WO2004024660A1

WO2004024660A1 - Process for production of 4-alkylphenols

Info

Publication number: WO2004024660A1
Application number: PCT/JP2003/010868
Authority: WO
Inventors: Yoshihisa Tsuji; Masayoshi Yamanaka; Hideharu Iwasaki
Original assignee: Kuraray Co., Ltd.
Priority date: 2002-09-12
Filing date: 2003-08-27
Publication date: 2004-03-25
Also published as: KR100618367B1; AU2003261766A1; CN1681758A; CN100357241C; KR20050044916A

Abstract

A process for the production of 4-alkylphenols, characterized by comprising the first step of reacting a 4-unsubstituted phenol with an alkyl alcohol or an alkyl ether in the presence of a synthetic zeolite at a temperature of 50 to 110°C, the second step of removing water contained in the liquid phase of the reaction mixture when an alkyl alcohol is used in the first step or an alcohol contained therein when an alkyl ether is used in the first step, and the third step of subjecting the resulting water- or alcohol-free reaction mixture to rearrangement at a temperature of 90 to 150°C in the presence of an acid catalyst. According to the process, 4-alkylphenols can be industrially advantageously produced with high selectivity and in high yield.

Description

4_Production method of alkylphenols

The present invention relates to a method for producing 4-alkylphenols.

The 4-identified alkylphenols produced according to the present invention are used as various synthetic raw materials, and in particular, 4-ter-fine t-butylphenol (hereinafter abbreviated as 4_TBP) controls the molecular weight of the polycarbonate resin. It is useful as a raw material for agents such as phenolic resins and surfactants. Background art

Conventionally, as a method for producing 4-alkylphenols, there is known a method of alkylating phenols by reacting the phenols with olefins, alcohols or ethers in the presence of a catalyst. As a method for producing 4-alkylphenols from phenols and olefins, there is known a method in which olefins are subjected to an addition reaction with phenols in the presence of an acid catalyst, followed by a disproportionation reaction (Japanese Patent Application Laid-Open No. Hei 8- Reference is made to Japanese Patent Application Publication No. 12610). In the case of this method, it is necessary to use high-purity olefins in order to suppress the generation of by-products derived from the olefins as raw materials. In particular, when low-boiling olefins are used, it is difficult to obtain high-purity olefins by means of distillation or the like, so that alcohols or ethers as raw materials are purified and then dehydration or dealcoholization thereof is performed. Must be carried out at a high selectivity, and the obtained olefins must be purified to a desired purity by using a purification means such as distillation, which increases the cost and is not economical. Meanwhile, Arco When using high-purity olefins as raw materials, there are advantages such as low preparation cost and easy handling compared to using high-purity olefins. On the other hand, if the water produced when alcohol is used as the raw material or the alcohol generated when ether is used as the raw material lowers the catalytic activity, it is necessary to remove the generated water or alcohol from the system. is there.

As a method for producing 4-alkyl phenols by reacting phenols and alcohols in the presence of a catalyst, for example, (1) phenol is mixed with a secondary alcohol or tertiary alcohol under a pressure of 4 atm or less (actually, air A method of reacting while evaporating water in the vicinity of pressure reduction, about 135 to 180 ° 0, in the presence of a dehydration condensation catalyst such as activated clay and sulfuric acid (U.S. Pat. No. 2,140,782) (2) tert-butanol (hereinafter abbreviated as TBA) having a water content of about 12 to 30% by weight and phenol are synthesized in the presence of a silica-alumina-based catalyst. (3) A method of alkylating phenol with TBA in the presence of a cation-exchange resin [Catalysis Letters] (Catlysis Letters), Volume 19, Volume 30 3 1 page 7, etc. (1 9 9 3 years) reference] it is known.

All of the above methods (1) to (3) are methods for producing 4-alkylphenols in one step. The activated clay used in the above method (1) has different properties depending on the place of production, mining location, etc., and thus has poor reproducibility of catalytic activity. In addition, the generated water is adsorbed between the layers, and the acidity tends to decrease. Activity decreases. When sulfuric acid is used, the protonic acid of sulfuric acid changes significantly depending on the amount of generated water, and the catalytic activity is greatly affected. Therefore, in method (1), it is necessary to evaporate water from the reaction system. When TBA is used, TBA inevitably increases the amount of TBA used because it azeotropes with water, which is economically disadvantageous. In method (2) above,

When the temperature is lower than 220 ° C, the ratio of ortho isomer increases rapidly, so it is necessary to carry out the reaction at a high temperature.In addition, since the reaction is carried out under pressure to maintain the liquid phase state, special Requires a pressure device. In the above method (3), the durability of the cation exchange resin is low and the cation exchange resin is gradually decomposed in order to carry out the reaction continuously for a long time at a temperature that promotes the dehydration reaction of TB A. Since acidic components such as sulfonic acid are gradually mixed into the reaction solution, there is a problem that the operation becomes complicated, for example, neutralization is required before a distillation step for obtaining a product.

Methods for producing 4-alkylphenols by reacting phenols and ether in the presence of a catalyst include, for example, (4) phenol in methyl tert-butyl ether (hereinafter referred to as MTBE) in the presence of a cation exchange resin. [Catalysis Letters], 1993, Vol. 19, Vol. 19

(See pages 309-317), (5) Hydroxyl aromatic compounds such as phenol and pyrocatechol and alkyl tertiary butyl ethers were added in the presence of sulfuric acid or ion exchange resin for 60-130. The reaction is carried out at a temperature of ° C to remove the produced alcohol, and the reaction is completed in the absence of the alcohol to convert the hydroxylated aromatic compound into tertiary butyl. No. 7-6 7 5 229).

