KR101362883B1 - A method for preparing (meth)acrylic acid phenyl ester - Google Patents

Abstract

The present invention is selected from the group consisting of (meth) acrylic anhydride and phenolic compound of lithium trifluoromethanesulfonate, copper trifluoromethanesulfonate, samarium trifluoromethanesulfonate and tin trifluoromethanesulfonate There is provided a process for the preparation of (meth) acrylic acid phenyl ester, which comprises reacting in the presence of at least one catalyst to produce (meth) acrylic acid phenyl ester.

Description

A method for preparing (meth) acrylic acid phenyl ester}

The present invention relates to a process for producing (meth) acrylic acid phenyl esters. More specifically, the present invention relates to a process for preparing (meth) acrylic acid phenyl esters using trifluoromethanesulfonate catalysts.

The (meth) acrylic acid phenyl ester can maintain high refractive index, low hygroscopicity, heat resistance, etc. of the phenyl ester, and is used in various fields such as plastics, paints, adhesives, paper processing agents, textile emulsions, lubricant additives, construction sealants, and inks. have. In general, esters are known to be prepared by reacting carboxylic acid with an alcohol without a catalyst or in the presence of a catalyst. However, it is known that (meth) acrylic acid and a phenolic compound are difficult to esterify. Therefore, various studies on the manufacturing method of (meth) acrylic-acid phenyl ester have been advanced for a long time.

Many methods of preparing (meth) acrylic acid phenyl esters are conventionally known. EP 0165529 discloses a process for preparing (meth) acrylic acid phenyl esters by dehydrating a (meth) acrylic acid and a phenolic compound at a temperature of 110 ° C. or higher in the presence of sulfuric acid, boric acid or p -toluene sulfonic acid catalyst. However, the production method has a low conversion rate to (meth) acrylic acid phenyl esters, so there is a problem in the industrial use. In addition, although the reaction temperature can be further increased in order to increase the conversion rate, a polymerization reaction of (meth) acrylic acid, (meth) acrylic anhydride or (meth) acrylic acid phenyl ester itself occurs, resulting in high yield of (meth) acrylic acid phenyl ester. There was a problem that can not be obtained and the color of the resulting product may also deteriorate.

As another method for producing (meth) acrylic acid phenyl esters, Japanese Patent Laid-Open No. 1975-023019 reacts a (meth) acrylic acid halide, which is more reactive than (meth) acrylic acid, with a phenolic compound in the presence of an organic base to produce a (meth) acrylic acid phenyl ester. Disclosed is a method of manufacturing. However, (meth) acrylic acid halides, which are reactive substances, are difficult to handle and are toxic, and may inevitably cause chlorine ions to remain in the product, thereby lowering the purity of the product. As a result, (meth) acrylic acid phenyl esters are used as starting materials. This may cause problems with the reaction.

It is an object of the present invention to provide a process for the preparation of (meth) acrylic acid phenyl esters with high conversion even at low reaction temperatures.

It is another object of the present invention to provide a method for producing (meth) acrylic acid phenyl ester in high yield and high purity by increasing the conversion rate.

It is a further object of the present invention to provide a process for the preparation of (meth) acrylic acid phenyl esters using non-toxic starting materials.

The present invention relates to a process for producing (meth) acrylic acid phenyl esters. The method for producing the (meth) acrylic acid phenyl ester includes (meth) acrylic acid anhydride and a phenol compound by using lithium trifluoromethanesulfonate, copper trifluoromethanesulfonate, samarium trifluoromethanesulfonate and tin trifluoromethane. Reacting in the presence of at least one trifluoromethanesulfonate catalyst selected from the group consisting of sulfonate salts to produce (meth) acrylic acid phenyl esters.

In one embodiment, the reaction can be carried out at 0-140 ° C., for example 20-60 ° C.

In one embodiment, the reaction can be carried out for 3-12 h, for example 5-12 h.

In one embodiment, the catalyst may be present at 0.01-3.0%, for example 0.1-1.0% by weight of the (meth) acrylic anhydride.

In one embodiment, the molar ratio of (meth) acrylic anhydride: the phenolic compound may be 1: 0.5-1.5, for example 1: 0.9-1.1.

