JPH0278637A - Method for producing isopropyl-p-terphenyls - Google Patents

Abstract

PURPOSE:To obtain the title substance in high yield by reacting p-terphenyl with propylene, propanol, propyl halide, polyisopropylbenzene, etc., in the presence of preferably H type mordenite catalyst. CONSTITUTION:p-Terphenyl is reacted with an isopropylating agent such As propylene, propanol, etc., in the presence of zeolite (preferably H type mordenite) having 7Angstrom pore diameter as a catalyst at 130-320 deg.C under 2-20kg/cm<2> to give the title substance. The reaction can be carried out by using a solvent or not using the solvent. For example, in case that a reaction mixture is almost solid as p-terphenyl is isoropylated with propylene at a temperature lower than the melting point of p-terphenyl, a solvent such as n-paraffin is required. The title substance is useful as a heating medium, solvent for pressure-sensitive paper, intermediate raw material of polymer, intermsdiate raw material for liquid crystal, etc.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to isopropyl-p-terphenyl compounds useful as intermediates for p-terphenyl compounds having a substituent at the 4-position, heat carriers, pressure-sensitive paper solvents, etc. Concerning a method for producing phenyls.

[Prior Art] Isopropyl-p-terphenyls are useful as heat carriers, pressure-sensitive paper solvents, etc. Among them, 4-isopropyl-p-terphenyl, 4,4°-diisopropyl-p
- Terphenyl and the like are highly useful as new polymer raw material intermediates or liquid crystal raw material intermediates because of their linear structure.

As a method for isopropylating terphenyl, Neftekhimiya, 9. p17. (1
969) describes a method for the isopropylation of terphenyl isomer mixtures with propylene in the presence of an aluminum chloride catalyst, and also Bull, Soc, Ch.
im, Fr.

11, 1) 4370 (1967) describes a method for isopropylating p-terphenyl with propyl chloride in the presence of an aluminum chloride catalyst.

However, when the isopropylation reaction of terphenyl is carried out using these conventional Friedel-Kranoz catalysts, the products are various isopropyl- It becomes a mixture of p-terphenyls, especially the selectivity of 4-isopropyl-p-terphenyl in isopropyl-p-terphenyl (
When the selectivity among isomers) is around 30% to 40%, the yield of 4-isopropyl-〇-terphenyl in the product (
Weight% in the compound with p-turf 1-nyl ring) is 10%
The degree is extremely low.

[Problem to be Solved by the Invention 1] Therefore, the present inventors conducted intensive research in order to solve the above problems, and found that 4-isopropyl- The present invention was completed based on the discovery that it is possible to produce isopropyl-terphenyl compounds rich in terphenyl or 4,4°-diisopropyl-terphenyl.

Therefore, an object of the present invention is to provide a method for producing isopropyl-p-terphenyls with excellent selectivity and yield of 4-isopropyl-terphenyl or 4.4"-diisopropyl-terphenyl. I'm in the middle of the day.

[Means for Solving the Problems] In other words, the present invention provides a method of finely dissolving p-terphenyl and one or more mixtures selected from propylene, propanol, propyl halide, and polyisopropylbenzenes. This is a method for producing isopropyl-terphenyls in the presence of a zeolite catalyst having a pore size of about 7.

The catalyst used in the present invention is a zeolite catalyst with a pore size of approximately 7 pores. Examples of the zeolite catalyst having a pore diameter of about 7 people include mordenite and metal-modified mordenite, but normal H-type mordenite is preferred. Note that the pore diameter of about 7 refers to the pore diameter that normal H-type mordenite has, and there is a width of about ±0.5 pores around 7 pores.

The acid strength of Biolite catalyst is that the heat of adsorption of ammonia is 85 K.
Acid points of joul/mol or more 0.1 to 3 mol/Kg
It is preferable to have it. When the number of acid sites is less than 0.1 mol/Ky, it is difficult to obtain an industrially sufficient conversion rate, and when it is more than 3 m01/Ng, carbonaceous precipitation becomes intense and the catalyst life is shortened.

The reaction temperature is usually 130°C to 310°C, preferably 150°C.
'C~250'C. When the reaction temperature exceeds 310°C, isomerization of the isopropyl group to the mountain position occurs, resulting in a decrease in the yield of 4-isopropyl-terphenyl or 4°4°-diisopropyl-p-terphenyl. Moreover, when the reaction temperature is lower than 130'C, the conversion rate of p-terphenyl decreases, and the yield of 4-isopropyl-p-terphenyl or 4.4-1 diisopropyl-terphenyl also decreases.

This reaction can be carried out with or without a solvent, but depending on the reaction conditions, e.g. the isopropylation of terphenyl with propylene is carried out at a reaction temperature lower than the melting point of p-terphenyl. When most of the reaction mixture in the reaction system is solid, a solvent is required.

