WO2008032389A1

WO2008032389A1 - Epoxy group-terminated (meth)acrylate and process for producing the same

Info

Publication number: WO2008032389A1
Application number: PCT/JP2006/318294
Authority: WO
Inventors: Hajime Kamikura; Satoshi Yamauchi; Katsufumi Kujira
Original assignee: Nippon Kasei Chemical Company Limited
Priority date: 2006-09-14
Filing date: 2006-09-14
Publication date: 2008-03-20

Abstract

It is intended to provide a novel epoxy group-terminated (meth)acrylate which does not cause troubles that target physical properties of a final product cannot be obtained, weather resistance thereof is lowered when it is used as a raw material, and so on. The epoxy group-terminated (meth)acrylate is represented by the general formula (1) and contains a compound represented by the general formula (2) or the general formula (3) at a content of 0.5% by weight or less. In a preferred embodiment of the invention, the (meth)acrylate is obtained by reacting a compound having an acryloyl group with a compound having an epoxy group, wherein the compounds are reacted after the compound having an acryloyl group and/or the compound having an epoxy group are/is purified through an extraction step. (In the respective formulae, Y represents an alkylene group having 2 to 6 carbon atoms and R represents a hydrogen atom or a methyl group.)

Description

Specification

Epoxy group-terminated (meth) acrylate and process for producing the same

Technical field

TECHNICAL FIELD [0001] The present invention relates to an epoxy group-terminated (meth) acrylate and a method for producing the same, and more particularly to a high-purity epoxy group-terminated (meth) acrylate and a method for producing the same useful as a raw material for paints and the like.

Background art

[0002] Epoxy group-terminated (meth) acrylates can be produced, for example, as follows.

First, monoallysidyl ether of a dioli compound, which is a compound having an epoxy group, is synthesized by a direct dehalogenation reaction between the dioli compound and epino and rhohydrin using an alkali compound. Next, the compound is transesterified by reacting with a compound having an allyloyl group, for example, (meth) acrylic acid ester (Patent Document 1).

Patent Document 1: JP-A-8-99968

[0003] In the above addition reaction, an unreacted diol compound remains depending on the reaction conditions. In addition, alkanediol diglycidyl ether with epihalohydrin attached to both ends of the diol compound is by-produced.

[0004] By the way, when a transesterification reaction with (meth) acrylic acid ester is carried out using a hydroxyalkaneglycidyl ether containing the above compound, the diol compound is diesterified at both ends. Converted to (meth) acrylate and mixed in the target (epoxy group-containing (meth) acrylate). Similarly, alkanediol diglycidyl ether remains as it is in the epoxy group-terminated (meth) acrylate.

[0005] For example, by transesterification of a hydroxybutyl monoglycidyl ether (hereinafter abbreviated as 14BDMGE) synthesized by the addition reaction of 1,4-butanediol (hereinafter abbreviated as 14BD) and epihalohydrin with an acrylate ester, Ability to produce glycidyloxypropyl acrylate (hereinafter abbreviated as 4HBAGE due to the name of raw material) In both 4H BAGE products, both unreacted diol compounds and diol compounds have both ends as esters. 1,4-Butanediol ditalylate converted to di (meth) atalylate (Hereinafter abbreviated as BDA) and 1,4-butanediol diglycidyl ether (hereinafter abbreviated as 14BDDGE) added with epino and rhohydrin at both ends of the dioli compound are considered to be mixed. It is thought that the compound derived from the monomer Nepino and rhohydrin is also mixed.

[0006] By the way, in the above-mentioned prior art, no mention is made regarding the purification of epoxy-terminated (meth) acrylate and the influence of the above-mentioned contaminants. However, when a coating or the like is produced using an epoxy group-terminated (meth) acrylate prepared by a prior art method, there is a problem that the weather resistance is low and the coating properties are remarkably deteriorated. . Specifically, when the carboxylic acid or acid anhydride as a cross-linking agent is added to the target main component epoxy group-terminated (meth) acrylate and reacted, the above-mentioned impurities reduce the cross-linking efficiency. A decrease in molecular weight (change in polymerizability) occurred, and the desired physical properties were not obtained.

Disclosure of the invention

Problems to be solved by the invention

[0007] The present invention has been made in view of the above circumstances, and its purpose is that when used as a raw material, the cross-linking efficiency and molecular weight, which are the target physical properties of the final target product, cannot be obtained, and the weather resistance is lowered. Thus, the present invention provides a novel epoxy group-terminated (meth) acrylate and a method for producing the same. Another object of the present invention is to provide a method for producing alkanediol monoglycidyl ether useful as a raw material for the above-mentioned epoxy group-terminated (meth) acrylate.

