JP2010275307A - Method for producing epoxy-terminated (meth) acrylate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of producing an epoxy-terminated (meth)acrylate at a high yield by carrying out a transesterification reaction and, in addition, removing a metal alcoholate used as a transesterification catalyst by hydrolysis. <P>SOLUTION: The method of producing an epoxy-terminated (meth)acrylate represented by formula (1) includes subjecting a (meth)acrylate compound and a compound comprising a glycidyl group represented by formula (2) to a transesterification reaction in the presence of a metal alcoholate while removing the resulting alcohol and the solvent out of the reaction system by distillation [in formulae (1) and (2), Y represents a 2C-8C saturated hydrocarbon group; in formula (1), R represents a hydrogen atom or a methyl group; in formula (2), Z represents a hydrogen atom or a protective group for a hydroxy group, or a metal atom; and, if Z is a metal atom, n represents the number equal to the valence of the corresponding metal ion]. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing an epoxy group-terminated (meth) acrylate.

  4-glycidyloxybutyl acrylate (hereinafter abbreviated as “4HBAGE”) and epoxy group-terminated (meth) acrylates typified by glycidyl methacrylate are useful compounds as raw materials for improving paints and resins ( Patent Documents 1 and 2). Among them, 4HBAGE is a very useful compound because it does not lose its flexibility even after crosslinking and exhibits excellent properties as a coating film.

  By the way, as a general manufacturing method of the epoxy group terminal (meth) acrylate represented by the following general formula (1), (meth) acrylic acid lower alkyl ester and diol monoglycidyl ether in the presence of a transesterification catalyst. Is transesterified under normal pressure (Patent Document 3).

（上記一般式（１）中、Ｙは炭素数２〜８の飽和炭化水素基を、Ｒは水素原子またはメチル基を表す。）

(In the general formula (1), Y represents a saturated hydrocarbon group having 2 to 8 carbon atoms, and R represents a hydrogen atom or a methyl group.)

  Examples of the transesterification catalyst include metal alcoholates typically represented by titanium alcoholates and the like, and organic tin, alkali metal or alkaline earth metal weak acid salts (for example, carbonates, acetates, and phosphates). Are known.

  After completion of the transesterification reaction, the used catalyst is generally removed, and a highly purified epoxy group-terminated (meth) acrylate is obtained as a distillate by distillation purification. As a method for removing the metal alcoholate of the transesterification reaction catalyst, for example, a method is known in which water is added and stirred at room temperature to hydrolyze the catalyst, and then removed by liquid separation or filtration (Patent Document 4). .

  By the way, epoxy group terminal (meth) acrylate is easily polymerized by heating during distillation, etc., and when the hydrolysis and / or removal of the metal alcoholate of the transesterification reaction catalyst is insufficient, the metal alcoholate or the metal component derived therefrom Remains in the system and accelerates the polymerization of the terminal (meth) acrylate of the epoxy group.

  Therefore, a method of obtaining an epoxy group-terminated (meth) acrylate without performing recovery as a distillate by distillation purification is preferable. In the case where it is sufficient, an epoxy group-terminated (meth) acrylate that is practically usable in terms of quality cannot be obtained unless it is subjected to distillation purification.

Japanese Patent Publication No. 48-22169 Japanese Patent No. 3645037 Japanese Patent No. 3794029 JP 2005-247810 A

  The object of the present invention is to efficiently perform the transesterification reaction, and further reliably remove the metal alcoholate used as the transesterification catalyst by sufficiently hydrolyzing it, and if necessary, extractive washing, etc. It is possible to obtain the target epoxy group-terminated (meth) acrylate with a high yield and a purity that can be practically used without removing it as a distillate by distillation purification that may cause polymerization and loss. It is to provide a manufacturing method that can be used.

  That is, the gist of the present invention is that a compound having a glycidyl group represented by the following general formula (2) and (meta) while removing the generated alcohol and solvent out of the reaction system by distillation in the presence of a metal alcoholate. A method for producing an epoxy group-terminated (meth) acrylate represented by the following general formula (1) by transesterification with an acrylate compound, wherein after obtaining an epoxy group-terminated (meth) acrylate, water is added. The epoxy group-terminated (meth) acrylate containing at least one of a solvent, a residual raw material, a residual alcohol, and a residual moisture after adding and heating to 30 ° C. or higher and then removing the hydrolyzate derived from the metal alcoholate The present invention resides in a method for producing an epoxy group-terminated (meth) acrylate, wherein a component having a lower boiling point is distilled off.

