KR101727332B1 - Method for producing hydroxyalkyl(meth)acrylic acid ester - Google Patents

Abstract

(Meth) acrylic acid ester can be efficiently produced without requiring a complicated purification step. A process for producing a vinyl ether-containing (meth) acrylic acid ester, which comprises reacting a vinyl ether-containing alcohol with a vinyl ether-containing (meth) acrylic acid ester- (Meth) acrylic acid ester.

Description

METHOD FOR PRODUCING HYDROXYALKYL (METH) ACRYLIC ACID ESTER BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a process for producing a hydroxyalkyl (meth) acrylic acid ester using a vinyl ether-containing alcohol.

As a method for producing a hydroxyalkyl (meth) acrylic acid ester, a method is generally used in which a diol, a monoester and a diester mixture are obtained from an alkane diol by an esterification reaction, and then a monoester is extracted and separated. Specifically, a method of reacting acrylic acid with an alkane diol in the presence of a strong acid (see, for example, Patent Document 1) has been reported, but it has disadvantages such as generation of by-products from strong acids and reduction in yield. As a method for solving this problem, there have been various reports on the transesterification reaction between an alkanediol and a (meth) acrylic acid ester (see, for example, Patent Documents 2 to 4). Also, methods for efficiently extracting and purifying 4-hydroxybutyl (meth) acrylate (see, for example, Patent Documents 5 to 6) have also been reported. However, in the ester exchange method from the alkane diol, since the obtained product is a mixture, an excessive extraction solvent is required to separate only the monoester, which is not efficient.

As a method for obtaining a hydroxyalkyl (meth) acrylic acid ester in two steps, there has been reported a method in which a vinyl ether-containing alcohol is ester-exchanged and then debenzylated in the presence of an acid catalyst and an alcohol (see, for example, Patent Document 7). However, in this method, since the acetal compound is produced during the de-vinylation reaction, it is necessary to remove the acetal compound, but it is not easy to work to remove the acetal compound in the reaction. In addition, the alcohol used excessively in this reaction must be discarded by washing with water, which is not efficient.

Patent Document 1: German Patent No. 15118572

Patent Document 2: JP-A-10-298143

Patent Document 3: Japanese Patent Application Laid-Open No. 11-43466

Patent Document 4: Japanese Patent Application Laid-Open No. 2000-159727

Patent Document 5: JP-A-8-53392

Patent Document 6: JP-A-2005-194201

Patent Document 7: JP-A-10-182555

It is an object of the present invention to provide a production method capable of efficiently producing a hydroxyalkyl (meth) acrylic acid ester without requiring a complicated purification step.

As a result of various investigations, the inventors of the present invention have found that a vinyl ether-containing (meth) acrylic ester is obtained by (meth) acrylating a vinyl ether-containing alcohol and then subjecting the vinyl ether- It has been found that an alkyl (meth) acrylic acid ester can be obtained in high yield, and that the water layer, which is separated and recovered after deprivinylation, is reusable.

That is, the present invention is as follows.

(1) A process for producing a vinyl ether-containing (meth) acrylic ester by (meth) acrylating a vinyl ether-containing alcohol with an ester exchange method to give a vinyl ether- (Meth) acrylic acid ester.

(2) The process for producing a hydroxyalkyl (meth) acrylic acid ester according to the above (1), wherein the reaction temperature during the de-vinylation reaction is 60 占 폚 or lower.

(3) The process for producing a hydroxyalkyl (meth) acrylic acid ester according to (1) or (2), wherein the vinyl ether-containing alcohol is represented by the following general formula (I) or (II)

[Chemical Formula 1]

(In the general formula (I), n represents an integer of 3 to 11.)

(2)

(In the general formula (II), A represents a cyclopentylene group or a cyclohexylene group.)

This application is a continuation-in-part of US patent application Ser. No. 08 / 292,754, filed on Dec. 1, 2008, which is hereby incorporated by reference in its entirety for all purposes. do.

According to the present invention, hydroxyalkyl (meth) acrylic acid ester can be efficiently obtained without complicated purification steps such as distillation, and water used in the debinylation step can be reused, so that the process is short It is also possible to provide a process for producing economical hydroxyalkyl (meth) acrylic acid esters.