Means for solving the problem

[0008] As a result of intensive studies, the inventors of the present invention, among the compounds mixed in a large amount in the epoxy group-terminated (meth) acrylate, are subjected to an extraction step with a water-organic solvent. The content of the compound can be limited to a certain amount or less, thereby obtaining the knowledge that the physical properties such as the weather resistance of the final target product can be improved as well as having a high purity, thereby completing the present invention. It came. That is, the present invention comprises a group of related inventions, and the gist of each invention is as follows.

The first gist of the present invention is characterized in that the content of the compound represented by the following general formula (2) or the compound represented by the following general formula (3) is 0.5% by weight or less. The following general formula (1 ) In the terminal (meth) acrylate of the epoxy group.

[Chemical 1]

CH _? = C— C— 0— Υ— 0— CH ₇ — CH— CH ₇

R u

CH Fu CH— CH 厂 O— Y— O— CH ₂ — CH— CH ₂ 3)

\ / \

(In the above formulas, Y represents an alkylene group having 2 to 6 carbon atoms, and R represents a hydrogen atom or a methyl group.)

[0011] The second gist of the present invention is a process for producing an alkanediol monoglycidyl ether represented by the general formula (4) obtained by reacting a diolu compound with epino and rhohydrin, comprising a diol compound The alkanediol monoglycidyl ether represented by the following formula (4) is characterized in that the crude alkanediol monoglycidyl ether is obtained by reacting with ephalohalohydrin to obtain a crude alkanediol monoglycidyl ether. It exists in the manufacturing method of glycidyl ether.

[0012] [Chemical 2]

HO— Υ— 0— CH 1 CH— CH (4)

0

(In the above formula, Υ represents an alkylene group having 2 to 6 carbon atoms.)

[0013] The third gist of the present invention is a method for producing an epoxy group-terminated (meth) acrylate represented by the general formula (1), wherein (meth) acrylic acid ester and the general formula (4) The alkane diol monoglycidyl ether shown above is used, and as the above alkanediol monoglycidyl ether, a crude alkanediol monoglycidyl ether obtained by reacting a diol compound with epihalohydrin is purified by extraction. It is represented by the general formula (1), characterized by using glycidyl ether. The present invention relates to a method for producing an epoxy-terminated (meth) acrylate.

[0014] Then, the fourth gist of the present invention is a method for producing an epoxy group-terminated (meth) acrylate having the general formula (1), wherein (meth) acrylic acid ester and the general formula (4) Wherein the above-mentioned reaction is carried out in the presence of at least the following two types of solvents (A) and (B):

The present invention resides in a method for producing an epoxy group-terminated (meth) acrylate having the formula (1).

(A) A solvent that can be azeotroped with by-produced alcohol, the azeotropic temperature of which is lower than the azeotropic temperature of alcohol and (meth) acrylic acid ester by-produced.

(B) A solvent whose boiling point is higher than the above azeotropic temperature.

The invention's effect

[0015] According to the present invention, when used as a raw material, the desired physical properties of the final target product can be obtained, and a novel epoxy group-terminated (meth) acrylate is provided without problems such as deterioration in weather resistance. The

BEST MODE FOR CARRYING OUT THE INVENTION

[0016] The present invention relates to an epoxy group-terminated (meth) acrylate which is represented by the following general formula (1).

[0017] [Chemical 3]

(In the above formula, Y represents an alkylene group having 2 to 6 carbon atoms, and R represents a hydrogen atom or a methyl group.)

[0018] In the general formula (1), Y is preferably an alkylene group having 3 to 6 carbon atoms, and an alkylene group having 4 carbon atoms is particularly preferable as a raw material for surface coating.

[0019] The epoxy group-terminated (meth) acrylate in the present invention is an alkane diol di (meth) acrylate represented by the following general formula (2) or an alkane diol diglycidyl ether represented by the following general formula (3). The content of is not more than 0.5% by weight.

[0020] [Chemical 4]

CH -NOCH-CH lO— Y— O— CH λ— C ^ H— _/ CH ₂ Δ (3)

ヽ 0 O

Hereinafter, the present invention will be described in detail by taking as an example the production of 4-hydroxybutyl acrylate monoglycidyl ether (4HBAGE) which is Y force.

