JPH02164857A - New halogenated aromatic diamine and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (at least one of X1 to X4 is Cl or Br and may be different with each other; R1 and R2 are H, methyl, ethyl, trifluoromethyl or trichloromethyl; n is 1-3). EXAMPLE:2,2-bis[4-(4-aminophenoxyethoxy)-3,5-dibromophenyl]propane. USE:Used as fire retardant additive or hardener of epoxy resin. Also useful as a raw material of polyamide, polyimide or bismaleimide, etc. PREPARATION:Halogenated aromatic diol expressed by formula II is reacted with nitrobenzene or nitrofluorobenzene in non-protonic polar solvent (e.g. N- methylpyrrolidone) and in the presence of base (e.g. sodium hydride) and nitro group is reduced to amine group to afford the compound expressed by the formula I.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is a novel halogenated compound which is useful as a reactive flame retardant or an epoxy resin curing agent, and is also useful as a raw material for polyamide, polyimide, bisimide, etc. This invention relates to aromatic diamines and their production methods.

(Prior Art) Compounds containing bromine or chlorine are often used as flame retardants to impart flame resistance to polymeric compounds. Furthermore, diamines having multiple amino groups are used as curing agents for epoxy resins used in copper-clad laminates and fiber reinforcement, and as raw materials for polyamides, polyimides, bisimides, and the like.

. Conventionally, several types of compounds have been known as halogenated aromatic diamines containing halogen elements such as bromine and chlorine, and they are used as epoxy resin curing agents and in order to improve flame retardancy, heat resistance, moisture absorption resistance, etc. Used in raw materials such as polyamide.

As a hardening agent for epoxy resin, Japanese Patent Publication No. 49-238
Epoxy resin compositions disclosed in Publication No. 4.0 and JP-A-6
There is a diaminodiphenylmethane type halogenated aromatic diamine such as the curing agent for epoxy resin prepreg shown in Japanese Patent No. 2-277435, but the reactivity is low because the halogen element of the nuclear substitution is close to the amino group.

Further, in order to improve the adhesion and impact resistance of a cured epoxy resin product, a diamine that can impart flexibility to the cured product is used. For example, in the flame-retardant epoxy resin varnish for copper-clad laminates disclosed in JP-A-58-8639, an ether bond represented by the formula [III] is used as a curing agent to improve both heat resistance and adhesion. 2,2-bis[4-(4-aminophenoxy)-3,5
-dibromophenyl]propane.

Furthermore, in the epoxy resin for fiber-reinforced prepreg disclosed in JP-A-62-36422, the formula [IV]... [rV] There are halogenated aromatic diamines that also have an ethylene oxide chain in addition to the ether bond.

As a raw material for polyamide resin, Japanese Patent Application Laid-Open No. 495989
There is a halogenated 2,4-diaminodiphenyl ether of self-extinguishing aromatic polyamide shown in No. 8.
In order to obtain a cured product of bisimide or polyimide resin that has excellent heat resistance and +iJ flexibility, aromatic diamines having an ether bond in the main chain are used.

For example, the heat-resistant bisimide resin composition disclosed in Japanese Patent Publication No. 63-17081, Japanese Patent Publication No. 63-17081: 337
Etherimide compounds shown in Publication No. 786,
Japanese Unexamined Patent Publication No. 58-. Ether cyanamide compounds disclosed in Japanese Patent Publication No. 105953, polyether amide imide polymer compositions disclosed in Japanese Patent Publication No. 172766/1983, polyamide trash l disclosed in Japanese Patent Publication No. 205322/1983 - For silicone polymers, etc., 2,2-bis[4-(4-aminophenoxy) having the above formula [+1[] = 3.5
-dibromophenyl]propane is exemplified.

(Problems to be Solved by the Invention) When 2,2-bis[4-(4-aminophenoxy)-3,5-dibromophenyl]propane represented by the formula [In] is used as an epoxy resin curing agent, 4 ether bonds
Although some adhesion properties have been imparted to the cured product due to human adhesion, it is still insufficient and there is a problem in that satisfactory adhesion properties with copper foil cannot be obtained.

In addition, in the case of a halogenated aromatic diamine having an ethylene oxide chain in addition to an ether bond in the main chain represented by formula [IV], the impact resistance is sufficient, but the terminal aminophenoxy group is bonded with an ester bond. Because of this, there was a problem that the heat resistance deteriorated.

Similarly, in the case of raw materials for bisimide and polyimide resins, when 2,2-bis[4(4-aminophenoxy)-3,5-dibromophenyl]propane represented by the formula [II+] is used, the heat resistance is Although it is excellent, there is still a problem that it is still a brittle material with no toughness due to insufficient adhesion.

