JPH0676353B2 - Method for producing bis (p-aminocumyl) benzenes - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing bis (p-aminocumyl) benzenes, and more particularly, to bis (p-aminocumyl) s in high yield from diisopropenylbenzenes and anilines. A method for producing benzenes.

Technical background of the invention and its problems Bis (p-aminocumyl) benzenes are polyamides,
It is a compound useful as a raw material for synthetic resins such as polyimide, polyamide-imide and epoxy, a resin additive and a dye.

Regarding the method for synthesizing the bis (p-aminocumyl) benzenes, for example, US Pat. No. 3,365,347 discloses an aromatic compound having an olefin substituent represented by diisopropenylbenzenes as a raw material,
A method of reacting an aromatic amine represented by aniline with activated clay as a catalyst is disclosed. However, in this document, there is no description of an example in the case where the diisopropenylbenzenes are m-forms, and the yield is unknown.

Also, West German Patent No. 2,111,193 discloses a method for producing bis (p-aminocumyl) benzenes similar to the above using an activated clay catalyst, but the raw material diisopropenylbenzenes are m-forms. In this case, there is a problem that the target compound bis (p-aminocumyl) benzenes cannot be obtained in high yield.

The inventors of the present invention have conducted extensive studies to solve the problems associated with the above-mentioned conventional techniques, and as a catalyst for producing bis (p-aminocumyl) benzenes from diisopropenylbenzenes and anilines. If a specific synthetic zeolite or a specific metal ion-exchanged montmorillonite is used, the target compound bis (p-aminocumyl) benzenes can be obtained in high yield and high selectivity. In this case, when a specific synthetic zeolite is used as a catalyst, bis (p-aminocumyl) which is the target compound is obtained in a higher yield and a higher selectivity when the diisopropenylbenzenes are in the m-form than in the p-form. The inventors have found that benzenes can be obtained and completed the present invention.

OBJECT OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and in particular, bis (p-aminocumyl) benzenes from m-isomer diisopropenylbenzenes and anilines. It is an object of the present invention to provide a method for producing bis (p-aminocumyl) benzenes, which is capable of producing bis (p-aminocumyl) benzene with high yield and high selectivity.

SUMMARY OF THE INVENTION In the method for producing bis (p-aminocumyl) benzenes according to the present invention, diisopropenylbenzenes and anilines are ion-exchanged with a synthetic zeolite catalyst selected from zeolite-X and zeolite-Y or aluminum ion. It is characterized by reacting in the presence of a montmorillonite catalyst.

In the present invention, since the above synthetic zeolite catalyst or metal ion-exchanged montmorillonite catalyst is used in the reaction of diisopropenylbenzenes and aniline, the target product bis (p-aminocumyl) benzene is produced by the conventional method. Compared to the activated clay-based process that has been used, it can be obtained with dramatically higher yield and higher selectivity.

DETAILED DESCRIPTION OF THE INVENTION The method for producing bis (p-aminocumyl) benzenes according to the present invention will be specifically described below.

The synthesis reaction of bis (p-aminocumyl) benzenes according to the present invention proceeds as shown in the following formula when the m-isomer is used as diisopropenylbenzenes and aniline is used as aniline.

In addition, P form is used as diisopropenylbenzenes,
When aniline is used as the aniline, it proceeds as shown in the following formula.

Diisopropenylbenzenes The diisopropenylbenzenes used as a starting material in the present invention are represented by the following general formula [II].

[In the formula, Y is halogen, amino, substituted amino, or a lower alkyl group, and m is an integer of 0-4. ] In the above diisopropenylbenzenes, the two Is used in the meta or para position.

Specific examples of such diisopropenylbenzenes include m-isopropenylbenzene, p-isopropenylbenzene, 2,5-diisopropenyltoluene and 3,5-
Diisopropenyltoluene, 3,5-diisopropenylchlorobenzene and the like are used.

Anilines The anilines used as a starting material in the present invention are represented by the following general formula [II].

[In the formula, R ₁ and R ₂ may be the same or different,
Hydrogen or an alkyl group having 1 to 3 carbon atoms, X is halogen or an alkyl group having 1 to 3 carbon atoms, and n is 0 to 0.
It is an integer of 4. ] Specific examples of such anilines include aniline, N-methylaniline, N, N-dimethylaniline, N
-Ethylaniline, 2-methylaniline, 2,6-xylidine (2,6-dimethylaniline), 3-isopropylaniline and the like are used.

Synthetic Zeolite Catalyst and Metal Ion Exchange Montmorillonite Catalyst In the present invention, synthetic zeolite or metal ion exchange montmorillonite is used as a catalyst when reacting the above-mentioned diisopropenylbenzenes and anilines.

Synthetic zeolites are hydrous aluminosilicates of alkali metals or alkaline earth metals, which have the general formula M ^{n +} _{x / y} [(Al
A compound represented by O ₂ ) × (SiO ₂ ) y] · mH ₂ O, of which, in the present invention, zeolite-X and zeolite-Y are used.