The feature of 4HBAGE of the present invention is represented by BDA (a compound represented by Y = 4 in the general formula (2)) or 14BDDGE (a compound represented by Y = 4 in the general formula (3)). Content) is limited to a certain range or less. The content of BD soot is 0.5% by weight or less, preferably 0.3% by weight or less, and the content of 14BDDGE is 0.5% by weight or less, preferably 0.3% by weight or less. . If the content exceeds the above, the object of the present invention cannot be achieved.

[0023] When the content of BDA is larger than the range specified in the present invention, the reason why the final target product cannot achieve the target physical properties is estimated as follows. That is, if there is a large amount of BDA, it is considered that the attalylate at both ends reacts with the polymer main chain to prevent cross-linking at that portion, resulting in a decrease in the cross-linking density, resulting in adverse effects on the physical properties of the resin.

[0024] The reason why the final object cannot achieve the target physical properties when the content of 14BDDGE is larger than the range specified in the present invention is estimated as follows. That is, since there is no acrylate group, it does not react with the polymer main chain, hinders polymerization, lowers the degree of polymerization, and decreases the molecular weight. As a result, it is considered that the physical properties of the fats are similarly adversely affected.

[0025] In particular, in recent years, 4HBAGE is frequently used as a raw material for surface coating, and in this case, stricter physical properties are required.

[0026] The method for producing 4HBAGE employed in the present invention is mainly a synthesis reaction of 14BDMGE, which is an ionic compound having an epoxy group, a separation step of the same compound, and a compound having 14BDMGE and an attalyl group ( 4HBAGE synthesis by reaction with (meth) acrylic acid ester Power of reaction and separation process of the same compound. The following describes the 4HBAGE manufacturing method for each of the above steps.

[0027] (Synthesis of 14BDMGE)

14BDMGE can be synthesized by a known method, for example, the method described in JP-A-8-99968. In general, an alkaline compound is used as a dehalogenating hydrogenation agent, and a dioli compound is directly subjected to a dehalogenation addition reaction with epino and lohydrin.

[0028] Here, the diol compound may be any α, ω-diol having two primary hydroxyl groups and having 2 to 6 carbon atoms. Specifically, ethylene glycol, diethylene glycol, triethylene glycol, 1, 3 Propanediol, 1,4 butanediol, 1,5 pentanediol, 1,6 hexanediol, neopentyl glycol and the like. Usually 1,4 butanediol is used. Hereinafter, 14BD will be described as an example of the diol compound. In addition, examples of the epihalohydrin include an epib oral mohydrin, an epichlorohydrin, an epichlorohydrin, a β-methyl ebibu oral mohydrin, a β-methyl epichlorohydrin, and the like. Usually, epichlorohydrin is used.

[0029] Here, the ratio (molar ratio) between 14BD and epihalohydrin to be subjected to the reaction is usually in the range of 1: 0.5 to 1:10, preferably 1: 2 to 1: 6. In general, when the mole ratio of epihalohydrin to 14BD is larger than the above range, 14BDDGE is generated more. On the other hand, when it is smaller than the above range, a large amount of unreacted 14BD is present. This is not preferable because the yield of 14BDMGE may decrease.

[0030] As the dehydrohalogenating agent, an alkaline compound is usually used. A weak alkali sodium carbonate may be used, but a strong alkali is preferred. Specifically, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, lithium hydroxide, etc. are preferred, especially sodium hydroxide and water. Acid potassium is preferred. The alkaline compound is usually added to the mixture of the diol diol compound, epino and rhohydrin as an aqueous solution, preferably as an aqueous solution of 10 to 60% by weight. The amount of the dehydrohalogenating agent used is usually 0.9 to 1.5, preferably 1.0 to 1.2, based on the amount of the charged diol, as an equivalent ratio.

[0031] As a reaction method, a mixture of a dioli compound, epino, and rhohydrin is mixed with denominated rogeny water. A method of adding a raw material is preferred. This is because the epoxy group easily undergoes cleavage decomposition when an excessive dehalogenated hydrogenation agent is present in the reaction system. The reaction temperature is generally 0-100 ° C, preferably 20-70 ° C. If the reaction temperature is too low, the reaction progresses slowly. On the other hand, if the reaction temperature is too high, side reactions such as hydrolysis may occur. The reaction time is usually about 2 to 20 hours. The reaction is usually carried out under azeotropic conditions between water produced by the reaction and epino and rhohydrin. Thereafter, the azeotropic water and the epihalohydrin are cooled and separated into two phases, but the epino and lohydrin may be returned to the reaction system to distill off only the water. As the reaction proceeds, the halogen salt precipitates, so the reaction is carried out with stirring. Further, after the reaction is completed, the precipitated halogen salt is usually removed by adding water or the like.

