JPH05112476A - Production of alkenylbenzene and its derivative - Google Patents

Abstract

PURPOSE:To obtain the title compound in high efficiency by reaction of an alkylbenzene with a conjugated diolefin. CONSTITUTION:The objective compound can be obtained by reaction of an alkylbenzene with a conjugated diolefin under such a condition as to be virtually free from both oxygen and water in the presence of a catalyst prepared by dispersion heat treatment of (A) metallic sodium with (B) potassium aluminate and/or potassium borate dehydrated under roasting.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing alkenylbenzene efficiently and safely by reacting an alkylbenzene with a conjugated diolefin in the presence of an alkali metal. More specifically, for example, o-xylene and 1,
The alkenylbenzene, 5- (o-tolyl) -pentene, obtained by reaction with 3-butadiene, is cyclized to form dimethyltetralin, which is dehydrogenated to dimethylnaphthalene and then oxidized to a high concentration. The present invention relates to a compound having high industrial value that can be converted into naphthalenedicarboxylic acid useful as a molecular raw material, and the present invention relates to a method for producing such a useful raw material.

[0002]

2. Description of the Related Art Conventionally, a method for producing a monoalkenylbenzene by reacting alkylbenzene and 1,3-butadiene in the presence of an alkali metal is known (see US Pat. No. 3,244,758).

However, the above-mentioned method has a drawback that a large amount of expensive metal potassium must be used in order to obtain a monoalkenylbenzene in a high yield. Further, in order to solve this problem, a method has been proposed in which, when 1,3-butadiene is blown into alkylbenzene to cause a reaction, metal potassium and metal sodium are used together as a catalyst so that a small amount of expensive metal potassium can be used. (Japanese Patent Publication No. 56-34570, US Pat. No. 3,766)
288, U.S. Pat. No. 3,953,535).

Further, a method has been proposed (US Pat. No. 4,990,717) in which potassium metal is supported on potassium carbonate or alumina to improve the production process in which the reaction of o-xylene and butadiene is carried out in a fixed bed.

However, since all of these methods directly use potassium metal, they are highly reactive to air, oxygen, water, etc., and ignite only by contact with these compounds, which is dangerous for fire safety. , Especially sodium-potassium (Na-K: nak) alloy is highly active against oxygen and water, ignites in contact with trace amounts of oxygen and water, and when coexisting with combustible substances (petroleum) in the vicinity, , Very dangerous.

British Patent No. 1269280 (1972)
(April 6, 2013), it is described that a diene has a reaction inhibitory action in an aromatic side chain alkylation reaction with an olefin using sodium and an anhydrous potassium compound as a catalyst.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems and to produce alkenylbenzene in a high yield without directly using expensive metallic potassium which has a high risk of ignition. Moreover, by reacting alkylbenzene with, for example, 1,3-butadiene in the presence of a catalyst having high activity and high selectivity for the alkenylation reaction, formation of a by-product which is difficult and complicated to separate from the target product Is intended to produce a high-purity target product, that is, alkenylbenzene, in a high yield. Further, it is an object to provide a method for producing an alkyltetralin by cyclizing the alkenylbenzene and a method for producing an alkylnaphthalene by dehydrogenating the alkyltetralin.

[0008]

The present invention comprises reacting an alkylbenzene with a conjugated diolefin such as 1,3-butadiene in the presence of a catalyst to produce an alkenylbenzene.
As a catalyst, a catalyst obtained by subjecting (a) an alkali metal to (b) a calcined and dehydrated potassium aluminate and / or potassium borate and a dispersion heat treatment is used, and an alkylbenzene is used in an environment in which oxygen and water are substantially absent. And a conjugated diolefin (for example, 1,3-butadiene) are reacted with each other to provide a method for producing alkenylbenzene and its derivatives.

