JPH05148165A - Production of 1-methylindane and diphenylbutane - Google Patents

Abstract

PURPOSE:To simultaneously obtain 1-methylindane used as a chemical raw material and diphenylbutane used as a solvent for pressure-sensitive duplicating paper, etc., by reacting benzene with 1, 3-butanediene in the presence of a high- silica mordenite at a specific temperature. CONSTITUTION:A high-silica mordenite having 132 silica/alumina ratio is packed in a solid bed reactor and the catalyst bed is heated to 200 deg.C while benzene under 30kg/cm<2> G pressure and a raw material in which molar ratio of benzene/1,3-butadiene is controlled to 100 is passed through the catalyst. Benzene is made to react with 1,3-butadiene while properly collecting the reactional product from 10hr to 300hr and while analyzing the collected reactional product with gas chromatography to simultaneously produce 1-methylindane useful as a raw material and a solvent for various kinds of chemical products and diphenylbutane useful as a solvent for pressure-sensitive duplicating paper, heat medium and electric insulation oil, etc., in high yield and with simple method.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing 1-methylindane and diphenylbutane.

[0002]

2. Description of the Related Art 1-Methylindane is useful as a raw material and a solvent for various chemical products. However, there is no efficient production method, and only a small amount is produced as a by-product in the synthesis of other substances. For example, methylindane is by-produced when synthesizing isobutylbenzene from toluene and propene using a catalyst in which Na-K alloy is dispersed on cesium oxide (US Pat. No. 4,982,035).

Diphenylbutane is a solvent for pressure-sensitive copying paper,
It is useful as a heat carrier, electric insulating oil, etc. The manufacturing method is using 96% sulfuric acid or hydrogen fluoride as a catalyst (Journal of American Chemical Society, 66, 8
16-817, 1944), or a method of one-step reaction from benzene and 1,3-butadiene using concentrated sulfuric acid or aluminum chloride as a catalyst (Journal of Organic Chemistry, Volume 31, pp. 1124-1127, 1966). It has been known. However, the yield of diphenylbutane is as low as about 15% (based on 1,3-butadiene). Also, 89-9
A method of reacting benzene with 1-phenylbutene using 6% by weight sulfuric acid as a catalyst is also known (Japanese Patent Laid-Open No. 63-23923).
No. 9 bulletin). This method significantly improves the yield, but the sulfonation of benzene reduces the purity of sulfuric acid,
It is difficult to recover and reuse the sulfuric acid catalyst.

Further, a method for producing an indane derivative by reacting a benzene derivative with isoprene in the presence of a solid acid catalyst is known (JP-A-3-190830). The solid acid catalyst there is specifically an inorganic solid acid catalyst or a proton-type strongly acidic ion exchange resin. Mordenite is mentioned as an inorganic solid acid catalyst. The reaction temperature is 0 to 200 ° C. If the reaction temperature is too high, side reactions occur and the yield decreases. The indane derivative that can be produced by this reaction is a 1,1-disubstituted product (at least one of the substituents is a methyl group), and 1-methylindane cannot be produced.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing 1-methylindane having a high yield. Another object of the present invention is to provide a method for producing diphenylbutane in a high yield and in a simple process, and to provide a method capable of producing 1-methylindane and diphenylbutane at a desired ratio at the same time. Is provided.

[0006]

According to the present invention, 1-methylindane and diphenylbutane are simultaneously produced by reacting benzene with 1,3-butadiene in the presence of a high silica mordenite catalyst at a reaction temperature of 200 ° C. or higher. Is the way to do it.

In the present invention, the catalyst is high silica mordenite. Here, high silica mordenite refers to proton mordenite having a silica / alumina molar ratio of more than 10, preferably 50 or more. The above-mentioned Japanese Patent Laid-Open No.
In the usual mordenite described in Japanese Patent Laid-Open No. 3-190830, the silica / alumina molar ratio is 8.3 to 10. In the present invention, when the molar ratio is 10 or less, the yield of 1-methylindane decreases.

The high silica mordenite can be prepared by subjecting a commercially available mordenite to an acid treatment. For example, high silica mordenite having a silica / alumina molar ratio of about 100 to 140 is prepared by first using commercially available Na-type mordenite (for example, Tosoh TSZ-600, silica / alumina ratio 10) in 2N hydrochloric acid at 80 ° C. for 1.5 hours. After ion exchange and washing, 600-7 under 10-20% steam
Steam at 00 ℃ for 3 hours, then at 90 ℃ for 8 hours with 12N hydrochloric acid to extract aluminum, then wash and dry, then steam at 700 ℃ for 3 hours under 10% steam. Can be prepared by

When the above-mentioned high silica mordenite is batchwise, it is used in an amount of 0.01 to 50% by weight based on the benzene / 1,3-1,3-butadiene mixed raw material. preferable.

