JP2005060289A - Method for producing phenolic compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cleavage reaction catalyst solving the problems of deactivating active point by cleavage reaction water and impairing catalyst skeleton at high reaction temperatures, and giving the corresponding phenolic compound in high yield, and to provide a method for producing the phenolic compound using the catalyst. <P>SOLUTION: The highly heat-resistant and highly active cleavage reaction catalyst consists of a polyorganosiloxane having functional group exhibiting acidity. The method for producing the corresponding phenolic compound comprises carrying out a cleavage reaction of an arylalkyl hydroperoxide using the catalyst. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present inventor relates to a method for producing alkylaryl hydroperoxides by a cleavage reaction and the acid catalyst used. More specifically, the present invention relates to a method for producing a hydroxyaryl compound using a polyorganosiloxane catalyst having an acidic functional group.

   An arylalkyl hydroperoxide compound decomposes into the corresponding hydroxyaryl compound, that is, a phenolic compound and a carbonyl compound, with intense heat generation in the presence of an acid catalyst such as sulfuric acid. This reaction is called cleave reaction, and is important as a method for producing phenol and acetone when the arylalkylhydroxyperoxide is cumene hydroperoxide, and as a method for producing cresol and acetone when cymene hydroperoxide is used.

  A mineral acid such as sulfuric acid is used as a homogeneous catalyst, but it is necessary to neutralize the sulfuric acid after the cleavage reaction, and there is always a problem with neutralized waste water and washing waste water. In order to reduce the discharge amount of the neutralized wastewater, there is a method of adsorbing and neutralizing the sulfuric acid catalyst by passing the reaction mixture to the basic ion exchange resin, but the total ion exchange capacity of the basic ion exchange resin used is Since it is finite, when a total amount of sulfuric acid equal to that amount is treated, it is regenerated with strong basic water, so that there is no change in that neutralized wastewater is generated.

  As a method of not generating such neutralization / washing waste water, there is a method of using a solid acid catalyst in which the acid catalyst forms a solid. For example, Texaco Chemical has a catalyst in which a heteropoly acid such as phosphotungstic acid, which is a strongly acidic compound, is supported on a clay compound in US 4898987, and difluorophosphoric acid, which is also a strongly acidic compound, is supported on a clay compound in US4876397. Although the catalyst has been reported, both the active component and the carrier are retained by physical adsorption, so in the reaction in which a ketone compound such as a phenolic compound or acetone is produced as in this reaction, For this reason, there is a concern that the active ingredient may be lost to the liquid layer.

  Zeolite compounds can be cited as solid acid catalysts that are less likely to cause the active component to flow away. For example, Mobil Oil has a proton-type ZSM-5 catalyst in EP 125066, a proton-type beta zeolite catalyst in EP 125065, and Texaco Chemical has a Y-type zeolite exchanged with La in JP 5-85974. EP 203632 describes that borosilicate zeolites containing boron in the framework are effective. However, the active site of the zeolite structure is formed by dehydrating silanol groups adjacent to aluminum or boron by firing. On the other hand, in this cleave reaction, in addition to the arylalkyl hydroperoxide which is the main raw material, about 5% to 20% of arylalkyl hydroperoxide is usually contained and decomposed. This carbinol compound is dehydrated by an acid catalyst that proceeds the cleave reaction and becomes an olefinic compound having a styrenic double bond. That is, when a hydroperoxide compound having a normal composition is used as a raw material, water always exists in the reaction system, and the active site of the zeolitic compound returns to the silanol structure before being fired and activated, The activity decreases after a certain period of use.

As a composite metal oxide catalyst that develops acidity in the presence of water, Mobil Oil has proposed a Fe ₂ O ₃ supported zirconia catalyst in WO 00/64849, and a WO ₃ supported zirconia catalyst in US 6,169,215, Since these support the iron salt and tungsten salt corresponding to a zirconia support | carrier in aqueous solution, and calcinate and use as a catalyst, there exists a possibility of the loss of an active site by the reverse reaction by presence of water.

  A strong acid ion exchange resin can be mentioned as a structure which does not have the fear of the deactivation and runoff by the change of the active point by water. A strongly acidic ion exchange resin is a polystyrene-divinylbenzene copolymer that has been polymerized by adding a small amount of divinylbenzene to styrene, and has a structure that has ion exchange capacity by sulfonating its phenyl group. have. Needless to say, the phenylsulfone group exhibits strong acidity under anhydrous conditions, but the characteristic feature is that the acid strength is slightly reduced even in the presence of water, and is due to the presence of water like a zeolite catalyst. There is no deactivation. Texaco Chemical reported in US 4,898,995 a method for obtaining phenol by cleaving cumene hydroperoxide at a reaction temperature of around 60 ° C. using a strongly acidic ion exchange resin of the type XN-1010 manufactured by Rohm and Haas. Yes.