The present invention allows for the production of (meth) acrylic acid phenyl esters at high conversion and high purity at low reaction temperatures. In addition, the present invention can solve the problem that the color of the (meth) acrylic acid phenyl ester can be deteriorated by using a non-toxic starting material, and (meth) acrylic acid in the reaction using the (meth) acrylic acid phenyl ester as a starting material. It is possible to make sufficient use of the phenyl ester.

The method for producing the (meth) acrylic acid phenyl ester of the present invention is characterized in that (meth) acrylic anhydride and a phenol compound are prepared using lithium trifluoromethanesulfonate, copper trifluoromethanesulfonate, samarium trifluoromethanesulfonate and tin trifluorine. And reacting in the presence of at least one trifluoromethanesulfonate catalyst selected from the group consisting of romethanesulfonic acid salts to produce (meth) acrylic acid phenyl esters.

The '(meth) acrylic acid phenyl ester' used in the present invention may include all forms of esters of (meth) acrylic acid, including the 'phenol compound' as well as the (meth) acrylic acid phenyl ester.

In the present invention, the catalyst is added to (meth) acrylic anhydride together with the phenolic compound, or to the phenolic compound together with (meth) acrylic anhydride, or added in any order of (meth) acrylic anhydride, phenolic compound, and catalyst. May be, but is not limited to these.

The catalyst is required not only to have high activity of the catalyst itself, but also to have high selectivity for catalyzing a specific reaction. The trifluoromethanesulfonate catalyst of the present invention has high selectivity in the esterification reaction of (meth) acrylic anhydride with a phenol compound. Therefore, when compared with the reaction without a catalyst and a reaction with another kind of catalyst, the conversion of the (meth) acrylic acid phenyl ester can be increased even at a low reaction temperature so that the (meth) acrylic acid phenyl ester can be produced in high yield and high purity. do.

In the present invention, the reaction may be carried out at 0-140 ℃, for example 20-60 ℃. If the reaction temperature is lower than 0 ° C, the reaction rate is lowered and the conversion to (meth) acrylic acid phenyl ester is low. If the reaction temperature is higher than 140 ° C, (meth) acrylic acid, (meth) acrylic anhydride or (meth) There is a problem that the polymerization reaction of the acrylic acid phenyl ester itself may occur and the polymerization reaction cannot be suppressed even when the polymerization reaction inhibitor is used. The present invention can be carried out at a low reaction temperature to prevent a decrease in yield and purity due to the polymerization reaction.

In the present invention, the reaction may be performed for 3-12 h, for example, 5-12 h.

In the present invention, the catalyst may be present in an amount of 0.01-3.0%, for example 0.1-1.0%, based on the weight of the (meth) acrylic anhydride, but is not limited thereto.

In the present invention, the molar ratio of the (meth) acrylic anhydride: the phenolic compound may be 1: 0.5-1.5, for example 1: 0.9-1.1.

In the present invention, the reaction is carried out neat without solvent or at least one solvent selected from the group consisting of toluene, xylene, n-hexane, cyclohexane, n-octane, ethyl ether, acetonitrile and methylene chloride. Can be performed in the presence.

In the present invention, the reaction may further include at least one polymerization inhibitor selected from the group consisting of butyl hydroxy toluene (BHT), p-benzoquinone and phenothiadine. The polymerization inhibitor may be included in an amount of 0.01-2.0% based on the weight of the (meth) acrylic anhydride, but is not limited thereto.

The present invention may further comprise the step of recovering (meth) acrylic acid produced after the reaction. Recovery of (meth) acrylic acid can further promote the esterification reaction to (meth) acrylic acid phenyl ester. The resulting (meth) acrylic acid can be recovered by distillation. Distillation conditions can be changed according to reaction conditions. For example, it can be carried out at a pressure condition of 5-100 mmHg, for example 5-20 mmHg, at a temperature condition of 30-100 ° C, for example 50-80 ° C. The recovered (meth) acrylic acid can be used to prepare (meth) acrylic anhydride, which is the reactant of the present invention.

In the present invention, the (meth) acrylic anhydride reacts (meth) acrylic acid halide with (meth) acrylic acid (method 1), and (meth) acrylic acid with methane sulfonyl chloride in the presence of an organic base containing triethylamine. It can be produced by the method (method 2), (meth) acrylic acid and acetic anhydride (method 3).