That is, when an alkenylbenzene is produced by reacting an alkylbenzene with a conjugated diolefin, oxygen and water are not substantially present, and (a) an alkali metal and (b) a calcined dehydration are used as a catalyst. A complicated by-product which is difficult to separate from the desired product by reacting alkylbenzene and 1,3-butadiene in the presence of a catalyst obtained by dispersing and treating the treated potassium aluminate and / or potassium borate. The method for producing alkenylbenzene and its derivatives is characterized in that the production of alkenylbenzene is suppressed and high-purity alkenylbenzene is produced in high yield. The present invention will be described in detail below.

The raw material alkylbenzene used in the method of the present invention is an alkylbenzene having 1 to 2 methyl groups or ethyl groups in the benzene nucleus, and specific compounds include toluene, ethylbenzene, o-xylene, m-xylene and p. -Xylene is given. Each of these alkylbenzenes is preferably used alone, and when a mixture is used, it becomes difficult to separate the desired product from the alkenylbenzenes, which are the reaction products, in high purity.

For example, in the reaction of o-xylene and 1,3-butadiene, if alkylbenzene such as toluene, p-xylene, m-xylene or ethylbenzene is mixed as an impurity, the purity of the target product is remarkably lowered. Therefore, the purity of o-xylene is preferably 95% or more, more preferably 98% or more. However, a trace amount of hydrocarbons having no alkyl group such as benzene and cyclohexane may be mixed.

Similarly, when toluene, ethylbenzene, m-xylene, or p-xylene is used, the purity of each individual product is preferably 95% or more, preferably 98% or more, and an alkyl group such as benzene or cyclohexane is preferably used. It does not matter that a small amount of hydrocarbons that do not have is mixed.

It is preferable that the starting material, alkylbenzene, is dehydrated and used in the reaction. As a dehydration method,
For example, adsorption separation by a suitable desiccant (for example, activated alumina, silica gel, molecular sieves, activated carbon, etc.), cryogenic separation, or a method of dehydrating by contacting with metallic sodium or metallic potassium in advance. The lower the water content in the raw material, the more preferable it is, and it is particularly preferable that the water content is not more than the measurement sensitivity of the Karl Fischer method, which is a usual water content measuring method, for example, several ppm or less.

Examples of the conjugated diolefin used in the present invention include butadiene and isoprene. 1,
The 3-butadiene may be produced by any method, and the purity of 1,3-butadiene may be any. For example, crude butadiene obtained by dehydrogenating butane or butene may be used as it is, or 1,3-butadiene obtained by purifying the crude butadiene by a method such as extraction may be used. Further, 1,3-butadiene is preferably dehydrated and used in the reaction. Examples of the dehydration method include adsorption separation using a suitable desiccant such as activated alumina, silica gel, molecular sieves, activated carbon, etc. or cryogenic separation. The lower the water content in 1,3-butadiene, the more preferable, and it is particularly preferable that the water content be several ppm or less.

The catalyst used in the reaction of the alkylbenzene and the conjugated diolefin in the present invention includes (a) an alkali metal, (b) a calcined and dehydrated potassium aluminate and /
Alternatively, it is a catalyst obtained by dispersing and heating potassium borate.

The alkali metal is preferably sodium, and the higher the purity, the better, but it does not matter even if it contains a small amount of a metal such as potassium, calcium, magnesium or aluminum. The purity is preferably 90% or more, and more preferably 99% or more.

(Dispersion Treatment Agent) Potassium aluminate as a dispersion treatment agent is a hydrate of potassium aluminate obtained by dissolving a chemical equivalent of aluminum hydroxide in an aqueous solution of potassium hydroxide to cause a reaction and then evaporating water. Is obtained. This potassium aluminate hydrate at 200 to 450 ° C
And dehydration treatment is performed for 3 to 10 hours to obtain anhydrous potassium aluminate.

Examples of potassium borate include potassium metaborate hydrate, potassium borate tetrahydrate, and potassium metaborate anhydrous. In the method of the present invention, all of them have a temperature of 200 ° C. or higher. What was calcinated and dehydrated at 200 to 450 ° C. for 3 to 12 hours at temperature is preferably used.