  The ion exchange resin has an excellent feature that its active site is not subject to a decrease in activity due to water, but it exhibits poor heat resistance due to its amorphous polystyrene-divinylbenzene copolymer as a skeleton. . In general, continuous use above 80 ° C. causes the polymer chain to decompose and become low molecular weight, giving an oligomeric eluate. In particular, a strongly acidic ion exchange resin having a structure called a gel-type ion exchange resin has a divinylbenzene content of about 4% and has increased activity by increasing the pores formed from polymer chains. Such a gel ion exchange resin with a low degree of crosslinking may even impair the physical strength as a catalyst due to softening of the polymer skeleton when the use temperature is high.

Nafion catalysts with skeletons of fluoromethylene groups have a low amount of active sites per unit weight of the catalyst, and in order to improve this, a catalyst in which a low molecular weight Nafion oligomer is physically supported on a high surface area silica gel is also being investigated. However, since it is also a supported catalyst, the amount of active sites that can be supported is limited.
Thus, there has been no example of a cleave reaction by an acid catalyst in which the active sites are not deactivated or washed away even in the presence of water and the catalyst structure is not impaired at all even at a reaction temperature of about 80 ° C.
U.S. Patent 4,898,995

The present invention provides an acid catalyst for cleave reaction that solves the above-mentioned problems of deactivation of active sites by water and damage of the catalyst skeleton at a high reaction temperature, and a corresponding phenol can be obtained in a high yield. With the goal.

As a result of intensive investigations to solve the above problems, the present inventors have conducted conventional alkylation hydroperoxide cleaving reaction using a polyorganosiloxane having an acidic functional group, and conventional zeolites or strongly acidic ion exchange resins. The inventors have found that the corresponding phenols can be obtained in a higher yield than the case of using a catalyst, and have completed the present invention.

That is, the present invention is a method for producing phenols using the following catalyst.
(1) A production method for obtaining a corresponding phenol by performing a cleavage reaction of an alkylaryl hydroperoxide using a polyorganosiloxane having a functional group exhibiting strong acidity.
(2) The said manufacturing method in case the functional group which shows strong acidity is a sulfonic acid.
(3) The said manufacturing method in case polyorganosiloxane contains a phenyl group.
(4) The said manufacturing method in case the polyorganosiloxane which has a functional group which shows strong acidity does not have a mesopore, but is comprised only from a micropore and a macropore.
(5) The said manufacturing method in case alkylaryl hydroperoxide is cumene hydroperoxide.

Using a solid acid catalyst having higher activity and higher heat resistance than before, an alkylaryl hydroperoxide can be subjected to a cleavage reaction to obtain the corresponding phenols in a high yield.

  The polyorganosiloxane having an acidic functional group used in the present invention is an organic functional group directly bonded to one or two silicon atoms as described in JP-A-8-208545 and JP-A-10-225838. It shows a macromolecule obtained by crosslinking an organic silicon moiety and silicon having no organic functional group-silicon bond with oxygen molecules in an arbitrary ratio. Since the macromolecular skeleton is composed of silicon and oxygen, it exhibits strength and heat resistance comparable to inorganic silica.

  Such a polyorganosiloxane having a functional group exhibiting strong acidity is an organic silicon compound having an organic functional group directly bonded to one or two silicon atoms as a raw material, for example, silicon having one or two organic functional groups. It is prepared by using an alkoxy compound, a silicon halide having one or two organic functional groups, and a silicon tetraalkoxide or tetrahalide having no organic functional group-silicon bond by any method.

  Here, organic functional groups directly bonded to silicon include aryl groups such as phenyl group, tolyl group and naphthyl group, methyl group, α-ethyl group, β-ethyl group, α-propyl group and α-butyl group. And a monofunctional organic functional group such as a lower alkyl group, or a bifunctional substituent such as a phenylidene group, a methylidene group or an ethylidene group bonded to two silicon atoms. Particularly preferred examples include a phenyl group and an α-propyl group.

  Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, phenoxy group, and halogen group, and examples thereof include chloro group, bromo group, fluoro group, and iodosyl group. Among these, an ethoxy group and a methoxy group are preferable examples because of the convenience during catalyst synthesis.