In the above methods (4) and (5), the durability of the cation exchange resin is low in the presence of the generated alcohol at the temperature at which the cation exchange resin decomposes the ether to generate olefins. The ion-exchange resin gradually decomposes and acidic components such as sulfonic acid gradually enter the reaction solution Therefore, there is a problem that the operation is complicated, for example, the neutralization is required before the distillation step for obtaining the product. In addition, when sulfuric acid is used, the generated olefins are isomerized by the sulfuric acid, so that there is a problem that the reaction product becomes complicated.

In recent years, synthetic zeolites have been attracting attention as catalysts that not only have excellent alkylation activity and selectivity for aromatic compounds, are non-corrosive, have low environmental pollution, and have excellent durability. When alkylating phenol with TB A, a method using synthetic zeolite includes, for example, (6) a method of gas-phase alkylation using a zeolite catalyst (US Pat. No. 4,391,998). Specification, U.S. Pat.No. 4,532,368, Japanese Patent Publication No. 52-12181), (7) in liquid phase in the presence of metal-containing Y-type zeolite A method of alkylating phenols with alcohols and / or ethers at a temperature of preferably from 200 to 320 ° C. (JP-A-62-2406337, JP-A-62 246 532), (8) As a method for alkylating phenol with TBA using a synthetic zeolite, a reaction in carbon tetrachloride in the presence of a HY-type zeolite [Journal Chemical Research (S) (see J. Chem. Research (S)), pp. 40-41 (1989)] Method using large diameter zeolite such as HY type and H / 3 type [Applied Catalysis A: Genera 1], Vol. 166, pp. 89-95 ( 1998), Volume 207, and Pages 183 to 190 (pp. 201).

The above method (6) not only requires a large amount of heat because the reaction is performed in the gas phase, but also has a low selectivity because the reaction temperature is close to the decomposition point of 41 TBP. Furthermore, for carbon deposit by phenol Degradation of catalyst activity is large. In the above method (7), there is a problem in that the selectivity of the generated 4-alkylphenols is low and 2-alkylphenols which are difficult to separate are by-produced. Regarding the contents of the literature describing the above method (8), the reaction conditions such as the pore structure of synthetic zeolite, properties such as acidity, temperature, feed rate of raw material, and raw material ratio are all determined by the catalytic activity and reaction selection. In the reaction examples, oligomers of C4 hydrocarbons were formed, so the selectivity of 4-TBP was low, and industrial production that could produce 4-—TBP in high yield was investigated. It does not consider an advantageous method.

An object of the present invention is to provide an industrially advantageous method capable of producing 4-alkylphenols with high selectivity and high yield. Disclosure of the invention

The present invention comprises reacting an unsubstituted phenol at the 4-position with an alkyl alcohol or an alkyl ether at a temperature of 50 to 110 ° C. in the presence of a synthetic zeolite (first step). If water is used, the generated water contained in the liquid phase in the obtained reaction mixture is removed, and if alkyl ether is used in the first step, it is contained in the liquid phase in the obtained reaction mixture. The produced alcohol is removed (second step), and then a rearrangement reaction is performed in the reaction mixture after removal of the produced water or alcohol at a temperature of 90 to 150 ° C in the presence of an acid catalyst ( Third step) A method for producing 4-alkylphenols.

In a preferred embodiment of the present invention, in the third step, when an alkyl alcohol is used in the first step, the water concentration in the liquid phase of the reaction mixture is adjusted to 0.5% by weight or less; If an alkyl ether is used in the above, the alcohol concentration in the liquid phase of the reaction mixture should be 0.5% by weight or less. The amount of unsubstituted phenols at the 4-position was adjusted to 1 to 10 times the molar amount of the alkyl alcohol or alkyl ether consumed in the alkylation reaction in the first step, and the rearrangement reaction was performed. Do. Further, 4-phenol is produced by using phenol as the unsubstituted 4-position phenol and using TBA as the alkyl alcohol or MTBE as the alkyl ether.

A feature of the present invention is that the alkylation reaction of 4-position unsubstituted phenols is carried out at a temperature in the range of 50 to 110 ° C. in the presence of synthetic zeolite (first step), and the obtained reaction mixture The water or alcohol generated in the alkylation reaction contained in the liquid phase is removed (second step), and then the mono-alkylated phenols contained in the reaction mixture after the removal of water or alcohol, 3-alkylation By-products such as phenols, 2,4-dialkylated phenols, 2,6-dialkylated phenols, 2,4,6-trialkylated phenols in the range of 90 to 150 ° C At this temperature, it can be efficiently converted to 4-alkylphenols in the presence of an acid catalyst (third step).

Due to the above characteristics, there is no remarkable decrease in the catalytic activity due to the generated water as seen in the above method (1), and TBA having a water content of about 12 to 30% by weight can be used as a raw material. . The catalyst deterioration as seen in the above methods (3) to (5) can be suppressed, and complicated operations such as neutralization operation can be avoided because the acidic component is not contained in the reaction solution. can do. Further, due to the above characteristics, the selectivity of 4-alkylphenols is high, and by-products of 2-alkylphenols which are difficult to separate as seen in the above method (7) can be suppressed. The formation of oligomers of C 4 hydrocarbons as seen in the above method (8) can be suppressed. Wear. Further, in the above-mentioned temperature range, the reaction mode is a liquid phase, so that deterioration of the catalyst due to carbon deposit as seen in the above method (6) can be suppressed. Furthermore, by removing water or alcohol generated in the second step, a decrease in the activity of the acid catalyst in the third step is suppressed, and 2,4-dialkylated phenols and 2,6-dialkylated phenols are reduced. The rearrangement reaction of alkyl groups from phenols and 2,4,6-trialkylated phenols to 41-alkylphenols proceeds in a short time with high selectivity. Then, even when an acidic cation exchange resin is used as an acid catalyst, 4-alkylphenols can be produced with good selectivity, and in this case, the temperature of the rearrangement reaction is lowered to 90 ° C. Since there is no generated water and alcohol, it is possible to suppress the outflow of acidic components and the deterioration of the ion exchange resin. BEST MODE FOR CARRYING OUT THE INVENTION

First, the first step will be described.