The present invention provides a novel compound that can impart sufficient fusibility to epoxy resins when used as a curing agent or as a raw material for bisimide or polyimide resins. It is.

(Means for Solving the Problems) The novel halogenated aromatic diamine shown by the present invention has a -release[1]% formula%[] (wherein at least one of Indicates bromine and may be different from each other.

R and R2 represent hydrogen, a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group, and may be the same or different. I represents an integer of 1 to 3. ) is a halogenated aromatic diamine.

Furthermore, the present invention provides -Release[11]%Formula% (wherein, at least one of X and ~X4 represents chlorine or bromine, and may be different from each other.

R and R2 represent hydrogen, a methyl group, an ethyl group, a 1-lifluoromethyl group, or a 1-lichloromethyl group, and may be the same or different from each other. n represents an integer of 1 to 3. ) and nitroglolobenzene or nitrofluorobenzene using a basic catalyst in an aprotic polar solvent, the bis(21
- phenyl ether) compound, and then the second I
- The above-mentioned - characterized in that the ~ro group is reduced to an amine group.
A method for producing a halogenated aromatic diamine represented by [1].

The present inventors have discovered that the halogenated aromatic diol represented by the above-mentioned -rho [n] can easily react with a halogenated benzene compound by converting it into alcohola-1~ using an appropriate basic catalyst. We found that the corresponding phenyl ether compound could be obtained, and we came to invent a new halogenated aromatic diamine.

In the halogenated aromatic diamine of the present invention, the effect of imparting flexibility becomes greater as the value of I) in -arson [1] increases, but when it is 4 or more, heat resistance is impaired, which is not preferable.

The nonprone polar solvent in the production method of the present invention is
Although the type is not particularly limited, it is necessary to stabilize the generated alcoholade anion, and in general, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, hexamethylphosphoric acid is used. Triamides, tetrahydrofurans, and the like are used. Naturally, high-boiling solvents are advantageous in order to shorten the reaction time, with N-methylpyrrolidone and hexamethylphosphoric triamide being preferred.

As the basic catalyst, at least one selected from the group consisting of an alkali metal carbonate, an alkali metal hydroxide and an activator, or an alkali metal hydride is used. Generally, potassium carbonate, potassium hydroxide and an activator, or sodium hydride are used. Stronger basic catalysts give higher yields of phenyl etherides, and among the above group, 1-lithium hydrides are most preferred.

The amount of basic catalyst used is the amount necessary to convert the corresponding hydroxyl group into alcohola-1. That is, at least 0.5 molar equivalent, preferably 1.0 molar equivalent or more of the basic catalyst is used.

The reduction of the bis(trophenyl ether) compound can be easily carried out by a conventional method. For example, it is a reaction between metals such as Sn, Fe, and Zn and hydrogen generated by acidic substances such as hydrochloric acid or acetic acid.
The ro group can be reduced to an amino group.

When the halogenated aromatic diamine of the present invention is used as an epoxy resin curing agent, the type of epoxy resin is not limited at all, and other conventionally known aromatic diamines and curing agents such as dicyandiamide, tertiary amines, etc. A curing accelerator such as imidazole may also be used.

When the halogenated aromatic diamine of the present invention is used as a raw material for polyamide, polyimide, bisimide, etc., the type of carboxylic acid component is not limited at all, and other conventionally known aromatic diamines may be used in combination. .

(Example) The present invention will be explained in more detail with reference to Examples below.

(Example 1) An example of the method for producing a novel halogenated aromatic diamine provided by the present invention is shown below.

300m with stirrer, condenser and thermometer
L no 3 [1 flask, Fire Guard FG-3600
(2,2-bis[4-hydroxyethoxy-3,5-dibromophenyl]propane, trade name manufactured by Teijin Kasei Co., Ltd.) 15.8g was added, and 100ml of N-methylpyrrolidone was added.
L was added and dissolved. Then, while stirring, the content is about 60
2.4 g of sodium hydride was added in portions and stirred.

Next, after adding 9.5 g of p-21-loglolbenzene and completely dissolving it, heating was started in an oil bath.
The reaction was carried out at 0°C for 3 hours. After cooling, the precipitated sodium chloride was filtered off, transferred to a pear-shaped flask, and N-methylpyrrolidone was distilled off under reduced pressure (58°C/4-mm H
g).

The product was then washed with methanol to remove resin components, filtered and dried to obtain 120 g of precipitate.

The content of di(p-nitrophenyl ether) compound in the precipitate was about 90%.

Next, the nitro group was reduced. 20 g of the above bis(p-nitrophenyl ether) compound was charged into an IL three-loaf flask equipped with a stirrer, a condenser, and a thermometer,
It was dissolved in 500 mL of benzene.