[0033] The embodiment of the process for producing the hydroxyalkyl (meth) acrylic acid ester of the present invention will be described in detail.

The process for producing the hydroxyalkyl (meth) acrylic acid ester of the present invention is a process for producing a vinyl ether-containing (meth) acrylic acid ester by subjecting a vinyl ether-containing alcohol to a (meta) acrylic ester by a transesterification method, And water is caused to coexist when it is carried out.

In the present invention, first, the hydroxyl group of the vinyl ether-containing alcohol is esterified to obtain a vinyl ether-containing (meth) acrylic acid ester. Examples of the esterification method include a dehydration esterification method using (meth) acrylic acid, an ester exchange method using a lower (meth) acrylic acid ester, and an acid halogen method using (meth) acrylic acid chloride. In the esterification method, since an acid catalyst is used, devinylation can occur at the same time and therefore it can not be applied. Further, the acid halogen method requires purification treatment such as washing with water, adsorption or distillation because the halogen is released and remains in the system through the reaction. On the other hand, the ester exchange method employs the ester exchange method in the present invention in that impurities are small and a purification operation is not necessary.

Examples of the vinyl ether-containing alcohol used in the present invention include 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, 9-hydroxynonyl vinyl ether, 10-hydroxydecanyl vinyl ether, A compound represented by the following general formula (I) such as hydroxydodecyl vinyl ether; A compound represented by the following general formula (II) such as cyclohexanedimethanol monovinyl ether; Phenyldimethanol monovinyl ether, and the like.

(3)

(In the general formula (I), n represents an integer of 3 to 11.)

[Chemical Formula 4]

(In the general formula (II), A represents a cyclopentylene group or a cyclohexylene group.)

Specific examples of the lower (meth) acrylic acid ester used in the ester exchange method include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and butyl (meth) acrylate. That is, as used herein, the lower (meth) acrylic acid ester refers to an ester substituent having an alkyl group having 4 or less carbon atoms.

From the viewpoint of short-time reaction, high ester conversion, and post-treatment after the reaction, it is preferable to use the lower (meth) acrylic acid ester in excess from the same amount with respect to the vinyl ether-containing alcohol compound. Concretely, it is preferable to use a lower (meth) acrylic acid ester in an amount of 1.0 to 20 moles per mole of the hydroxyl group of the vinyl ether-containing alcohol compound. When the amount of the lower (meth) acrylic acid ester used is less than 1.0 mol based on 1 mol of the hydroxyl group of the vinyl ether-containing alcohol compound, the reaction does not proceed sufficiently. When the amount is more than 20 mol, a long time is required for the concentration step after the reaction, do.

Examples of the catalyst used in the ester exchange method include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; Alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate; Alkali metal alkoxides such as lithium methoxide, sodium methoxide, sodium triethoxide, potassium t-butoxide and the like; Alkali metal amides such as lithium amide, sodium amide and potassium amide; Titanium alkoxides such as tetramethyl ortho titanate, tetraethyl ortho titanate, tetra propyl ortho titanate, tetraisopropyl ortho titanate, and tetrabutyl ortho titanate; Other aluminum alkoxide; Tin alkoxide; And the like. A titanium alkoxide or an aluminum alkoxide is more preferable in that the side reaction is suppressed to the utmost and the catalyst can be easily removed by adding water after completion of the reaction.

The amount of the catalyst to be used is preferably in the range of usually 0.01 to 5.0% by weight based on the total amount of the lower (meth) acrylic acid ester and the vinyl ether-containing alcohol compound. Even if the amount of the catalyst is increased more than necessary, there is almost no influence on the reaction rate, and on the contrary, a large amount of water is required in removing the catalyst.

In the transesterification reaction in the present invention, a known polymerization inhibitor may be added and used in combination. Examples of the polymerization inhibitor include phenols such as hydroquinone and hydroquinone monomethyl ether (also referred to as " methoquinone "); Sulfur compounds such as phenothiazine, ethylene thiourea and the like; Copper salts such as dibutyldithiocarbamate and the like; Manganese salts such as manganese acetate; N-oxyl compounds such as nitro compounds, nitroso compounds, and 4-hydroxy-2,2,6,6-tetramethylpiperidinoxyl; And the like. The addition amount of the polymerization inhibitor is preferably 0.1% by weight or less with respect to the produced ester. When the amount exceeds 0.1% by weight, coloring due to the additive may occur.