Further, in the present invention, it is preferable to use a synthetic zeolite obtained by exchanging ^{Mn +} ions of these zeolites with protons, alkaline earth metal ions, transition metal ions, and rare earth metal ions. Synthetic zeolite is 300-6 in air before use
It is preferably used after firing at a temperature of 00 ° C.

In the present invention, it is also possible to use montmorillonite ion-exchanged with metal ions as a catalyst. Examples of the metal ions include aluminum ions.

In the present invention, the ion exchange of synthetic zeolite and montmorillonite can be carried out by a known method.

When the diisopropenylbenzenes and the anilines are reacted with each other, a synthetic zeolite catalyst selected from zeolite-X and zeolite-Y or a montmorillonite ion-exchanged with aluminum ion is used as a catalyst, and the target compound is bis (p-aminocumyl). ) Benzene is obtained in high yield and high selectivity. In particular, when m-diisopropenylbenzene is used as a starting material, the yield of 1,3-bis (p-aminocumyl) benzenes, which is a target compound, is dramatically increased by using the above synthetic zeolite catalyst. .

For example, in the case of producing 1,3-bis (p-aminocumyl) benzenes by reacting m-diisopropenylbenzene and aniline, if a calcium-exchanged Y-type synthetic zeolite catalyst is used, 1,3-bis (p-aminocumyl) is used. ) The yield of benzenes reaches 74%. On the other hand, when activated clay that is classified as a solid acid catalyst like the synthetic zeolite and taught in the above-mentioned US Pat. No. 3,365,347 is used as a catalyst, 1,3-bis (p-aminocumyl) is obtained.
The yield of benzenes reaches only 40%.

In the following example, when an aluminum-exchanged montmorillonite catalyst is used in the reaction of p-diisopropenylbenzene and aniline to produce 1,4-bis (p-aminocumyl) benzenes, 1,4-bis (p- The yield of aminocumyl) benzenes reaches 91%. On the other hand, when the activated clay that is classified as the aluminum-exchanged montmorillonite catalyst and is also taught in the above-mentioned US Pat. No. 3,365,347 is used as the catalyst, 1,4-bis (p-aminocumyl) benzenes are used. The yield of is only about 80%.

These facts suggest that, in the reaction according to the present invention, the specific synthetic zeolite catalyst as described above and the specific metal ion exchange montmorillonite catalyst as described above function as unique catalysts.

Reaction Conditions The reaction between diisopropenylbenzenes and anilines using the synthetic zeolite catalyst or the metal ion-exchanged montmorillonite catalyst according to the present invention can be carried out under normal pressure or under pressure. When the reaction is carried out under normal pressure, it is preferable to carry out the reaction at a temperature of about 195 ° C. or lower, which is a temperature lower than the boiling point of the starting material. When the reaction is carried out under pressure, the reaction can be carried out at a temperature of 195 ° C or higher.

In the present invention, it is preferable to carry out the reaction under pressure at a high reaction temperature of, for example, 220 to 260 ° C., since the yield of the desired bis (p-aminocumyl) benzenes is increased.

The reaction between the diisopropenylbenzenes and the anilines according to the present invention is preferably carried out in a state where the anilines are in a large excess. Usually, the latter is 3 mol or more, more preferably 5 to 20 mol, relative to 1 mol of the former. Used in quantity. In addition, a suitable solvent can be used in the reaction, and as such a solvent, various hydrocarbons, decane, dodecane, cumene, benzene, toluene, chlorobenzene and the like can be used.

The reaction can be carried out batchwise or continuously.
When the reaction is carried out in a batch system, the synthetic zeolite catalyst is preferably used in an amount of 3 to 20 parts by weight per 100 parts by weight of diisopropenylbenzenes. In the continuous reaction, it is preferable to carry out the reaction so that the residence time is about 10 to 180 minutes.

To separate and purify the target compound, bis (p-aminocumyl) benzenes, from the reaction mixture obtained after the completion of the reaction, a usual separation and purification means is used, and one example thereof is as follows. First, the synthetic zeolite catalyst or the metal ion-exchanged montmorillonite catalyst is removed from the reaction mixture by filtration, and the obtained filtrate is concentrated or cooled as it is to precipitate crude crystals of the target compound. The crude crystals are recrystallized from an appropriate solvent to obtain purified crystals of the target compound.

In the present invention, the used synthetic zeolite catalyst can be reused by washing with acetone, methanol, ethanol or the like under heating.

As described above, bis (p-aminocumyl) benzenes are obtained. Specific examples of the bis (p-aminocumyl) benzenes include 1,3-bis (p-aminocumyl) benzene and 1,4- Bis (p-aminocumyl) benzene, 1,3-bis (pN-methyl-aminocumyl) benzene, 1,4-bis (pN, N'-dimethyl-aminocumyl) benzene and the like are shown.

EFFECTS OF THE INVENTION In the present invention, when reacting diisopropenylbenzenes and anilines, zeolite-X, zeolite-
Since a synthetic zeolite catalyst selected from Y or a montmorillonite catalyst ion-exchanged with aluminum ions is used, the target product, bis (p-aminocumyl) benzene, is used as a catalyst in activated clay which has been used in the conventional method. High yields and high selectivities are obtained compared to the process.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 First, a Ca-exchanged Y-type zeolite was prepared from the Y-type synthetic zeolite as follows.