（上記一般式（１）及び（２）中、Ｙは炭素数２〜８の飽和炭化水素基を表す。上記一般式（１）中、Ｒは水素原子またはメチル基を表す。上記一般式（２）中、Ｚは、水素原子、水酸基の保護基または金属原子を表し、ｎは、Ｚが金属原子である場合の、対応する金属イオンの価数に等しい数を表す。）

(In the general formulas (1) and (2), Y represents a saturated hydrocarbon group having 2 to 8 carbon atoms. In the general formula (1), R represents a hydrogen atom or a methyl group. In 2), Z represents a hydrogen atom, a hydroxyl-protecting group or a metal atom, and n represents a number equal to the valence of the corresponding metal ion when Z is a metal atom.)

  According to the present invention, the target epoxy group-terminated (meth) acrylate can be obtained in a high yield and with a purity that can be practically used without performing distillation that may cause polymerization and loss.

  Hereinafter, the present invention will be described in detail.

  In the method for producing an epoxy group-terminated (meth) acrylate of the present invention, first, in the presence of a metal alcoholate, a compound having a glycidyl group represented by the general formula (2) (hereinafter simply referred to as “compound having a glycidyl group”) Transesterification reaction between (abbreviated) and (meth) acrylate compound is carried out.

  From the viewpoint of appropriately proceeding the transesterification reaction, the molar ratio of the total amount of water in the reaction system is usually 5 times or less, preferably 3 times or less, more preferably 1.5 times or less as a ratio to the metal alcoholate. .

  As a method for reducing the water content in the reaction system, for example, a raw material (meth) acrylate compound or an excessive amount of the solvent in the case of using a solvent in the transesterification reaction is used, and distillation is performed before adding the metal alcoholate. By doing so, a method of previously removing moisture in the reaction system out of the system can be mentioned. Moreover, the method etc. which reduce the total amount of water | moisture content by a process with a dehydrating agent are also mentioned. Usually, a Karl Fischer moisture meter is used to measure moisture.

  The compound having a glycidyl group used as a raw material can be obtained by a known production method, for example, the production method described in Patent Document 3 above. In general, an alkali compound is used, and a hydroxyl group of an alcohol corresponding to the structure of a target compound having a glycidyl group and an epihalohydrin are directly dehalogenated and added. The epoxy group-terminated (meth) acrylate obtained by the production method of the present invention has excellent flexibility, but the presence of the intermediate group Y in the general formula (2) is a main factor that imparts excellent flexibility. It is guessed. The terminal group Z of the compound having a glycidyl group represented by the general formula (2) is particularly preferably a hydrogen atom, but generally used if an epoxy group terminal (meth) acrylate is obtained by reaction. It may be a structure substituted with a protecting group for a hydroxyl group. Alternatively, the terminal group Z may be a metal atom, that is, a metal alkoxide. In this case, a number of alkoxide residues equal to the valence n of the metal ion corresponding to the metal atom are bonded to the metal atom.

  In the general formula (2), Y of the intermediate group may be a saturated hydrocarbon group having 2 to 8 carbon atoms, and a part or all of the intermediate group has an alicyclic structure represented by, for example, a cyclohexane ring. You may have. Specific examples of the compound having a glycidyl group include ethylene glycol monoglycidyl ether, 1,3-propanediol monoglycidyl ether, 1,4-butanediol mono, as represented by a compound name having a structure in which the terminal group Z is a hydrogen atom. Diol monoglycidyl ethers such as glycidyl ether, 1,6-hexanediol monoglycidyl ether, 1,8-octanediol monoglycidyl ether, 1,4-cyclohexanedimethanol monoglycidyl ether, 1,4-cyclohexanediol monoglycidyl ether Is mentioned. In the general formula (2), specific examples of the terminal group Z being a hydroxyl protecting group include a vinyl group, a methoxymethyl group, a 2-methoxyethoxymethyl group, a benzyloxymethyl group, a methylthiomethyl group, A methyl group, an ethyl group, etc. are mentioned. Further, in the general formula (2), when the terminal group Z is a metal atom, specific examples of the metal species include alkali metal and alkaline earth such as lithium, sodium, potassium, magnesium, calcium, aluminum, and titanium. Or a metal capable of constituting a metal alcoholate of a transesterification catalyst.

