JP2000297062A - Production of hydroxyalkyl (meth)acrylate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a hydroxyalkyl (meth)acrylate containing a primary hydroxyl group as a main reaction product in a reaction between an epoxy compound (A) and (meth)acrylic acid (B). SOLUTION: An epoxy compound (A) is reacted with (meth)acrylic acid (B) in the presence of an alkaline earth metal salt (C) or an alkaline earth metal oxide (D) and the epoxy group is (meth)acrylated to give a hydroxy group-containing (meth)acrylate. Magnesium hydroxide, magnesium acetate, magnesium (meth)acrylate or magnesium chloride is used as the alkaline earth metal salt (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing hydroxyalkyl (meth) acrylate, and more particularly to a method for producing hydroxyalkyl (meth) acrylate obtained by subjecting an epoxy group to (meth) acryloylation. It is.

[0002]

2. Description of the Related Art As a method for producing hydroxyalkyl (meth) acrylate, for example, JP-A-10-26544
No. 0 discloses a method for obtaining a hydroxyalkyl (meth) acrylate by subjecting a compound having an epoxy group to (meth) acryloylation in the presence of a catalyst such as an amine or an ammonium salt to open the epoxy group and obtain a hydroxyalkyl (meth) acrylate. ing.

[0003] In general, catalysts used for cyclizing an epoxy compound by ring-opening with (meth) acrylic acid and the like include amines such as triethylamine and dimethylbutylamine, and ammonium such as tetramethylammonium salt and tetrabutylammonium salt. Salts, phosphines such as triphenylphosphine, and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole are used.

[0004]

However, hydroxyalkyl (meth) acrylates obtained by subjecting a compound having an epoxy group to (meth) acryloylation in the presence of a generally used catalyst have a primary hydroxyl group and a secondary alkyl group. The mixture is obtained as a mixture of hydroxyalkyl (meth) acrylates having a hydroxyl group, but the hydroxyalkyl (meth) acrylate having a secondary hydroxyl group is generally the main product. Secondary hydroxyl groups are less reactive than primary hydroxyl groups, and compounds having secondary hydroxyl groups are further subjected to a reaction such as esterification with respect to hydroxyalkyl (meth) acrylate, which is the main product. It was difficult to do.

The problem to be solved by the present invention is that a compound having an epoxy group is subjected to (meth) acryloylation to open the epoxy group to form a hydroxyalkyl (meth) acrylate having a primary hydroxyl group. It is to provide a method of manufacturing as a product.

[0006] The present inventors have set out to solve the above-mentioned problems.
As a result of intensive studies, the epoxy compound is reacted with (meth) acrylic acid in the presence of an alkaline earth metal salt or an oxide of an alkaline earth metal to convert the epoxy group into (meth) acryloyl. They have found that it is possible to synthesize a hydroxyalkyl (meth) acrylate having a primary hydroxyl group as a product, and have completed the present invention.

That is, the present invention provides an epoxy compound (A) and a (meth) acrylic acid (B) in order to solve the above-mentioned problems.
Is reacted in the presence of an alkaline earth metal salt (C) or an oxide (D) of an alkaline earth metal to convert the epoxy group to (meth) acryloyl, thereby obtaining a (meth) acrylate having a hydroxyl group. And a method for producing a (meth) acrylate.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION According to the production method of the present invention, an epoxy compound (A) and a (meth) acrylic acid (B) are mixed with an alkaline earth metal salt (C) or an alkaline earth metal oxide (D).
(Meth) acrylate having a primary hydroxyl group as a main product obtained by reacting the epoxy group with (meth) acryloyl to obtain a (meth) acrylate having a primary hydroxyl group. .

The alkaline earth metal salt (C) used in the present invention includes, for example, magnesium hydroxide, magnesium chloride, magnesium fluoride, magnesium bromide,
Magnesium salts of inorganic acids such as magnesium iodide, magnesium sulfate, magnesium nitrate, magnesium phosphate; such as magnesium acetate, magnesium (meth) acrylate, magnesium formate, magnesium propionate, magnesium oxalate, magnesium benzoate, magnesium lactate Magnesium carboxylate; magnesium salt of organic sulfonic acid such as magnesium methanesulfonate and magnesium p-toluenesulfonate; zinc hydroxide, zinc chloride, zinc fluoride, zinc bromide, zinc iodide, zinc sulfate zinc zinc nitrate, phosphorus Zinc salts of inorganic acids such as zinc acid; zinc salts of carboxylic acids such as zinc acetate, zinc (meth) acrylate, zinc formate, zinc propionate, zinc oxalate, zinc benzoate; zinc methanesulfonate, p-toluenesulfone Yes, like zinc acid Zinc salts of sulfonic acid, and the like, These may be used alone or may be used in combination.