  Examples of the functional group exhibiting acidity include Bronsted acidity and Lewis acidity, but Bronsted acid functional groups are preferable, and sulfonic acid groups are particularly preferable. The acidic functional group may be formed on a polyorganosiloxane raw material compound, or may be formed after the raw material is made into a polyorganosiloxane with a macromolecule. In JP-A-10-225838, a polyorganosiloxane having a target phenyl sulfonate group is obtained from triethoxysilylphenyl sulfonic acid obtained by sulfonating phenylchlorosilane with sulfuric anhydride and then reacting with ethanol and tetraalkoxysilane. ing. Japanese Patent Application Laid-Open Nos. 9-110767 and 9-110989 disclose a target γ-sulfone from γ-trihydroxysilylpropyl sulfonic acid obtained by oxidizing γ-mercaptopropyltriethoxysilane with hydrogen peroxide and tetraalkoxysilane. A polyorganosiloxane having acid propyl groups is obtained. Further, after obtaining a polyorganosiloxane having a γ-mercaptopropyl group from γ-mercaptopropyltriethoxysilane and tetraethoxysilane, this solid is treated with hydrogen peroxide to obtain the desired γ-sulfonic acid propyl group. The method of obtaining the polyorganosiloxane which has is mentioned. In these, since the below-mentioned silica pore can be controlled, the method using a triethoxysilyl phenylsulfonic acid is mentioned as a preferable example.

The obtained acidic functional group-containing polyorganosiloxane usually has pores. The pores can be divided into micropores of 2 nm or less, mesopores of 2 to 10 nm, and macropores of 10 nm or more. The size and volume of the pores are measured by a nitrogen adsorption method using a commercial device such as ASAP. Is possible. Mesopores are described as gaps formed by agglomeration of primary particles formed from polyorganosiloxane macromolecules, that is, in the case of acidic functional group-containing polyorganosiloxane having 2 nm mesopores, primary particles Can be calculated as 2.0 / (2 ^0.5-1 ) = 4.8 nm. Since each primary particle is formed from an atomic level silicon-oxygen network, it only has micropores that can only diffuse small molecules such as water. Aggregates of primary particles forming mesopores are called secondary particles, and the voids of the secondary particles are called macropores and have a pore diameter of 10 nm or more. These macropores dominate the material diffusion inside and outside the catalyst particles, and have a great influence on the catalyst activity and life. The acidic functional group-containing polyorganosiloxane used in the present invention more preferably has a structure having no mesopores. If it has mesopores, heavy substances and the like may accumulate in mesopores due to long-term use, which may cause a decrease in activity. In order to avoid such accumulation, it is more preferable to apply a structure having no mesopores. The structure may be formed by any known method, but when triethoxysilylphenylsulfonic acid is used, the following method can be given as a preferred example. The triethoxysilylphenylsulfonic acid obtained from phenylchlorosilane, which is the above-mentioned, contains triethoxyphenylsilane derived from phenylchlorosilane that has not been reacted in chlorination, but the conditions for sulfonation are set appropriately. Alternatively, by using a separation means such as distillation, the purity is 90% or more and the molar ratio of triethoxysilylphenylsulfonic acid to tetraalkoxysilane is kept larger than 0.15, so that the primary particles formed become about 3 nm and mesopores. It is possible to form a structure in which macropores are remarkably observed.

  The amount of the acidic functional group per unit weight of the catalyst of the acidic functional group-containing polyorganosiloxane thus obtained is not particularly limited, but a certain amount or more of the functional group is necessary for application as a catalyst. The minimum amount is expressed as 0.2 m equivalent / g-catalyst. The upper limit is limited by increasing the proportion of the organosilicon compound in which the organic functional group used as a raw material is directly bonded to one or two silicon atoms relative to the silicon compound not having the bond between the organic functional group and silicon. When an organosilicon compound in which an excessive amount of an organic functional group is directly bonded to one or two silicon atoms is used, a strongly acidic functional group-containing polyorganosiloxane that is a macromolecule cannot be maintained in a solid state. ~ It is not preferable because it becomes oily. The molar ratio is preferably 0.5 / 1 or less.

   The strongly acidic functional group-containing polyorganosiloxane may be a powder obtained by synthesis or may be formed into a molded body by a known method. However, binders such as silica sol usually require a sintering temperature of 500 ° C. or higher. However, when applied to the present catalyst, it is necessary to suppress sintering to 200 ° C. or lower to prevent thermal decomposition of organic functional groups. When used in powder form, it can be used in a bag or net-like container or bag made of a material that is not affected by the reaction solvent.

