JPH05255188A - Production of unsaturated carboxylic acid ester - Google Patents

Abstract

PURPOSE:To provide the subject production method capable of maintaining its excellent efficiency over a long period by using a specified catalyst in producing an unsaturated carboxylic acid ester from an unsaturated carboxylic acid and an olefin. CONSTITUTION:In the method for producing an unsaturated carboxylic acid ester, a fluorinated crystalline metasilicate prepared by treating a crystalline metasilicate such as ZSM-5 with fluorine is used as a catalyst when producing an unsaturated carboxylic acid ester such as ethyl acrylate from an unsaturated carboxylic acid and an olefin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an unsaturated carboxylic acid ester, and more specifically, in producing an unsaturated carboxylic acid ester from an unsaturated carboxylic acid and an olefin, a specific catalyst The present invention relates to an efficient production method capable of obtaining an unsaturated carboxylic acid ester with a long life, low cost, and high yield over a long period of time.

[0002]

2. Description of the Related Art Conventionally, various methods have been proposed as a method for producing an unsaturated carboxylic acid ester by reacting an unsaturated carboxylic acid with an olefin. For example, a technique using an oxide catalyst such as sulfuric acid / silica is disclosed in JP-B-47-7775 (catalyst for gelling sulfuric acid and silica sol) or JP-B-46-1.
6725 (catalyst of sulfuric acid and silver nitrate). Further, a technique using a heteropolyacid catalyst is disclosed in JP-B-53-6131 and JP-A-48-39425.
Japanese Patent Publication (phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, etc.), Japanese Patent Publication No. 56-30334 (silicotungstic acid), and the like. And the technology using an ion-exchange catalyst is disclosed in Japanese Examined Patent Publication No. 45-2.
8969 gazette (strongly acidic cation exchange resin) and West German Patent No. 2411901 (DOWEX-50-WX-8, DOW CHEMIC)
AL manufactured) and the like. However, these prior arts have the drawback of being inefficient, requiring the use of a large excess of olefins to react with the unsaturated carboxylic acid ester. Furthermore, West German Patent No. 2411901 describes a method of using a saturated carboxylic acid and / or its ethyl ester as a solvent. However, in this method, since the carboxylic acid ester is obtained by a transesterification reaction, the solvent It also has a problem of large consumption. Further, a technique using a zeolite-based solid acid catalyst is disclosed in US Pat. No. 3,492,341 (H-type mordenite),
No. 4365084 (SiO ₂ / Al ₂ O ₃ ≧ 12, CI
Value = 1 to 12 crystalline zeolite) and JP-A-57-10
No. 6640 (Crystalline metal silicate with silica / metal oxide ≧ 12), others JP-A-57-56045, JP-A-61-249949, JP-A-3-14
It is disclosed in Japanese Patent No. 5440. Among these, for example, in JP-A-61-249949, a carboxylic acid ester is prepared by reacting a carboxylic acid with an olefin by using a zeolite having an outer surface acid point / total acid point ≧ 0.07 as a catalyst. A method of manufacturing is disclosed. However, this method has drawbacks that only cyclic or branched olefins can be used and the yield of carboxylic acid ester is low. Also, JP-A-57-5604
Japanese Patent Publication No. 5 discloses a method for producing a carboxylic acid ester from a carboxylic acid and an olefin by using a cation-exchangeable layered clay or a crystalline aluminosilicate as a catalyst. However, in this method, saturated carboxylic acid is used as carboxylic acid, and unsaturated carboxylic acid is not used. Furthermore, these improved techniques are disclosed in JP-A-3-14.
Japanese Patent No. 5440 discloses a method for producing an unsaturated carboxylic acid ester from an unsaturated carboxylic acid and an olefin by using a crystalline metallosilicate as a catalyst. But,
This method has a problem that the selectivity and yield of the unsaturated carboxylic acid ester decrease as the reaction time increases. Further, in the above-mentioned conventional technique, since it is necessary to raise the reaction temperature, there is a problem in that when an unsaturated carboxylic acid is used, the polymerization reaction of the unsaturated carboxylic acid occurs at the same time and the yield of the target product decreases. Further, in a reaction in which a soluble acid (liquid acid) such as sulfuric acid is used as a catalyst, there are problems in recovery of the catalyst and corrosiveness.
Therefore, it is desirable to use a solid acid, but in that case, there have been drawbacks such as the necessity of using a large excess of olefin and the low production efficiency.