While stirring on a hot water bath, add 160 g of iron powder and 40 g of concentrated hydrochloric acid in advance.
Activated iron prepared in mL was added little by little over 1 hour, and then reacted at 70 to 75°C for 2 hours. Then, 40 mL of water was added and the reaction was continued for an additional hour.

After cooling, insoluble matter is filtered off, the benzene solution is transferred to a separating funnel, washed twice with water, dried over anhydrous sodium sulfate 11 for a day and night, and the benzene is volatilized to obtain the crude halogenated aromatic diamine of the present invention 14. The crude product 5-I obtained above was purified by repeated recrystallization with a methanol/chloroform mixed solvent to obtain 11 g of crystals with a purity of 99% or higher.

The analysis values of the crystals are as follows.

1) Melting point; 102°C 2) Elemental analysis value; C: 45.64% (calculated value 45.73%) TI: 3.
76% (3,72%) N: 3.3/1% (3,44%); 3) Infrared absorption spectrum (KBr); 345 (i, 3374 am
-' (pri-NT(,,)2972.2876c
m-'(CI(,+)1.238cm-'(Ar-
0-) 1,000-1-100cnv'(-C",, T-
1s O-)736cm-' (Ar-Br) 4) J-1 nuclear magnetic resonance spectrum 1-(CDC13); δ
(ppm/TMS) 7.30 (41-1, Br-Ar-H)
6.5-6.9 (8H, Ar-H) 4.34
(8TL -CH2-)3.1.0
(41(,-NH2)1.60 (6I
(,-CHI) Figures 1 and 2 show the infrared absorption spectrum and 'I of the cyamine compound produced in Example 1.
(The nuclear magnetic resonance spectrum is shown respectively.

From the analytical data of Example 1, the aromatic diamine compound obtained in Example 1 has the formula [1], which is the novel aromatic diamine of the present invention.
It was confirmed that it was 2,2-bis[4,-(4-aminophenoxyel-1-oxy)-3,5-dibromophenyl]propane having the formula %[1].

(Example 2) Since the novel aromatic diamine of the present invention has bromine, it is clear that it is useful as a flame retardant. The characteristics of resin prepreg will be described.

Epicote 1001 (bisphenol type epoxy resin, trade name manufactured by Shell Chemical Co., Ltd.) 90 g, 2,2-bis[4-(4-aminophenoxyel-1-oxy)-3,5-dibromo produced according to Example 1] Phenylcob° Roban 41g! ; and 1 g of dicyandiamide with 200 g of methyl ethyl ketone and N.

N-Dimethylformami+: After dissolving in 20 g of mixed solvent, it was impregnated onto a glass cloth base material with a thickness of 0.18 mm so that the adhesion amount was 40% by weight, and dried at 160°C to obtain a prepreg. .

Next, use 8 sheets of prepreg and lay it at 170℃, 50kg/
An epoxy resin laminate was produced by molding for 2 hours under conditions of 0 m2.

A test piece with a width of 25 rnm and a length of 50 mm was cut out from this laminate, and a bending test was conducted at a pressure between the supports of 111125 mm. Also LJ 1. A flame resistance test was conducted according to the law.

(Comparative Example 1) In Example 2, 2,2-bis[4-(4-aminophenoxy)-3,5-dibromophenyl]propane 3 was used as a curing agent instead of the bromine-containing aromatic diamine of the present invention.
An epoxy resin laminate was prepared in the same manner as in Example 2 except that 6 g was used, and a bending test and a UL method flame resistance test were conducted.

(Comparative Example 2) Similarly to Comparative Example 1, an epoxy resin laminate was prepared using 10 g of 4,4'-diaminodiphenylmethane as a curing agent and 20 g of decabromodiphenyl ether as a flame retardant, and was tested for bending test and U17 method flame resistance. The test results of Example 2 and Comparative Example 1.2 are shown in Table 1.

From Table 1, it is clear that the halogenated aromatic diamine of the present invention is useful as a flame retardant and a curing agent for making cured epoxy resins flame retardant, flexible, and tough.

Table 1 Test Results (Example 3) Next, the characteristics of the bisimide polymer when the halogenated aromatic diamine of the present invention is used as a raw material will be described.

50 equipped with stirring device, condenser and gas introduction tube
10.8 g of maleic anhydride was placed in a 0 mL three-Low flask and dissolved in 100 mL of acetone. 2,2-bis[4,
-(4-Aminophenoxyethoxy)-3,5-dibromophenyl]propane solution of 43.7 g in acetone 200
mL was added dropwise over 2 hours. After the dropwise addition was completed, the mixture was stirred at room temperature for 8 hours. After filtering out the precipitated amic acid and washing with acetic acid to remove excess maleic anhydride,
Dry under reduced pressure.

