JPH0899968A - Production of (meth)acrylate having epoxy group - Google Patents

Abstract

PURPOSE: To obtain the subject compound useful as a modifying agent for coatings or resins by reacting the monoglycidylether of a diol compound with a (meth)acrylic acid lower alkyl ester. CONSTITUTION: (A) A (meth)acrylic acid lower alkyl ester and (B) a diol monoglycidyl ether of formula I (Y is divalent hydrocarbon which may contain an oxygen atom in the main chain) are subjected to an ester exchange reaction in the presence of an ester exchange catalyst (preferably titanium alkoxide) preferably at 60-120 deg.C to obtain the objective compound of formula II (R is H, methyl). The component B is preferably obtained by subjecting a diol of formula: HO-Y-OH and an epoxyhalohydrin to a ring-opening addition reaction in the presence of a catalyst (preferably boron trifluoride complex), adding a hydrogen halide-removing agent (preferably an alkali(ne earth) metal hydroxide) to the reaction mixture, and subsequently recovering the objective compound from the obtained reaction mixture.

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 epoxy group-containing (meth) acrylate useful as a raw material for paints, etc.

[0002]

2. Description of the Related Art A (meth) acrylate compound having a glycidyl group represented by 2-glycidyloxyethyl methacrylate is useful as a raw material for paints or resin modifiers as disclosed in JP-B-48-22169. It is a compound. This compound exhibits a property useful as a coating film by performing vinyl polymerization at the (meth) acryloyl group portion and then performing a crosslinking reaction with other functional groups at the epoxy group portion of the side chain.

[0003]

As a method for producing this compound, hydroxyethyl (meth) acrylate is subjected to ring-opening addition reaction with epihalohydrin, and then produced by 2-
A method of ring-closing (3'-halo-2-hydroxypropyloxy) ethyl (meth) acrylate with an alkali is known. (Zh. Org. Khim., 11 (8),
1616-19 (1975))

[0004]

[Chemical 4]

(R represents a hydrogen atom or a methyl group, and X represents a halogen atom) However, in this method, a side reaction is apt to occur, and particularly 2
The decomposition reaction of the raw material (meth) acrylate is likely to occur in the ring closure reaction in the second stage. As a result, (meth) acrylic acid and diol are produced as by-products, and the by-products are further reacted to produce various types of by-products.

[0006] These side reactions not only lower the yield of the product, but also lower the purity of the product, and when the product is used as a resin raw material, it has a drawback of causing gelation of the resin. As another synthetic method, a method of reacting halogenated ethyl glycidyl ether with a metal salt of (meth) acrylic acid is known. (Sint. Nov. Mono
merov 62-67 (Ref. Zh., Khim,
1973, Abstr. NO. 19N181))

[0007]

[Chemical 5]

However, in this method, it is difficult to obtain the halogenated ethyl glycidyl ether as a raw material, and it is difficult to adopt it as an industrial production method. Therefore, an object of the present invention is to provide an industrially advantageous method for producing a (meth) acrylate having a glycidyl group at the terminal.

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventors have conducted a transesterification reaction between a monoglycidyl ether of a diol compound and a (meth) acrylic acid lower alkyl ester in the presence of a transesterification catalyst. so,
It was found that the target compound can be obtained in high yield and high purity.

The monoglycidyl ether of a diol compound used as a raw material in this method is disclosed in JP-B-58-4286.
7 and Collection Czechoslov. C
hem. Commun, 32 (10) 3794-9 (1
967), a diol compound and epihalohydrin are subjected to a ring-opening addition reaction in the presence of an acidic catalyst to give a haloalcohol,
It can be easily produced by a two-step method in which a glycidyl ether is formed by ring closure in the presence of an alkali, or a one-step method in which a diol compound and epihalohydrin are directly subjected to a dehalogenation addition reaction using an alkali compound. That is, the reaction between the diol and the epihalohydrin proceeds easily, and the generation of by-products is less than that in the method in which the hydroxyalkyl (meth) acrylate and the epihalohydrin are reacted, and the obtained monoglycidyl ether, diglycidyl ether, unreacted Separation of monoglycidyl ether from a mixture of diols and the like can be easily carried out by ordinary separation operations such as extraction and distillation. In addition, the transesterification of the high-purity glycidyl monoether thus obtained with the (meth) acrylic acid lower alkyl ester easily proceeds, and the (meth) acrylate having a glycidyl group at the terminal is obtained in good yield. can do.