Among these alkaline earth metal salts (C), hydroxyalkyl (meth) having a primary hydroxyl group
Magnesium salts and zinc salts are preferred in that acrylates can be obtained in high yield and by-products are small, and among the magnesium salts and zinc salts, magnesium hydroxide, magnesium acetate, magnesium (meth) acrylate, Magnesium chloride, zinc hydroxide, zinc acetate,
Zinc (meth) acrylate and zinc chloride are particularly preferred.

The alkaline earth metal oxide (D) used in the present invention includes, for example, magnesium oxide,
Zinc oxide, and the like.

The alkaline earth metal salt (C) or alkaline earth metal oxide (D) may be a compound of any of an anhydride and a hydrate, and is not particularly limited.

The amount of the alkaline earth metal (C) or alkaline earth metal oxide (D) used as a catalyst is not particularly limited, but is usually an epoxy compound (A) and (meth) acrylic acid (B). Is preferably in the range of 0.01 to 30.00 parts by weight with respect to 100 parts by weight in total.
A range of 0.1 to 10 parts by weight is particularly preferred.

In the above-described method for adding a catalyst, the solid can be added in any form, either as it is or in a solution such as an aqueous solution.

The epoxy compound (A) used in the present invention
For example, one in one molecule such as methyl glycidyl ether, ethyl glycidyl ether, n-propyl glycidyl ether, n-butyl glycidyl ether, iso-butyl glycidyl ether, sec-butyl glycidyl ether, n-hexyl glycidyl ether Alkyl glycidyl ethers having an epoxy group (hereinafter, referred to as “monofunctional”); and a glycidyl ether group in which an aromatic group such as phenyl glycidyl ether, biphenyl glycidyl ether, cresyl glycidyl ether, and naphthyl glycidyl ether is adjacent Functional aromatic glycidyl ethers; bisphenol A epoxy resin, bisphenol F epoxy resin, phenol AD epoxy resin, tetramethyl bisphenol A epoxy resin, bis Bisphenol type epoxy resins such as enol S type epoxy resin and their ethylene oxide adducts, propylene oxide adducts and caprolactone adducts, resorcinol diglycidyl ether, diglycidyl ether of 1,6-dihydroxynaphthalene, dimethylbisphenol C diglycidyl ether Phenol-type glycidyl ethers such as phenol type bifunctional (having two glycidyl groups in one molecule; hereinafter the same);

1,6-diglycidyloxynaphthalene type epoxy resin, 1- (2,7-diglycidyloxynaphthyl) -1- (2-glycidyloxynaphthyl) methane, 1,1-bis (2,7-di Naphthalene-type bifunctional glycidyl ethers such as glycidyloxynaphthyl) -1-phenylmethane; such as trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, tris (2-hydroxyethyl) cyanurate triglycidyl ether; Trifunctional glycidyl ethers; tetrafunctional glycidyl ethers such as tetrahydroxyphenylethane tetraglycidyl ether and bisresorcinol tetraglycidyl ether; phenol novolak type epoxy resin, orthocresol novola Glycidyl ethers such as epoxy resin, bisphenol A novolak epoxy resin and bisphenol AD novolak epoxy resin; polyethylene glycol polyglycidyl ether, polypropylene glycol polypropylene glycol, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether ,
Glycidyl ethers of polyhydric alcohols such as glycerin triglycidyl ether and sorbitol tetraglycidyl ether; epoxy compounds in which an aromatic group and an epoxy group are adjacent such as styrene oxide; and the like.

Among these epoxy compounds, the compounds represented by the general formula (I)

[0018]

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(Wherein R is a hydrogen atom or a molecular weight of 15 to 3)
000 represents a hydrocarbon group, and n represents a real number of 1 to 500. Glycidyl ethers represented by the general formula (II)

[0020]

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(Wherein, R ₁ represents an aromatic group, R ₂ represents a hydrogen atom or a hydrocarbon group having a molecular weight of 15 to 2,000, and n represents an integer of 1 to 10). Compound having a structure in which an epoxy group is directly substituted, and a compound represented by the general formula (III)

[0022]

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(Wherein R represents methylene or dimethylmethylene, and n represents an integer of 0 to 100), by applying the production method to the present invention to a bisphenol-type diglycidyl ether represented by the formula: In particular, a hydroxyalkyl (meth) acrylate having a primary hydroxyl group can be produced as a main product.