40 g of Y-type zeolite (manufactured by Toyo Soda Co., Ltd.), 150 g of calcium nitrate (tetrahydrate) and 1350 g of water were placed in a 2 l separable flask equipped with a condenser and a stirrer, and reacted at 100 ° C. for 6 hours. Thereafter, the solid content was filtered off by centrifugation. The solid component thus filtered off was placed in the 2 l flask described above, 150 g of calcium nitrate and 1350 g of water were added, the mixture was reacted again at 100 ° C. for 6 hours, and then the filtration was repeated. This operation was repeated once more. Then, the solid matter separated by centrifugation was washed with 1500 ml of water three times at room temperature. After washing with water, the solid content was dried at 80 ° C. for 3 hours and then calcined at 500 ° C. for 8 hours to obtain a Ca—Y type zeolite.

The composition of the Ca-Y type zeolite thus prepared is
The Ca exchange rate was 83.4% by weight with Ca5.96% by weight and Na 1.18% by weight.

Next, using the Ca-Y type zeolite obtained as described above as a catalyst, 1,3-bis (p-aminocumyl) benzene was produced as follows.

Aniline 93g (1mol), m-diisopropenylbenzene 1
5.8g (0.1mol) and Ca-Y type zeolite as catalyst 1.
58 g (10% by weight based on m-diisopropenylbenzene) was charged into a 200 ml round-bottomed flask equipped with a stirrer and a condenser, and reacted at 194 ° C. for 2 hours. After the catalyst was filtered from the obtained reaction liquid, the reaction liquid was subjected to a gas chromatographic analysis. As a result, the yield of 1,3-bis (p-aminocumyl) benzene was 74 mol%.

The results are shown in Table 1 for comparison.

Example 2 A proton-exchanged Y-type zeolite (proton exchange rate 93%) was prepared in the same manner as in Example 1.

Next, using the obtained HY type zeolite catalyst, Example 1
1,3-bis (p-aminocumyl) benzene was produced in the same manner as in. The yield of 1,3-bis (p-aminocumyl) benzene was 67%.

Example 3 In the same manner as in Example 1, Ca-exchanged X zeolite (Ca
Exchange rate 85%) was prepared.

Next, using the obtained Ca-X type zeolite catalyst, Example 1
1,3-bis (p-aminocumyl) benzene was produced in the same manner as in. 1,3-bis (p-aminocumyl)
The yield of benzene was 65%.

Example 4 An Al-exchanged montmorillonite (Al exchange rate: 88%) was prepared in the same manner as in Example 1.

Next, using the obtained Al-exchanged montmorillonite catalyst, the amount of m-diisopropenylbenzene was adjusted to 2 in Example 1.
Same as Example 1 except 2.1 g (0.14 mol)
The production of 1,3-bis (p-aminocumyl) benzene was carried out. The yield of 1,3-bis (p-aminocumyl) benzene was 65%.

Example 5 1,4-bis (p-aminocumyl) benzene was produced in the same manner as in Example 4 except that p-diisopropenylbenzene was used as the diisopropenylbenzenes. 1,4-bis (p-aminocumyl)
The yield of benzene was 91%.

Example 6 1,4-bis (p-N-methylaminocumyl) benzene was produced in the same manner as in Example 4 except that N-methylaniline was used as the aniline. . The yield of the desired product was 85%.

Comparative Example 1 1,4-bis (p-aminocumyl) benzene was produced in the same manner as in Example 5 except that activated clay was used as the catalyst. The yield of 1,4-bis (p-aminocumyl) benzene was 80%.

Comparative Example 2 1,4-bis (p-N-methylaminocumyl) benzene was produced in the same manner as in Example 6 except that activated clay was used as the catalyst. The yield of the desired product was 55%.

Comparative Example 3 In the same manner as in Example 4 except that activated clay was 3.16 g and the reaction time was 3 hours in Example 4, 1,
4-bis (p-aminocumyl) benzene was produced. The yield of 1,4-bis (p-aminocumyl) benzene is 4
It was 0%.

The yield of 3-bis (p-aminocumyl) benzene was 40%.

The above results are shown in Table 1.

From Table 1, when the bis (p-aminocumyl) benzene is produced by reacting diisopropenylbenzenes with aniline, the above synthetic zeolite catalyst or metal ion exchanged montmorillonite catalyst is used, bis (p-aminocumyl) It can be seen that the yield of benzene is improved as compared with the case where activated clay is used as a catalyst.

Claims (3)

[Claims] 1. A method of reacting diisopropenylbenzenes and anilines in the presence of a synthetic zeolite catalyst selected from zeolite-X and zeolite-Y or a montmorillonite catalyst ion-exchanged with aluminum ions. Method for producing bis (p-aminocumyl) benzenes. 2. The method according to claim 1, wherein the diisopropenylbenzenes are m-diisopropenylbenzene and p-diisopropenylbenzene. 3. The method according to claim 1, wherein the anilines are aniline, N-methylaniline and N, N'-dimethylaniline.