(Preparation of catalyst) The ratio of metallic sodium to potassium aluminate and / or potassium borate may be any ratio, but the final ratio of metallic sodium is 0.1 to 30% by weight based on the total amount of the catalyst. %, Preferably 0.5
-20% by weight, more preferably 1-10% by weight. As a method for preparing the catalyst used in the method of the present invention, a method in which metallic sodium is dispersed and heat-treated into fine particles of potassium aluminate and / or potassium borate which have been subjected to the above-mentioned baking and dehydration treatment is used. The dispersion heat treatment is preferably performed in an inert gas such as nitrogen, helium, argon or hydrogen.

For the dispersion heat treatment, a so-called wet dispersion supporting method in which an inert solvent is dispersed and supported, and a dry dispersion supporting method in which no solvent is used are employed. In this method, the catalyst prepared by any method can be used. The temperature at which the carrier is dispersed and supported is 100 to 450 ° C.,
Preferably 100 to 250 ° C, more preferably 110
It is performed in the range of up to 200 ° C.

The inert solvent dispersion supporting method is a method in which metallic sodium is stirred together with a dispersion treating agent in an inert solvent. For example, when 3% by weight of metallic sodium is dispersed and supported, 97 parts of potassium aluminate as a dispersant is simultaneously added to 3 parts of metallic sodium in 1000 parts of solvent o-xylene, and the mixture is stirred at 130 to 160 ° C. under high pressure at high speed. Although the method is adopted, it is also possible to prepare a dispersion liquid which is dispersed at an appropriate dispersion ratio in advance, and further add a treating agent such as potassium aluminate into the solvent and disperse the dispersion liquid.

Examples of the inert solvent include m-octane and n-octane.
Nonane, decane, undecane, dodecane, etc. have 8 carbon atoms
To 20 and a boiling point of 100 to 230 ° C., preferably 1
Examples of the paraffin include 30 to 200 ° C. Among them, it is industrially preferable to use alkylbenzene used as a reaction raw material.

The carrier catalyst thus uniformly dispersed and supported is
Before introducing and reacting a conjugated diolefin, for example 1,3-butadiene, a mixture of alkylbenzene and catalyst is added to
The activity can be improved by pretreatment and reaction at 00 to 200 ° C. for 1 to 5 hours.

The (a) alkali metal used in the present invention is (b) calcined and dehydrated potassium aluminate and /
Alternatively, potassium borate and a dispersion-heat-treated catalyst may be used in combination with a carbonate such as potassium carbonate or sodium carbonate. That is, carbonate may be present in the baking dehydration treatment of potassium aluminate or the like. Examples of the carbonate include potassium carbonate, sodium carbonate, magnesium carbonate and the like.

In the method of the present invention, alkylbenzene and 1,3
-The reaction with butadiene is carried out in the substantial absence of water and oxygen. Therefore, it is desirable that the raw materials introduced into the reaction system from outside the system, that is, alkylbenzene and 1,3-butadiene, are dehydrated as described above. Furthermore, since the space of the reaction system is substantially free of oxygen and water, it is filled with a dry inert gas such as dry nitrogen or dry argon, or under pressure reaction conditions above the boiling point of alkylbenzene, the space It is desirable to fill the part with vapor such as alkylbenzene.

In the present invention, the reaction is preferably carried out at a temperature in the range of 100 to 200 ° C. Reaction temperature is 100 ℃
In the following, the reaction time becomes long, and if the temperature exceeds 200 ° C., side reaction products increase, which is not preferable. Preferred reaction temperature is 1
It is 10-180 degreeC. The reaction molar ratio of 1,3-butadiene to alkylbenzene can be appropriately selected under ordinary conditions. For example, alkylbenzene: 1,3-butadiene = 1: 0.001-0.5, preferably 1: 0.
It can be carried out in the range of 01 to 0.3, particularly preferably 1: 0.05 to 0.2.

The reaction time is 0.05 to 10 hours. The reaction time depends on the amount of catalyst (g-catalyst / g
-Alkylbenzene), catalyst composition (g-sodium metal / g-potassium aluminate and / or potassium borate),
It is related to the reaction temperature (° C) and the ratio of alkylbenzene to 1,3-butadiene (g-alkylbenzene / g-1,3-butadiene), and the purity of the target product and the usage pattern of the catalyst, for example, whether or not it is recycled. An appropriate time is adopted from the above. In general, the reaction time becomes longer as the numerical value of the above factors decreases, but the preferable reaction time is 0.2 to 8 hours, particularly preferably 0.3 to 4 hours.