In the transesterification reaction, it is preferable to breathe a small amount of molecular oxygen to prevent polymerization of the reaction solution during the reaction. The molecular oxygen is preferably used in a diluted state, and air is preferably used. In addition, the blowing of molecular oxygen is also preferable in order to prevent polymerization of (meth) acrylic acid esters which are evaporated and are present as a vapor or condensed on a wall surface of the upper furnace or the like.

Molecular oxygen means a ground state triplet oxygen molecule (0 ₂ ) made by two oxygen atoms, and can be directly involved in the reaction, but it can interact directly with the catalyst or the reaction reagent Refers to an oxygen molecule that may be involved in the reaction after being converted into a state of singlet oxygen, an oxygen atom, a superoxide, a peroxide, and the like. The amount of molecular oxygen to be introduced is influenced by the shape of the reactor and the agitating power, but it may be blown at a rate of 5 to 500 ml / min (25 to 2500 ml / min as air) per mole of the raw vinyl ether-containing alcohol. When the amount of molecular oxygen introduced is less than 5 ml / min, the effect of inhibiting polymerization is not sufficient. When the amount of molecular oxygen introduced is more than 500 ml / min, the effect of pushing off the lower (meth) Resulting in loss of acrylic acid ester.

The transesterification reaction in the present invention is preferably carried out at 60 to 120 ° C under atmospheric pressure or reduced pressure. If the temperature is less than 60 ° C, the reaction rate becomes extremely slow, and if it exceeds 120 ° C, the polymerization of the vinyl ether-containing (meth) acrylic acid ester obtained in the transesterification reaction tends to occur and tends to cause coloring.

The transesterification reaction can be carried out in a manner generally known to those skilled in the art of producing (meth) acrylic acid esters. In the ester exchange reaction, it is necessary to azeotropically remove the by-produced lower alcohol with a lower (meth) acrylic acid ester and / or a solvent. For this reason, as the reaction apparatus, for example, a batch type reaction vessel with a rectification column attached thereto is used.

After completion of the ester exchange reaction, the catalyst is deactivated by water, and the excess low-boiling component is distilled off with a concentrating apparatus. The distillation by a low-boiling-point concentrating apparatus is preferably carried out under normal pressure or reduced pressure while maintaining the temperature of the liquid at 90 占 폚 or lower, more preferably in the range of 50 to 70 占 폚. When the temperature of the liquid exceeds 90 캜, the possibility of causing coloring or polymerization of the vinyl ether-containing (meth) acrylic acid ester increases.

The vinyl ether-containing (meth) acrylic acid ester in which the low-boiling component has been removed by distillation can be filtered to eliminate insoluble components such as remaining inactivated catalysts. In filtering, it is preferable to use a filter aid such as diatomaceous earth in order to efficiently remove insolubles.

Next, a method for obtaining a hydroxyalkyl (meth) acrylic acid ester by subjecting a vinyl ether-containing (meth) acrylic acid ester to a de-vinylation reaction will be described.

In the present invention, the devinylation reaction is carried out in the presence of an acid catalyst. As the acid catalyst that can be used, sulfuric acid, sodium hydrogen sulphate, paratoluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid and a solid acid (zeolite, amberlite, , Nafion, etc.). The amount of the catalyst to be used is preferably 0.01% by weight to 10% by weight, more preferably 0.1% by weight to 5% by weight, based on the vinyl ether-containing (meth) acrylate ester to be reacted. , The reactivity is remarkably lowered, and the de-vinylation reaction may be extremely delayed. On the other hand, if it is more than 10% by weight, impurities may be generated while there is almost no influence on the reaction rate.

The de-vinylation reaction according to the present invention is characterized in that water is coexistent. By carrying out water in the coexistence, the by-produced aldehyde can be easily removed during the debinylation reaction. The amount of water to be used is not particularly limited as far as it is equal to or more than the equimolar amount based on the vinyl ether-containing (meth) acrylic acid ester. Preferably, the reaction is rapidly proceeded by using 2-fold molar amount or more based on the vinyl ether-containing (meth) do. When water is used at a smaller ratio than the equimolar amount, the reaction stops in the middle.