The present invention will be described below step by step. Step 1: Ring-opening addition reaction of epihalohydrin and diol In the presence of a catalyst, ring-opening addition reaction of the oxirane ring of epihalohydrin and hydroxyl group of diol is carried out, so that one hydroxyl group of diol is 3-halo-2-hydroxypropyloxy. Substitute with a group.

The diol compound has two primary hydroxyl groups.
Any α, ω-diol may be used, and specifically, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1 , 6-hexanediol, 1,8-octanediol, 1,10-decanediol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, p-bis (hydroxymethyl) benzene, polytetramethylene ether glycol and the like.

In the above ring-opening addition reaction, a diether body is usually produced in addition to the monoether body. When the molecular weight of the diol compound used in the reaction becomes large, the physical properties such as the boiling point and the solubility in the solvent of the monoether body and the diether body to be formed become close to each other, so that it becomes difficult to separate them.
Therefore, usually, an alkylene diol having 2 to 10 carbon atoms or diethylene glycol, triethylene glycol, tetraethylene glycol, tri-1,3-propanediol, di-1,4-butanediol, or the like has an oxygen atom in the middle thereof. It is preferable to use an alkylene diol containing 4 to 10 carbon atoms. Particularly preferred is an alkylene diol having 2 to 8 carbon atoms which may contain oxygen in the middle.

When the reaction ratio of epihalohydrin to diol is reduced to suppress the formation of the diether, it is possible to use polyethylene glycol or polytetramethylene ether glycol having a higher molecular weight. In that case, However, it is preferable to use a diol having an average molecular weight of 500 or less. As epihalohydrin, epichlorohydrin or epibromohydrin is used, but epichlorohydrin is preferably used because it is easily available.

The ratio of diol to epihalohydrin used in the reaction is usually in the range of 1: 1.5 to 2: 1 by molar ratio. When the molar ratio of epihalohydrin to diol is high, the production of diether increases, and when the molar ratio is low, unreacted diol remains in a large amount, and in any case, the yield of the target monoether decreases, which is preferable. Absent. The best yield of monoether to diol is obtained when the reaction is carried out at a molar ratio of about 1: 1. For the reaction of the diol and epihalohydrin, it is preferable to prepare a liquid in which the diol and the catalyst are mixed in the reactor first, and then gradually add epihalohydrin to the reactor, rather than charging both of them into the reactor at the same time. By doing so, by-products of diether can be suppressed, and side reactions such as polymerization due to temperature rise due to reaction heat can be suppressed.

As the catalyst, acidic catalysts, tertiary amines, 4
Although a quaternary ammonium salt or the like can be used, a Lewis acid catalyst such as boron trifluoride diethyl ether complex or tin tetrachloride, especially a boron trifluoride ether complex is preferable. The amount of the catalyst used is usually 0.
It is 1 to 10 mol%.

The reaction temperature is -20 ° C to 100 ° C, preferably about 0 to 70 ° C. The reaction is preferably carried out above the melting point of the diol. The reaction can be carried out without solvent, but a solvent inert to the reaction such as hydrocarbon or ether can be used. When the reaction temperature is lower than the melting point of the diol, a solvent is used to maintain the reaction system in the liquid phase.

The reaction is usually completed in about 10 minutes to 20 hours after mixing the diol and epihalohydrin. The completion of the reaction can be confirmed by confirming the disappearance of epihalohydrin by gas chromatography or the like. The reaction mixture obtained in this reaction usually contains about 20 to 50% of a monoether (which is ring-opened into a haloalcohol type), depending on the molar ratio of the diol and epihalohydrin to be used in the reaction, several to 40. % Of diether and several to 40% of unreacted diol are contained, and in addition to these, polymer, catalyst and the like are also present.

Although it is possible to immediately separate the monoether from the reaction mixture, the reaction mixture is usually treated as it is with a dehydrohalogenating agent to ring-close, and then separated. Step 2: Ring Closing Reaction of Oxirane Ring A dehydrohalogenating agent is added to the reaction mixture containing the monoether and diether of the haloalcohol obtained in the above reaction to carry out the ring closing reaction of the oxirane ring.