In the first step, unsubstituted phenols at the 4-position are reacted with alkyl alcohol or alkyl ether at a temperature of 50 to 110 ° C in the presence of synthetic zeolite to alkylate the phenols at the 4-position. Do.

Examples of 4-substituted phenols include phenol, 2-cresol, 3-cresol, 2-ethylphenol, 3-ethylphenol, 2-propylphenol, 3-propylphenol, 2-isopropylphenol, 3-isopropylphenol, and 3-isopropylphenol. 2-tert-butylphenol, 3_tert-butylphenol and the like.

As the alkyl alcohol, an alkyl alcohol corresponding to the alkyl group to be introduced is used. For example, methanol, ethanol, 1-pro Examples include panol, 2-propanol, 1-butanol, 2-butanol, TBA, pentanol, hexanol, hexanol, and benzyl alcohol. The amount of the alkyl alcohol to be used is preferably in the range of 0.1 to 2 mol, more preferably in the range of 0.2 to 1 mol, per 1 mol of the 4-substituted phenol.

As the alkyl ether, an alkyl ether corresponding to the alkyl group to be introduced is used. For example, dimethyl ether, geethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, di-isobutyl ether, MTBE, ethyl tert-butyl ether, n-propyl tert-butyl ether, isopropyl tert-butyl ether, n-butyl tert-butyl ether, isobutyl tert-butyl ether and the like. The amount of the alkyl ether used is preferably in the range of 0.1 to 2 mol, more preferably in the range of 0.2 to 1 mol, per 1 mol of the unsubstituted phenol at the 4-position. Examples of synthetic zeolites are large-diameter zeolites such as X-type, Y-type,] 3-type, L-type, mordenite, medium-diameter zeolites such as ZSM and SAPO, and MCM. Mesoporous silicate and the like can be mentioned. Among these, Y-type,] 3-type, L-type and mordenite are preferred. Usually, the synthetic zeolite has an alkali metal, an alkaline earth metal, or the like in an ionic form in the zeolite. In the present invention, at least a part of these is converted to a transition metal ion, an aluminum ion, and a proton. Those that have been exchanged with at least one ion selected from the group consisting of

As a synthetic zeolite, in order to enhance the reaction efficiency, the acidity of zeolite, that is, the silica / alumina ratio is small, and It is preferable that the alkali metal and the earth metal of the metal are substituted by hydrogen atoms. Further, in order to improve the selectivity of the 4-alkylphenol, it is preferable to use a zeolite having pores corresponding to the molecular size of the 4-alkylphenol. For example, when producing 41 TBP, it is preferable to use mordenite, type 3 zeolite as the zeolite species, and it is preferable that the silica / alumina ratio be in the range of 1 to 200. And those having a range of 5 to 150 are more preferable, and those having a range of 5 to 50 are particularly preferable.

The shape of the synthetic zeolite is not particularly limited, and powdery, condylar, massive, and the like can be used. Further, a powdery or granular material may be molded and used. Examples of the shape of the molded product include a spherical shape, a cylindrical shape, a ring shape, and a star shape. In addition, the size of the particles of the synthetic zeolite is not particularly limited. It goes without saying that the smaller the particles, the larger the surface area and the higher the reaction activity. 1-800 micron particles are used.

The amount of the synthetic zeolite used depends on the reaction system. For example, in the case of a batch system, the amount is preferably in the range of 1 to 100% by weight based on the 4-substituted phenols. And more preferably in the range of 5 to 25% by weight. If the amount of synthetic zeolite used is small, the reaction speed tends to be slow, and if it is large, it is economically disadvantageous, and either case is not preferable.

The alkylation reaction is performed in the presence or absence of a solvent. The solvent is not particularly limited as long as it is inert to the reaction. For example, aliphatic hydrocarbons such as hexane, heptane, octane, nonane, decane and cyclohexane; aromatics such as benzene, toluene, xylene and mesitylene Group hydrocarbons; tetrasalt Carbon halides, 1,2-dichloroethane, and halogenated hydrocarbons such as benzene are used. Of these, the use of toluene is preferred. When a solvent is present, the amount of use is not particularly limited, but from the viewpoint of reaction efficiency, operability, economy, etc., it is in the range of 1 to 20 times the weight of the 4-substituted phenols. Is preferred. ^ The alkylation reaction is performed at a relatively low temperature in the range of 50 to 110 ° C. When the reaction temperature is lower than 50 ° C, the progress of the reaction becomes extremely slow, and the reaction efficiency becomes poor. When the reaction temperature exceeds 110 ° C, not only does the selectivity of the target 4-alkylphenol decrease, but also the raw material alkyl alcohol or alkyl ether or the 4-position unsubstituted phenol. The molecules have a high molecular weight, and the by-products of compounds having a high boiling point increase.

The alkylation reaction can be performed under any of normal pressure, reduced pressure, and increased pressure. The reaction mode may be a batch type or a continuous type. It can be carried out in a fixed bed system in which a 4-layer unsubstituted phenol and an alkyl alcohol or alkyl ether are passed through a bed filled with synthetic zeolite, or in a fluidized bed system or a moving bed system.

The alkylation reaction time is preferably in the range of 1 to 30 hours, more preferably in the range of 5 to 10 hours. If the reaction time is less than 1 hour, the reaction does not proceed sufficiently, and the reaction efficiency tends to be low.If the reaction time is more than 30 hours, by-products of compounds having a high boiling point increase. There is a tendency, either case is not preferable.