In the production method of the present invention, the reaction can be carried out without a solvent or in the presence of an organic solvent inert to the reaction. Examples of the organic solvent inert to the reaction include aromatic hydrocarbons such as toluene and xylene;
Aliphatic hydrocarbons such as hexane, n-heptane, n-octane and cyclohexane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers such as dipropyl ether and dipropylene glycol diethyl ether; ethyl acetate and butyl acetate And the like.

When the organic solvent is used, the total amount of the epoxy compound (A) and the (meth) acrylic acid (B) is 1
The range is preferably up to 300 parts by weight, more preferably from 20 to 100 parts by weight, per 100 parts by weight.

The amount of (meth) acrylic acid used in the production method of the present invention is not particularly limited, but is usually preferably in the range of 0.1 to 10.0 mol with respect to 1.00 mol of epoxy group. .

The reaction temperature in the production method of the present invention is usually preferably in the range of 50 to 130 ° C., preferably 70 to 1 ° C.
A range of 20 ° C. is particularly preferred. When the reaction is carried out at a temperature lower than 50 ° C., the reaction rate tends to be low, so that it is not preferable. Absent.

In the reaction in the production method of the present invention, it is preferable to carry out the reaction in the presence of a polymerization inhibitor in order to prevent the polymerization of (meth) acrylic acid (B) and the generated (meth) acrylate. Further, in the reaction in the production method of the present invention, oxygen or a mixture of oxygen and an inert gas, for example, air or an oxygen / argon mixed gas is added to the reaction solution and / or the reaction mixture over the entire reaction time in order to enhance the polymerization prevention effect. Preferably, it is introduced above the liquid level.

Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, 2,4-dimethyl-t-
Butylphenol, 3-hydroxythiophenol, p
Phenols and quinones such as -benzoquinone, 2,5-dihydroxy-p-benzoquinone; catechols such as t-butylcatechol; diphenylenediamine, phenyl-α-naphthylamine, N, N'-diamphthyl-p-phenylenediamine Aromatic amines such as diethanolamine and toluethanolamine; aromatic sulfurs such as phenothiazine; copper powder, copper dithiocarbamate, copper dimethyldithiocarbamate, copper oxide, copper chloride, copper chloride and copper sulfate Salts; sulfur, chloride second
Iron, nitro compounds, and the like. These compounds can be used alone or in combination of two or more.

The amount of the polymerization inhibitor used is usually from 100 to 10,000 ppm based on (meth) acrylic acid.
Is preferable.

In the production method of the present invention, purification after the reaction can be carried out by a known method such as washing with water, filtration and distillation. For example, the target hydroxyalkyl (meth) acrylate can be obtained by removing the catalyst from the reaction mixture by filtration or washing with water and then removing the remaining solvent and (meth) acrylate.

[0032]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The "conversion rate" in the following Examples and Comparative Examples indicates the conversion rate at the end of the reaction, and is indicated by a value calculated by the following formula.

Conversion (%) = 100-100 × (area of gas chromatography of epoxy compound (A) / (area of gas chromatography of epoxy compound (A) + area of gas chromatography of all reaction products) sum)

The “acrylate selectivity” in the table is:
The selectivity of hydroxy (meth) acrylate with respect to all the reaction products was shown and represented by a value calculated by a calculation formula.

Acrylate selectivity (%) = 100 × (1
Area of gas chromatography of hydroxyalkyl (meth) acrylate having a secondary hydroxyl group + area of gas chromatography of hydroxyalkyl (meth) acrylate having a secondary hydroxyl group / (sum of areas of gas chromatography of all reaction products)

However, Example 12 is shown by a value calculated by a calculation formula.

Acrylate selectivity (%) = 100 × (C
+ D + E) / (sum of gas chromatography areas of all reaction products)

(Wherein C is 2,2-bis (4- (2-
The area of gas chromatography of acryloyloxy-3-hydroxypropoxy) phenyl) propane was calculated as
Is 2,2-bis (4- (3-acryloyloxy-2)
The area of the gas chromatography of -hydroxypropoxy) phenyl) propane is represented by E: 2- (4- (2-acryloyloxy-3-hydroxypropoxy) phenyl-2- (4- (3-acryloyloxy-2-hydroxy) The area of gas chromatography of propoxy) phenyl) propane is shown respectively.)