The debinylation reaction according to the present invention is an exothermic reaction. At this time, by controlling the reaction temperature to 60 占 폚 or less, preferably 0 占 폚 to 40 占 폚, it becomes possible to obtain a hydroxyalkyl (meth) acrylic acid ester of high purity. As a method of controlling the reaction temperature, there can be mentioned a method of cooling the reactor or gradually adding a vinyl ether-containing (meth) acrylic acid ester to the aqueous catalyst solution. In addition, acetaldehyde is produced as a by-product at the time of the reaction, but acetaldehyde can be rapidly removed by decompression in the system, and the reaction can be promoted.

After completion of the de-vinylation reaction, the aqueous layer is separated and removed from the reaction residue. At this time, in order to raise the resolution, for example, solvents such as toluene and xylene may be used alone or in combination of two or more. The water in the water layer obtained by separating and removing can be reused as water coexisting in the devinylation reaction in the subsequent production.

Since the separated organic layer contains a catalyst, it is neutralized with a base and separated and removed. Examples of the base include hydroxides or salts of alkali metals and alkaline earth metals such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate and sodium hydrogencarbonate. It is preferable to use them as an aqueous solution and separate and remove them after neutralization.

After neutralization, excess alkali is removed by washing with water or a neutral salt aqueous solution, and excess water is removed by concentration, or when the solvent is used, the solvent is distilled off. Concentration is preferably carried out under normal pressure or reduced pressure while maintaining the temperature of the liquid at 90 占 폚 or lower, more preferably in the range of 50 占 폚 to 80 占 폚. If the temperature of the liquid exceeds 90 占 폚, the possibility of causing coloration or polymerization of the hydroxyalkyl (meth) acrylic acid ester becomes high.

After the concentration, the insoluble matter such as neutralized salts remaining can be removed by filtration. It is preferable to use a filter aid such as diatomaceous earth in order to efficiently remove insolubles during filtration.

The method for producing the hydroxyalkyl (meth) acrylic acid ester of the present invention does not require a purification step such as distillation since water is used in the de-vinylation reaction and a hydroxyalkyl (meth) acrylic acid ester of high purity can be obtained .

Example

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited thereto.

[Example 1]

(Synthesis of vinyloxybutyl methacrylate)

1000 g of 4-hydroxybutyl vinyl ether (HBVE manufactured by Maruzen Petrochemical Co., Ltd.), 3000 g of methyl methacrylate and 0.65 g of methoquinone were placed in a 4 L four-necked round bottom separable flask, and a rectifying column (15- Tube, and a thermometer. Heating was started while introducing dry air at 100 ml / min with stirring, and the pressure was adjusted to about 40 kPa so that the temperature of the liquid in the flask at the time of reflux was 75 캜 to remove water in the system. After confirming that the water content in the system was 300 ppm or less, 8.6 g of titanium tetraisopropoxide as a catalyst was added and the pressure in the flask was controlled to about 60 kPa so that the reaction temperature was 95 ± 5 ° C. When the temperature (overhead temperature) of the upper portion of the rectifying column is monitored during the heating and refluxing, the reflux ratio is adjusted so that the top temperature is about 60 ° C since methanol is close to the azeotropic temperature between methanol and methyl methacrylate. Methanol The reaction was carried out while distilling off as an azeotropic mixture with methyl.

Since the top temperature began to rise from the time when the reaction time had elapsed after 4 hours, the reflux ratio was gradually increased and the reaction was continued. When the reaction solution at the fifth hour of the reaction was analyzed by gas chromatography, the ester conversion was 99.2%, and the reaction was terminated. The reaction solution was cooled, and when the temperature of the liquid reached 75 캜, 250 g of 17% by weight of saline was added to hydrolyze the catalyst. After the mixture was allowed to stand for 15 minutes, the organic layer was taken in an eggplant type flask by decantation, and the excess methyl methacrylate was distilled off under reduced pressure using a rotary evaporator. Then, The liquid in the flask was filtered to obtain 1522 g of the target vinyl oxybutyl methacrylate.