The reaction mixture obtained by the alkylation reaction is subjected to the second step after removing the synthetic zeolite from the reaction mixture as necessary.

Next, the second step will be described.

In the second step, if alkyl alcohol is used in the first step, The water generated from the liquid phase of the obtained reaction mixture is removed, and when alkyl ether is used in the first step, the alcohol generated from the liquid phase of the obtained reaction mixture is removed.

Examples of the method for removing water include a method of dehydrating by distillation, a method of blowing an inert gas such as nitrogen or argon into the reaction mixture, and a method of dehydrating with a moisture adsorbent, for example, a molecular sieve, zeolite, alumina, or activated carbon. And the like. Examples of the method for removing alcohol include a method of removing by distillation, a method of blowing an inert gas such as nitrogen and argon into the reaction mixture, and an adsorption and removal method using an alcohol adsorbent such as molecular sieve, zeolite, alumina, and activated carbon. Method. In order to significantly maintain the activity of the acid catalyst used in the third step described below, the concentration of water or alcohol remaining in the liquid phase of the reaction mixture subjected to the rearrangement reaction is adjusted to 0.5% by weight or less. Is preferred. If the amount exceeds 0.5% by weight, the activity of the acid catalyst is not sufficiently exhibited, and the rearrangement reaction rate in the third step is significantly reduced.

Next, the third step will be described.

In the third step, the 2-alkylated phenols, tri-alkylated phenols, 2,4-dialkylated phenols, 2,6-dialkylated phenols, 2,4,6-triols formed in the first step The alkyl group is eliminated from the alkylated phenols and the like, causing a “alkyl group rearrangement reaction” to be added to the 4-position of the unsubstituted phenols at the 4-position, thereby obtaining 4-alkylphenols.

Examples of the acid catalyst include synthetic zeolite and acidic cation exchange resin.

As a synthetic zeolite, alkyl at the 4-position of 4-substituted phenols In order to introduce a group, it is preferable to use zeolite having pores corresponding to the molecular size of the target 4-alkylphenol. Further, it is preferable that zeolite has a low acidity (silica-alumina ratio), and further has a zeolite in which an alkali metal, an alkaline earth metal, or the like, is replaced with a hydrogen atom. If the acidity of the synthetic zeolite is too high, the decomposition reaction of the intended 4-alkylphenols is accelerated, and the selectivity of the 4-alkylphenols tends to decrease, which is not preferable. For example, when producing 4 TBP, it is preferable to use j8 type or Y type zeolite as the zeolite species, and it is preferable that the silica Z alumina ratio is in the range of 1 to 200, Those having a range of from 150 to 150 are more preferable, and those having a range of 5 to 50 are particularly preferable.

Since synthetic zeolite adsorbs water, it is preferable to use it after dehydration treatment in advance. The dehydration treatment is performed, for example, by heating at a temperature of 100 to 300 ° C. for several hours. The dehydration treatment may be performed under a stream of nitrogen or air. The synthetic zeolite may be the same as or different from that used in the alkylation reaction. In carrying out the rearrangement reaction, the synthetic zeolite used in the alkylation reaction may be removed, or the rearrangement reaction may be carried out without removal.

The amount of the synthetic zeolite used depends on the reaction method. For example, in the case of a batch method, the amount is 1 to 10% based on the total weight of the raw material 4-substituted phenols and the product 4-alkyl phenols. It is preferably in the range of 0% by weight, and more preferably in the range of 5 to 25% by weight in consideration of the reaction efficiency. If the amount of synthetic zeolite used is small, the reaction speed is slow, and if it is large, it is economically disadvantageous, and neither is preferred. The acidic cation exchange resin may be any cation exchange resin exhibiting acidity, such as a styrene sulfonic acid type resin.

The shape of the acidic cation exchange resin is not particularly limited as long as it can exhibit a function as a catalyst, and is usually a fine particle having an average particle diameter of 0.01 to 10 mm, a spherical shape, a cylindrical shape, or the like. Can be used. The amount of the acidic cation exchange resin used varies depending on the reaction system.For example, in the case of the patch system, the amount is 1 to 1 with respect to the total weight of the raw material 4-substituted phenols and the product 4-alkyl phenols. It is preferably in the range of 100% by weight, and more preferably in the range of 5 to 25% by weight in consideration of the reaction efficiency. When the amount of the acidic cation exchange resin used is small, the reaction rate is low, and when the amount is too large, it is economically disadvantageous, and either case is not preferable.

The rearrangement reaction is performed in the presence or absence of a solvent. The solvent is not particularly limited as long as it is inert to the reaction. Examples thereof include aliphatic hydrocarbons such as heptane, octane, nonane, decane and methylcyclohexane; aromatic hydrocarbons such as toluene, xylene and mesitylene; Halogenated hydrocarbons such as benzene are used. Among them, it is preferable to use toluene. When a solvent is present, the amount of use is not particularly limited.However, in consideration of the reaction efficiency, operability, economy, etc., the 4-substituted unsubstituted phenols as raw materials and the 4-alkylphenols as products are used. The weight is preferably in the range of 1 to 20 times the total weight.

The rearrangement reaction is performed at a temperature in the range of 90 to 150 ° C. If the reaction temperature is too high, the introduced alkyl group is decomposed and returns to the raw material, so that the conversion of alkylated phenols decreases and the selectivity of 4-alkylphenols decreases. If the reaction temperature is too low, the speed of the rearrangement Very slow and economically disadvantageous.

The rearrangement reaction can be performed under any of normal pressure, reduced pressure, and increased pressure. The reaction mode may be a batch type or a continuous type. It can be carried out in a fixed bed system in which the reaction mixture obtained in the second step is passed through an acid catalyst, or in a fluidized bed system or a moving bed system.