[0020]

[Chemical 6]

As the dehydrohalogenating agent, a strong alkali is preferable, and sodium hydroxide and potassium hydroxide are particularly preferable, but other alkali hydroxides such as barium hydroxide, calcium hydroxide and lithium hydroxide, and weaker ones are more preferable. Alkali sodium carbonate or the like can also be used. The alkaline compound is usually in the form of an aqueous solution, preferably 10 to 60%
Add to the reaction mixture as an aqueous solution.

The amount of alkali added is equivalent to the amount required to neutralize the acid formed, which is determined by the amount of epihalohydrin added to the diol in the previous step. Specifically, the equivalent ratio to the amount of epihalohydrin used in the reaction in the previous step is 0.8 to 1.1, and more preferably 0.9 to 1.1.
It is used about 1.05 times.

When the amount of the alkali is too small, the ring-closing reaction does not proceed sufficiently and the halogen-containing compound remains, which adversely affects the stability of the product and the operability of the next step. On the contrary, if the amount is too large, the decomposition reaction proceeds, and the yield and the purity decrease. In this ring-closing reaction, addition of a solvent is usually unnecessary, but a solvent may be added if desired. As the alkali salt of hydrogen halide usually precipitates along with the reaction,
Agitation is required.

Since the reaction is an exothermic reaction, the reaction is usually performed while cooling and adjusting the addition rate of the alkali so that the reaction temperature does not rise excessively. The preferred reaction temperature is 0
If the reaction temperature is too high, the decomposition reaction is likely to occur. The reaction is completed about 10 minutes to 5 hours after the addition of the alkali is completed. Step 3: Direct substitution reaction of diol and epihalohydrin The diol and epihalohydrin can also be directly reacted in the presence of a dehydrohalogenating agent.

[0025]

[Chemical 7]

This method has a slower reaction rate and a slightly lower yield than the above-mentioned two-step reaction, but is simple. In this direct substitution reaction, as the diol, the epihalohydrin, and the dehydrohalogenating agent, any of the above can be used. The amount of the dehydrohalogenating agent used is generally about 0.8 to 1.1 in terms of an equivalent ratio with respect to the epihalohydrin used. A solvent may or may not be used in the reaction.

As a reaction method, a method of adding a dehydrohalogenating agent to a mixture of diol and epihalohydrin is preferable. This is because when an excess dehydrohalogenating agent is present in the reaction system, the epoxy group easily undergoes cleavage decomposition. The reaction is carried out at a temperature of 0 to 100 ° C, preferably 20 to 70 ° C. If it is too low, the reaction proceeds slowly, while if it is too high, side reactions such as hydrolysis easily occur. The reaction time is usually about 2 to 20 hours.
As the halogen salt precipitates as the reaction progresses, the reaction is carried out with stirring.

Step 4: Separation of monoether and diether: Water and an organic solvent are mixed with the reaction mixture obtained in the above Step 2 or 3 and liquid-liquid extraction is performed to extract unreacted diol and salts on the aqueous phase side. The monoether and diether are collected on the organic phase side. As the organic solvent, a solvent which is incompatible with water, such as an aliphatic hydrocarbon, an aromatic hydrocarbon, a halogenated hydrocarbon, an ester, an ether, a ketone or an alcohol can be used. Relatively polar solvents such as hydrocarbons, esters, ethers, ketones, etc. are preferred due to their high ability to extract ether from water. If the reaction mixture of step 2 or 3 already contains a sufficient amount of organic solvent, the addition of additional organic solvent is not necessary. The extraction is usually performed at 10 to 60 ° C.

Monoether and diether are separated from the organic phase containing ether by distillation. Distillation is usually performed under reduced pressure to prevent decomposition of the epoxy compound. The organic phase containing ether is preferably washed with water to remove the mixed diol component prior to distillation. The diether does not react in the transesterification reaction in the next step and is mixed in the (meth) acrylate having a glycidyl group of the product as it is. Therefore, in this distillation step, the mixing amount of the diether is suppressed to 5% by weight or less. desirable. The diether recovered as a by-product can be used for applications such as a resin modifier. In addition, the diol transferred into the aqueous phase during extraction can be recovered by extraction or distillation and reused as necessary.

