JPH07118251A - Production of glycidyl (meth)acrylate - Google Patents

Abstract

PURPOSE:To efficiently obtain a high-purity glycidyl (meth)acrylate by reacting (meth)acrylic acid with epichlorohydrin in the presence of a specific catalyst, then dehydrochlorinating the reaction product with a basic compound, distilling away unreacted epichlorohydrin, treating with an adsorbent, and finally distilling. CONSTITUTION:(Meth)acrylic is reacted with epichlorohydrin in the presence of a quaternary ammonium salt (e.g. tetramethylammonium chloride) as a catalyst to give (meth)acrylic acid epichlorohydrin ester, which is then dehydrochlorinated with a basic compound (e.g. sodium hydroxide) to give glycidyl (meth)acrylate. The glycidyl (meth)acrylate is washed with water, and excessive epichlorohydrin is distilled away under reduced pressure to give crude glycidyl (meth)acrylate. Then the crude glycidyl (meth)acrylate is treated with a silica-alumina-based adsorbent and distilled to give the high-purity glycidyl (meth)acrylate hardly containing epichlorohydrin in a high yield.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention In the production of glycidyl acrylate or glycidyl methacrylate [hereinafter, acrylic acid and methacrylic acid are collectively referred to as (meth) acrylic acid], most of the epichlorohydrin remaining depends on the raw material. The present invention relates to a method for producing high-quality glycidyl (meth) acrylate that does not contain methacrylic acid.

[0002]

2. Description of the Related Art Glycidyl acrylate or glycidyl methacrylate having a polymerizable acryloyl group or methacroyl group and an epoxy group in one molecule is widely used as a reactive monomer in the field of plastics because of its structural characteristics. . For example, there are a wide variety of materials such as paints, adhesives, pressure sensitive adhesives, fiber modifiers, dispersants and resist materials.

Generally, three methods are known as methods for producing (meth) acrylic acid glycidyl ester. The first method is a method using (meth) acrylic acid and epichlorohydrin as raw materials, which has already been disclosed in JP-B-37-7454. The second method is a method using an alkali metal (meth) acrylic acid salt and epichlorohydrin as raw materials, which has already been disclosed in JP-B-45-28762. The third method is a method using methyl (meth) acrylate and glycidol as raw materials, which has already been disclosed in JP-B-47-38421. Since the first and second methods use epichlorohydrin as a raw material, there is a problem that epichlorohydrin remains in the product. The third method is because the raw material glycidol is hydrolyzed at a low temperature,
It is difficult to obtain a highly pure and stable product, and the purity of the product also fluctuates significantly.

[0004]

In the method for producing glycidyl (meth) acrylate as a raw material for epichlorohydrin, which is the first method or the second method, distillation is performed to remove unreacted epichlorohydrin or by-products. In the case of carrying out, the product still contains several thousand ppm of epichlorohydrin. If an organic chlorine compound is mixed in the product, it will cause problems such as: (a) Impairment of worker health due to the carcinogenicity of epichlorohydrin (b) Catalyst poison for group transfer polymerization (c) Corrosion in the electronic and electrical fields There was a drawback that the industrial use was limited.

As a method for improving these problems,
A method has been proposed in which an alkali metal salt of (meth) acrylic acid and epichlorohydrin are reacted with a quaternary ammonium salt as a catalyst, and then a heteropolyacid or an alkali metal salt is added to inactivate the quaternary ammonium salt and then distilled. (Japanese Patent Laid-Open No. 63-255273). However, it is not always satisfactory in terms of purity and epichlorohydrin content.

The present invention provides a method for producing a highly purified glycidyl (meth) acrylate that does not contain epichlorohydrin in a high yield.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to achieve the above-mentioned object, and as a result, as a catalyst in a method for producing glycidyl (meth) acrylate from epichlorohydrin and (meth) acrylic acid. If distilled without sufficient removal of the quaternary ammonium salt used, 1,3-dichloro-2-propanol produced from the chlorohydrin compound by-produced during the reaction and unreacted epichlorohydrin, and the product glycidyl (meth) acrylate It was found that the epoxy exchange reaction with and the formation of epichlorohydrin is promoted, and that the remaining quaternary ammonium salt can be removed with a silica-alumina adsorbent, and the present invention has been completed.