[0032] Completion of the reaction can be confirmed by confirming disappearance of the raw material by gas chromatography or the like. The remaining raw material is recovered by a reduced pressure removal method or the like. The above reaction produces alkanediol monoglycidyl ether (crude 14BDMGE: 1,4 butanediol monoglycidyl ether) represented by the following general formula (4).

[0033] [Chemical 5]

(In the above formula, Y represents an alkylene group having 2 to 6 carbon atoms.)

[0034] (14BDMGE separation process)

The crude 14BDMGE obtained above is purified by extraction. That is, in the separation of 14BDMGE, extraction with a water-insoluble organic solvent in the presence of water is preferable from the solution after the synthesis reaction in order to stably and efficiently remove impurities. Extraction in the present invention can be performed either batchwise or continuously. Considering industrial advantages, for example, continuous extraction by the Karl column method (Sumitomo Heavy Industries, Ltd.) is preferable.

[0035] The ability to explain the continuous extraction method using a curl column below. Keeping the extraction rate of the target component 14BDMG E high, and two impurities, 14BD (which changes to BDA during the synthesis of the next step) and 14BDDGE The extraction is performed in two stages in order to efficiently remove the.

[0036] (1): In the first stage extraction, 14BDMGE and 14BD are extracted into the aqueous phase, and 14 BDDGE is extracted and removed into the organic solvent phase. In the second stage extraction, the organic solvent is extracted from the first stage aqueous phase. Extract only 14BDMGE into the phase and separate from 14BD. Here, it is possible to reverse the purpose of the first stage and the second stage. That is, (2): 14BDMGE is extracted together with 14BDDGE in the first stage organic phase and separated from 14BD, and 14BDMGE is extracted in the second stage aqueous phase and separated from 14BDDGE. Specific examples of the water-insoluble organic solvent at this time include water-insoluble organic solvents such as aromatic hydrocarbons such as benzene, toluene and xylene, and chain saturated hydrocarbons such as N-hexane and N-heptane. A solvent is mentioned. Of these, toluene is preferred for both the first and second stages.

[0037] Hereinafter, the extraction method (1) will be described in detail. In the first stage, water and toluene are added to the 14BD MGE synthesis reaction solution described above for extraction. That is, in the curl column type continuous extraction, water and the 14BDMGE-containing reaction crude liquid are continuously added from the upper part of the column tower, and toluene is continuously added from the lower part of the column tower. 14B DDGE is extracted and removed from the upper phase (toluene phase), and 14BDMGE and 14BD are extracted to the lower phase (aqueous phase). Here, the ability to extract a small amount of 14BDMGE in the toluene phase In order to increase the solubility of 14BDMGE in the aqueous phase, it is also effective to add a solubility regulator such as methanol to the water to be added.

[0038] The appropriate temperature in the column is a force that is limited by the extraction efficiency, the boiling point of the solvent used, and the freezing point of water. The amounts of water and methanol and toluene used are as follows. That is, the amount of water / methanol mixture used is 0.5 to 20 times the mass ratio of 14BDMGE. The methanol concentration is 0-60% by weight with respect to water. If there is more than this, separability may be impaired. The amount of toluene used is 1 to 20 times the mass ratio of 14BDMGE. If the amount of toluene is less than this, 14BDDGE is mixed with the water (and methanol) phase in the form of being dragged by 14B DMGE, and the extraction efficiency decreases. Moreover, when there is more toluene than the said range, it will cause a bad manufacturing cost.

[0039] In the second stage, extraction is performed by adding toluene to the aqueous phase of the first stage. That is, the first-stage aqueous phase is continuously added from the top of the column tower, and toluene is continuously added from the bottom of the column tower. 14BDMGE is extracted from the upper phase (toluene phase) and 14BD is extracted and removed from the lower phase (water phase). The amount of toluene used is 1 to 30 times the mass ratio of 14BDMGE in the first stage water phase. If the amount of toluene used is less than this, 14B DMGE may be mixed into the water (and methanol) phase in a form that is dragged by 14BD, which may reduce the extraction efficiency. Also, If the amount of use of Lwen is larger than the above range, it will cause a bad manufacturing cost.

