomethyl derivative represented by general formula (b), 17.5 g of α,α°-dichloro-P-xylene (
The procedure was carried out in the same manner as in Example 4, except that 19.0 g (0.1 mol) of p-toluenesulfonic acid was used as a reaction accelerator before the second stage reaction. 25.8 g of oily aniline resin was obtained.

The aromatic amine resin obtained by the method of the present invention as described above had an amine equivalent of 0.671, and its composition was almost the same as that of the resin obtained in Example 4.

〔Effect of the invention〕

As explained above, the method for producing an aromatic amine resin of the present invention uses inexpensive raw materials, can be carried out by simple operations, and is a non-polluting method that produces no by-products.

Furthermore, since the bishalogenomethyl derivative represented by the general formula (b) is used, a catalyst is not necessarily required for the reaction. Furthermore, aromatic amine resins can be produced in various forms, from liquid at room temperature to resin with a high softening point, depending on the purpose.

In addition, since the aromatic amine resin obtained by the method of the present invention is a resin consisting of a primary amine, isocyanation,
It can be easily converted into maleimide, epoxidized, etc., and can also be used as a raw material for polyamide, etc.

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

Furthermore, the prepolymer using the aromatic amine resin is
Since it is soluble in low melting point solvents, good prepolymers can be easily obtained.

The aromatic amine resin obtained by the method of the present invention has the above-mentioned effects.
Chelate resins, ion exchange resins, molding materials, insulation paints,
It can be used in many ways, including adhesives, rubber modifiers, additives for various resins, deoxidizers, and raw materials for polyimide, polyamide, and polyamideimide.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] General formula (a) ▲Mathematical formulas, chemical formulas, tables, etc.▼(a) (In the formula, R is a halogen atom, a hydroxyl group, a lower alkoxy group having 4 or less carbon atoms, or a lower lower alkoxy group having 5 or less carbon atoms. represents an alkyl group, and R may be the same or different from each other,
It may form a ring. l represents 1 or 2, m represents 0~
Indicates an integer of 3. ), and an aromatic amine compound represented by the general formula (b) General formula (c) characterized by reacting a bishalogenomethyl derivative represented by group, alkyl-substituted phenylene group, diphenylene group, diphenyl ether group or naphthylenyl group, R is a halogen atom, a hydroxyl group, a carbon number 4
It represents the following lower alkoxy group or lower alkyl group having 5 or less carbon atoms, and R may be the same or different from each other, and may form a ring. l represents 1 or 2,
m represents an integer of 0 to 3, and n represents an integer of 0 to 300. ) A method for producing an aromatic amine resin represented by