Method 1 has a problem in that handling of (meth) acrylic acid halide is difficult and the stability of the reaction is inferior. Method 2 further requires filtration and washing steps in the process of removing the organic base after completion of the reaction, and the odor of the organic base itself. Due to the inconvenience of work, excessive waste liquid is generated and environmentally and economically bad. Thus, preferably (meth) acrylic anhydride can be prepared by Method 3.

In particular, in the case of method 3, it is composed of lithium trifluoromethanesulfonate, copper trifluoromethanesulfonate, samarium trifluoromethanesulfonate and tin trifluoromethanesulfonate which are catalysts used in the present invention. It can be carried out in the presence of one or more catalysts selected from the group, having the effect of no further use or purification of the catalyst. The catalyst may be present in 0.01-3.0%, for example, 0.1-1.0% by weight of the (meth) acrylic acid, but is not limited thereto.

In addition, in method 3, the molar ratio of (meth) acrylic acid: acetic anhydride may be 1: 0.2-0.5, for example 1: 0.45-0.5.

In addition, in method 3, at least one polymerization inhibitor selected from the group consisting of butyl hydroxy toluene (BHT), p-benzoquinone and phenothiadine may be further included. The polymerization inhibitor may be included as 0.01-2.0% based on the weight of the (meth) acrylic anhydride, but is not limited thereto.

In the present invention, the phenolic compound is a phenol, o, m or p-halogen substituted phenol, 2,3,5-trihalogen substituted phenol, pentahalogen substituted phenol, o, m or p-C1-C10 alkyl substituted Phenol, o, m or p-C1-C10alkoxy substituted phenol, o, m or p-phenyl substituted phenol, o, m or p-phenoxy substituted phenol, o, m or p-benzyl substituted phenol, o, m or p-nitro substituted phenol, o, m or p-cyano substituted phenol, o, m or p-cumyl phenol, o, m or p-cresol, catechol, hydroquinone, α-naphthol and β -May be selected from the group consisting of naphthol.

In the present invention, the (meth) acrylic acid phenyl ester may be further purified by using a process of washing, alkali washing, distillation and filtration, depending on the kind of phenolic compound used, the solvent or the presence or absence of a polymerization inhibitor.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

Example

Preparation Example: Preparation of Methacrylic Anhydride

Methacrylic acid (344.36 g, 4.0 mol), acetic anhydride (204.18 g, 2.0 mol), butyl hydroxy toluene (0.09 g, 0.4 mmol) and copper trifluoromethanesulfonate (1.02 g, (meth) acrylic acid in a 1 L reactor 0.3% by weight of) was added under stirring. The resulting mixture was reacted at 60 ° C. and atmospheric pressure for 1 hour, and then the resulting acetic acid was further reacted for 6 hours while removing the resulting acetic acid under reduced pressure of 40-150 mmHg. Analysis of the resulting methacrylic anhydride 271.6g (yield: 88.1%, purity: 97.0%) by GC (Analysis condition: Young Gin device 6000 GC, 1% in acetone, (Oven condition: start at 50 ℃, 10 ℃ / min of The temperature was raised to 250 ° C. at a rate of temperature increase).

Example 1 Preparation of Methacrylic Acid Phenyl Ester

Methacrylic anhydride (271.6 g, 1.75 mol) obtained in the preparation example was placed in a reactor, and phenol (165.4 g, 1.75 mol, dissolved at 50 ° C) was slowly added dropwise. After reacting at 50 ° C. for 1 hour, analysis of GC confirmed the end of the reaction. After the reaction was completed, the reactor was decompressed under the conditions of 70 ° C. and 5-20 mm Hg to recover the resulting methacrylic acid. GC analysis confirmed that the methacrylic acid recovery was completed. The recovered methacrylic acid was 126.5 g (yield: 84%, purity: 97%). After the methacrylic acid recovery was completed, the methacrylic acid phenyl ester was obtained by distilling the reactor under reduced pressure at 80 ° C and 2-3 mmHg. The obtained methacrylic acid phenyl ester 154.09 g (yield: 95%, purity: 99%) was confirmed by GC.

Example 2: Preparation of (meth) acrylic acid β-naphthol ester

200 g of diethyl ether and β-naphthol (144.17 g, 1 mol) were introduced into a 1 L reactor in the above-mentioned preparation example to methacrylic anhydride (154.17 g, 1 mol). The reaction was terminated by refluxing for 4 hours. To the final reaction was added work-up by adding 1N aqueous sodium hydroxide solution, washed again with distilled water, dried by adding magnesium sulfate, filtered and the solvent removed. 210.1 g (yield: 99%, purity: 99%) of (meth) acrylic acid (beta) -naphthol ester obtained were confirmed by GC.