(Synthesis of 4-hydroxybutyl methacrylate)

16 g of paratoluenesulfonic acid and 200 g of pure water were charged into a 1 L four-neck separable flask, and a stirrer, a thermometer, an air inlet tube, and a vacuum pump with a cooling trap were provided. 500 g of vinyloxybutyl methacrylate synthesized as described above was slowly added to the flask. The pressure in the system was adjusted to 20 kPa and the reaction proceeded while stirring the acetaldehyde produced. At this time, the flask was cooled with ice water and the reaction temperature was maintained at 15 to 30 ° C. After 3 hours of the reaction, the reaction conversion was almost 100% by analysis by gas chromatography, and the reaction was terminated. 100 g of toluene and 50 g of 17% by weight of saline were added to the reaction completion solution, and the resultant was subjected to oil-water separation. Only the organic layer was taken out (the water layer was used as Example 4). The organic layer was washed with 70 g of a 5 wt% sodium hydrogencarbonate aqueous solution using a separatory funnel, followed by washing with 70 g of 17 wt% saline. The organic layer was taken in an eggplant type flask and the excess toluene was distilled off under reduced pressure using a rotary evaporator and then filtered by suction filtration to obtain 395 g of a target 4-hydroxybutyl methacrylate (yield: 92.2%, purity 991%).

[Example 2]

(Synthesis of vinyloxybutyl acrylate)

1000 g of 4-hydroxybutyl vinyl ether (HBVE manufactured by Maruzen Petrochemical Co., Ltd.), 3000 g of ethyl acrylate and 0.65 g of methoquinone were placed in a 4 L four-necked round bottom separable flask, and a rectifying column (15- A thermometer was installed. Heating was started while introducing dry air at 100 ml / min with stirring, and the pressure was adjusted to about 40 kPa so that the temperature of the liquid in the flask at reflux was 75 캜 to remove water in the system. After confirming that the water content in the system was 300 ppm or less, 8.6 g of titanium tetraisopropoxide as a catalyst was added and the pressure in the flask was controlled to about 60 kPa so that the reaction temperature was 95 ± 5 ° C. When the temperature (overhead temperature) of the upper portion of the rectifying column is monitored during the heating and refluxing, the reflux ratio is adjusted so that the top temperature is about 70 ° C because the temperature is close to the azeotropic temperature between the produced ethanol and ethyl acrylate. The reaction was carried out while distilling off as water.

Since the top temperature began to rise from the time when the reaction time had elapsed after 4 hours, the reflux ratio was gradually increased and the reaction was continued. When the reaction solution at the fifth hour of the reaction was analyzed by gas chromatography, the ester conversion was 99.0%, and the reaction was terminated. The reaction solution was cooled, and when the temperature of the liquid reached 75 캜, 250 g of 17% by weight of saline was added to hydrolyze the catalyst. After the mixture was allowed to stand for 15 minutes, the organic layer was taken up in an egg-shaped flask by a tilting method, and the excess ethyl acrylate was distilled off under reduced pressure using a rotary evaporator. Then, the liquid in the egg plant type flask was filtered by suction filtration, Of vinyloxybutyl acrylate was obtained.

(Synthesis of 4-hydroxybutyl acrylate)

16 g of paratoluenesulfonic acid and 200 g of pure water were charged into a 1 L four-neck separable flask, and a stirrer, a thermometer, an air inlet tube, and a vacuum pump with a cooling trap were provided. 500 g of vinyloxybutyl acrylate synthesized as described above was slowly added to the flask. The pressure in the system was adjusted to 20 kPa, and the reaction proceeded while stirring the acetaldehyde produced. At this time, the flask was cooled with ice water and the reaction temperature was maintained at 15 to 30 ° C. Three hours after the reaction, the reaction conversion was 99.9% by analysis by gas chromatography, and the reaction was terminated. 200 g of toluene and 50 g of 17% by weight of saline were added to the reaction completion solution, and water separation was performed to remove only the organic layer. The organic layer was washed with 70 g of a 5 wt% sodium hydrogencarbonate aqueous solution using a separatory funnel, followed by washing with 70 g of 17 wt% saline. The organic layer was taken in an eggplant-shaped flask, and the excess toluene was distilled off under reduced pressure using a rotary evaporator, and then filtered by suction filtration to obtain 389 g (yield: 92.0%, purity: 99.0%) of the target 4-hydroxybutyl acrylate %).

