JPS61293942A - Production of alkenyl-substituted aromatic phenol - Google Patents

Abstract

PURPOSE:To produce the titled compound useful as a raw material of resin modifier for polycarbonate, etc., in high selectivity and yield with long catalytic life, by carrying out the catalytic dehydrogenation of an alkyl-substituted phenol in the presence of a specific composite catalyst. CONSTITUTION:The objective compound such as m-isopropenylphenol can be produced by the catalytic dehydrogenation of an alkyl-substituted phenol such as m-isopropylphenol, optionally in an inert gas such as N2 at 400-700 deg.C and a liquid space velocity of 0.1-10hr<-1>in the presence of a composite catalyst produced by using an iron oxide such as ferric nitrate as a main component and an oxide of a group IV metal of the periodic table such as germanium oxide, zirconium nitrate, etc., as an auxiliary component and if necessary, adding chromium oxide such as chromium nitrate thereto. USE:Raw material of agricultural chemicals or raw material for the production of 2-bis(hydroxyphenyl)propane which is a modifier for epoxy resin, polyamide resin, etc.

Description

Detailed Description of the Invention [Technical Field of the Invention] The present invention catalytically dehydrogenates alkyl-substituted phenols to produce 2-bis( The present invention relates to a method for producing alkenyl group-substituted phenols useful as raw materials for producing (hydroxyphenyl)propane.

[Prior art]

Conventional methods for obtaining alkenyl-substituted phenols include, for example, 2-hydroxy-2-propyl.

There is a method of dehydrating phenols in the presence of an acid catalyst, but the yield is not very good. As a reaction method different from this, several methods have been reported so far regarding the reaction of catalytically dehydrogenating alkyl group-substituted phenols to obtain alkenyl group-substituted phenols. For example, JP-A No. 53-43491 discloses a method using a catalyst containing iron oxide as the main active ingredient, either alone or in combination with an alkaline earth metal oxide as a carrier. There is a problem that the conversion rate of is low and the yield of the target product is low. Also, JP-A-54-55529
No. 55-154930 discloses a method using a catalyst containing chromium oxide as the main component, but in both of these methods, the conversion rate of the raw material is 40% or less and the target product is not obtained. The yield is also low and problematic. Looking more closely at the catalyst composition of these publications, the catalyst of JP-A-54-55529 is a catalyst containing chromium oxide alone or a combination of chromium oxide and oxides of zinc, manganese, titanium, and zirconium. , regarding its catalytic activity, the yield of the target vinylphenols is 40
There is a problem as it is low at less than %. In addition, as a comparative example, the publication describes a method for dehydrogenating p-ethylphenol using a commercially available catalyst combining iron oxide, chromium oxide, and potassium oxide, but the conversion rate was 11.5%, p- -Ethynylphenol selectivity is even lower at 29.4%. Although the composition ratio of the metal oxides in the commercially available catalyst is not specified in the publication, it is known that the metal oxides correspond to the three components of coughing, and therefore the present inventors also applied the present invention to the catalyst. When we investigated the dehydrogenation activity of the compound, we found that its activity was too low to be of practical use. The catalyst disclosed in JP-A-55454930 uses a catalyst containing chromium oxide as a main component in combination with metal oxides such as tin and iron. The specification does not mention anything about the ratio of each metal oxide constituting the catalyst, but for example, regarding the chromium oxide-iron oxide catalyst shown in Example 2, the composition ratio is 100% chromium oxide. It is a catalyst mainly composed of chromium oxide, which is calculated to be approximately 50 parts iron oxide to 4 parts by weight. As mentioned above, the activity of this catalyst is low and poses a practical problem.

Further, JP-A-58-49328 discloses a method for obtaining ethynylphenol by reacting ethylphenol in the presence of an oxide containing barium and tin. However, in this method, the conversion rate of the raw material ethylphenol is low, and the yield of the target ethynylphenol is low.

In general, it is well known that even if the constituent components of a catalyst are the same, changing the content ratio can significantly change the catalytic activity.
Considering that it is difficult to predict the relationship between the structure of a catalyst and the activity of the reaction for which it is used, it is possible to discover new catalysts with higher activity than before by revisiting conventional catalysts and adding new considerations. It seems that there is a sex.

[Problem that the invention seeks to solve]

Based on this viewpoint, the present inventors have determined that when producing alkenyl group-substituted phenols by catalytic dehydrogenation of alkyl group-substituted phenols, the present inventors can select alkenyl group-substituted phenols in a higher yield and at a higher rate than in conventional methods. The aim of this study was to develop a catalyst that can be obtained at low yields and has a long lifespan.