[0040] Acquisition of toluene phase 14BDMGE is carried out by removing toluene by a method such as distillation under reduced pressure. Thereby, 14BD DMGE with 14BDDGE and 14BD content reduced can be obtained. The recovered toluene can again be used for extraction removal.

[0041] As a method of reducing the content of 14BDDGE, 14BD, BDA and other impurities, a force that can be considered as a distillation method is generally used. The boiling point of these compounds is close to the target 14BD MGE or 4HBAGE. Therefore, separation by distillation alone, so-called rectification, is difficult. Moreover, the target product is thermally unstable and difficult to rectify.

[0042] As described above, it is possible to obtain 4HBAGE with a reduced content of BDA and 14BDDGE as a product by preliminarily purifying 14BDMGE as a raw material of 4HBAGE by extraction.

[0043] (4HBAGE synthesis reaction)

Purified 14BDMGE obtained by extraction as described above and (meth) acrylic acid ester are transesterified in the presence of a transesterification catalyst to produce the desired 4HBAGE. By purifying (meth) acrylic acid ester in advance by a method such as extraction, 4HBAGE with a reduced content of BDA and 14BDDGE can be obtained as a product.

[0044] Here, as the (meth) acrylic acid ester, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester and the like are preferable. is there.

[0045] The amount of (meth) acrylic acid ester used is usually about 1.1 to 3 times as a mole ratio to diol monoglycidyl ether. Since the reaction is a force equilibrium reaction in which a lower alcohol is produced, the reaction can be further advanced by distilling the produced lower alcohol out of the reaction system. The reaction may be either a continuous type or a batch type. Although the reaction can be carried out in the absence of a solvent, it is preferably carried out in the presence of an organic solvent. In the present invention, the reaction is preferably carried out in the presence of at least the following two types of solvents (A) and (B).

[0046] (A) A solvent that can azeotrope with by-produced alcohol, and the azeotropic temperature of the solvent is a by-product. Solvent lower than the azeotropic temperature of coal and (meth) acrylic acid ester (hereinafter referred to as organic solvent A).

(B) Its boiling point is higher than the above azeotropic temperature !, solvent (hereinafter referred to as organic solvent B).

[0047] The organic solvent A acts as a solvent for distilling off alcohol (usually lower alcohol) generated in the reaction process to the outside of the reaction system. By satisfying the above azeotropic temperature condition, the generated alcohol can be distilled out of the system without taking out the raw material (meth) acrylic acid ester.

[0048] By satisfying the above azeotropic temperature condition, the organic solvent B stays in the system as it is, and the reaction temperature of the reaction system can be increased without affecting the above-described action of the organic solvent A. Acts as a possible solvent. As a result, it functions as a solvent for dilution to accelerate the reaction and to suppress the polymerization of (meth) acrylic acid ester. Furthermore, the organic solvent B can be used as the extraction solvent in the following step.

[0049] As described above, the transesterification reaction is performed in the presence of the organic solvent A and the organic solvent B, so that the organic alcohol generated without taking the raw material (meth) acrylate ester out of the system is organic. The reaction can proceed while distilling out of the system azeotropically with solvent A, and organic solvent B remains in the system as it is and can be used as an extraction solvent in the next step.

[0050] Examples of the organic solvent A include hydrocarbon-based organic solvents such as n-pentane, n-xane, and n-heptane. Xane is preferred. On the other hand, examples of the organic solvent B include aromatic solvents such as benzene, toluene and xylene, but toluene is particularly preferable in consideration of extraction operation and subsequent solvent removal.

[0051] In the present invention, the solvent may be used in a mixed system of three or more. The organic solvent is introduced into the reaction system by a method such as batch charging from the beginning of the reaction or sequential addition. The amount of organic solvent A to be used is a force determined by the composition ratio with the alcohol to be produced. It is necessary to use more than the amount by which this alcohol is distilled out of the system. In addition, if the amount of organic solvent B used is too large, it will be difficult to recover, so usually the same amount as organic solvent A is appropriate.