Step 5: Transesterification of diol monoglycidyl ether with lower alkyl ester of (meth) acrylic acid The diol monoglycidyl ether obtained above and the lower alkyl ester of (meth) acrylic acid are added in the presence of an ester exchange catalyst. Transesterification is carried out to produce the desired (meth) acrylate having a glycidyl group.

[0031]

[Chemical 8]

As the (meth) acrylic acid lower alkyl ester, (meth) acrylic acid methyl ester, ethyl ester, butyl ester and the like are used. Particularly preferred is methyl ester or ethyl ester. The reaction can be carried out continuously or batchwise. The reaction is
It can be carried out in the presence or absence of a solvent, but it is preferable to use the starting material (meth) acrylic acid lower alkyl ester in excess as a solvent. Usually, the lower alkyl (meth) acrylate is used in a molar ratio of 2 to 5 times that of the diol monoglycidyl ether.

Although a lower alcohol is by-produced in this reaction, since this reaction is an equilibrium reaction, the reaction can be further promoted by distilling the produced lower alcohol out of the reaction system. As the transesterification catalyst, titanium alcoholate, organic tin, a weak acid salt of alkali metal or alkaline earth metal (carbonate, acetate, phosphate, etc.),
A general transesterification catalyst such as an alkali metal alkoxide is used. Preferably titanium alcoholate,
Organotin compounds are used. Strong acids such as sulfuric acid react with the epoxy groups and are preferably avoided.

The amount of the catalyst used is usually 0.1 to 10 mol% based on the diol monoglycidyl ether. The reaction temperature is usually 50 to 130 ° C, preferably 60 to 120 ° C. If the reaction temperature is too low, the reaction progresses slowly, and conversely, if it is too high, the polymerization of the acryloyl group becomes remarkable. Even at the above reaction temperature, it is preferable to use a polymerization inhibitor and to introduce oxygen into the reaction system in order to prevent the polymerization of the acryloyl group.

As the polymerization inhibitor, phenothiazine, p
-Aromatic amines such as phenylenediamine, hydroquinone, phenol derivatives such as p-methoxyphenol,
A nitroso compound, an aromatic nitro compound, etc. can be used alone or in combination. It is preferable to introduce oxygen into the reaction system after diluting it with an inert gas so that the reaction system does not enter the explosion range. Oxygen concentration is usually 0.1
It is introduced as a gas at 10% by volume, preferably 1-5% by volume.

When the transesterification reaction is complete, water is added to the reaction mixture to deactivate the catalyst. The amount of water added is preferably about 0.5 to 10 (volume) times the reaction mixture. The reaction mixture is then extracted with an organic solvent to obtain an organic solvent phase containing ((meth) acrylate having a glycidyl group. When this is distilled to distill the organic solvent,
A (meth) acrylate having a glycidyl group is obtained as a product. Also in this distillation, it is preferable to use a polymerization inhibitor and molecular oxygen together. Since the unreacted (meth) acrylic acid lower alkyl ester remains in the reaction mixture of the transesterification reaction, it is preferable to remove it by simple distillation prior to the extraction. It is also possible to distill together the organic solvent when distilling the organic solvent from the organic solvent phase obtained by extraction, but the solvent and the (meth) acrylic acid lower alkyl ester must be further separated from the distillate. . Further, when water is added to deactivate the catalyst, metals such as titanium and tin in the catalyst form insoluble compounds and precipitate, so it is preferable to remove by filtration prior to extraction.

The glycidyl group-containing (meth) acrylate thus obtained has a purity of usually 90% or more, though it depends on the purity of the monoether used, and can be used as it is as a raw material for a resin. . If a higher purity is required, it can be easily purified to a desired purity by distillation.

Example 1 Synthesis of 1,4-butanediol monoglycidyl ether by a two-step method and transesterification reaction with methyl acrylate using the same Step a: 1,4-butanediol and epichlorohydrin Ring-Opening Addition Reaction of 90 g (1 mol) of 1,4-butanediol and 0.7 g of boron trifluoride ether complex were charged into a 500 ml flask and heated to 55 ° C. under a nitrogen blanket. With stirring, 92.5 g (1 mol) of epichlorohydrin was added dropwise thereto over 2 hours.