The rearrangement reaction time is preferably in the range of 1 to 20 hours from the viewpoint of suppressing the generation of by-products in the reaction and increasing the selectivity of the desired 4-alkylphenol.

In performing the rearrangement reaction, the ratio of the 4-position unsubstituted phenol in the reaction mixture is adjusted to a specific range by an operation such as adding the 4-position unsubstituted phenol to the reaction solution, and the selectivity of the 4-alkylphenol is selected. And the reaction speed can be increased. The amount of 4-position unsubstituted phenols in the reaction mixture is 1% based on the amount of alkyl groups introduced in the first step, that is, based on the alkyl alcohol or alkyl ether consumed in the alkylation reaction in the first step. It is preferably in the range of from 10 to 10 moles. If the amount is less than 1 mole, alkyl from 2,4-dialkylated phenols, 2,6-dialkylated phenols, 2,4,6-trialkylated phenols, etc. It is difficult to cause a rearrangement reaction of the group, and when the molar ratio exceeds 10 times, the conversion of unsubstituted phenols at the 4-position tends to decrease.

The reactions and operations in the first to third steps can be performed in the same reactor, or can be performed in successive reactors.

The 4-alkylphenols produced according to the present invention can be isolated and purified by the methods used for isolation and purification of ordinary organic compounds. For example, if necessary, the acid catalyst is filtered off from the reaction mixture, and the filtrate is distilled and re-dissolved. Isolate and purify 4-alkylphenols by performing operations such as crystallization and chromatography. Example

Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. In the table, 2-TBP represents 2-tert-butylphenol, and 2,4-DTBP represents 2,4-di-tert-butylphenol. The composition (%) after the reaction was determined by gas chromatography-analysis [column: G-100 (Chemical substance evaluation and research institute), detector: FID (hydrogen flame ionization detector), detector, vaporization chamber temperature : 270 ° C, temperature rise pattern: Hold at 80 for 3 minutes-Temperature rise to 250 ° C at 10 ° C / minute → Hold at 250 for 15 minutes] Is expressed as a percentage. The selectivity (%) of 4-—TBP is expressed on the basis of phenol, and the yield (%) of 4-—TBP is expressed on the basis of TBA or MTBE. Reference example 1

(First step)

Zeolite type 3 zeolite (substituted with 50.0 g (53 1 mmol) of phenol and protons) was placed in a 10 OmL flask equipped with a stirrer, condenser and thermometer. H-; 8) 12.5 g was prepared and stirred. The temperature was raised to 100 ° C., and 2.2.6 g (266 mmo 1) of TBA having a water content of 13% by weight was added dropwise over 3 hours. The mixture was stirred at the same temperature for 3 hours to carry out an alkylation reaction. As a result of analyzing the reaction solution by gas chromatography, the composition of the reaction solution was phenol (42.0%), 4-TBP (50.1%), 2-TBP (4.7%), 2,4-DTBP (3.1%) with a phenol conversion of 46.2%, a selectivity of 4−1 TBP of 81.9%, and a yield of 4−1 TBP of 75.9% It was. Example 1

(First step)

A 10-mL O.L.F. flask equipped with a stirrer, condenser and thermometer was charged with 50.0 g (531 mmo1) of phenol and i3-type zeolite substituted with proton (Sudo 'H—BEA—25) 12.5 g, manufactured by Chemie, was charged and stirred. The temperature was raised to 90 ° C., and 2.6 g (266 mmo 1) of TBA having a water content of 13% by weight was dropped from the syringe over 3 hours. The mixture was stirred at the same temperature for 5 hours to carry out an alkylation reaction. The reaction mixture was analyzed by gas chromatography to determine the formation ratio of each compound, the conversion of phenol, the selectivity for 41 TBP, and the yield. Table 1 shows the results.

(Second step)

The zeolite was removed from the reaction mixture obtained in the first step by filtration. Water was removed from the obtained filtrate by distillation under reduced pressure [26.7 to 4.7 kPa (200 to 35 mmHg), internal temperature 90 to 120 ° C]. The water concentration of the mixture after the removal of water was measured and found to be 0.1% by weight. The amount of phenol was 1.1 in a molar ratio to TBA consumed in the alkylation reaction in the first step.

(Third step)

A 100-mL Ovolo flask equipped with a stirrer, cooling tube and thermometer was charged with the dehydrated mixture obtained in the second step and the Y-type zeolite substituted with protons (Tosoichi Co., Ltd.) HSZ-360 HUA) 1 2. 5 g was charged, the temperature was raised to 120 ° C., and the mixture was stirred for 1 hour to perform a rearrangement reaction. The reaction mixture was analyzed by gas chromatography to determine the formation ratio of each compound and the selectivity and yield of 4-TBP. Table 1 shows the results. Example 1

Items

Process Step phenol 39. 4 39. 4 Composition of reaction solution 4-TBBP 54. 25. 8.0

(%) 2-TBP 3.8.1.5

2,4-1 D T B P 2.6 1 .2 Furnol conversion () 4 2 .5

4 Selectivity of TBP (%) 6 1.2 9 5.6

Yield (%) of 4-TBP 52.1.81.3 Example 2

(Second step)

] -Type zeolite was removed from the reaction mixture obtained in the first step of Example 1 by filtration. Water was removed from the obtained filtrate by subjecting it to vacuum distillation [26.7 to 4.7 kPa (200 to 35 mmHg), internal temperature 90 to 120 ° C]. The water concentration of the mixture after the removal of water was measured and was 0.1% by weight. The amount of phenol was 1.1 in molar ratio to TBA consumed in the alkylation reaction in the first step.