That is, according to the present invention, acrylic acid or methacrylic acid is reacted with epichlorohydrin using a quaternary ammonium salt as a catalyst to produce a monochlorohydrin ester of acrylic acid or methacrylic acid, and then dehydrochlorination is performed using a basic compound. In the method for producing glycidyl acrylate or glycidyl methacrylate by reaction, (1) after completion of the reaction, excess epichlorohydrin is distilled off, followed by a step of treating with a silica-alumina adsorbent and (2) a distillation step It is a method for producing glycidyl acrylate or glycidyl methacrylate.

Furthermore, in the method for producing glycidyl acrylate or glycidyl methacrylate by reacting an alkali metal acrylate or an alkali metal methacrylate with epichlorohydrin using a quaternary ammonium salt as a catalyst, (1) after the reaction is completed, A method for producing a glycidyl ester of acrylic acid or methacrylic acid, which comprises performing a step of performing a silica-alumina-based adsorbent treatment after distilling off excess epichlorohydrin and (2) a distillation step.

The silica-alumina-based adsorbent used in the present invention may be any one capable of adsorbing and removing the quaternary ammonium salt without polymerizing glycidyl (meth) acrylate of the product, and specifically, bentonite, Perlite,
Natural minerals such as kaolin, zeolite and activated clay, or other solid acid minerals derived from them having similar properties and solid silicic acid substances artificially synthesized and having similar properties to the natural minerals It is illustrated.

The amount of the adsorbent added is 0.05 to 5% by weight based on the crude glycidyl (meth) acrylate after the reaction.
Is. If the amount added is less than 0.05% by weight, the quaternary ammonium salt cannot be sufficiently removed, and it is not possible to prevent epichlorohydrin from being mixed in the product. Also, 5
The effect does not change even if it is added in excess of weight%. The treatment temperature can be room temperature to 80 ° C., and the treatment time can be 15 minutes to 90 minutes.

In the method of the present invention, (meth) acrylic acid and epichlorohydrin are subjected to an addition reaction with a quaternary ammonium salt as a catalyst to obtain a chlorohydrin compound, and then a basic compound such as sodium hydroxide or potassium hydroxide is used. Method for producing glycidyl (meth) acrylate by dehydrochlorination and ring closure, and (meth) acrylic acid by reacting an alkali metal (meth) acrylic acid salt with epichlorohydrin using a quaternary ammonium salt as a catalyst This is a production method applied to the method for producing glycidyl.

The quaternary ammonium salt used as a catalyst is
Tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, trimethylethylammonium chloride, trimethylbenzylammonium chloride, triethylmethylammonium chloride, triethylbenzylammonium chloride and the like are preferable.

A polymerization inhibitor is added during the reaction,
As the polymerization inhibitor, phenothiazine, hydroquinone, hydroquinone monomethyl ether, N, N'-diphenylparaphenylenediamine, etc. are used.

The present invention is usually carried out in the absence of a solvent, but any organic solvent containing no halogen element can be applied to a non-polar or polar solvent and an azeotropic solvent with epichlorohydrin.

[0016]

【Example】

Example 1 430.5 g (5 mol) of methacrylic acid and 2081.9 g (22.5 mol) of epichlorohydrin were placed in a flask equipped with a stirrer, a thermometer, and a reflux condenser, and then 7.58 g (0 mol) of tetramethylammonium chloride. .05
Mol, 1 mol% relative to the raw material methacrylic acid), and phenothiazine 0.55 g (0.0028 mol) were added, and the temperature was 90 ° C.
The mixture was stirred for 3 hours to carry out the reaction. Then, 433 g (5.2 mol) of 48% sodium hydroxide was added dropwise over 6 hours, and the ring-closing reaction was carried out under the conditions of 80 ° C. and 200 mmHg. After completion of the reaction, the product was washed with 1000 g of water and unreacted epichlorohydrin was heated at 60 ° C. and 50 mmH.
The crude glycidyl methacrylate was distilled off under the conditions of g
9.0 g was obtained.