The reaction is a batch reaction in which the starting materials, alkylbenzene, 1,3-butadiene, and a catalyst are simultaneously charged from the beginning, and the reaction is carried out. First, the alkylbenzene and the catalyst are charged, and then 1,3-butadiene is quantitatively determined as the reaction time elapses. Either a semi-batch reaction for introducing or a continuous reaction for continuously introducing alkylbenzene, 1,3-butadiene and a catalyst into the reactor may be adopted, or a suitable combination thereof may be used. Reaction or continuous reaction is preferable.

Two formats are employed for the continuous reaction. That is, in the method of the present invention, the catalyst is a solid fine powder catalyst in which metallic sodium is dispersed in potassium aluminate and / or potassium borate carrier, so that alkylbenzene is continuously flowed through the fixed bed of the catalyst to obtain 1, There are a method of carrying out a continuous reaction while introducing 3-butadiene, and a method of carrying out a reaction while dispersing and stirring a catalyst in a reaction system.

The continuous reaction system may be any of a tubular reactor, a column reactor and a tank reactor. A preferred method for continuous reaction is to provide a plurality of reaction zones,
This is a so-called cross-flow type continuous system in which 1,3-butadiene is quantitatively introduced into each reaction zone.

The reaction operation is not particularly limited as long as the alkylbenzene and 1,3-butadiene can be sufficiently catalyst-mixed in the presence of the catalyst.
In the introduction method of introducing 3-butadiene, a resinous or gum-like substance, which is presumed to be a polymer of 1,3-butadiene, adheres to the vicinity of the inlet of 1,3-butadiene to cause a clogging phenomenon. Therefore, a mixed phase of 1,3-butadiene and an alkylbenzene, for example, a liquid phase mixture of liquid butadiene and an alkylbenzene, a gas phase of 1,3-butadiene and a liquid alkylbenzene is added to a reaction system in the presence of a catalyst.
A method of introducing 1,3-butadiene and alkylbenzene in the form of a liquid mixture is preferable. Alternatively, the clogging phenomenon can be prevented by supplying 1,3-butadiene to the reaction zone space to cause an absorption reaction on the surface of the reaction liquid in which the catalyst is present. It is also possible to increase the stirring effect at the same time when the butadiene is introduced together with the carrier gas. As the carrier gas, an inert gas from which oxygen and water have been removed, such as nitrogen, argon or hydrogen is suitable.

Further, the reaction can be preferably carried out by providing suitable stirring, but it is also possible to introduce 1,3-butadiene in the gas phase into the reaction system and to have a stirring effect with the gas. It is desirable that the stirring is of a strength required to uniformly disperse the catalyst in the reaction system and further to uniformly mix the reaction raw material and the reaction product. When the reaction is carried out in a liquid phase dispersion reaction system, after the reaction, the used catalyst can be separated from the reaction product system by a known means such as centrifugal sedimentation or gravity sedimentation, or liquid-solid phase at a lower temperature. Any known means such as separation of solid phase from, for example, filtration, centrifugation and the like may be used. The separated catalyst can be recycled and reused in the reaction system.

When the catalyst is deactivated and the catalytic function is lost, metallic sodium is deactivated in the potassium aluminate and potassium borate phases. Therefore, it can be reused by being oxidized and calcined with the organic substance attached, regenerated and reused.

According to the method of the present invention, toluene and 1,3-
In the reaction of butadiene, 5-phenyl-pentene is synthesized, in the reaction of o-xylene and 1,3-butadiene, 5- (o-tolyl) -pentene is produced, and in the reaction of p-xylene and 1,3-butadiene, Is 5- (p-tolyl) -pentene, 5- (m-tolyl) pentene is used in the reaction of m-xylene and 1,3-butadiene, and 5- (phenyl) -hexene is used in the reaction of ethylbenzene and butadiene. Each is synthesized.