[0003]

Therefore, the present inventors have
In view of the above situation, the inventors have earnestly conducted research to develop an efficient method for producing an unsaturated carboxylic acid ester having a long catalyst life, low cost, high yield, and easy separation / purification. As a result, in producing an unsaturated carboxylic acid ester from an unsaturated carboxylic acid and an olefin, by using a fluorinated crystalline metallosilicate obtained by fluorinating a specific crystalline metallosilicate as a catalyst, it was found that the above object can be achieved It was The present invention has been completed based on such findings. That is, according to the present invention, when the unsaturated carboxylic acid ester is produced from the unsaturated carboxylic acid and the olefin, Si /
M ≧ 6 (atomic ratio) (where M is Al, Ga, B, Fe,
It is one or more metal atoms selected from Zn, Cr, Mn and In. The present invention provides a method for producing an unsaturated carboxylic acid ester, which comprises using a fluorinated crystalline metallosilicate obtained by fluorinating the crystalline metallosilicate according to 1) above.

First, the reaction which proceeds in the method of the present invention is, for example, RCOOH + H ₂ C═CH ₂ → RCOOC ₂ H ₅ (wherein R is an unsaturated alkyl group.). That is, this is a reaction in which an olefin is added to a carboxyl group while maintaining the unsaturated property of the unsaturated alkyl group. In the method of the present invention, various unsaturated carboxylic acids, which are one of the raw materials,
It may be appropriately selected according to the desired product. Specifically, for example, acrylic acid, methacrylic acid, crotonic acid,
Examples thereof include vinyl acetic acid, 2-pentenoic acid, 3-pentenoic acid, 4-pentenoic acid, cinnamic acid, maleic acid and fumaric acid. Among these, acrylic acid produces industrially important products such as ethyl acrylate.

Further, various olefins as the other raw material can be used. Specifically, for example, ethylene, propylene, 1-butylene, 2-butylene, isobutylene, other chain-like and branched olefins [various pentenes (1-pentene, 2-pentene,
Isopentene, etc.), hexene, heptene,
Octene, nonene, decene, etc.], cyclic olefins (cyclopentene, cyclohexene, methylcyclopentene, methylcyclohexene) and styrene. Particularly, chain-free olefins such as ethylene, propylene and 1-butylene are preferred.

The catalyst used in the present invention is a fluorinated crystal obtained by fluorinating a crystalline metallosilicate having a Si / M (atomic ratio) of 6 or more, preferably 6 to 5,000, more preferably 10 to 1,000. It is a sex metallosilicate. Here, M is Al, Ga, B, Fe, Zn, C as described above.
It is one or more metal atoms selected from r, Mn and In. As this M, Al is particularly preferable. For example, there are ZSM-5, ZSM-11 and their proton exchange or various metal ion exchange type zeolites, which are easily available. In addition to the above crystalline aluminosilicate, crystalline gallosilicate, crystalline galloaluminosilicate, crystalline ferroaluminosilicate, etc. can be used. Further, if necessary, it can be molded by adding a binder to the crystalline metallosilicate, there are various binders used here, for example, various silica sol and various alumina sol, further, synthetic mica, sepiolite, Layered compounds such as kaolinite and smectite minerals such as montmorillonite, bentonite, hectorite and savonite can be mentioned.