In the present invention, the reaction temperature is 200 ° C. or higher, preferably 200 to 290 ° C., particularly 200 to 250.
℃. When the reaction temperature is lower than 200 ° C., the yield of 1-methylindane becomes extremely small, which is inconvenient. This phenomenon is described in JP-A-3-190830,
This is in stark contrast to the method of making 1-disubstituted indane. The yield of 1-methylindane becomes higher as the reaction temperature becomes higher than 200 ° C.

Although the reaction time depends on the reaction temperature and the like, it is generally 0.5 to 4 hours in a batch system and 0.1 to 10 hours ^-1 in a liquid space velocity (LHSV) in a continuous system. It is a degree.

The molar ratio of benzene / 1,3-butadiene is preferably 10-200, more preferably 30-
It is preferably 120. When the molar ratio is less than 10, the intermediate substance phenylbutene or 1,3-
Oligomerization of 1,3-butadiene occurs, and the rate of catalyst activity deterioration increases. On the other hand, when the molar ratio exceeds 200, the amount of benzene recycled increases, which is economically disadvantageous.

Although the reaction solvent may not be used, if it is used, saturated hydrocarbon such as cyclohexane, hexane, heptane is preferably used.

In the present invention, 1-methylindane is generally obtained in desired yields of 25-70%. Diphenylbutane is obtained in the desired yield of 20-70%. Diphenylbutane is 1,1-diphenylbutane, 1,2-
Diphenylbutane, 1,3-diphenylbutane, 2,3
An isomer mixture consisting of diphenylbutane. The reaction products 1-methylindan and diphenylbutane can be easily separated from the reaction raw materials and intermediates by a known separation means such as distillation. Further, the high silica mordenite, which is a catalyst, can be easily separated and recovered from the reaction system by filtration or the like, and can be reused if necessary.

[0015]

【Example】

[0016]

Example 1 A fixed bed reactor was charged with 20 ml of high silica mordenite with a silica / alumina molar ratio of 132. While feeding benzene at 30 kg / cm ² G, ² times the above catalyst bed
After heating to 00 ° C., a raw material whose benzene / 1,3-butadiene molar ratio was adjusted to 100 was circulated at LHSV = 1.0 hr ⁻¹ . After that, the reaction product for 10 to 300 hours was appropriately sampled and analyzed by gas chromatography. The results obtained by the analysis are shown in Table 1. The yield is 1,
Calculated based on 3-butadiene.

[0017]

Examples 2-3: The reaction temperatures were 220 ° C and 240 ° C, respectively.
The same procedure as in Example 1 was carried out except that The results are shown in Table 1.

[0018]

Comparative Example 1 The procedure of Example 1 was repeated except that the reaction temperature was 170 ° C. The results are shown in Table 1.

From Examples 1 to 3 and Comparative Example 1, it can be seen that the yield of 1-methylindane increases as the reaction temperature increases.

[0020]

Example 4 Example 4 was repeated except that the raw material benzene / 1,3-butadiene molar ratio was 40.
The results are shown in Table 1.

[0021]

Example 5 The reaction temperature was set to 220 ° C. and benzene / 1,
Example 1 was repeated except that the 3-butadiene molar ratio was 60. The results are shown in Table 1.

[0022]

Comparative Example 2 The procedure of Example 1 was repeated except that H + type zeolite Y was used instead of the high silica mordenite.
The results are shown in Table 1.

1-Methylindane produced only trace amounts.

[0024]

[Table 1]

[0025]

INDUSTRIAL APPLICABILITY 1-Methylindane can be obtained in high yield. Further, diphenylbutane can be obtained at a high yield simultaneously with 1-methylindane, and the production ratio of 1-methylindane and diphenylbutane can be set to a desired ratio. In the method of the present invention, the separation of the catalyst is easy, steps such as washing of the product are unnecessary, and the process is simple.

Front page continuation (72) Inventor Tadashi Niwa, 1-3-1, Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture Tonen Corporation Research Institute (72) Hiroshi Ueno 1-3-chome, Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture No. 1 Tonen Co., Ltd. Research Institute

Claims (1)

[Claims] 1. A 1-methylindane which simultaneously produces 1-methylindane and diphenylbutane by reacting benzene and 1,3-butadiene at a reaction temperature of 200 ° C. or higher in the presence of a high silica mordenite catalyst. A method for producing diphenylbutane.