[Means and operations for solving the problems] As a result, the inventors discovered that the above object could be achieved by employing the following method, and completed the present invention.

That is, according to the method of the present invention, alkyl group-substituted phenols are reacted in the presence of a catalyst containing iron oxide (fa) as a main component and a metal oxide (b) of a metal of group 1 of the periodic table as a subcomponent. Provided is a method for producing an alkenyl group-substituted phenol, the method comprising catalytically dehydrogenating the alkenyl group-substituted phenol.

C Catalyst] The catalyst used in the present invention is a catalyst containing iron oxide (a) as a main component and a metal oxide (b) of a metal of group Ⅰ of the periodic table as an ilJ component.

Specific examples of the Group I metal oxides used in the present invention include silicon oxide, germanium oxide, tin oxide, lead oxide, titanium oxide, zirconium oxide, and hafnium oxide. In the catalyst of the present invention, as the metal oxide (b), two or more metal oxides from the group of metal oxides mentioned above can be combined as necessary and used as the metal oxide (bl).

In the catalyst of the present invention, the proportion of iron oxide (al) in the catalyst is such that the number of iron atoms is usually 50 to 99, preferably 60 to 90, per 100 of the total metal atoms in the catalyst. The content of the components constituting the catalyst is from 0.1 to 40, preferably from 1 to 30.

In the present invention, iron oxide (Al) is used as a component of the catalyst.As for the chromium content, the number of chromium atoms is usually 0.5 to 10 per 100 total metal atoms in the catalyst.

When chromium oxide is contained as a component of the catalyst, it is preferable to obtain a catalyst with stable catalytic activity over a long period of time without reducing the initial activity of the catalyst, that is, with a long life.

As a method for preparing the catalyst of the present invention, for example, a mixture of an iron compound, at least one metal compound selected from Group 1 VA and Group 1 VB of the periodic table, and optionally a chromium compound is heated at a predetermined temperature as described below. A method for obtaining the catalyst of the present invention by calcining with Here, specific examples of iron compounds, metal compounds of Group ⅠA and Group 1VB metals, and chromium compounds include oxides of these metals, inorganic acid salts such as nitrates, hydrochlorides, and sulfates, acetates, Examples include organic acid salts such as oxalates, organometallic compounds, metal hydroxides, and metal alkoxides, which are known to be able to be converted into metal oxides by calcination. In the present invention, this is the case.

More specifically, the compounds include iron nitrate, silicon tetrachloride, sodium silicate, germanium nitrate, germanium chloride, zirconium nitrate, zirconium chloride, titanium chloride, titanyl nitrate, magnesium nitrate, magnesium chloride, magnesium sulfate, and nitric acid.

Calcium, calcium chloride, chromium nitrate, chromium chloride, inorganic acid salts such as potassium chromate, organic acid salts such as iron acetate, germanium acetate, magnesium acetate, calcium oxalate, methylmagnesium chloride, diethyldichlorosilane, dibenzene chromium metal hydroxides such as silicon hydroxide, titanium hydroxide, magnesium hydroxide, and metal alkoxides such as ethyl orthosilicate, t-butylalkoxyzirconium, and t-butylalkoxytitanium. In the present invention, conventionally known methods can be employed to obtain the mixture of metal compounds described above. Specifically, the method includes, for example, a method of adding an alkali to a mixed salt aqueous solution of the metal to obtain a mixed metal hydroxide, a method of impregnating and supporting a metal oxide with a salt aqueous solution of another metal, or a method of impregnating and supporting a metal oxide with a salt aqueous solution of another metal. Examples include a method of immersing an object, and a method of kneading and mixing metal oxides or metal salts. In the present invention, among these methods, it is preferable to use a method of adding ammonia water or an aqueous solution containing an alkali metal to the mixed salt aqueous solution.

In the present invention, the catalyst of the present invention is obtained by calcining a mixture of the various types of metal compounds described above.
The temperature is 1000°C, preferably 500 to 700°C. The firing time varies depending on the firing temperature, but is usually 0.5
~3 hours. Firing is usually carried out in the atmosphere, but it can also be carried out in an atmosphere of an inert gas such as nitrogen.

〔reaction〕

In the present invention, alkenyl group-substituted phenols are produced by reacting and catalytically dehydrogenating alkyl group-substituted phenols in the presence of the catalyst.