As described above, the alkenylbenzene which is the target product of the present invention is subjected to a cyclization reaction and then dehydrogenation to give a compound useful as a raw material for drugs and polymer materials, that is, monoalkylnaphthalene and dialkylnaphthalene. Can be In this case, the purity of pentene or hexene when cyclizing phenyl-pentene, phenyl-hexene or tolylpentene becomes a problem. That is, the main object phenyl-pentene, phenyl-hexene, tolyl-pentenes are those in which the so-called arylalkene olefinic double bond is located at the 1 or 2 position. In the reaction of isomers having different bond positions, for example, o-xylene and butadiene, 5- (o-tolyl) -pentene- (1), 5-
(O-Tolyl) -pentene- (2), 5- (o-tolyl) -pentene- (3), 5- (o-tolyl) -pentene- (4), etc. are by-produced and mixed in a considerable amount. .. In other toluene, ethylbenzene, p-xylene, m-xylene, and phenylpentene, phenylhexene, and tolylpentene synthesized by the reaction of butadiene, isomers having different olefinic double bond positions are by-produced and mixed. Among these isomers, those having an olefinic double bond at the 1 or 2 position can be cyclized and converted into alkyltetralin, but other isomers cannot be converted into alkyltetralin, and the desired alkyl It reacts with tetralin to form a high boiling point product, which lowers the yield of the desired product. Moreover, it is extremely difficult to remove the isomer having the olefinic double bond at the 3,4,5 position from the alkenylbenzene which is the target product of the method of the present invention. For example, o-xylene and 1,3- Reaction mixture with butadiene (the desired product is 5- (o-tolyl) -pentene- (2) and 5- (o-
Even if the crude rectification of (tril) -pentene- (1)) is rectified at a reflux ratio of 20 using a rectification column having a theoretical plate number of 50, the above isomers can hardly be separated. On the other hand, in the reaction product obtained by the method of the present invention, such a side reaction which is difficult to separate is extremely small, and therefore the yield of the cyclization reaction product is extremely high.

The alkenylbenzene is cyclized into an alkyltetralin by a method known per se, that is, by contacting with an acid catalyst such as sulfuric acid, solid phosphoric acid or silica alumina at a temperature of 100 to 250 ° C. for 10 seconds to 10 hours. You can

Alkyl tetralins can be prepared by a method known per se, that is, alumina-chromia, Pt / Al ₂ O ₃
5 seconds to 1 at a temperature of 350 to 450 ° C with a dehydrogenation catalyst such as
Dehydrogenated alkylnaphthalene can be obtained by contacting for 0 minutes.

Alkylnaphthalene is prepared by a method known per se, that is, a solid acid catalyst such as silica-alumina, ZSM-5, Y-type zeolite, H-type mordinite and 200
The isomerization can be carried out by catalyzing at a temperature of ~ 450 ° C for 5 seconds to 10 hours. For example, 1,5-dimethylnaphthalene can be changed to 2,6-dimethylnaphthalene.

According to the present invention, dimethylnaphthalene, which is a compound useful as a raw material for polymer materials, can be produced from alkylbenzene as follows.

That is, for example, o-xylene and 1,3-
Butadiene is reacted with a catalyst in which sodium metal is dispersed in potassium aluminate to produce 5- (o-tolyl) -pentene, and the 5- (o-tolyl) -pentene is prepared by a method known per se. Cyclize,
1,5-dimethyltetralin is produced, and then 1,
2,6-Dimethylnaphthalene can be produced by isomerizing 5-dimethylnaphthalene.

By further oxidizing the 2,6-dimethylnaphthalene, naphthalene-2,6-dicarboxylic acid can be produced.

[0042]

INDUSTRIAL APPLICABILITY Among the reaction products obtained by the method of the present invention, the side products which are difficult to separate are extremely small, and therefore the yield of the cyclization reaction product is extremely high.