Further, the "primary alcohol selectivity" in the table
Indicates the ratio of the hydroxyalkyl (meth) acrylate having a primary hydroxyl group to the sum of the hydroxyalkyl (meth) acrylate having a primary hydroxyl group and a secondary hydroxyl group, and is represented by a value calculated by a calculation formula.

Primary alcohol selectivity (%) = 100 ×
(Area of gas chromatography of hydroxyalkyl (meth) acrylate having primary hydroxyl group) / (Area of gas chromatography of hydroxyalkyl (meth) acrylate having secondary hydroxyl group)

However, in the twelfth embodiment, the value is calculated by the following formula.

Primary alcohol selectivity (%) = 100 ×
(2 × F + G) / (2 × F + 2 × G + 2 × H) (where F is the area of gas chromatography of 2,2-bis (4- (2-acryloyloxy-3-hydroxypropoxy) phenyl) propane. And G is 2,2-
The area of gas chromatography of bis (4- (3-acryloyloxy-2-hydroxypropoxy) phenyl) propane is represented by H as 2- (4- (2-acryloyloxy-3-hydroxypropoxy) phenyl-2- ( 4
The gas chromatography areas of-(3-acryloyloxy-2-hydroxypropoxy) phenyl) propane are respectively shown. )

Example 1 A 100 ml four-necked flask equipped with a reflux condenser, a stirrer, and a thermometer was charged with 20.0 g (0.133 mol) of phenylglycidyl ether.
19.7 g of toluene and 0.49 g of magnesium hydroxide
(0.084 mol), and 9.6 g of acrylic acid was added at room temperature.
(0.133 mol), hydroquinone 1 as a polymerization inhibitor
000 ppm was charged. Next, while stirring the content, a mixed gas consisting of 7% oxygen and 93% nitrogen was blown into the flask at a rate of 5 ml / min.
Heated to ° C. 1 after the temperature of the contents reaches 100 ° C
The reaction was performed for 0 hours. After completion of the reaction, the resultant was washed twice with 20.0 g of a 20% aqueous sodium hydroxide solution, and further washed once with 20.0 g of a 5% aqueous sodium sulfate solution. After washing, toluene was distilled off under reduced pressure, and a mixture of primary alcohol and secondary alcohol, that is, 1-acryloyloxy-2-hydroxy-3-phenoxypropane and 2-acryloyloxy-1-hydroxy-3-phenoxypropane 19.0 g of a mixture (hereinafter, referred to as a mixture of hydroxyalkyl acrylates) was obtained. After the completion of the reaction, the conversion based on gas chromatography was 75%. The acrylate selectivity was 96%, and the primary alcohol selectivity was 55%.

<Example 2> In Example 1, magnesium oxide 0.1 g was used instead of magnesium hydroxide 0.49 g.
Except using 49 g, it carried out similarly to Example 1, and obtained 19.2 g of hydroxyalkyl acrylate mixtures.
The conversion, acrylate selectivity, and primary alcohol selectivity based on gas chromatography obtained in the same manner as in Example 1 are shown in Table 1.

Example 3 A mixture of hydroxyalkyl acrylate was prepared in the same manner as in Example 1 except that 1.50 g of magnesium hydroxide was used instead of 0.49 g of magnesium hydroxide. 5 g were obtained. The conversion, acrylate selectivity, and primary alcohol selectivity based on gas chromatography obtained in the same manner as in Example 1 are shown in Table 1.

Example 4 The procedure of Example 3 was repeated, except that 9.6 g of acrylic acid was replaced by 34.4 g of methacrylic acid and 36.2 g of toluene.
A mixture of primary and secondary alcohols, ie, 1-
28.0 g of a mixture of hydroxy-2-methacryloxy-3-phenoxypropane and 2-hydroxy-1-methacryloxy-3-phenoxypropane were obtained. Example 1
Table 1 shows conversion, acrylate selectivity and primary alcohol selectivity based on gas chromatography obtained in the same manner as in Example 1.
It was shown to.