[Example 3]

(Synthesis of cyclohexanedimethanol vinyl ether methacrylate)

300 g of cyclohexanedimethanol monovinyl ether (CHMVE, manufactured by Maruzen Petrochemical Co., Ltd.), 600 g of methyl methacrylate and 0.20 g of methoquinone were placed in a 1 L four-neck round bottom flask, A thermometer was installed. Heating was started while introducing dry air at 100 ml / min with stirring, and the pressure was adjusted to about 40 kPa so that the temperature of the liquid in the flask at the time of reflux was 75 캜 to remove water in the system. After confirming that the water content in the system was 300 ppm or less, 2.6 g of titanium tetraisopropoxide as a catalyst was added, and the pressure in the flask was controlled to about 60 kPa so that the reaction temperature was 95 ± 5 ° C. When the temperature (overhead temperature) of the upper portion of the rectifying column was monitored at the time of heating and refluxing, the reflux ratio was adjusted so that the temperature at the top of the column was about 60 ° C because methanol was close to the azeotropic temperature between methanol and methyl methacrylate. The reaction was carried out while distilling off as an azeotropic mixture with methyl.

Since the overhead temperature started to increase from the time when 2 hours of reaction had elapsed, the reflux ratio was gradually increased and the reaction was continued. When the reaction solution at the third hour of the reaction was analyzed by gas chromatography, the ester conversion was 99.4%, and the reaction was terminated. The reaction solution was cooled, and when the temperature of the liquid reached 75 캜, 100 g of 17% by weight saline was added to hydrolyze the catalyst. After the mixture was allowed to stand for 15 minutes, the organic layer was taken up in an egg-shaped flask by a tilting method, the excess methyl methacrylate was distilled under reduced pressure using a rotary evaporator, and the liquid in the egg- 385 g of cyclohexanedimethanol vinyl ether methacrylate was obtained.

(Synthesis of cyclohexanedimethanol monomethacrylate)

6.4 g of paratoluenesulfonic acid and 80 g of pure water were put into a 500 mL four-neck separable flask, and a stirrer, a thermometer, an air inlet tube, and a vacuum pump with a cooling trap were provided. 200 g of cyclohexanedimethanol vinyl ether methacrylate synthesized as described above was slowly added to the flask. The pressure in the system was adjusted to 20 kPa, and the reaction proceeded while stirring the acetaldehyde produced. At this time, the flask was cooled with ice water and the reaction temperature was maintained at 15 to 30 ° C. Two hours after the reaction, the reaction conversion was 99.9% by analysis by gas chromatography, and the reaction was terminated. 80 g of toluene and 30 g of 17% by weight saline solution were added to the reaction completion solution, followed by water separation to remove only the organic layer. The organic layer was washed with 20 g of a 5 wt% sodium hydrogencarbonate aqueous solution using a separatory funnel, and then washed with 30 g of 17 wt% saline solution. The organic layer was taken in an eggplant type flask and the excess toluene was distilled off under reduced pressure using a rotary evaporator and then filtered by suction filtration to obtain 163 g of the desired cyclohexanedimethanol monomethacrylate (yield: 91.5%, purity 99.4%).

[Example 4]

(Method for producing 4-hydroxybutyl methacrylate by water reuse)

In a 1 L four-neck separable flask, an aqueous layer (whole amount) separated after the reaction in Example 1 was charged, and a stirrer, a thermometer, an air inlet tube, and a vacuum pump with a cooling trap were provided. 500 g of vinyloxybutyl methacrylate synthesized in Example 1 was slowly added to the flask. The pressure in the system was adjusted to 20 kPa, and the reaction proceeded while stirring the acetaldehyde produced. At this time, the flask was cooled with ice water and the reaction temperature was maintained at 15 to 30 ° C. Three hours after the reaction, the reaction conversion was 99.9% by analysis by gas chromatography, and the reaction was terminated. 100 g of toluene was added to the reaction completion solution, and the organic layer was taken out by water separation. The organic layer was washed with 70 g of a 5 wt% sodium hydrogencarbonate aqueous solution using a separatory funnel, followed by washing with 70 g of 17 wt% saline. The organic layer was taken in an eggplant type flask and the excess toluene was distilled off under reduced pressure using a rotary evaporator and then filtered by suction filtration to obtain 398 g of 4-hydroxybutyl methacrylate (yield: 92.8%, purity 99.2%).