  The cleavage reaction of arylalkyl hydroperoxide using a strongly acidic functional group-containing polyorganosiloxane can be carried out in a temperature range of 20 to 200 ° C., but in order to obtain a sufficient reaction rate, 40 ° C. or higher, more preferably 60 ° C. or higher, In addition, a temperature range of 150 ° C. or lower is preferable in order to prevent an increase in by-product impurities.

As the arylalkyl hydroperoxide to be used, those having a concentration of 5 to 90% by weight can be used. However, in order to obtain a certain volumetric efficiency, it is preferable that the concentration be equal to or higher than the concentration obtained by the oxidation reaction. In the case of high concentration, it may be diluted with a low boiling point solvent such as acetone, an oxidation raw material such as cumene, or a hydrocarbon solvent inert to the reaction such as benzene or toluene in order to reduce the calorific value. . The arylalkyl hydroperoxide used in the present invention is represented by the following formula (1). The aryl group is preferably a phenyl group, and both R ₁ and R ₂ are preferably aliphatic hydrocarbon groups, and particularly preferably methyl groups.

（Arはアリール基を表し、R₁およびR₂はそれぞれ独立して脂肪族炭化水素基、芳香族炭化水素基または水素原子を表す。）
反応は回分式、連続式、または半回分式のいずれでも構わない。反応生成物の組成を安定させるためには、連続反応とし反応条件を制御する方法が好ましい。

(Ar represents an aryl group, and R ₁ and R ₂ each independently represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a hydrogen atom.)
The reaction may be batch-wise, continuous, or semi-batch. In order to stabilize the composition of the reaction product, a method of controlling the reaction conditions as a continuous reaction is preferable.

  The reaction may be a suspended bed or a fixed bed. An example is a method in which a low-boiling solvent such as acetone is added to form a suspended bed, and the reaction is carried out near the boiling point of the acetone to remove heat by the latent heat of vaporization of acetone. However, in the case of a suspended bed, a filtration step is required in the subsequent step, and the catalyst particles are pulverized by stirring, so a fixed bed apparatus is more preferable. Particularly, examples of excellent heat removal efficiency include a jacket cooling method described in JP-A-5-85974 and a reactive distillation method described in US Pat. No. 6,169,215.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
(Reference Example 1)

(1) Synthesis of ethanolic solution of sulfonic acid group-containing ethoxysilane 100 ml of methylene chloride and 130.0 g (0.62 mol) of phenyltrichlorosilane were added to a three-necked 300 ml round bottom flask equipped with a dropping funnel and cooled with ice. . To this, 20 ml of a methylene chloride solution containing 50.0 g (0.63 mol) of anhydrous sulfuric acid was added dropwise over 1 hour. After dropping, the mixture was stirred at room temperature for 1 hour. Next, methylene chloride was distilled off, and 114 g of absolute ethanol was added dropwise over 2 hours while removing hydrogen chloride under a nitrogen stream. 214.0 g of the obtained phenylsulfonic acid group-containing ethoxysilane ethanol solution was used as a raw material for the sulfonic acid component in the sol-gel preparation of a polyorganosiloxane catalyst having a sulfonic acid group-containing hydrocarbon group.
(2) Preparation of polyorganosiloxane catalyst 1 42.0 g (0.06 mol) of the sulfonic acid group-containing alkoxysilane ethanol solution and 150.0 g of tetraethoxysilane in a three-neck 1000 ml round bottom flask equipped with a stirring rod. (0.72 mol) and 100 ml of ethanol were added and mixed. Water 29.0g was dripped at this over 15 minutes, and it stirred at 60 degreeC for 3 hours. After allowing to cool, 140.0 g of water was added dropwise, and when 35 ml of 28% aqueous ammonia was added dropwise, the reaction solution rapidly solidified. This was allowed to stand at room temperature for 4 hours and then aged at 60 ° C. for 3 days. After aging, the solvent was distilled off at 100 ° C. under a reduced pressure of 10 mmHg to obtain a dry solid. Subsequently, the operation of adding 300 ml of 2N hydrochloric acid and stirring for 30 minutes at room temperature was repeated twice to return the sulfonic acid group to the H ⁺ type. After the acid treatment, it was washed with 500 ml of ion exchanged water and dried at 100 ° C. under a reduced pressure of 10 mmHg for 10 hours to obtain 62.0 g of a polyorganosiloxane catalyst 1 having a sulfonic acid group-containing hydrocarbon group. When the solid acid amount of this catalyst was measured, it was 0.87 meq / g. The specific surface area measured by the nitrogen gas adsorption method is 741 m ² / g, the pore volume with a pore diameter of 0.9 to 50 nm is 0.49 cc / g, and the pore volume with a pore diameter of 2 to 50 nm is 0.14 cc. / G, and the mesopore existence ratio was 30%.
(Reference Example 2)