Example 5 The procedure of Example 1 was repeated, except that 0.49 g of magnesium hydroxide was used instead of 0.4 g of magnesium acetate.
Except using 49 g, it carried out similarly to Example 1, and obtained 25.0 g of hydroxyalkyl acrylate mixtures.
The conversion, acrylate selectivity, and primary alcohol selectivity based on gas chromatography obtained in the same manner as in Example 1 are shown in Table 1.

Example 6 The procedure of Example 1 was repeated, except that 0.49 g of magnesium hydroxide was used instead of 0.49 g of magnesium hydroxide.
24.9 g of a mixture of hydroxyalkyl acrylates were obtained. The conversion, acrylate selectivity, and primary alcohol selectivity based on gas chromatography obtained in the same manner as in Example 1 are shown in Table 1.

Example 7 In Example 1, magnesium chloride 0.1 g was used in place of 0.49 g of magnesium hydroxide.
Except using 49 g, it carried out similarly to Example 1, and obtained 22.9 g of hydroxyalkyl acrylate mixtures.
The conversion, acrylate selectivity, and primary alcohol selectivity based on gas chromatography obtained in the same manner as in Example 1 are shown in Table 1.

<Example 8> In Example 1, 0.49 g of zinc chloride was used instead of 0.49 g of magnesium hydroxide.
23.0 g of a mixture of hydroxyalkyl acrylates was obtained in the same manner as in Example 1 except for using. The conversion, acrylate selectivity, and primary alcohol selectivity based on gas chromatography obtained in the same manner as in Example 1 are shown in Table 1.

<Example 9> 23.7 g of a mixture of hydroxyalkyl acrylate was prepared in the same manner as in Example 1 except that 0.49 g of zinc acetate was used instead of 0.49 g of magnesium hydroxide. I got Example 1
Table 1 shows conversion, acrylate selectivity and primary alcohol selectivity based on gas chromatography obtained in the same manner as in Example 1.
It was shown to.

<Example 10> In Example 1, 20.0 g of phenylglycidyl ether and 19.7 g of toluene were used.
And 0.49 g of magnesium hydroxide, 20.0 g (0.154 mol) of n-butyl glycidyl ether,
35.5 g of toluene and 1.7 g of magnesium hydroxide
(0.030 mol) and the amount of acrylic acid was increased from 9.6 g to 33.2 g (0.464 mol) in the same manner as in Example 1 except that primary alcohol and 2 Mixtures of secondary alcohols, i.e., 2-acryloyloxy-1-hydroxy-3-n-butoxypropane and 1
26.1 g of a mixture of -acryloyloxy-2-hydroxy-3-n-butoxypropane were obtained. Conversion based on gas chromatography obtained in the same manner as in Example 1,
Table 1 shows the acrylate selectivity and primary alcohol selectivity.

<Example 11> In Example 1, 20.0 g of phenylglycidyl ether and 19.7 g of toluene were used.
And 0.49 g of magnesium hydroxide, 20.0 g (0.167 mol) of styrene oxide, toluene 3
7.3 g and magnesium hydroxide 1.9 g (0.032
Mol) and the amount of acrylic acid used was increased from 9.6 g to 36.0 g (0.500 mol)
In the same manner as in Example 1, a mixture of a primary alcohol and a secondary alcohol, that is, a mixture of 1-acryloyloxy-2-hydroxy-2-phenylethane and 2-acryloyloxy-1-hydroxy-2-phenylethane 2
4.3 g were obtained. Conversion based on gas chromatography obtained in the same manner as in Example 1, acrylate selectivity, 1
The selectivity of the secondary alcohol is shown in Table 1.

<Example 12> In Example 1, 20.0 g of phenylglycidyl ether and 19.7 g of toluene were used.
And 20.0 g of bisphenol A diglycidyl ether (0.059 g) in place of 0.49 g of magnesium hydroxide.
Mol), 30.3 g of toluene and 1.4 g (0.024 mol) of magnesium hydroxide, the amount of acrylic acid used was increased from 9.6 g to 25.4 g (0.353 mol), and the reaction time was increased. Was changed from 10 hours to 15 hours, and a primary alcohol and 2
Mixtures of secondary alcohols, i.e., 2,2-bis (4- (2
-Acryloyloxy-3-hydroxypropoxy) phenyl) propane, 2,2-bis (4- (3-acryloyloxy-2-hydroxypropoxy) phenyl) propane and 2- (4- (2-acryloyloxy-3-)
23.5 g of a mixture of (hydroxypropoxy) phenyl-2- (4- (3-acryloyloxy-2-hydroxypropoxy) phenyl) propane were obtained. Conversion based on gas chromatography obtained in the same manner as in Example 1,
Table 1 shows the acrylate selectivity and primary alcohol selectivity.