According to the method of the present invention, metallic sodium as a catalyst is dispersed in a specific ratio with finely powdered potassium aluminate and / or potassium borate powder, which is dehydrated by high temperature firing, without allowing oxygen and water to substantially exist. By reacting alkylbenzene with 1,3-butadiene in the presence of a treated catalyst, there is no need to directly use a metal sodium-potassium (Na-K: Nak) alloy, which has a high risk of expensive ignition, and yet alkenyl. It is possible to suppress the production of by-products, which are highly active and highly selective for the oxidization reaction, and therefore difficult and complicated to separate from the target product, and to manufacture the target product with high purity in high yield. became. The catalyst used in the method of the present invention has the advantage that it can be easily separated without the need for separation such as nuck when preparing a catalyst, and the cost is low.

[0044]

The present invention will be described in detail below with reference to examples.

Needless to say, the present invention is not limited to this embodiment. In the following Examples and Comparative Examples, the yield and purity of the target product are as defined below. In addition, “part” simply means “part by weight”.

(Yield and Purity) After filtering the entire reaction mixture at room temperature, about 500 g of the reaction mixture was placed in a Widmer rectification column at 22 mmHg (abs).
) Was distilled under reduced pressure to separate a fraction having a rectification column top temperature of 75 ° C. or lower, a fraction of 75 to 170 ° C., and a residue. Then, a fraction at 75 to 175 ° C. was collected as an alkenyl compound obtained by alkenylating xylene with 1,3-butadiene. The yield of alkenyl compound in the total reaction mixture was calculated from the ratio of this alkenyl compound fraction in the sample.

The fraction of the alkenyl compound is analyzed by gas chromatography to determine the content (% by weight) of 5- (tolyl) -pentene (2) and 5- (tolyl) pentene (1). The yield of the product was calculated. The unreacted xylene was contained in the alkenyl compound fraction in an amount of 0.1% by weight or less.

Similarly for the reaction product of toluene and butadiene, 5-phenylpentene (1) and 5-phenyl-
The content of the penten (2) was determined and the yield of the desired product was calculated.

The yield when xylenes and ethylbenzene were used as the alkylbenzene was calculated by the following formula.

[0050]

[Equation 1] The reaction product of toluene and butadiene was calculated by the following formula.

[0051]

[Equation 2]

[0052]

Example 1 (A) Preparation of Fine Particle Dispersion Liquid of Metallic Sodium It was heated under reflux in the presence of metallic sodium in advance, distilled, and then dehydrated with a molecular sieve to contain substantially no water. After blowing dry high-purity nitrogen (oxygen content of 1 ppm or less, water content of 0.1 ppm or less) into 500 parts of o-xylene to expel and remove dissolved oxygen, 4.0 parts of metallic sodium (purity 99.9%) And was emulsified and dispersed at 110 to 120 ° C. for 30 minutes in the above nitrogen atmosphere using an emulsification disperser to prepare an emulsified dispersion of metallic sodium.

(B) Preparation of Anhydrous Potassium Aluminate and Dispersion A powder of potassium aluminate trihydrate (commercial grade) was added to 5 parts.
0 to 200 ° C for 2 hours, 200 to 250 ° C for 2 hours, 2
Raise the temperature from 50 ° C to 450 ° C in 2 hours and then increase to 5 ° C at 450 ° C.
After the time calcination and dehydration treatment, it was cooled to room temperature in dry nitrogen gas to obtain 100 parts of potassium aluminate. The particles are pulverized to an average particle size of 100 μm, further dried in a reaction vessel under a nitrogen atmosphere at 200 ° C., cooled to 120 ° C., 1000 parts of dehydrated and purified o-xylene is added, and the mixture is dispersed for 30 minutes using an emulsifying disperser. As a dispersion of potassium aluminate.

(C) Preparation of Metal Sodium-Potassium Aluminate Dispersion Catalyst The above-mentioned potassium sodium aluminate dispersion was charged with the above metal sodium fine particle dispersion under high speed stirring and heated to 145 ° C., and heated at that temperature for 1 hour. It was processed into a predetermined catalyst dispersion.