[0052] Transesterification catalysts include titanium alcoholates, organotins, alkali metal or alkaline earth metal weak acid salts (carbonates, acetates, phosphates, etc.), alkali metal alcoholics. A common transesterification catalyst such as a catalyst is used. Among these, titanium alcoholate or organic tin compound is preferable. The amount of the catalyst used is usually 0.1 to 10 mol% with respect to 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 progress of the reaction will be slow, while if it is too high, the polymerization of the acryloyl group may become remarkable. Also, the distillation temperature of alcohol varies depending on the type of (meth) acrylic acid ester and azeotropic solvent used, but it cannot be generally stated. However, in consideration of suppressing polymerization of the allyloyl group, usually 30 to: L00 It is in the range of ° C.

[0053] Even at the reaction temperature described above, it is preferable to use a polymerization inhibitor and further introduce oxygen into the reaction system in order to prevent the polymerization of the allyloyl group.

[0054] Examples of the polymerization inhibitor include aromatic amines such as phenothiazine and p-phenylenediamine, phenol derivatives such as hydroquinone and p-methoxyphenol, nitroso compounds, and aromatic-toxic compounds. Two or more of these may be used in combination.

[0055] Oxygen is preferably introduced into the reaction system after being diluted with an inert gas so that the reaction system does not fall within the explosion range. The oxygen concentration is usually 0.1 to 10% by volume, preferably 1 to 5% by volume.

[0056] When the transesterification reaction is completed, water is usually 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. Further, when water is added to deactivate the catalyst, metals such as titanium and tin in the catalyst form an insoluble compound and precipitate, so it is preferable to filter and remove it prior to extraction. Next, the reaction mixture is extracted with an organic solvent to obtain an organic solvent phase containing 4HBA GE, which is an epoxy group-terminated (meth) acrylate. When this is distilled to distill the organic solvent, 4HBA GE ((meth) acrylate having a glycidyl group) is obtained as a product. In this distillation, it is preferable to use a polymerization inhibitor and molecular oxygen in combination. It should be noted that since unreacted (meth) acrylic acid lower alkyl ester remains in the reaction mixture of the transesterification reaction, it is preferably removed by simple distillation prior to extraction. This is because the unreacted (meth) acrylic acid lower alkyl ester can be distilled together when distilling off the organic solvent from the organic solvent phase obtained by extraction. This is because the solvent and the (meth) acrylic acid ester must be further separated, which is troublesome. [0057] (4HBAGE separation process)

Usually, unreacted (meth) acrylic acid ester is recovered by removing under reduced pressure from the reaction solution containing 4HBAGE produced above. The organic solvent phase containing 4 HBAGE is obtained by simple extraction of the remaining liquid after recovery with an organic solvent, and then distilled to distill the organic solvent, thereby reducing the contents of BDA and 14BDDGE. 4HBAGE can be obtained as a product. Further, the extraction described in the “14BDMGE separation step” can be performed in the “4HBAGE separation step”.

[0058] The 4HBAGE of the present invention obtained by the above method was used as a normal product when used for automotive coatings, home appliances, information technology-related substrates, and particularly for these top coats. Compared to cases, the physical properties of the final product obtained are significantly improved.

Example

[0059] Hereinafter, the present invention will be described in more detail than examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

[0060] Example 1:

About manufacture of 4HBAGE, it describes for every said process. The content of the main component and each impurity was measured by gas chromatography under the following conditions.

[0061] [Table 1]

GC Shimadzu GC— 1 7 0 0

Kabililary column J & W DB- 1 7 0 1 column

30 m X 0.25 mm I D

Temperature 5 0 ° C, hold for 4 minutes, then rise to 2 7 0 until 8 in 7 minutes Detector F ID 2 50 ° C