(1) Synthesis of ethanolic solution of sulfonic acid group-containing ethoxysilane 100 ml of methylene chloride and 39.1 g (0.19 mol) of phenyltrichlorosilane were added to a three-necked 300 ml round bottom flask equipped with a dropping funnel and cooled with ice. To this, 20 ml of a methylene chloride solution containing 37.3 g (0.47 mol) of anhydrous sulfuric acid was added dropwise over 1 hour. After the dropwise addition, the reaction was carried out under reflux for 2 hours, and then 46.0 g of ethanol was added dropwise over 1 hour while removing hydrogen chloride under a nitrogen stream, and then methylene chloride was distilled off. Further, 46.0 g of ethanol was added and refluxed for 2 hours. 162.7 g of the obtained sulfonic acid group-containing ethoxysilane ethanol solution was used as a raw material for the sulfonic acid component in the sol-gel preparation of a polyorganosiloxane catalyst having a sulfonic acid group-containing hydrocarbon group.
(2) Preparation of polyorganosiloxane catalyst 2 138.0 g of the sulfonic acid group-containing alkoxysilane ethanol solution and 119.0 g of tetraethoxysilane (0.57 mol) were added to a three-neck 1000 ml round bottom flask equipped with a stir bar. ), 100 ml of ethanol was added and mixed. To this, 24.0 g of water was added dropwise over 15 minutes and stirred at 60 ° C. for 3 hours. After allowing to cool, 120.0 g of water was added dropwise, and when 35 ml of 28% aqueous ammonia was added dropwise, the reaction solution rapidly solidified. This was allowed to stand at room temperature for 4 hours and then aged at 60 ° C. for 3 days. After aging, the solvent was distilled off at 100 ° C. under a reduced pressure of 10 mmHg to obtain a dry solid. Subsequently, the operation of adding 300 ml of 2N hydrochloric acid and stirring for 30 minutes at room temperature was repeated twice to return the sulfonic acid group to the H ⁺ type. Subsequently, it was washed with 500 ml of ion-exchanged water and dried at 100 ° C. under a reduced pressure of 10 mmHg for 10 hours. By the above operation, 55.1 g of a polyorganosiloxane catalyst 2 having a sulfonic acid group-containing hydrocarbon group was obtained. When the solid acid amount of this catalyst was measured, it was 1.42 meq / g. Further, the specific surface area measured by the nitrogen gas adsorption method is 464 m ² / g, the pore volume of the pore diameter of 0.9 to 50 nm is 0.21 cc / g, and the presence of the pore is not recognized at the pore diameter of 2 to 50 nm, It was found to be a solid acid catalyst without mesopores.
(Comparative Example 1)

Amberlyst 15 manufactured by Rohm and Haas as a catalyst was suspended in 1 g of 20 g of benzene solvent, and 20 g of 80 wt% cumene hydroperoxide solution was added dropwise at 80 ° C. over 30 minutes. The amount of catalyst relative to the cumene hydroperoxide added is 6.25% by weight. Stirring at 80 ° C. was continued for 30 minutes after the completion of the dropwise addition, and the cumene hydroperoxide concentration in the reaction mixture determined by iodometry was 36.2% by weight. Since the cumene hydroperoxide concentration when the reaction does not proceed at all is 40% by weight, the conversion rate of cumene hydroperoxide in this reaction is calculated as (40-36.2) / 40 = 10 mol%.
Hereinafter, the weight% indicating cumene hydroperoxide concentration and the mol% indicating conversion are both abbreviated as%.
(Comparative Example 2)

The reaction was conducted in the same manner as in Comparative Example 1 except that proton-type USY zeolite was used. The cumene hydroperoxide concentration 30 minutes after the completion of dropping was 36.2%. Calculated as 10%.
(Comparative Example 3)