(Third step)

The dehydrated mixture obtained in the second step and 100 g of phenol were added to a tetrafluoro flask having an internal volume of 20 OmL equipped with a stirrer, a condenser and a thermometer. As a result, the amount of phenol was adjusted to 6 in a molar ratio to the TBA consumed in the alkylation reaction in the first step. Thereto, 12.5 g of Y-type zeolite substituted with protons (as described above) was charged, heated to 120 ° C., and stirred for 1 hour to carry out a rearrangement reaction. Reaction solution The product was analyzed by gas chromatography to determine the production ratio of each compound and the selectivity and yield of 41 TBP. Table 2 shows the results.

Table 2

Example 3

(Second step)

] -Type zeolite was removed from the reaction mixture obtained in the first step of Example 1 by filtration. The obtained filtrate was subjected to distillation under reduced pressure [26.7 to 4.7 kPa (200 to 35 mmHg), internal temperature 90 to 120] to remove water. The water concentration of the mixture after the removal of water was measured and was 0.1% by weight. The amount of phenol was 1.1 in molar ratio to the TBA consumed in the alkylation reaction in the first step.

(Third step)

The dehydrated mixture obtained in the second step and an acidic cation exchange resin (Amberlyst 15E, manufactured by Organo Co., Ltd.) were placed in a 10-mL OmL flask equipped with a stirrer, cooling tube and thermometer. ) 12.5 g was charged, the temperature was raised to 90 ° C, and the mixture was stirred for 1 hour to carry out a rearrangement reaction. The reaction mixture was analyzed by gas chromatography to determine the formation ratio of each compound and the selectivity and yield of 41-TBP. Table 3 shows the results. Table 3

Example 3

Term huge

Phenol 39. 4 38. 2 Composition of reaction solution 41 TBP 54. 26. 00

() 2-T BP 3.8. 1.0

2,4-DTBP 2.6.6 Phenol conversion () 4 2.5

4 Selectivity of TBP (%) 6 1.2 9 7.4

4 Yield (%) of TBP 52.187.7.7 Example 4

(First step)

205.0 mL (1.33 mo 1) of phenol and β-type zeolite substituted with proton (Suedeミ -Β 製 Α—25) 12.5 g, prepared by Kemi One, and stirred. The temperature was raised to 100 ° C., and 2.6 g (266 mmo 1) of TBA having a water content of 13% by weight was dropped from the syringe over 3 hours. The mixture was stirred at the same temperature for 3 hours to carry out an alkylation reaction. The reaction solution was analyzed by gas chromatography, and the formation ratio of each compound, the conversion of phenol and the selectivity and yield of 41 TBP were determined. Table 4 shows the results.

(Second step)

From the reaction mixture obtained in the first step,) type 3 zeolite was removed by filtration. Water was removed from the obtained filtrate by distillation under reduced pressure [26.7 to 4.7 kPa (200 to 35 mmHg), internal temperature 90 to 120 ° C]. The water concentration of the mixture after water removal was measured, and was found to be 0.15% by weight.

(Third step)

A 10 OmL mL of 4-loff equipped with a stirrer, condenser and thermometer

1.9 12.5 g of the mixture after dehydration obtained in the second step and Y-type zeolite substituted with protons (as described above) were charged to Lasco, and the temperature was raised to 120 ° C. After stirring for an hour, a rearrangement reaction was performed. The reaction mixture was analyzed by gas chromatography, and the formation ratio of each compound and the selectivity and yield of 41 TBP were determined. Table 4 shows the results.

Table 4

Example 4

Term huge

Phenol 7 3.6 69.5 Composition of reaction solution 4-TBP 23. 4 29.6

(%) 2-T BP 1.8. 0.8

2,4-DTBP 1.20.2 Phenol conversion (%) 18.4

4-TBP selectivity (%) 90.9 96.7

Yield of 4-TBP (%) 83.9 8.90.0 Comparative Example 1

A 50 O g (53 1 mm o 1) phenol and / 3 type zeolite substituted with protons were placed in a 100 O mL flask equipped with a stirrer, condenser and thermometer. (H-BEA-25, manufactured by Zuido Chemie) 12.5 g was charged and stirred. The temperature was raised to 100 ° C., and TBA 22.6 g (266 mmo 1) having a water content of 13% by weight was added dropwise over 3 hours. The mixture was stirred at the same temperature for 2 hours to carry out an alkylation reaction. As a result of analyzing the reaction solution by gas chromatography, the composition of the reaction solution was phenol (39.0%), 4-TBP (54.0%), 2-TBP (4.0%), , 4-DTBP (3.0%), the conversion of phenol is 44.5%, the selectivity of 4 TBP is 88.8%, and the yield of 4 TBP is 79.0 %. When the water concentration of the reaction solution was measured, it was 5.0% by weight. Thereafter,) type 3 zeolite was removed by filtration. 12.5 g of the filtrate obtained above and the proton-substituted Y-type zeolite (as described above) were placed in a 10-mL OmL flask equipped with a stirrer, cooling tube and thermometer. The mixture was heated to 12 Ot: and stirred for 5 hours, but the rearrangement reaction did not proceed. Comparative Example 2

Zeolite type 3 zeolite (substituted with 50.0 g (53 1 mm o 1) of phenol and proton) was added to a 100 OmL tetrafluoro flask equipped with a stirrer, condenser and thermometer. 12.5 g of H—B EA—25) manufactured by Chemie was charged and stirred. The temperature was raised to 90 ° C., and 9.7 g (266 mmo 1) of syringe TBA was added dropwise over 3 hours. The mixture was stirred at the same temperature for 5 hours to carry out an alkylation reaction. The reaction solution was analyzed by gas chromatography, and the formation ratio of each compound, the conversion of phenol, the selectivity of 41-TPP, and the yield were determined. Table 5 shows the results. When the water concentration of the reaction solution was measured, it was 1.0% by weight. Thereafter,) type 3 zeolite was removed by filtration.