After completion of the dropwise addition, stirring was continued for 30 minutes, and it was confirmed by gas chromatography that epichlorohydrin had disappeared. The reaction rate of 1,4-butanediol is about 68.
%, And the reaction yields with respect to 1,4-butanediol were 47% monoether and 16% diether.

Step B: Ring-closing reaction of epoxy ring The reaction solution obtained above is water-cooled to 30 ° C. and stirred for 48 hours.
% NaOH aqueous solution 75 g (NaOH 0.9 mol) 1
It dripped over time. After completion of dropping, the mixture was further stirred for 30 minutes, and it was confirmed by gas chromatography that the reaction had proceeded sufficiently, and the reaction was completed.

Step c: Separation of 1,4-butanediol monoglycidyl ether 325 g of water was added to the above reaction solution, and dichloromethane 15
It was extracted 4 times with 0 ml, and the ether was collected in the dichloromethane layer. Then, the dichloromethane extract was washed with 50 ml of water. After distilling dichloromethane off from the extract, 1,4-butanediol monoglycidyl ether was recovered by simple distillation under a reduced pressure of 5 mmHg. First fraction 5
After removing g, 1,4-distilled at a distillation temperature of 115 ° C to 117 ° C.
Butanediol monoglycidyl ether 45 g (0.3
1 mol) was obtained. The purity of the obtained monoglycidyl ether was determined by gas chromatography to be 1,
4-Butanediol monoglycidyl ether 96.1
%, 1,4-butanediol diglycidyl ether 1.
It was 7% and 1,4-butanediol was 1.2%.

Step D: Transesterification Reaction of Monoglycidyl Ether and Methyl Acrylate 45 g (0.31 mol) of 1,4-butanediol monoglycidyl ether obtained above and 93.4 g (1.08 mol) of methyl acrylate And titanium tetra-n-
5.3 g (0.016 mol) of butoxide was charged into a flask equipped with a Witmer tube, and the reaction was carried out while distilling off the methanol produced under reflux. Reaction temperature 92-9
The reaction was carried out at 7 ° C. for 5 hours, and the reaction was terminated when the conversion rate of 1,4-butanediol monoglycidyl ether reached 98%. During this time, the distillation temperature at the top of the column was 57 to 78 ° C.
Met.

After cooling the reaction solution, 100 ml of water was added,
The catalyst was hydrolyzed by heating. Distillation removed methyl acrylate with water. The distillation was completed when the column top temperature reached 100 ° C. The obtained concentrated liquid was cooled and then filtered to remove the deposited catalyst decomposition product. The filtrate was extracted with 200 ml of dichloromethane. The dichloromethane phase was treated with activated carbon and then dichloromethane was distilled off to obtain 55.3 g (0.28 mol) of 4-hydroxybutyl acrylate glycidyl ether as a bottom liquid.

The purity of the obtained 4-hydroxybutyl acrylate glycidyl ether was determined by gas chromatography to be 4-hydroxybutyl acrylate glycidyl ether 90.4%, 1,4-butanediol monoglycidyl ether 0.4%, , 4-butanediol diglycidyl ether was 1.0%. The consistent yield from the 1,4-butanediol used in the reaction was 28%.

Example 2 Synthesis of 1,4-butanediol monoglycidyl ether by one-step method 45 g (0.5 mol) of 1,4-butanediol and 46.3 g (0.5 mol) of epichlorohydrin were placed in a flask. After charging and cooling with water at 30 ° C, 48% NaOH with stirring
Aqueous solution 41.6 g (NaOH 0.5 mol) was added dropwise over 1 hour.

After completion of dropping, the reaction solution was analyzed by gas chromatography after stirring for an additional hour. The reaction rate of 1,4-butanediol was 49%, and the reaction yields with respect to 1,4-butanediol were 33% monoether and 1% diether. Unreacted epichlorohydrin also remained considerably. This reaction liquid was treated in the same manner as in Step C of Example-1 (separation of 1,4-butanediol monoglycidyl ether) to obtain 15 g of 1,4-butanediol monoglycidyl ether (purity 95%).