Next, 6.39 g (1% by weight relative to crude glycidyl methacrylate) of artificial zeolite made by Nippon Steel Co., Ltd. (1% by weight with respect to crude glycidyl methacrylate) was added, and the mixture was stirred at 40 ° C. for 1 hour for adsorption treatment, filtered, and treated with an adsorbent. 620.8 g of glycidyl methacrylate was obtained.

Next, the quaternary ammonium salt was analyzed for the reaction solution before and after the adsorbent treatment. Model: Dionex Ion Chromatograph 2000
By i / SP.

Before treatment: 90 ppm After treatment: 1 ppm or less

Further, using a simple distillation column, distillation was carried out at 3 mmHg and a bottom temperature of 75 ° C. to obtain 65-66 ° C./3 mmH.
Thus, 465.6 g of glycidyl methacrylate fraction (distillation yield: 75.0%) was obtained.

<Gas Chromatographic Analysis> Model: GC14-A manufactured by Shimadzu Corporation Measuring conditions: Column: PEG-HT 5%, inner diameter 3 mm, length 2 m Injection temperature 280 ° C., column temperature 80 ° C. to 260 ° C., 7 Temperature rising condition of 0.5 ° C./min Measurement of purity of glycidyl compound; Obtained from peak area with retention time of about 7.8 minutes. Calculation of epichlorohydrin content; calculated using cyclohexane as an internal standard. The detection limit was 0.002%.

<Analysis result of main fraction> Purity of glycidyl metaglycidylate: 99, 4% content of epichlorohydrin; not detected (shown as ND in the table below) The results are shown in Table 2.

[0023]

[Table 1]

[0024]

[Table 2]

Examples 2 to 8 As in Example 1, acrylic acid or methacrylic acid shown in Table 1 was reacted with epichlorohydrin in the presence of the catalyst shown in Table 1. 0.55 g of phenothiazine was used as a polymerization inhibitor. A ring closure reaction with sodium hydroxide was performed under the same conditions as in Example 1, followed by washing with water, and then unreacted epichlorohydrin was distilled off under reduced pressure to obtain crude glycidyl (meth) acrylate. Then, the adsorbents shown in Table 1 were used for treatment and further distilled at 3 mmHg. The results are shown together in Table 2.

Example 9 Sodium methacrylate obtained by synthesizing sodium methacrylate by a neutralization reaction between 430.6 g (5 moles) of methacrylic acid and 200.0 g (5 moles) of sodium hydroxide and dehydrating it. A mixture of 540.5 g and epichlorohydrin 2081.9 g (22.5 mol) was placed in a flask equipped with a stirrer, a thermometer, and a reflux condenser, and then tetramethylammonium chloride 7.58 g.
(0.05 mol), phenothiazine 0.55 g (0.0
(028 mol) was added, and the mixture was stirred at 90 ° C. for 3 hr to carry out the reaction. After completion of the reaction, the product was washed with 1000 g of water and unreacted epichlorohydrin was heated at 60 ° C. and 50 mmH.
It was distilled off under the condition of g to obtain crude glycidyl methacrylate.
Next, 6.39 g of artificial zeolite manufactured by Nippon Steel Corporation
(1% by weight to the crude glycidyl methacrylate) is added,
Stir at 40 ℃ for 1 hour, perform adsorption treatment and filter,
610.0 g of glycidyl methacrylate treated with an adsorbent
Obtained.

The liquids before and after the adsorbent treatment were analyzed in the same manner as in Example 1. Analysis of quaternary ammonium salt Before adsorption treatment: 96 ppm After adsorption treatment: 1 ppm or less The results are shown in Table 2.

Further, using a simple distillation column, distillation was carried out at 3 mmHg and a bottom temperature of 75 ° C., and 65-66 ° C./3 mmH.
441.0 g (distillation yield: 72.3%) of a glycidyl methacrylate fraction of g was obtained. The results are shown below.

Analysis of main fraction Purity of glycidyl methacrylate; 99.0% epichlorohydrin content; not detected

Comparative Examples 1 and 2 The reaction and purification were carried out in the same manner as in Example 1 without using any adsorbent, and vacuum distillation was carried out to obtain products. The results are also shown in Table 2.

Comparative Examples 3 and 4 Using various activated carbons as adsorbents, reaction and purification were carried out in the same manner as in Example 1, and vacuum distillation was carried out to obtain products.
The results are also shown in Table 2.