The alkyl group-substituted phenols used as raw materials for the present invention are monovalent or polyvalent phenols having one or more alkyl groups, and one of the alkyl groups has two or more carbon atoms, preferably has 2 to 5 carbon atoms, more specifically ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, 5eC-butylphenol, n-pentylphenol, methyl (ethylphenol), methyl-n ~ Examples include propylphenol, methylisopropylphenol, diethylphenol, dimethylisopropylphenol, ethylnaphthol, isopropylnaphthol, etc. Among these, 0-ethylphenol, m-ethylphenol, p-ethylphenol, m-isopropylphenol, Isopropylphenol s m-n-propylphenol, p-n-propylphenol, Kano n-
Preferred are alkyl-substituted phenols having an alkyl group having 2 to 4 carbon atoms, such as butylphenol.

In the present invention, the reaction conditions for carrying out the catalytic dehydrogenation reaction are that the reaction temperature is usually 400 to 700°C, preferably 50°C.
The temperature is in the range of 0 to 600°C, and the feed rate of the raw material to the catalyst layer is usually 0.1 expressed in liquid hourly space velocity (LHSV).
~1 Ohr-', preferably 0.1-3 hr-'. Further, in the present invention, an inert gas such as nitrogen and/or a diluent such as steam may be used as necessary. When adding steam, the amount of steam is usually 3 to 30 times the mole, preferably 7 times the mole of the reaction raw material.
~20 times the molar amount is used.

When steam is added, the selectivity of the target alkenyl group-substituted phenol is improved and the life of the catalyst is also extended, which is preferable.

In the present invention, the reaction is usually carried out in a catalytic flow system, and the catalyst bed used may be of any type, such as a fixed bed, moving bed, or fluidized bed.

The alkenyl group-substituted phenols obtained by the method of the present invention correspond to the alkyl group-substituted phenols as raw materials, and specifically include ethynylphenol, isopropenylphenol, 1-propenylphenol, 2-propenylphenol, ethynylnaphthol, Examples include isopropenylnaphthol.

〔Effect of the invention〕

According to the method of the present invention, alkenyl group-substituted phenols can be obtained in high yield and high selectivity. The life of the catalyst is also longer than that of conventional catalysts.

〔Example〕

Hereinafter, the method of the present invention will be specifically explained using examples.

Example 1 Ferric nitrate (Fe(N03) 3 ・91120)
303 g and chromium nitrate (Cr(NO3) 3 .
9H20) 12.8g was dissolved in about 31g of distilled water, and further 20.6g of 20% by weight silica sol manufactured by Nissan Chemical ■ was added and mixed thoroughly. Add 250 ml of approximately 25% by weight commercially available ammonia water to this solution at room temperature with strong stirring.
Added between ~3 minutes. The pH of the solution was 10.5.

After continued stirring for about 5 minutes, the resulting brown slurry was washed by repeated decantation and filtration, and the resulting cake was dried in a drier at about 90° C. for 20 hours. Furthermore, this cake was baked at 650° C. for 3 hours in the air.

When the composition of the composite oxide thus obtained was measured by atomic absorption spectrometry, it was found to be Fe:Si:Cr= in atomic ratio %.
The ratio was 87:9:4. The lumpy catalyst was crushed into 20 to 32 meshes and sieved, and 20 ml of this was filled into a normal quartz reaction tube with an inner diameter of 30n+Φ. The temperature of the catalyst bed is 560℃
m-isopropylphenol and water were quantitatively supplied to this via a preheated vaporization mixer kept at about 330°C, and the mixture was allowed to pass through the catalyst layer.

At this time, the liquid hourly space velocity (LHSV) for m-isopropylphenol was 0.3 hr-', and -
The LHSV of Chikusui was 0.4 hr-'. The reaction product was analyzed by gas chromatography to determine the conversion rate of the raw material m-isopropylphenol and the selectivity of the product. Table 1 shows the results when the reaction was continued for about 5 hours and steady reaction results were obtained.

Table 1 m-isopropylphenol conversion rate 71.7% Product selectivity (based on raw material mol%) m-isopropenylphenol 95.0% toethylphenol 1.2m-isopropylphenol 0.9m+I'-cresol 0. 3 phenol
0.4 Others
2.2 Example 2 202 g of ferric nitrate nonahydrate, chromium nitrate nonahydrate 4.
Germanium oxide 5 is added to an aqueous solution 2β in which 28g of
．． After adding 0.5It of an aqueous solution in which 03g was dissolved,
25% ammonia water was gradually added to adjust the pH of the solution to 7. The generated precipitate was washed with water, filtered, and then dried at 90°C for a day and night.
Next, it was fired at 700°C for 3 hours to form FezO3/GeO2.
- A Cr2O3 catalyst was prepared. The composition of this composite oxide is Fe:Ge:Cr-88,8:
9.1: It was 2.1. 20 to 32 pieces of bulk catalyst
The mixture was crushed into a mesh and 20 ml was placed in a conventional quartz reaction tube. Temperature 560℃5? This was reacted with m-ethylphenol and water. The results are shown in Table 2.