(D) Synthesis reaction of 5- (o-tolyl) pentene The catalyst dispersion prepared in (C) above was charged with o-xylene dehydrated and purified as described above in a nitrogen atmosphere with stirring.
The composition described in 1. was stirred at 140 to 145 ° C. for 1 hour, and 1,3-butadiene was introduced at a ratio of 0.1 mol to 1 mol of o-xylene and reacted.

After completion of the reaction, the mixture was immediately cooled to 100 ° C.,
While maintaining the temperature at 100 ° C., stirring was stopped and the mixture was allowed to stand for 30 minutes to separate the reaction product mixture into a catalyst and a target liquid phase.
The desired product 5- (o-tolyl) pentene was distilled under a reduced pressure of 22 mmHg abs. To determine the yield and purity of 5- (o-tolyl) pentene. The results are shown in Table 1.

[0057]

[Table 1]

[0058]

Examples 2 to 8 and Comparative Examples 1 to 5 Further, as Examples 2 to 8 and Comparative Examples 1 to 5, under the same conditions as in Example 1 above, except that the catalyst composition, amount, reaction temperature and reaction time were variously changed. The results obtained by carrying out the reaction are shown in Tables 1 and 2.

[0059]

[Table 2] As can be seen from Tables 1 and 2, according to the method of the present invention, high-purity 5- (o-tolyl) pentene can be obtained in high yield.

[0060]

Examples 9 to 13 and Comparative Examples 6 to 7 Using p-xylene instead of o-xylene in Example 1, 1,3
-Alkenylation reaction with butadiene was performed.

The preparation and reaction of the catalyst were carried out under the same conditions and operating methods as in Example 1. The results are shown in Table 3.

As can be seen from Table 3, according to the method of the present invention, high-purity 5- (p-tolyl) pentene can be obtained in high yield.

[0063]

[Table 3]

[0064]

Example 14 (A) Preparation of catalyst In this example, a catalyst prepared by melting sodium metal and supporting it on potassium aluminate was used.
That is, potassium aluminate hydrate prepared by firing potassium aluminate hydrate at 450 ° C. for 5 hours had an average particle size of 10
Finely divided into particles of 0 μm or less, and further 200
After drying at 0 ° C, 6 parts of metallic sodium was added to 200 parts of the cooled solution, and high speed dispersion treatment was performed at 150 ° C for 60 minutes.
Add 1000 parts of dehydrated ethylbenzene, and add 6 at 130 ° C.
The catalyst was prepared by treating for 0 minutes. (B) 5- (Phenyl) -hexene synthesis reaction To the catalyst prepared in (A) above, 2000 parts of ethylbenzene dehydrated and purified as in Example 1 was added, and the temperature was adjusted to 135 to 140 ° C.
Then, 150 parts of 1,3-butadiene was introduced for 1.0 hour to react. After completion of the reaction, immediately cool to 80 ° C., stop stirring while maintaining the temperature, and let stand for 30 minutes,
The reaction product liquid was separated into a catalyst and a target liquid phase. The desired product, 5-phenyl-hexene, was distilled under a reduced pressure condition of 25 mmHg abs. The yield and purity were determined. As a result, the purity was 98.5.
%, And the yield was 88.7%.

[0065]

Example 15 The reaction between toluene and 1,3-butadiene is carried out at a reaction temperature of 105 to 115 ° C. using a metal sodium-potassium aluminate dispersion treatment catalyst prepared under the same conditions as in the operation method of Example 14. It was

As a result, 5 with a yield of 85% and a purity of 98.5% was obtained.
-Phenyl-pentene was obtained.

[0067]

Example 16 This example is an example of synthesizing 2,6-dimethylnaphthalene by cyclization reaction, dehydrogenation reaction and isomerization reaction of 5- (o-tolyl) -pentene.

(A) Synthesis of 1,5-dimethyltetralin by cyclization reaction of 5- (o-tolyl) -pentene 5- (o-tolyl) -pentene having a purity of 99.0% obtained in Example 1 The cyclization reaction was carried out using a 10% toluene solution of. Using solid phosphoric acid as a catalyst, the reaction temperature is 15
As a result of carrying out in a nitrogen atmosphere at 0 to 200 ° C., the conversion rate of the raw material was 100%, and the production selectivity of 1,5-dimethyltetralin which was a cyclization product was 95% or more.