The symbols in Tables 1 and 2 showing the monomers, catalysts, adsorbents, etc. are as follows. <Monomer> MAA: Methacrylic acid AA: Acrylic acid MANa: Sodium methacrylate ECH: Epichlorohydrin GMA: Glycidyl methacrylate GA: Glycidyl acrylate <Catalyst> TMAC: Tetramethylammonium chloride TEBAC: Triethylbenzylammonium chloride TEAC: Tetraethylammonium Chloride <Adsorbent> Kyoward # 700PL: Kyowa Chemical Co., Ltd. synthetic aluminum silicate Kyoward # 600: Kyowa Chemical Co., Ltd. synthetic aluminum silicate DA-1A: Mizusawa Chemical Co., Ltd. activated alumina Zeostar NA- 100P: Nippon Kagaku Kogyo Co., Ltd. Synthetic zeolite Artificial zeolite: Nippon Steel Co., Ltd. artificial zeolite Granular Shirasagi KL: Takeda Yakuhin Co., Ltd. Activated carbon Carborafin: Takeda Goods (Ltd.) granular activated carbon

[0033]

The glycidyl (meth) acrylate produced by the present invention efficiently removes the quaternary ammonium salt, which causes epichlorohydrin during the distillation process, so that the product contains almost no epichlorohydrin. In addition, a product having a purity of 99% or more can be obtained in good yield.

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[Procedure amendment]

[Submission date] March 24, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction content]

[0004]

In the method for producing glycidyl (meth) acrylate using epichlorohydrin as the raw material, which is the first method and the second method, in order to remove unreacted epichlorohydrin or a by-product, When distillation is carried out, the product still contains several thousand ppm of epichlorohydrin. If an organic chlorine compound is mixed in the product, it will cause problems such as: (a) Impairment of worker health due to the carcinogenicity of epichlorohydrin (b) Catalyst poison for group transfer polymerization (c) Corrosion in the electronic and electrical fields use on the industry there has been a drawback that is limited to.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

Furthermore, in a method for producing glycidyl acrylate or glycidyl methacrylate by reacting an alkali metal acrylate or an alkali metal methacrylate with epichlorohydrin using a quaternary ammonium salt as a catalyst, (1) after the reaction is completed, After distilling off excess epichlorohydrin, a step of performing a silica-alumina-based adsorbent treatment and (2) a distillation step are performed, and glycidyl acrylate or glycyl methacrylate is characterized.
This is a method for producing zircon .

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

Next, 6.39 g (1% by weight based on crude glycidyl methacrylate ) of artificial zeolite manufactured by Nippon Steel Corporation was added, and the mixture was stirred at 40 ° C. for 1 hour for adsorption treatment and then filtered to obtain an adsorbent. 620.8 g of the treated glycidyl methacrylate was obtained.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

[0022] <main fraction analysis results> meta-purity acrylic acid glycidyl; content of 99,4% epichlorohydrin; the not detected (hereinafter shown in the Table ND) results are shown in Table 2. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 9, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Title of invention

[Correction method] Change

[Correction content]

Title: Method for producing glycidyl (meth) acrylate

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C07B 61/00 300

Claims (2)

[Claims] 1. An acrylic acid or methacrylic acid and epichlorohydrin are reacted with a quaternary ammonium salt as a catalyst to produce a monochlorohydrin ester of acrylic acid or methacrylic acid, and then a dehydrochlorination reaction is performed using a basic compound. In the method for producing glycidyl acrylate or glycidyl methacrylate, (1) after completion of the reaction, a step of distilling off excess epichlorohydrin and then treating with a silica-alumina-based adsorbent
And (2) a distillation step. A method for producing glycidyl acrylate or glycidyl methacrylate. 2. A method for producing glycidyl acrylate or glycidyl methacrylate by reacting an alkali metal acrylate or an alkali metal methacrylate with epichlorohydrin using a quaternary ammonium salt as a catalyst, wherein (1) after the reaction is completed, A step of distilling off excess epichlorohydrin and then treating with a silica-alumina-based adsorbent
And (2) a distillation step. A method for producing glycidyl acrylate or glycidyl methacrylate.