As the solvent used in the reaction, among the solvents used in ordinary Friedel-Crach reactions, those having a boiling point of 100° C. or higher, such as n-paraffin having 7 or more carbon atoms, trans-decalin, nitrobenbin, etc., are preferable.

The reaction pressure is normal pressure to 30 Kl/crtr, preferably 2 to 9/ci to 20 Kl/cri. Even if the pressure is high, it will not adversely affect the reaction, but it is not necessary to use a particularly high pressure.

The isopropylating agent used in the reaction is one or a mixture of two or more selected from propylene, propanol, propyl halide, and polyisopropylbenzenes. p
-The amount of isopropylating agent used for terphenyl is
When the purpose is to produce 4-isopropyl-terphenyl, an isopropyl group (isopropyl group + propylene propanol ten propyl halide) and an aromatic group (p
-terphenyl polyisopropylbenzenes) molar ratio (isopropyl group/aromatic 1) = 0.25 to 2, preferably 0.5 to 1.5, and 4,4°°-diisopropyl- p-terphenyl 1! For the purpose of manufacturing, molar ratio (isopropyl group / aromatic group) = 0.5 ~
3, preferably 1.5 to 2.5. When this molar ratio exceeds 3, more triisopropyl-〇-terphenyls, tetraisopropyl-p-terphenyls, etc. are produced.

The reaction can be carried out either in a flow format or in a batch format. The former is suitable for mass production, and the latter is suitable for small quantity production. In either type of reaction, the catalyst and reaction product can be easily separated by solid-liquid separation. The zeolite catalyst that has lost its activity is calcined at about 500'C in the presence of air diluted with nitrogen, for example.
It can be easily regenerated by removing the carbon deposited on the surface and can be reused.

The reaction product is converted into isopropyl-terphenyls by separating side reaction products such as unreacted terphenyl, benzene, trans-isopropylation agent, etc. by means such as distillation or crystallization. Unreacted p-terphenyl has a high melting point;
If it is attempted to be removed by distillation, it may crystallize at the outlet of the distillation column and cause blockage, so it is preferable to add toluene or n-hebutane as a solvent and remove it in advance by crystallization.

The 4- contained in this isopropyl-p-terphenyls
Isopropyl-p-terphenyl and 4,4°-diisopropyl-p-terphenyl can be separated by means such as distillation and crystallization. and 4-isopropyl-
Kano taro 1 nil and 4.4”-shiitsubu 1] building-p-
The reaction products obtained by separating terphenyl can be used as heat carriers, solvents, and the like.

[Example] Hereinafter, the method of the present invention will be specifically explained based on Examples and Comparative Examples.

Example 1.3 and Comparative Example 1 In a pressurized reaction vessel equipped with a stirrer, p-terphenyl (TP) and a solid acid catalyst shown in Table 1 were charged, and 206 mm parts of rhopentadecane was charged as a solvent. The reaction was carried out under the conditions shown in Table 1 while supplying propylene at a predetermined pressure. The solid acid catalyst used was mordenite in Examples 1 and 3, and silica alumina in Comparative Example 1, each having a heat of adsorption of ammonia of 85 Kjou.
The catalyst contained 1.70 mol and 0.3 mol of acid sites per 1 kg of catalyst of 1/mol or more. Table 2 shows the proportion of compounds with terphenyl rings in the reaction product, and
Table 3 shows the isomer ratios of monoisopropyl-p-terphenyl and diisopropyl-terphenyl.

Example 2 and Comparative Example 2.3 In a pressurized reaction vessel equipped with a stirrer, p-terphenyl ([P)
and isopropylbenzene (cumene, PBz), diisopropylbenzene (DPBZ) or].liisopropylbenzene (TPBz) and a solid acid catalyst, and a reaction was carried out under the conditions shown in Table 1. The solid acid catalyst used was mordenite in Example 2 and silica alumina in Comparative Examples 2 and 3.

The results are shown in Tables 2 and 3.

[Effect of the invention 1] According to the method of the present invention, isopropyl-p-terphenyls rich in useful 4-position substituents and 4,4°-position substituents can be produced in high yields while overcoming the drawbacks of aluminum chloride catalysts. It can be manufactured in

Patent applicant: Nippon Steel Chemical Co., Ltd.

Claims (2)

[Claims] (1) Reacting p-terphenyl with one or a mixture of two or more selected from propylene, propanol, propyl halide, and polyisopropylbenzenes in the presence of a zeolite catalyst with a pore diameter of approximately 7 Å. Characteristic method for producing isopropyl-p-terphenyls. (2) The method for producing isopropyl-p-terphenyls according to claim 1, wherein the powder X-ray diffraction pattern of the zeolite catalyst is the same as that of mordenite.