(B) Synthesis of 1,5-dimethylnaphthalene by dehydrogenation reaction of 1,5-dimethyltetralin Dehydration using a 10% toluene solution of 1,5-dimethyltetralin obtained by the method of (A) above. An elementary reaction was performed.
As a result of dehydrogenation at 400 ° C. in a hydrogen atmosphere using a 0.3% Pt / Al ₂ O ₃ catalyst as a dehydrogenation catalyst, 1,5-
1,5-Dimethylnaphthalene was obtained with a conversion of dimethyltetralin of 00% and a selectivity of 1,5-dimethylnaphthalene of 97%.

(C) Synthesis of 2,6-dimethylnaphthalene by isomerizing 1,5-dimethylnaphthalene 1,5-dimethylnaphthalene obtained by dehydrogenation by the method (B) above is isomerized to give 2,5-dimethylnaphthalene. An experiment was conducted to synthesize 6-dimethylnaphthalene.

As a result of carrying out the isomerization reaction in a nitrogen atmosphere in the presence of an alumina dispersed catalyst containing 30% of H-type mordenite at a temperature of 350 to 400 ° C. using a 10% toluene solution of 1,5-dimethylnaphthalene. , 1,5-dimethylnaphthalene 10%, 2,6-dimethylnaphthalene 43
%, 1,6-dimethylnaphthalene 44%, and another naphthalene compound 3%. When this was crystallized and separated, 50% of 98% pure 2,6-dimethylnaphthalene was recovered.

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Claims (13)

[Claims] 1. A catalyst for producing an alkenylbenzene by reacting an alkylbenzene with a conjugated diolefin in the presence of a catalyst, wherein the catalyst is (a) an alkali metal (b) calcined and dehydrated potassium aluminate and / or boric acid. Using potassium and dispersion heat treated catalyst, and
A method for producing alkenylbenzene and a derivative thereof, which comprises reacting an alkylbenzene with a conjugated diolefin in an environment where oxygen and water are substantially absent. 2. The method according to claim 1, wherein the alkylbenzene is any one selected from toluene, ethylbenzene, o-xylene, p-xylene and m-xylene. 3. The method according to claim 1, wherein the conjugated diolefin is 1,3-butadiene or isoprene. 4. The method according to claim 1, wherein (a) the alkali metal is sodium. 5. The production method according to claim 1, wherein the potassium aluminate and / or potassium borate has been calcined and dehydrated at a temperature of 200 ° C. or higher. 6. The production method according to claim 1, wherein the dispersion heat treatment of (a) an alkali metal and (b) a calcined and dehydrated potassium aluminate and / or potassium borate is carried out in an inert gas atmosphere. 7. The method according to claim 6, wherein at least one selected from nitrogen, helium, argon and hydrogen is used as the inert gas. 8. The production method according to claim 1, wherein the dispersion heat treatment temperature of (a) an alkali metal and (b) potassium dehydration and / or potassium borate subjected to baking dehydration treatment is 100 to 450 ° C. 9. The production method according to claim 1, wherein the dispersion heat treatment of (a) an alkali metal and (b) baking dehydration treatment of potassium aluminate and / or potassium borate is carried out by an inert solvent dispersion supporting method. 10. Alkylbenzene as an inert solvent,
The production method according to claim 9, wherein a paraffinic hydrocarbon having a carbon number of 8 to 20 and a boiling point of 100 to 230 ° C, preferably 130 to 200 ° C is used. 11. A combination of (a) an alkali metal (b) calcined and dehydrated potassium aluminate and / or potassium borate, and a dispersion heat treated catalyst and a carbonate.
10. The manufacturing method according to 10. 12. A method for producing alkyltetralin, which comprises cyclizing the alkenylbenzene obtained by the method according to claim 1. 13. A method for producing an alkylnaphthalene, which comprises dehydrogenating alkyltetralin obtained by the method according to claim 12.