Table 2 Temperature: 560°C, LHSt/=0.8hr-'.

Water/Ethylphenol = 15 mol/mol Conversion rate to m-ethylphenol 76.4% Product selectivity m-Nylphenol 94.7% Cresols 2.4 Phenols 1.3 Example 3 Example 1 In catalyst preparation, after adding silica sol,
Furthermore, Fe2O3・SiO□・CaO・C was prepared in the same manner as in Example 1 except that calcium hydroxide powder was mixed.
A composite metal oxide called r2O3 was prepared.

Its composition is Fe:Si:Ca:Cr=86 in atomic percentage
:8:2:4.

Using this catalyst, 6-methyl-3-methylisopropylphenol was subjected to a dehydrogenation reaction. The results are shown in Table 3.

Table 3 Reaction temperature 560°C, 6-methyl-3-ethylbenzene trace
Sono Iya
3.1 Example 4 In Example 1, instead of adding silica sol, zirconyl nitrate [Zr0(NO3)2 ・2t120349
．． Fe was added in the same manner as in Example 1 except for adding 1 g.
A composite oxide of 203-Zr02-Cr2O3 was prepared, and its composition was 78:18:4 in atomic ratio. Table 4 shows the results of a dehydrogenation reaction of p-isobrolphenol using this as a catalyst.

Table 4 Reaction temperature: 560°C, LtlSV = 0.8 hr.

Water/isobrolphenol = 17 mol/molp
- Isopropylphenol conversion rate 77.5% Product selectivity p- Isopropenylphenol 96.2% p-
Nylphenol 1.8 p-ethylphenol 1.7 Others
0.3 Comparative Example 1 Nissan Girdler Catalyst G64A whose main component is iron oxide
was crushed into 20 to 32 meshes and sieved for use.

The composition of this catalyst was approximately as follows. Fe20dyo7
3.5wt%, Cr2O3 is 1.9wt%, K2CO2
is 21.6wt%.

Dehydrogenation reaction of m-isopropylphenol was carried out in the same manner as in the example. The results are shown in Table 5.

Table 5 Reaction temperature 560°C, LH9V = 0.8 hr, 70 water/m-isobrolphenol-17 mol/mol
Toisopropylphenol conversion rate (%) 27.2%
Phenol 12.1 Aromatic Hydrocarbon 4.5 Comparative Example 2 A catalyst consisting of iron oxide and chromium oxide was prepared in the same manner as in Example 1 except that silica sol was not added. Its composition is Fe: Cr in atomic percentage
=94:6. Using this catalyst, m-isopropylphenol was dehydrogenated in the same manner as in Example 1. As a result, the conversion rate of m-isopropylphenol was 13%, and the selectivity of m-isopropenylphenol was 67%.
and the catalyst performance was low.

Comparative Example 3 Iron oxide-strontium oxide obtained using ferric nitrate and strontium nitrate as raw materials (composition is Fe in atomic %)
Dehydrogenation reaction of m-isopropylphenol was carried out in the same manner as in Example 1 using: 5r=92:8.

The yield was 17.5%, and the m-isopropenylphenol selectivity was 65%.

Comparative Example 4 Table 6 shows the results of a dehydrogenation reaction of m-isopropylphenol using silicon oxide alone prepared from the Nissan Chemical silica sol used in Example 1 as a catalyst.

Table 6 Reaction temperature 560°C, LH5V = Q, 811r-'
, water/isopropylphenol = 15 mol/mol
Toisoprobylphenol conversion rate 82% Product selectivity m-isopropenylphenol 47% Ethylphenol 22%; Nylphenols 17 Cresol
8 Others
6 Comparative Example 5 A dehydrogenation reaction of m-ethylphenol was carried out using zirconium oxide prepared from zirconyl nitrate. The results are shown in Table 7.

Claims (2)

[Claims] (1) Catalytic dehydrogenation of alkyl group-substituted phenols in the presence of a catalyst containing iron oxide (a) as a main component and a metal oxide (b) of a group IV metal of the periodic table as a subcomponent. A method for producing alkenyl group-substituted phenols characterized by: (2) The method according to claim (1), wherein the catalyst contains chromium oxide in addition to iron oxide (a) and metal oxide (b).