Example 3 Synthesis of 1,4-butanediol monoglycidyl ether by a one-step method and transesterification reaction with methyl acrylate using the same, 90 g (1 mol) of 1,4-butanediol, epichlorohydride Phosphorus 92.5 g (1 mol) and tetrahydrofuran 200 g were charged into a flask, and after cooling to 5 ° C., 83.2 g (NaOH) of 48% NaOH aqueous solution was stirred with stirring.
1 mol) was added dropwise over 1 hour. The reaction liquid became a highly viscous slurry. After the completion of the dropping, the temperature was raised to 30 ° C., the mixture was further stirred for 1 hour, and the reaction solution was analyzed.
The conversion of 4-butanediol was slight and only 0.03 mol of 1,4-butanediol monoglycidyl ether was produced. From this, the precipitated solid is NaO.
It was estimated to be H. The temperature of this reaction solution is further raised to 50 to 60
When the reaction was carried out at 0 ° C for 1 hour, the conversion rate of 1,4-butanediol reached 58%. The reaction yield based on 1,4-butanediol was 30% of monoether (43.6 g,
0.30 mmol), 1.2% of diether (2.4
g, 0.012 mmol).

300 g of water was added to this reaction solution to obtain 150
The operation of extracting the ether form from the aqueous phase with ml of dichloromethane was repeated 4 times (150 ml × 4 times). Here, the extracted dichloromethane phase was not washed with water. After recovering the solvent from this dichloromethane extract at atmospheric pressure, 1,4-butanediol monoglycidyl ether was distilled with a distillation apparatus equipped with a Witmer rectification tube. Pressure 3mmHg
Then, after the initial distillation of 3.5 g was cut, the tower top temperature was 104 to 111.
28.5 g of a main fraction was obtained at ℃.

The purity of the obtained monoglycidyl ether was 1,4-
Butanediol monoglycidyl ether 86.3%,
1,4-butanediol diglycidyl ether 0.6
% And 1,4-butanediol were 12.7%. 1,
The large amount of 4-butanediol seems to be due to the fact that the dichloromethane extract was not washed with water.

22.6 g of 1,4-butanediol monoglycicyl ether, 46.8 g of methyl acrylate, 50 mg of phenothiazine, and 1.6 g of sodium carbonate as a transesterification catalyst were used in the same apparatus as in Example 1 under normal pressure. The transesterification reaction was carried out under reflux. The reflux temperature is 8
There was almost no change at 8 ° C. When the composition of the reaction solution was analyzed 3.5 hours after the start of reflux, the conversion of 1,4-butanediol monoglycidyl ether was 10%. From this, it was judged that the sodium carbonate catalyst needs to react at a higher temperature.

Methyl acrylate was distilled off from the reaction solution until the internal temperature reached 105 ° C., and then ethyl acrylate 28.
4 g was added, and the transesterification reaction was continued while removing the produced lower alcohol from the top of the column. Tower top temperature is 6
The reaction temperature was 0 to 80 ° C., and the reaction temperature was 105 to 130 ° C. The reaction was stopped 1 hour after the start of the reaction. When the reaction solution was analyzed, the conversion of 1,4-butanediol monoglycidyl ether was 98%, and the yield of 4-hydroxybutyl acrylate glycidyl ether was 55% based on 1,4-butanediol monoglycidyl ether. there were. A large amount of high boiling components were formed. This is probably because the reaction temperature was considerably high.

Comparative Example-1 Synthesis of 4-hydroxybutyl acrylate glycidyl ether from 4-hydroxybutyl acrylate and epichlorohydrin by two-step method 144 g of 4-hydroxybutyl acrylate and boron trifluoride ether complex as a catalyst. 7 g was placed in a flask, the temperature was raised to 55 ° C., and 92.5 g of epichlorohydrin was added dropwise over 2 hours while stirring. After completion of the dropping, analysis by gas chromatography revealed that the conversion of 4-hydroxybutyl acrylate was about 70%, and most of it was converted to the chloroether form.

The reaction solution was water-cooled and stirred while stirring for 48 hours.
75% aqueous NaOH solution was added dropwise over 1 hour. After completion of the dropping, the reaction solution was analyzed by gas chromatography to find that 4-hydroxybutyl acrylate glycidyl ether had been formed, but the decomposition products and the reaction products thereof, 1,4-butanediol and 1,4-butanediol, A considerable amount of butanediol diacrylate and 1,4-butanediol monoglycidyl ether were produced.