[0007] Such a crystalline metallosilicate is
As the fluorine treatment agent used for elementary treatment, gas phase
A contact treatment agent or a liquid phase contact treatment agent can be used. This
There are various types of vapor-phase contact treatment agents.
Physically, for example, various CFC gases [CFC-134a
(CFH₂CF₃), Freon-11 (CFCl₃), Freon-12 (CF₂
Cl₂), Freon-13 (CF₃Cl), Freon-21 (CHFCl₂) 、
Freon-22 (CHF₂Cl), Freon-23 (CHF₃), CFC-
113 (CF₂ClCFCl₂), Freon-114 (CF₂ClCF ₂Cl) etc.)
, Trifluoroethanol, pentafluorobe
Nazonitrile, octafluoropentanol, etc.
Be done. In addition, various liquid phase contact treatment agents are available.
Specifically, for example, hydrofluoric acid, sodium fluoride
System, ammonium fluoride, boron trifluoride, monofluor
Examples thereof include acetic acid. And these fluorinated agents
When fluorinating crystalline metallosilicates using
The treatment conditions are not particularly limited, and fluorine treatment
It cannot be uniquely determined because it varies depending on the properties of the agent.
Yes. For example, when using a gas phase contact treatment agent,
Fluorine treatment is performed at 200 to 600 ° C. On the other hand, liquid phase contact
When using a treating agent, the treatment is generally performed at 50 to 150 ° C.
It is processed.

The present invention is a method for producing an unsaturated carboxylic acid ester by reacting an unsaturated carboxylic acid with an olefin using a fluorinated crystalline metallosilicate as a catalyst, and this reaction is usually carried out in the presence of a solvent. Done below.
As the reaction solvent, various kinds can be used, but aromatic hydrocarbons are preferably used. Here, as the aromatic hydrocarbons, for example, benzene, toluene, xylenes (o-, m-, p-xylene), trimethylbenzenes (hemimelitene, pseudocumene,
Mesitylene), tetramethylbenzenes (prenitene,
Isodulene, durene), ethylbenzene, diethylbenzenes (o-, m-, p-diethylbenzene), ethyltoluenes (o-, m-, p-ethyltoluene), cumene, cymene, naphthalene, methylnaphthalenes (α
-, Β-methylnaphthalene) and dimethylnaphthalenes (10 types of isomers such as 1,2-; 1,3-; 1,4-; 2,3-dimethylnaphthalene) and the like.

In the method of the present invention, reaction conditions may be appropriately selected depending on the situation. For example, the reaction temperature is 50 to 30.
The temperature is 0 ° C, preferably 75 to 200 ° C. Reaction temperature is 5
If the temperature is lower than 0 ° C, the reaction may not proceed sufficiently. If the temperature exceeds 300 ° C, the unsaturated carboxylic acid tends to be easily polymerized and decomposed. The reaction pressure is from normal pressure to 20.
The pressure is 0 atm, preferably 5 to 150 atm. Also,
In the method of the present invention, the use ratio of the unsaturated carboxylic acid as a raw material and the olefin is not particularly limited, and may be appropriately determined depending on the type of raw material used, the type of catalyst or solvent used, the reaction temperature and the like. For example, the molar ratio of unsaturated carboxylic acid and olefin is 1: 1000 to 1000: 1, preferably 1: 100 to 100: 1. In the method of the present invention, in consideration of the fact that the reaction of unsaturated carboxylic acid and olefin in a ratio of 1: 1 proceeds, the utilization efficiency of the raw material becomes extremely poor outside the above range. The amount of the fluorinated crystalline metallosilicate used as the catalyst is, for example, the amount of unsaturated carboxylic acid oil permeated to the weight of the packed catalyst (weight space velocity; WH
SV) as 0.01 to 100 hr ^-1 , preferably 0.05
It is about 10 hr ^-1 . The WHSV is less than 0.01 hr ^-1, the utilization efficiency of the catalyst is deteriorated, when it exceeds 100 hr ^-1 yield of unsaturated carboxylic acid ester of interest is insufficient extremely low. Further, the amount of aromatic hydrocarbons used as a solvent is usually 0.01% by weight relative to the unsaturated carboxylic acid.
To 200, preferably 0.1 to 100. When it is lower than 0.01, polymerization is likely to occur, and when it is higher than 200, the production efficiency is lowered. In the method of the present invention, unsaturated carboxylic acid which is an unreacted raw material during the esterification reaction,
A polymerization inhibitor may be added, if necessary, in order to suppress the polymerization reaction of the olefin and the unsaturated carboxylic acid ester of the product. As the polymerization inhibitor, hydroquinone or the like is used in a weight ratio of 0 to unsaturated carboxylic acid.
It may be added at a ratio of 0001 to 0.1.