Internal standard (Noel alcohol) · · '1 6.0 minutes

1 4 BD 1 4.1 min

/ 1 4 BDMGE · · · 1 9. 4 minutes

U Anon 3 Λ

BDA 2 0.5 minutes

4HBAGE-----2 3.0 minutes

14 BDDGE · · ·-24.7 minutes

[0062] (14BDMGE synthesis reaction) A 3 L four-necked flask equipped with a distillation apparatus, thermometer, and stirrer was charged with 14BD: 370 g (4.1 1 mol) and epichlorohydrin: 1500 g (16.21 mol). While stirring and heating and depressurization, dropwise addition of a 48 wt% NaOH aqueous solution: 360 g (4.32 mol) was started. At the reaction liquid temperature of 65 ° C and the reaction pressure of 150 mmHg, azeotropy of water produced by the reaction and epichlorohydrin began. Azeotropic water and epichlorohydrin were cooled and separated into two phases. The epichlorohydrin in the lower phase was distilled off only water while returning to the system. After 5 hours, the dropwise addition of the aqueous NaOH solution was completed, and further, heating and decompression were continued for 30 minutes, and then the reaction was completed. In order to remove NaCl produced as a by-product, 810 g of water was added, stirred for 30 minutes, allowed to stand for 30 minutes, and the aqueous phase was taken out. Next, epichlorohydrin remaining in the reaction solution was recovered by a vacuum removal method. At this point, the crude 14BDMGE weight is 540g, and the composition is 1,4BDMGE content of the main component: 64.3% by weight, 14BD of the raw material: 2.2% by weight, 14BDGE of the by-product: 14. 1% by weight. The yield of 14BDMGE relative to 14BD charged was 58%, and the weight in terms of 100% purity was 347 g.

[0063] (14BDMGE separation step)

The above synthesis reaction was repeated 2 batches. A portion of the crude 14BDMGE obtained: 1000g (containing 4BDMGE643g), water: 1000g, toluene: 3000g was used, and liquid-liquid extraction (1 stage of extraction) was performed in a continuous extraction column. ), And by-product derived from epichlorohydrin was recovered together with 14BDDGE in the toluene phase, and 14BDMGE and 14BD were recovered in the aqueous phase.

[0064] Next, using 9300 g of toluene and the aqueous phase, liquid-liquid extraction (extraction second stage) was performed in a continuous extraction tower, 14BD was recovered in the aqueous phase, and 14BDMGE was recovered in the toluene phase. . And toluene was collect | recovered by the reduced pressure removal method from the toluene phase, and 14BDMGE liquid: 612g was obtained. The composition was 1,4BDMGE content of the main component: 98.5% by weight, impurities 14BD: not more than 0.1% by weight, and 14BDDGE: not more than 0.1% by weight. The 14BDMGE recovery rate after extraction and purification was 95.2% (93.8% in terms of purity).

[0065] (4HBAGE synthesis reaction)

In a 3 L four-necked flask equipped with a distillation apparatus, thermometer, and stirring apparatus, the above 1,4BDMG E solution: 600 g (4.0 mol), acrylic acid methyl ester: 516 g (6.0 mol), titanium tetra-n —Butoxide: 28 g, p-methoxyphenol: 0.24 g, toluene: 400 g, n-hexane: Charged 400g. The temperature was raised under stirring, and methanol Zn-hexane was azeotropically distilled at a reaction solution temperature of 73 to 90 ° C and a distillation temperature of 50 to 64 ° C. In the meantime, 400 g of n-hexane was continuously added. Thereafter, the reaction was carried out for 8 hours to complete the reaction.

[0066] (4HBAGE separation process)

Unreacted acrylic acid methyl ester was recovered from the reaction solution by a vacuum removal method. Then, water: 500 g and toluene: lOOOOg were added to the remaining liquid, stirred for 30 minutes and allowed to stand for 60 minutes, followed by liquid separation. 4HBAGE was recovered in the toluene layer, and unreacted 1,4BDMGE was recovered in the aqueous phase.

[0067] Next, after removing a trace amount of solids in the toluene phase by suction filtration using filter paper, toluene was recovered by a depressurizing removal method to obtain 4HBAGE as the target product. As a result, 695 g of 4HBAGE having a purity of 99.5% by weight was recovered. Impurity BDA was 0.1 wt% or less, and 14BDDGE was 0.1 wt% or less.

[0068] Comparative Example 1:

After 14BDMGE synthesis reaction in the same manner as in Example 1, NaCl · epichlorohydrin was removed to obtain a crude 14BDMGE solution. Next, crude 14BDMGE¾200 g (containing 14BDMGE 128.6 g) was distilled using a distillation apparatus equipped with a Witmer rectification tube. Under the conditions of a pressure of 2 mmHg, a tower top temperature of 105 ° C, and a bottom temperature of 155 ° C, 101 g of 14BDMGE solution was obtained. Composition: main component 1, 4BDMGE content: 94.8% by weight, impurities 14BD: 2.0% by weight, 14BDDGE: 2.2% by weight. The 14BDMGE recovery rate after distillation was 78.5% (74.5% in terms of purity).