12.5 g of the filtrate obtained above and the proton-substituted Y-type zeolite (as described above) were placed in a 10-mL OmL flask equipped with a stirrer, cooling tube and thermometer. Charged, the temperature was raised to 120 ° C, and a rearrangement reaction was carried out with stirring. The reaction liquid obtained 1 hour and 5 hours after the start of the reaction was analyzed by gas chromatography, and the production ratio of each compound, the conversion of phenol, and the selectivity and yield of 41-TBP were determined. Table 5 shows the results. Table 5

Example 5

(First step)

A 100 OmL inner volume flask equipped with a stirrer, condenser and thermometer was charged with 50.0 g (53 1 mmo1) of phenol and a jS-type zeolite substituted with proton (Sued * Chemie). H-BEA-25) (12.5 g) was charged and stirred. The temperature was raised to 100, and 24.2 g (266 mmo1) of syringe MTBE was added dropwise over 3 hours. The mixture was stirred at the same temperature for 5 hours to carry out an alkylation reaction. The reaction mixture was analyzed by gas chromatography, and the formation ratio of each compound, the conversion of phenol, the selectivity of 41-TBP, and the yield were determined. Table 6 shows the results.

(Second step)

] -Type zeolite was removed by filtration from the reaction mixture obtained in the first step. The resulting filtrate was subjected to distillation under reduced pressure [26.7 kPa (200 mmHg), internal temperature of 30 to 40 ° 〇] to remove methanol. The methanol concentration of the mixture after the removal of methanol was measured and was 0.1% by weight. The amount of phenol was 1.1 in molar ratio to MTBE consumed in the alkylation reaction in the first step. (Third step)

A 10-mL OmL flask equipped with a stirrer, condenser, and thermometer was used to add the methanol-removed mixture obtained in the second step and Y-type zeolite substituted with protons (as described above). 12.5 g was charged, the temperature was raised to 120 ° C., and the mixture was stirred for 1 hour to carry out a rearrangement reaction. The reaction mixture was analyzed by gas chromatography, and the formation ratio of each compound and the selectivity and yield of 4-TBP were determined. Table 6 shows the results.

Table 6

Example 5

Term huge

Process Step Phenol 49.23.9.4 Composition of reaction solution 4-TBP 45.95.8.0

(%) 2-T B P 2.5 1.5

2, 4 -DTBP 2.4. 1.2 Phenol conversion (%) 46.0

4 Selectivity of TBP (%) 73.0 95.6

4-TBP Yield (%) 67.3 81.3 Example 6

(Second step)

From the reaction mixture obtained in the first step of Example 5, / 3 type zeolite was removed by filtration. The resulting filtrate was subjected to vacuum distillation [26.7 kPa (200 mmHg), internal temperature of 30 to 40 ° C] to remove the methanol. The methanol concentration of the mixture after the removal of methanol was measured and found to be 0.1% by weight. The amount of phenol was 1.1 in molar ratio to MTBE consumed in the alkylation reaction in the first step.

(Third step)

The 20 mL O2 mL flask equipped with a stirrer, condenser and thermometer was charged with the methanol-free mixture and phenol obtained in the second step. Was added. Thereby, the amount of phenol was adjusted to 6 in molar ratio with respect to MTBE consumed in the alkylation reaction in the first step. Thereto, 12.5 g of proton-substituted Y-type zeolite (as described above) was charged, heated to 120 ° C., and stirred for 1 hour to carry out a rearrangement reaction. The reaction mixture was analyzed by gas chromatography to determine the production ratio of each compound and the selectivity and yield of 4-TBP. Table 7 shows the results.

Table 7

Example 7

(Second step)

From the reaction mixture obtained in the first step of Example 5,) type 3 zeolite was removed by filtration. The resulting filtrate was subjected to distillation under reduced pressure [26.7 kPa (200 mmHg), internal temperature of 30 to 40 ° C] to remove methanol. The methanol concentration of the mixture after the removal of methanol was measured and found to be 0.1% by weight. The amount of phenol was 1.1 in molar ratio to MTBE consumed in the alkylation reaction in the first step.

(Third step)

A 100 OmL inner volume flask equipped with a stirrer, cooling tube and thermometer was charged with the mixture obtained after the removal of methanol obtained in the second step, and zeolite type 3 (Sued 'Chemie, H— B EA— 2 5) 12.5 g Then, the temperature was raised to 120 ° C., and the mixture was stirred for 1 hour to carry out a rearrangement reaction. The reaction solution was analyzed by gas chromatography to determine the formation ratio of each compound and the selectivity and yield of 41 TBP. Table 8 shows the results.

Table 8

Example 7

Term huge

Process

Phenol 49.2 39.5 Composition of reaction solution 4-TBP 45.95 58 .6

(%) 2-T B P 2.5 .1 .1

2,4-DTBP 2.4.08 1 Phenol conversion (%) 4 6.0

4-TBP selectivity (%) 7 3.0 96.8

Yield of 4-TBP () 67.3 89.1 Example 8

(Second step)

From the reaction mixture obtained in the first step of Example 5,) type 3 zeolite was removed by filtration. The resulting filtrate was subjected to vacuum distillation [26.7 kPa (200 mmHg), internal temperature 30 to 40 ° C] to remove methanol. The methanol concentration of the mixture after the removal of methanol was measured and found to be 0.1% by weight. The amount of phenol was 1.1 in molar ratio to MTBE consumed in the alkylation reaction in the first step.