The reaction was conducted in the same manner as in Comparative Example 1 except that the catalyst used was a proton-type USY zeolite containing 1% F atoms by fluorine treatment. The concentration of cumene hydroperoxide 30 minutes after the completion of the dropping was 26.4%. Therefore, the conversion rate of cumene hydroperoxide is calculated to be 34%.
(Comparative Example 4)

When the reaction was conducted in the same manner except that Nafion was used as the catalyst in Comparative Example 1, the concentration of cumene hydroperoxide 30 minutes after the completion of dropping was 1.1%, and the conversion of cumene hydroperoxide was 97%. Calculated.
(Comparative Example 5)

  When the reaction was carried out in the same manner as in Comparative Example 1 except that the silica gel-supported Nafion was used, the cumene hydroperoxide concentration 30 minutes after the completion of the dropping was 0.2%. Therefore, the conversion rate of cumene hydroperoxide was 99. % Or more is calculated.

The reaction was carried out in the same manner except that the sulfonic acid phenyl group-containing organopolysiloxane synthesized in Reference Example 1 was used as the catalyst in Comparative Example 1. As a result, the cumene hydroperoxide concentration 30 minutes after the completion of the dropping was 0.1% or less. Therefore, the conversion rate of cumene hydroperoxide is calculated to be 99% or more.
(Comparative Example 6)

The same operation was performed at 80 ° C. using benzene in the same manner except that the amount of the catalyst used in Comparative Example 1 was reduced to 1/5 and Nafion was used as the catalyst. The amount of catalyst relative to the cumene hydroperoxide added is 1.25% by weight. Since the cumene hydroperoxide concentration 30 minutes after the completion of dropping was 30.5%, the conversion rate of cumene hydroperoxide was calculated to be 24%.
(Comparative Example 7)

  In Comparative Example 6, the same operation was performed except that silica gel-carrying Nafion was used as the catalyst. Since the cumene hydroperoxide concentration 30 minutes after the completion of dropping was 11.7%, the conversion of cumene hydroperoxide was calculated to be 71%.

  The reaction was carried out in the same manner as in Comparative Example 6 except that the sulfonic acid phenyl group-containing organopolysiloxane synthesized in Reference Example 1 was used. The cumene hydroperoxide concentration 30 minutes after the completion of the dropping was 0.1%. Therefore, the conversion rate of cumene hydroperoxide is calculated to be 99% or more.

The reaction was conducted in the same manner as in Comparative Example 6 except that the catalyst was the non-mesoporous sulfonic acid phenyl group-containing organopolysiloxane synthesized in Reference Example 2. As a result, the cumene hydroperoxide concentration after 30 minutes from the completion of the dropping was 0.00. Since it was 2%, the conversion rate of cumene hydroperoxide is calculated to be 99% or more.
(Comparative Example 10)

   In Comparative Example 7, the catalyst used after completion of the reaction was filtered off and used again as a reaction catalyst twice. In the second reaction, the cumene hydroperoxide concentration 30 minutes after the completion of the dropping was 26.5%, so the conversion rate of cumene hydroperoxide was calculated to be 34%.

   In Example 2, the catalyst used after completion of the reaction was filtered off and used again as a reaction catalyst twice. In the second reaction, the cumene hydroperoxide concentration 30 minutes after the completion of the dropwise addition was 1.0%. Therefore, the conversion rate of cumene hydroperoxide is calculated to be 98%.

In Example 3, the catalyst used after completion of the reaction was filtered off and used again as a reaction catalyst twice. In the second reaction, cumene hydroperoxide concentration 30 minutes after the completion of dropping was 0.2%, so the conversion rate of cumene hydroperoxide is calculated to be 99% or more.

Claims (6)

A production method for obtaining a corresponding phenolic compound by performing a cleavage reaction of an arylalkyl hydroperoxide using a polyorganosiloxane having a functional group exhibiting acidity as a catalyst. 2. The production method according to claim 1, wherein the acidic functional group is sulfonic acid. The production method according to claim 1 or 2, wherein the polyorganosiloxane having a functional group exhibiting acidity contains a phenyl group. The production method according to any one of claims 1 to 3, wherein the polyorganosiloxane having a functional group exhibiting acidity does not have mesopores but is composed only of micropores and macropores. The production method according to claim 1, wherein the arylalkyl hydroperoxide is cumene hydroperoxide. A catalyst used for a cleaving reaction to obtain a corresponding phenolic compound from an arylalkyl hydroperoxide, comprising a polyorganosiloxane having a functional group exhibiting acidity.