Next, using 100 g of 14BDMGE obtained by distillation and performing 4 HBAGE synthesis reaction and methyl acrylate removal by the same method as in Example 1, water: 83 g, toluene: 166 g were added, and 30 After stirring for 60 minutes and allowing to stand for 60 minutes, liquid separation was performed, and 4HBAGE was recovered in the toluene layer. After removing trace solids in the toluene phase by suction filtration using filter paper, toluene was collected by vacuum removal to obtain the target product, 4HBAGE. As a result, 116 g of 4HBAGE having a purity of 94.9% was recovered. BDA (impurity) 2.4 weight ^_0/0, 14BDDGE was 1.9 wt%.

Claims

The content of the compound represented by the following general formula (2) or the compound represented by the following general formula (3) is 0.5% by weight or less, and is represented by the following general formula (1) Epoxy group terminal (meth) acrylate.

[Chemical 1]

0

II

CHn = C— C— 0— Y— 0— CH _? — CH— CH (1)

R ^υ

0 0

II II,

CH ₂ = C— C— 0— Y— 0— C— C = CH ₂ (2)

CH -CH-CH ₇ -0— Y— O— CH — CH— CH ₂ 3

ヽ O

[2] The epoxy group-terminated (meth) attaly according to claim 1, wherein the content of the compound represented by the general formula (2) and the compound represented by the general formula (3) is 0.5% by weight or less, respectively. rate.

[3] The epoxy group-terminated (meth) acrylate according to claim 1, obtained by purification by an extraction step.

[4] An epoxy group-terminated (meth) arylate represented by the general formula (1) obtained by reacting a compound having an taliloyl group with a compound having an epoxy group, and having the acryloyl group by an extraction step 2. The epoxy group-terminated (meth) acrylate according to claim 1, which is obtained by purifying a compound and Z or a compound having the epoxy group and then reacting them.

[5] The terminal end of the epoxy group according to claim 4, wherein the content of the compound represented by the general formula (2) after purification of the compound having an allyloyl group and the compound having Z or an epoxy group is 0.5% by weight or less. (Meta) Atarirate.

[6] The end of the epoxy group according to claim 4, wherein the content of the compound represented by the general formula (3) after purification of the compound having an allyloyl group and the compound having Z or an epoxy group is 0.5% by weight or less. (Meta) Atarirate.

[7] The epoxy group-terminated (meth) acrylate according to claim 1, wherein Y in the general formula (1) is an alkylene group having 4 carbon atoms.

[8] The epoxy group terminal according to any one of claims 1 to 7, which is used as a raw material for surface coating.

(Meta) Atarirate.

[9] A method for producing an alkanediol monoglycidyl ether represented by the general formula (4) obtained by reacting a dioli compound with epino and rhohydrin, comprising reacting a diol compound with an epihalohydrin. A method for producing an alkanediol monoglycidyl ether represented by the following formula (4), wherein after obtaining a crude alkanediol monoglycidyl ether, the crude alkanediol monoglycidyl ether is purified by extraction.

[Chemical 2]

10. The production method according to claim 9, wherein the extraction is continuous extraction.

11. The production method according to claim 9, wherein the extraction is performed in two stages.

12. The production method according to claim 11, wherein the extraction is performed in two steps of separating the alkanediol monoglycidyl ether and the alkanediol diglycidyl ether and then separating the alkanediol monoglycidyl ether and the diol compound.

[13] A method for producing an epoxy group-terminated (meth) acrylate having the general formula (1),

A method for reacting (meth) acrylic acid ester with alkanediol monoglycidyl ether represented by the general formula (4). As the above-mentioned alkanediol monoglycidyl ether, diol compound, epino, and rhohydrin are combined. An epoxy group terminal (meth) represented by the above general formula (1) is characterized by using an alkanediol monoglycidyl ether obtained by extracting the crude alkanediol monoglycidyl ether obtained by the reaction. A method for producing attalylate.

14. The production method according to claim 13, wherein the extraction is continuous extraction.

15. The production method according to claim 13, wherein the extraction is performed in two stages.

16. The production method according to claim 15, wherein the extraction is performed in two steps of separating the alkanediol monoglycidyl ether and the alkanediol diglycidyl ether and then separating the alkanediol monoglycidyl ether and the diol compound.

[17] A method for producing an epoxy group-terminated (meth) acrylate having the general formula (1),

It also has the ability to react the (meth) acrylic acid ester with the alkanediol monoglycidyl ester represented by the general formula (4), and at least in the presence of the following two types of solvents (A) and (B) The process for producing an epoxy group-terminated (meth) acrylate represented by the general formula (1), wherein