500 ml of dichloromethane was added to this reaction solution.
Was diluted with water, filtered, and the filtrate was washed with 50 ml of water. When this dichloromethane was analyzed by gas chromatography, the product contained about 50% of 4-hydroxybutyl acrylate glycidyl ether and about 20% of 1,4-butanediol monoglycidyl ether.

Comparative Example-2 Synthesis of 4-hydroxybutyl acrylate glycidyl ether from 4-hydroxybutyl acrylate and epichlorohydrin by a one-step method 72 g (0.5 mo of 4-hydroxybutyl acrylate)
l) and epichlorohydrin 46.3 g (0.5 mo)
1) was charged into a flask, and while cooling with water while stirring, 48%
41.7 g of NaOH aqueous solution (0.5 mol as NaOH)
l) was added dropwise over 1 hour so that the reaction temperature did not exceed 40 ° C. Since a white viscous solid was precipitated in the reaction solution and stirring became impossible, 100 ml of tetrahydrofuran was added midway. After the completion of the dropping, the reaction solution was analyzed.
A large amount of 1,4-butanediol produced by hydrolysis of hydroxybutyl acrylate is produced.
The formation of hydroxybutyl acrylate glycidyl ether was trace.

[0056]

INDUSTRIAL APPLICABILITY According to the present invention, an acrylate having a glycidyl group can be industrially advantageously produced.

Claims (9)

[Claims] 1. A (meth) acrylic acid lower alkyl ester and the following general formula [II]: (Wherein, Y represents a divalent hydrocarbon group which may contain oxygen in the main chain) and a diol monoglycidyl ether represented by the formula (6) are subjected to an ester exchange reaction in the presence of an ester exchange catalyst. The following general formula [I] (In the formula, R represents a hydrogen atom or a methyl group, and Y represents the same as the above-mentioned general formula [II]), and a method for producing a (meth) acrylate having an epoxy group. 2. A diol and epihalohydrin represented by the following general formula [III]: HO-Y-OH [III] (wherein Y represents the same as the general formula [II] shown above). The ring-opening addition reaction is carried out in the presence of a catalyst, then a dehydrohalogenating agent is added to the reaction mixture to carry out a ring-closing reaction, and the diol monoglycidyl ether represented by the above general formula [II] is recovered from the obtained reaction mixture. A method for producing a (meth) acrylate having an epoxy group represented by the general formula [I], which comprises subjecting this to a lower alkyl ester of (meth) acrylic acid in the presence of an ester exchange catalyst. 3. A diol represented by the general formula [III] is reacted with epihalohydrin in the presence of a dehydrohalogenating agent to recover a diol monoglycidyl ether represented by the general formula [II] from the reaction mixture, A method for producing a (meth) acrylate having an epoxy group represented by the general formula [I], which comprises subjecting this to a lower alkyl ester of (meth) acrylic acid in the presence of an ester exchange catalyst. 4. The method according to claim 1, wherein after water is added to the reaction mixture of the transesterification reaction to deactivate the transesterification catalyst, the (meth) acrylate having an epoxy group is extracted with an organic solvent. 4. The method for producing a (meth) acrylate having an epoxy group according to any one of 3 above. 5. The transesterification catalyst is selected from titanium alcoholate, organic tin compounds, alkali metal or alkaline earth metal carbonates, carboxylates and phosphates. 4. The method for producing a (meth) acrylate having an epoxy group according to any one of 4 above. 6. A compound represented by the formula [II] or [III]
6. The method for producing an epoxy group-containing (meth) acrylate according to claim 1, wherein the valent hydrocarbon group Y is an alkylene group having 2 to 8 carbon atoms. 7. The production of an epoxy group-containing (meth) acrylate according to claim 2, wherein the dehydrohalogenating agent is an alkali metal or alkaline earth metal hydroxide. Method. 8. The method for producing a (meth) acrylate having an epoxy group according to claim 2, wherein the catalyst for the ring-opening addition reaction is a boron trifluoride complex. 9. The method for producing a (meth) acrylate having an epoxy group according to claim 1, wherein the transesterification reaction is carried out at 60 to 120 ° C.