[0010]

EXAMPLES Next, the present invention will be described in more detail with reference to production examples, examples and comparative examples. In addition, the following manufacturing example,
All were carried out using a closed pressure reaction vessel equipped with a stirrer (1000 cc autoclave). The examples and comparative examples were carried out using a fixed bed flow type reaction tube (30 cc). Production Example 1 (Preparation of Catalysts A and B) 4.95 g of sodium aluminate and 30.30 g of tetra-n-propylammonium bromide were dissolved in 255 g of water to prepare a solution A. On the other hand, white carbon [Nipseal LP, manufactured by Nippon Silica Industry Co., Ltd.] 73.4 was added to an alkaline aqueous solution prepared by dissolving 9.90 g of sodium hydroxide in 520 g of water.
1 g was dissolved to obtain a solution B. Then, the above A liquid and B
The liquid and the liquid were mixed at room temperature for 12 minutes, and the mixture was further stirred for 1 hour to prepare silica-alumina gel. The silica-alumina gel was placed in an autoclave and the temperature was adjusted to 15
Hydrothermal synthesis was performed at 0 ° C. for 48 hours. After cooling, the internal solution was filtered, washed with water, and dried at 120 ° C. for 12 hours. X-ray diffraction analysis of the product confirmed that it was ZSM-5. The obtained ZSM-5 was calcined at 550 ° C. for 6 hours to obtain sodium type ZSM-5. This sodium type ZSM-5 was added to a 10 times amount of 1N ammonium nitrate aqueous solution, and a heat treatment was performed at 80 ° C. for 4 hours while stirring,
After cooling, the content was filtered and washed with water. In addition, the same operation 3
After repeating once, the contents are filtered, washed with water, and then at 120 ° C for 1
It was dried for 2 hours to give ammonium type ZSM-5. This ammonium type ZSM-5 was burned at 600 ° C. for 6 hours to give H.
Mold ZSM-5 was obtained. Elemental analysis of this product revealed that Si / Al = 23 (atomic ratio). Silica sol was added to the crystalline aluminosilicate, H-type ZSM-5, so that the binder content was 20 wt%, and the mixture was molded, dried at 120 ° C. for 3 hours, and further calcined in air at 600 ° C. for 6 hours to form pellets. Catalyst A for comparison
H-type ZSM-5 which is crystalline aluminosilicate as
Got The catalyst preparation tube was filled with 15 g of this catalyst A, and 25
10 vol% Freon-1 diluted with nitrogen at 0 ° C
34a was supplied at 100 ml / min for 2 hours for fluorine treatment to obtain a fluorinated crystalline aluminosilicate as catalyst B.

Preparation Example 2 (Preparation of Catalyst C) In the preparation of the catalyst of Preparation Example 1, the sodium aluminate content was 2.56 g and the sodium hydroxide content was 10.5 g.
A catalyst C was prepared in the same manner as in Production Example 1 except that the amount was changed to 40 g. An elemental analysis of this product revealed that S
It was i / Al = 38 (atomic ratio). Preparation Example 3 (Preparation of Catalyst D) In the preparation of the catalyst of Preparation Example 1, the sodium aluminate content was 0.50 g and the sodium hydroxide content was 11.
A catalyst D was prepared in the same manner as in Production Example 1, except that the amount was changed to 33 g. An elemental analysis of this product revealed that Si /
Al = 90 (atomic ratio). Preparation Example 4 (Preparation of Catalyst E) 15 g of the catalyst A prepared in Preparation Example 1 was added to a 10-fold amount of 0.2N aqueous ammonium fluoride solution, and the mixture was heated at 80 ° C. for 4 hours and then dried at 120 ° C. for 3 hours. Then 600
The catalyst E was obtained by calcining in air at 6 ° C. for 6 hours. Preparation Example 5 (Preparation of Catalysts F and G) Preparation Example 1 was carried out in the same manner as Preparation Example 1, except that 18.78 g of gallium nitrate nonahydrate was used in place of sodium aluminate in the preparation of Catalyst A. Catalyst F was prepared. This product had Si / Ga = 30 by X-ray diffraction analysis and elemental analysis.
It was a crystalline gallosilicate having the same structure (atomic ratio) as ZSM-5. Further, this catalyst F was subjected to a fluorine treatment in the same manner as in Production Example 1 to obtain a catalyst G as a fluorine treatment catalyst.