(Third step)

The mixture obtained after the removal of methanol obtained in the second step and an acidic cation exchange resin (Amberlyst 15 from Organo Co., Ltd.) are placed in a 10-mL OmL flask equipped with a stirrer, condenser and thermometer. E) 12.5 g was charged, the temperature was raised to 90 ° C., and the mixture was stirred for 1 hour to carry out a rearrangement reaction. The reaction mixture was analyzed by gas chromatography to determine the formation ratio of each compound and the selectivity and yield of 4-TBP. Table 9 shows the results. Table 9

Example 9

(First step)

A 20-mL mL of a flask equipped with a stirrer, condenser, and thermometer was charged with phenol 12.5.0 g (1.33 mo1) and proton-substituted i3-type zeolite (Suede). · H-BEA-25, manufactured by Chemi Corporation, 12.5 g was charged and stirred. The temperature was raised to 100 ° C., and MTBE 24.2 g (266 mmo 1) was added dropwise from the syringe over 3 hours. The mixture was stirred at the same temperature for 5 hours to carry out an alkylation reaction. The reaction mixture was analyzed by gas chromatography, and the formation ratio of each compound, the conversion of phenol, the selectivity of 41-TBP, and the yield were determined. The results are shown in Table 10.

(Second step)

From the reaction mixture obtained in the first step, // 3 zeolite was removed by filtration. The obtained filtrate was subjected to distillation under reduced pressure [26.7 kPa (200 mmHg), internal temperature 30 to 40] to remove methanol. The methanol concentration of the mixture after the removal of methanol was measured to be 0.15% by weight.

(Third step)

A 10 OmL mL of 4-loff equipped with a stirrer, condenser and thermometer Into Lasco, 12.5 g of the mixture after removal of methanol obtained in the second step and Y-type zeolite substituted with protons (as described above) were added, and the temperature was raised to 120 ° C. After stirring for an hour, a rearrangement reaction was performed. The reaction mixture was analyzed by gas chromatography to determine the formation ratio of each compound and the selectivity and yield of 4-TBP. The results are shown in Table 10.

Table 10

Example 9

Term

Step Step Phenol 7 3.6 69.5 Composition of reaction solution 4-TBP 23. 4 29.6

(%) 2-T BP 1.8. 0.8

2,4-DTBP 1.20.2 Phenol conversion (%) 18.4

4-TBP selectivity (%) 90.9 96.7

4— Yield of TBP (%) 83.9 99.0 Comparative Example 3

(Second step)

From the reaction mixture obtained in the first step of Example 5, type 3 zeolite was removed by filtration. The methanol concentration of the reaction solution was measured and found to be 5.0% by weight.

12.5 g of the filtrate obtained above and the proton-substituted Y-type zeolite (as described above) were placed in a 10-mL OmL flask equipped with a stirrer, cooling tube and thermometer. Charged, the temperature was raised to 120 ° C, and the mixture was stirred for 5 hours, but the rearrangement reaction did not proceed.

Industrial potential

According to the present invention, 4-alkylphenols can be industrially advantageously produced with high selectivity and high yield. As a result, high purity Kilphenols can be manufactured

Claims

The scope of the claims

1. In the presence of synthetic zeolite, unsubstituted phenols at the 4-position are reacted with alkyl alcohol or alkyl ether at a temperature of 50 to 110 ° C.

(First step) When an alkyl alcohol is used in the first step, water produced in the liquid phase is removed from the obtained reaction mixture, and when an alkyl ether is used in the first step, Removes the produced alcohol contained in the liquid phase in the obtained reaction mixture (second step), and then removes the produced water or alcohol from the reaction mixture to 90 to 15 A method for producing a 4-alkylphenol, wherein a rearrangement reaction is carried out at a temperature of 0 in the presence of an acid catalyst (third step).

2. In the presence of synthetic zeolite, unsubstituted phenols at the 4-position are reacted with alkyl alcohol at a temperature of 50 to 110 ° C (first step), and contained in the liquid phase in the obtained reaction mixture. The generated water is removed (second step), and then a rearrangement reaction is performed in the reaction mixture after removing the generated water at a temperature of 90 to 150 ° C. in the presence of an acid catalyst (second step). 3. The method for producing a 4-alkylphenol according to claim 1, wherein the three steps are:

3. The method for producing 4-alkylphenols according to claim 2, wherein, in the third step, the water concentration in the liquid phase of the reaction mixture is adjusted to 0.5% by weight or less to carry out the rearrangement reaction.

4. In the third step, the amount of 4-position unsubstituted phenols in the reaction mixture is adjusted to 1 to 10 times the molar amount of the alkyl alcohol consumed in the alkylation reaction in the first step. 4. The method for producing a 4-alkylphenol according to claim 2 or 3, wherein the rearrangement reaction is carried out by adjusting.

5. The method according to any one of claims 2 to 4, wherein the 4-position unsubstituted phenol is phenol, and the alkyl alcohol is tert-butanol. 2. The method for producing a 4-alkylphenol according to item 1.

6. In the presence of synthetic zeolite, unsubstituted 4-position phenols and alkyl ether are reacted at a temperature of 50 to 110 ° C (first step), and the resulting reaction mixture is reacted in a liquid phase. Then, the rearrangement reaction is carried out at a temperature of 90 to 150 ° C. in the reaction mixture after the removal of the generated alcohol, in the presence of an acid catalyst. (Third step) The method for producing 4-alkylphenols according to claim 1, characterized in that:

7. The method for producing a 4-alkylphenol according to claim 6, wherein, in the third step, the rearrangement reaction is carried out by adjusting the alcohol concentration in the liquid phase of the reaction mixture to 0.5% by weight or less. '

8. In the third step, the amount of unsubstituted phenols at the 4-position in the reaction mixture is adjusted to 1 to 10 times the molar amount of the alkyl ether consumed in the alkylation reaction in the first step. The method for producing a 4-alkylphenol according to claim 6 or 7, wherein a rearrangement reaction is carried out.

9. The method for producing a 4-alkylphenol according to claim 6, wherein the 4-position unsubstituted phenol is phenol, and the alkyl ether is methyl tert-butylether.