Example 3: Preparation of (meth) acrylic acid cumyl phenyl ester

The same procedure as in Example 1 was carried out except that cumylphenol was used in the same molar number instead of phenol in Example 1. 266.34 g (yield: 95%, purity: 99%) of (meth) acrylic acid cumyl phenyl ester obtained were identified by GC.

Example 4: Preparation of (meth) acrylic acid 2-phenyl phenyl ester

In Example 1, except that 2-phenylphenol was used in the same molar number instead of phenol, it was carried out in the same manner as in Example 1. 226.37 g (yield: 95%, purity: 99%) of (meth) acrylic-acid phenyl phenyl ester obtained were confirmed by GC.

Comparative Example 1-2:

Except for the use of the catalyst, the type and equivalent of the catalyst used, the reaction temperature and the reaction time were carried out in the same manner as in Example 1-3, except that the following changes.

Conversion rates, yields, and purity were calculated in the usual manner for Examples 1-4 and Comparative Examples 1-2, and the results are shown in Table 1 below.

Phenol compound catalyst Reaction temperature
(℃) Reaction time
(h) Yield (%) water(%) designation content
(mol) * designation content
(%) ** Example 1 phenol One Cu (OTf) ₂ 0.3 50 One 95 99 Example 2 β-naphthol One Cu (OTf) ₂ 0.3 35 4 99 99 Example 3 Cumylphenol One Cu (OTf) ₂ 0.3 50 One 95 99 Example 4 2-
Phenylphenol One Cu (OTf) ₂ 0.3 50 One 95 99 Comparative Example 1 phenol One - - 50 One fail Comparative Example 2 phenol One CH ₃ CO ₂ Na 0.3 50 One  70 75

*: Based on 1 mol methacrylic anhydride

**: by weight of methacrylic anhydride

As shown in Table 1, the production method of the present invention, regardless of the presence or absence of a substituent in the phenolic compound, it can be seen that the ester of the methacrylic acid phenolic compound can be produced in high purity and high yield with high conversion rate (See Examples 1-3).

Claims (11)

A method for producing a (meth) acrylic acid phenyl ester, comprising reacting (meth) acrylic anhydride with a phenolic compound in the presence of a copper trifluoromethanesulfonate catalyst to produce a (meth) acrylic acid phenyl ester.
The process of claim 1, wherein the reaction is performed at 0-140 ° C. 3.
The process of claim 2, wherein the reaction is carried out at 20-60 ° C. 4.
The method of claim 1, wherein the reaction is performed for 3-12 h.
The process according to claim 1, wherein the catalyst is present at 0.01-3.0% by weight of the (meth) acrylic anhydride.
The method according to claim 1, wherein the molar ratio of (meth) acrylic anhydride: the phenolic compound is 1: 0.5-1.5.
The process of claim 1, wherein the reaction is carried out neat without solvent or is selected from the group consisting of toluene, xylene, n-hexane, cyclohexane, n-octane, ethyl ether, acetonitrile and methylene chloride. A process for carrying out in the presence of at least one solvent.
The process of claim 1, wherein the reaction further comprises at least one anti-polymerization agent selected from the group consisting of butyl hydroxy toluene (BHT), p-benzoquinone and phenothiadine.
The method of claim 1, further comprising recovering the (meth) acrylic acid produced after the reaction.
The process according to claim 1, wherein the (meth) acrylic anhydride is prepared by reacting (meth) acrylic acid and acetic anhydride in the presence of a copper trifluoromethanesulfonate catalyst.
The phenolic compound according to claim 1, wherein the phenolic compound is phenol, o, m or p -halogen substituted phenol, 2,3,5-trihalogen substituted phenol, pentahalogen substituted phenol, o, m or p- C1-C10 Alkyl substituted phenol, o, m or p- C1-C10alkoxy substituted phenol, o, m or p -phenyl substituted phenol, o, m or p -phenoxy substituted phenol, o, m or p -benzyl substitution Phenol, o, m or p -nitro substituted phenol, o, m or p -cyano substituted phenol, o, m or p -cumyl phenol, o, m or p -cresol, catechol, hydroquinone, α- Naphthol and β-naphthol.