Example 1 10 g of catalyst B was packed in a fixed bed flow type reaction tube, and the reaction temperature was 130 ° C. and the reaction pressure was 30 kg / cm ² G. Ethylene / acrylic acid (molar ratio) = 4, paraxylene / acrylic acid /
Hydroquinone (weight ratio) = 2/1 / 0.00025 is used as a raw material and acrylic acid is used as a catalyst for WHSV = 0.4 hr ^−1.
The esterification reaction was carried out. The reaction results are shown in Table 1. Examples 2 to 5 Esterification reactions were carried out in the same manner as in Example 1 using the catalyst C, catalyst D, catalyst E and catalyst G, respectively. The results are shown in Table 1.

Comparative Example 1 10 g of catalyst A was packed in a fixed bed flow type reaction tube, and the reaction temperature was 130 ° C. and the reaction pressure was 30 kg / cm ² G. Ethylene / acrylic acid (molar ratio) = 4, paraxylene / acrylic acid /
A raw material of hydroquinone (weight ratio) = 2/1 / 0.025 was subjected to an esterification reaction with WHSV = 0.4 hr ⁻¹ of acrylic acid with respect to a catalyst. The reaction results are shown in Table 1. Comparative Example 2 10 g of catalyst F was filled in a fixed bed flow type reaction tube, and the reaction temperature was 130 ° C. and the reaction pressure was 30 kg / cm ² G. Ethylene / acrylic acid (molar ratio) = 4, paraxylene / acrylic acid /
A raw material of hydroquinone (weight ratio) = 2/1 / 0.025 was subjected to an esterification reaction with WHSV = 0.4 hr ⁻¹ of acrylic acid with respect to a catalyst. The reaction results are shown in Table 1.

Example 6 The esterification reaction was carried out in the same manner as in Example 1 except that the catalyst C was used in place of the catalyst B and toluene was used in place of para-xylene as the solvent in the esterification reaction of Example 1. It was The results are shown in Table 1.

[0015]

[Table 1]

[0016]

[Table 2]

[0017]

As described above, according to the method of the present invention, by using a fluorinated crystalline metallosilicate as a solid catalyst, the life of the catalyst is long and the unsaturated carboxylic acid ester is produced in a high yield over a long period of time. It can be manufactured efficiently. Further, since the solid catalyst is used, separation and purification of the produced unsaturated carboxylic acid ester are facilitated. Therefore, according to the method of the present invention, an unsaturated carboxylic acid ester can be produced industrially advantageously at low cost. Further, the obtained unsaturated carboxylic acid ester can be effectively used as an industrial raw material for fibers, paints, adhesives and the like.

Claims (2)

[Claims] 1. When producing an unsaturated carboxylic acid ester from an unsaturated carboxylic acid and an olefin, Si / M ≧ 6 (atomic ratio) as a catalyst (wherein M is Al, Ga,
It is one or more metal atoms selected from B, Fe, Zn, Cr, Mn and In. 2.) A process for producing an unsaturated carboxylic acid ester, which comprises using a fluorinated crystalline metallosilicate obtained by fluorinating the crystalline metallosilicate according to 1) above. 2. The method for producing an unsaturated carboxylic acid ester according to claim 1, wherein a solvent composed of aromatic hydrocarbons is used.