Comparative Example 1 In a 100 ml four-necked flask equipped with a reflux condenser, a stirrer, and a thermometer, 19.7 g of toluene, 9.6 g (0.133 mol) of acrylic acid and 20 g of phenylglycidyl ether were placed. 0g (0.1
33 mol), 2-methylimidazole 0.4 as a catalyst
9 g and hydroquinone 1000 ppm as a polymerization inhibitor
Was charged. Next, while stirring the contents, the contents were heated to 100 ° C. while a mixed gas consisting of 7% oxygen and 93% nitrogen was blown into the flask at 5 ml / min. The reaction was carried out for 10 hours after the temperature of the contents reached 100 ° C. After completion of the reaction, a 5% aqueous solution of sodium sulfate 2
Washed twice with 0.0 g. After washing, toluene was distilled off under reduced pressure to obtain a mixture of primary alcohol and secondary alcohol, that is, 2-acryloyloxy-1-hydroxy-3-phenoxypropane and 1-acryloyloxy-2-hydroxy-3-phenoxy. Propane (hereinafter,
20.0 g of a mixture of hydroxyalkyl acrylates).

After the completion of the reaction, the conversion based on gas chromatography was 92%. The acrylate selectivity was 64%. Further, the primary alcohol selectivity was 34%.

Comparative Example 2 A mixture of hydroxyalkyl acrylate 19 was prepared in the same manner as in Comparative Example 1 except that 0.49 g of triphenylphosphine was used instead of 0.49 g of 2-methylimidazole. .8
g was obtained. Table 2 shows the conversion, acrylate selectivity, and primary alcohol selectivity based on gas chromatography obtained in the same manner as in Comparative Example 1.

Comparative Example 3 Comparative Example 1 was repeated except that 0.49 g of N, N'-tetramethylenediamine was used instead of 0.49 g of 2-methylimidazole.
In the same manner as described above, 26.9 g of a mixture of hydroxyalkyl acrylate was obtained. Table 2 shows the conversion, acrylate selectivity, and primary alcohol selectivity based on gas chromatography obtained in the same manner as in Comparative Example 1.

Comparative Example 4 Comparative Example 1 was repeated except that 0.49 g of 1,8-diazabicyclo (5,4,0) undecene was used in place of 0.49 g of 2-methylimidazole. In the same manner, 20.9 g of a mixture of hydroxyalkyl acrylate was obtained. Table 2 shows the conversion, acrylate selectivity, and primary alcohol selectivity based on gas chromatography obtained in the same manner as in Comparative Example 1.

Comparative Example 5 A mixture of hydroxyalkyl acrylate 23 was prepared in the same manner as in Comparative Example 1 except that 0.49 g of tetraethylammonium chloride was used instead of 0.49 g of 2-methylimidazole. 0.0 g was obtained. Table 2 shows the conversion, acrylate selectivity, and primary alcohol selectivity based on gas chromatography obtained in the same manner as in Comparative Example 1.

Comparative Example 6 16.0 g of a mixture of hydroxyalkyl acrylate was prepared in the same manner as in Comparative Example 1, except that 0.49 g of dicyandiamide was used instead of 0.49 g of 2-methylimidazole. I got Table 2 shows the conversion, acrylate selectivity, and primary alcohol selectivity based on gas chromatography obtained in the same manner as in Comparative Example 1.

<Comparative Example 7> In Comparative Example 1, lithium chloride 0.1% was used instead of 0.49 g of 2-methylimidazole.
Except using 49g, it carried out similarly to the comparative example 1, and obtained 20.5g of hydroxyalkyl acrylate mixtures. Table 2 shows the conversion, acrylate selectivity, and primary alcohol selectivity based on gas chromatography obtained in the same manner as in Comparative Example 1.

Comparative Example 8 A mixture of hydroxyalkyl acrylate 21 was prepared in the same manner as in Comparative Example 1, except that 0.49 g of sodium acrylate was used instead of 0.49 g of 2-methylimidazole. .8
g was obtained. Table 2 shows the conversion, acrylate selectivity, and primary alcohol selectivity based on gas chromatography obtained in the same manner as in Comparative Example 1.