[Example 5]

(A method for producing 4-hydroxybutyl methacrylate in the case of a reaction temperature of 60 ° C or more)

16 g of paratoluenesulfonic acid and 200 g of pure water were charged into a 1 L four-neck separable flask, and a stirrer, a thermometer, an air inlet tube, and a vacuum pump with a cooling trap were provided. 500 g of vinyloxybutyl methacrylate synthesized in Example 1 was added all at once to the flask, and the pressure was immediately set to 20 kPa, and the reaction proceeded with stirring while removing the generated acetaldehyde from the system. At this time, the flask was left without cooling, and the reaction temperature rose to 65 占 폚. After 3 hours of the reaction, the reaction conversion was almost 100% by analysis by gas chromatography, and the reaction was terminated. 100 g of toluene and 50 g of 17% by weight saline were added to the reaction completion solution, and the organic layer was taken out by water separation. The organic layer was washed with 70 g of a 5 wt% sodium hydrogencarbonate aqueous solution using a separatory funnel, followed by washing with 70 g of 17 wt% saline. The organic layer was taken in an eggplant-shaped flask, and the excess toluene was distilled off under reduced pressure using a rotary evaporator, and then filtered by suction filtration to obtain 385 g of a target 4-hydroxybutyl methacrylate (yield: 89.9% 97.0%).

As described above, when the reaction temperature exceeds 60 ° C, the yield is slightly lower than that of Example 1.

[Comparative Example 1]

(Production method of 4-hydroxybutyl methacrylate in the coexistence of diol)

16 g of paratoluenesulfonic acid and 200 g of ethylene glycol were charged into a 1 L four-neck separable flask, and a stirrer, a thermometer, an air inlet tube, and a vacuum pump with a cooling trap were provided. 500 g of vinyloxybutyl methacrylate synthesized in Synthesis Example 1 was slowly added to the flask. The reaction was allowed to proceed while the produced acetal was removed from the system under stirring at a pressure of 20 kPa. At this time, the flask was maintained at a temperature of 15 to 30 캜 while cooling with ice water. Three hours after the reaction, the reaction conversion rate was 78% by analysis by gas chromatography. Further, since the acetal compound remained in the reaction system by the analysis, the reaction was continued by heating to 50 占 폚. Since the reaction conversion rate at 1 hour after the start of heating was 98.4%, the reaction was terminated. 200 g of toluene and 150 g of 5 wt% saline were added to the reaction completion solution, and the organic layer was taken out by water separation. The organic layer was washed with 70 g of a 5 wt% sodium hydrogencarbonate aqueous solution using a separatory funnel, followed by washing with 70 g of 17 wt% saline. The organic layer was taken in an egg yolk flask and the excess toluene was distilled off under reduced pressure using a rotary evaporator and then filtered by suction filtration to obtain 395 g of the target 4-hydroxybutyl methacrylate (yield: 87.6%, purity 92.3%).

From the above results, high purity hydroxyalkyl (meth) acrylic acid ester can be obtained in high yield by allowing water to coexist during the debinylation reaction to obtain hydroxyalkyl (meth) acrylate. In addition, it can be seen from Example 4 that the water layer which is separated and recovered after the debinylation is reusable in the devinylation reaction in the subsequent production.

Claims (3)

The vinyl ether-containing alcohol represented by the following general formula (I) or (II) is (meth) acrylated by a transesterification method to give a vinyl ether-containing (meth) acrylic acid ester, (Meth) acrylate having a vinyl ether group in the presence of an acid catalyst in an amount of from 0.01 to 10% by weight based on the vinyl ether-containing (meth) ) ≪ / RTI >
[Chemical Formula 1]

(In the general formula (I), n represents an integer of 3 to 11.)
(2)

(In the general formula (II), A represents a cyclopentylene group or a cyclohexylene group.) The method according to claim 1,
Wherein the reaction temperature during the de-vinylation reaction is 60 占 폚 or lower. delete