Next, the above amic acid 5
2 g, acetic anhydride] 4 mL, triethylamine7.
2 mL, and 1.25 g of nickel(II) acetate tetrahydrate
was added and dissolved in 200 mL of acetone.

The reaction was then carried out at reflux temperature for 5 hours under a nitrogen stream. After cooling, the reaction mixture was reprecipitated in water, filtered, neutralized with an aqueous solution of hydrogen carbonate, and thoroughly washed with water.

After drying under reduced pressure, the product was purified by repeating recrystallization with a mixed solvent of methanol/chloroform to obtain 50 g of bismaleimide of the bromine-containing aromatic diamine of the present invention.

Next, a cured product of this bismaleimide compound was prepared and its mechanical properties were measured.

35 g of the above bismaleimide compound was cured at 170°C for 30 minutes at contact pressure between stainless steel mirror plates sandwiching a 2 mm thick Teflon spacer, and then at 170°C for 2 hours at 10 kg/cm'' to form a 2 mm x 100 mm square cured product. 200°C for 1 hour in a dryer, and finally at 280°C.
I did an after cure for 1 hour.

A test piece with a length of 50 mm and a length of 5 mm was cut out from this cured product, and a bending test was conducted with a distance between fulcrums of 30 mm. (Comparative Example 3) In Example 3, instead of the bromine-containing aromatic diamine of the present invention, , 2,2-bis[4,-(4-aminophenoxy)-3,5-dibromophenyl]propane was used as the diamine component, but in the same manner as in Example 3, a bismaleimide compound and a cured product thereof were prepared. Then, a bending test was conducted.

(Comparative Example 4) Similarly to Comparative Example 3, using 4,4'-diaminodiphenylmethane as the diamine component, a bismaleimide compound and a cured product thereof were prepared and subjected to a bending test.

The test results of Example 3 and Comparative Examples 3.4 are shown in Table 2.

Table 2 Bending Test Results From Table 2, it is clear that the halogenated aromatic diamine of the present invention is useful for making the maleimide-based cured product flexible and tough.

(Effects of the Invention) According to the present invention, a novel halogenated aromatic diamine is provided which is useful as a hardening agent for both gas and epoxy resins and is also useful as a raw material for polyamides, polyimides, bismaleimides, etc. be done.

[Brief explanation of the drawing]

FIG. 1 shows infrared absorption spectra 1 to 1 of the bromine-containing aromatic diamine of Example 1, which is a novel compound of the present invention, and FIG. 2 shows the same <'H nuclear magnetic resonance spectrum. 1゜2゜3゜Procedural amendments issued)

Claims (1)

[Claims] 1. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] (In the formula, at least one of X_1 to X_4 represents chlorine or bromine, and they are different from each other. R_1 and R_2 represent hydrogen, a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group, and may be the same or different from each other. n represents an integer of 1 to 3.) A halogenated aromatic diamine represented by 2. The compound represented by the general formula [I] is 2,2-bis[
The halogenated aromatic diamine according to claim 1, which is 4-(4-aminophenoxyethoxy)-3,5-dibromophenyl]propane. 3. General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [II] (In the formula, at least one of X_1 to X_4 represents chlorine or bromine, and they may be different from each other. R_1 and R_2 represents hydrogen, a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group, and may be the same or different from each other. n represents an integer of 1 to 3.)
By reacting the halogenated aromatic diol represented by nitrobenzene or nitrofluorobenzene in an aprotic polar solvent using a basic catalyst, a bis(nitrophenyl ether) compound of the halogenated aromatic diol can be obtained. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] (In the formula, at least one of X_1 to X_4 One represents chlorine or bromine, and they may be different from each other. R_1 and R_2 represent hydrogen, a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group, and may be the same or different from each other. n represents an integer of 1 to 3.) A method for producing a halogenated aromatic diamine. 4. The compound represented by the general formula [II] is 2,2-bis(4
The method for producing a halogenated aromatic diamine according to claim 3, wherein the halogenated aromatic diamine is -hydroxyethoxy-3,5-dibromophenyl)propane. 5. The basic catalyst according to claim 3 or 4, wherein the basic catalyst is at least one selected from the group consisting of an alkali metal carbonate, an alkali metal hydroxide and activated copper, or an alkali metal hydride. A method for producing a halogenated aromatic diamine. 6. Claim 3 or 4, wherein the basic catalyst is at least one member selected from the group consisting of potassium carbonate, potassium hydroxide and activated copper, or sodium hydride.
The method for producing a halogenated aromatic diamine as described in .