Comparative Example 9 In Comparative Example 1, 0.49 g of 2-methylimidazole was used instead of 0.49 g of cuprous chloride.
Except having used 9 g, it carried out similarly to the comparative example 1, and obtained 6.0 g of hydroxyalkyl acrylate mixtures. Table 2 shows the conversion, acrylate selectivity, and primary alcohol selectivity based on gas chromatography obtained in the same manner as in Comparative Example 1.

<Comparative Example 10> In Comparative Example 1, chromium chloride (I) was used in place of 0.49 g of 2-methylimidazole.
I) Mixture of hydroxyalkyl acrylate in the same manner as in Comparative Example 1 except that 0.49 g was used.
0 g was obtained. Table 2 shows the conversion, acrylate selectivity, and primary alcohol selectivity based on gas chromatography obtained in the same manner as in Comparative Example 1.

[0066]

[Table 1]

[0067]

[Table 2]

From the results shown in Tables 1 and 2, the production method of the embodiment of the present invention shows that the primary hydroxyl group is smaller than that of the comparative example using 2-methylimidazole or triphenylphosphine which is a conventional catalyst. It is clear that the yield of the compound having is large.

[0069]

According to the method for producing hydroxyalkyl (meth) acrylate of the present invention, the yield of the compound having a primary hydroxyl group can be reduced as compared with the conventional production method using 2-methylimidazole or triphenylphosphine as a catalyst. There is an advantage that there are many. Since the primary hydroxyl group has a high reaction rate with (meth) acrylic acid, the production method of the present invention is useful as a method for producing an intermediate material when producing a polyfunctional (meth) acrylate.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C07C 69/54 C07C 69/54 Z C08G 59/17 C08G 59/17 // C07B 61/00 300 C07B 61/00 300 F Term (reference) 4H006 AA02 AC28 AC41 AC48 BA06 BA07 BA29 BA30 BA32 BA37 BJ50 BN10 KA19 KE20 4H039 CA60 CA66 CH70 4J036 AD08 AJ01 AJ02 AJ03 AJ05 CA21

Claims (7)

[Claims] An epoxy compound obtained by reacting an epoxy compound (A) with a (meth) acrylic acid (B) in the presence of an alkaline earth metal salt (C) or an alkaline earth metal oxide (D). A method for producing a (meth) acrylate, comprising obtaining a (meth) acrylate having a hydroxyl group obtained by converting the group into a (meth) acryloyl group. 2. The method for producing a (meth) acrylate having a primary hydroxyl group according to claim 1, wherein a magnesium salt or a zinc salt is used as the alkaline earth metal salt (C). 3. The method according to claim 1, wherein the alkaline earth metal salt (C) is magnesium hydroxide, magnesium acetate, magnesium (meth) acrylate or magnesium chloride.
A method for producing a (meth) acrylate having a primary hydroxyl group according to the above. 4. The method for producing a (meth) acrylate having a primary hydroxyl group according to claim 1, wherein zinc hydroxide, zinc acetate, zinc (meth) acrylate or zinc chloride is used as the alkaline earth metal salt (C). 5. The (meth) acrylate having a hydroxyl group obtained by subjecting an epoxy group to (meth) acryloylation according to claim 1, wherein magnesium oxide or zinc oxide is used as the alkaline earth metal oxide (D). For producing (meth) acrylate 6. The epoxy compound (A) represented by the general formula (I): (In the formula, R represents a hydrogen atom or a hydrocarbon group having a molecular weight of 15 to 30,000, and n represents a real number of 1 to 500.)
A glycidyl ether represented by the general formula (II): (Wherein, R ₁ represents an aromatic group, R ₂ represents a hydrogen atom or a hydrocarbon group having a molecular weight of 15 to 2,000, and n represents 1 to 1)
Represents an integer of 0. 6. An epoxy compound selected from the group consisting of compounds having a structure in which an epoxy group is directly substituted on an aromatic represented by the formula (1).
The method for producing a (meth) acrylate having a primary hydroxyl group according to the above item. 7. An epoxy compound (A) of the general formula (II)
I) (Wherein R represents methylene or dimethylmethylene,
n represents an integer of 0 to 100. (2) a bisphenol type diglycidyl ether represented by the formula (1):
6. The method for producing a (meth) acrylate having a primary hydroxyl group according to 5.