The (meth) acrylate compound used as a raw material is not particularly limited, and general (meth) acrylic acid ester compounds can be widely used. For example, an alcohol generated from the (meth) acrylate compound to be used is, for example, It is preferable to remove out of the reaction system by a method such as distillation, extraction or insolubilization to bias the equilibrium. In this case, when removing the alcohol produced by distillation out of the reaction system, (meth) acrylate is used in order to keep the loss due to distillation of the compound having a glycidyl group used as a raw material out of the reaction system. It is preferable to use a (meth) acrylate compound selected from the group of compounds in which the boiling point of the alcohol produced from the compound by the transesterification reaction is lower than the boiling point of the compound having a glycidyl group used in the transesterification reaction. In addition, when the equilibrium can be biased by insolubilization of the generated alcohol, a (meth) acrylate compound composed of a higher boiling alcohol may be used without being limited by the boiling point of the generated alcohol. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, and i-butyl. (Meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (Meth) acrylate, glycidyl (meth) acrylate, etc. are mentioned. In particular, from the viewpoint of production efficiency, it is preferable to produce an alcohol having a low boiling point, and therefore methyl (meth) acrylate produced from methanol is more preferred. Although the reaction efficiency is lowered due to the competitive reaction of the hydroxyl group, a hydroxyl group-containing (meth) acrylate compound or a di (meth) acrylate compound can also be used by biasing the equilibrium of the reaction system. Specific examples of hydroxyl group-containing (meth) acrylate compounds and di (meth) acrylate compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and ethylene glycol. Examples include di (meth) acrylate and 1,4-butanediol di (meth) acrylate.

  The use ratio of the (meth) acrylate compound is usually 1 to 10 times mol, preferably 1.1 to 5 times mol, of the compound having a glycidyl group to be used. Since the transesterification reaction is an equimolar reaction between the (meth) acrylate compound and the compound having a glycidyl group, when the use ratio of the (meth) acrylate compound is less than the above range, the transesterification reaction is not completed, Yield may be reduced. Moreover, when the usage-amount of a (meth) acrylate compound exceeds said range, there is no effect by it and it is not practical. In addition, regarding a di (meth) acrylate compound, it considers as 2 times mole per molecule.

  Examples of the metal alcoholate of the transesterification reaction catalyst include titanium alcoholate, zirconium alcoholate, aluminum alcoholate, and antimony alcoholate. The alcohol constituting the metal alcoholate is not particularly limited. Examples of such alcohol include methanol, ethanol, n-propanol, i-propanol, n-butanol, t-butanol, n-octanol, 2-ethylhexanol, stearyl alcohol, cyclohexanol, phenol, benzyl alcohol and the like. Alcohol. Among the metal alcoholates, titanium alcoholates such as titanium tetramethoxide, titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetra-n-butoxide (hereinafter abbreviated as “TBT”) are preferable, and TBT is particularly preferable. .

  The ratio of the metal alcoholate used is usually 0.001 to 0.1 times mol, preferably 0.005 to 0.05 times mol, of the compound having a glycidyl group. When the proportion of metal alcoholate used is less than the above range, the transesterification reaction progresses slowly or the reaction is not completed, and when it exceeds the above range, no improvement effect on the amount of use can be expected. Operation such as removal may be difficult.

  In the transesterification reaction, it is preferable to use a polymerization inhibitor for the purpose of preventing polymerization of the (meth) acryloyl group. As the polymerization inhibitor, aromatic amines such as phenothiazine and p-phenylenediamine; 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and 4-hydroxy-2,2,6,6 -N-oxylamine such as tetramethyl-1-piperidinyloxy (HTEMPO); phenol derivatives such as hydroquinone and p-methoxyphenol (hereinafter abbreviated as "MEHQ"); nitroso compounds; aromatic nitroso compounds; dibutyldithiocarbamine Examples thereof include copper-based compounds such as acid copper (hereinafter abbreviated as “CBC”), alkyl-substituted copper dithiocarbamates such as copper dimethyldithiocarbamate, or copper acetate; and lead-based compounds such as lead stearate. Two or more of these polymerization inhibitors may be used in combination. Depending on the type of the polymerization inhibitor, there are some which can obtain a higher polymerization prevention effect by introducing oxygen into the reaction system. In this case, it is preferable to introduce oxygen gas diluted with an inert gas into the reaction system so that the reaction system does not enter the explosion range, and it is preferable to introduce the oxygen gas by blowing it into the reaction solution. More preferred.

  The usage-amount of a polymerization inhibitor is 0.01-1 weight part normally with respect to 100 weight part of compounds which have a glycidyl group, Preferably it is 0.1-0.3 weight part.

  Since the transesterification reaction is an equilibrium reaction, in order to carry out the transesterification reaction in a high yield, the alcohol produced from the (meth) acrylate compound to be used is reacted with a reaction system by a method such as distillation, extraction or insolubilization. It is preferable to remove the balance and bias the balance. The method for removing the produced alcohol out of the reaction system is not particularly limited, but in general, removal by distillation is preferable because of the simplicity of the method, and the (meth) acrylate compound and various solvents used as a raw material are produced. More preferably, it is removed from the reaction system using azeotropy with the alcohol. The solvent to be used is preferably one that azeotropes with the generated alcohol, and more preferably has a lower azeotropic temperature than the azeotropic temperature of the (meth) acrylate compound and the generated alcohol. These solvents are preferably those that do not react with the raw material (meth) acrylate compound or the compound having a glycidyl group. Examples of such solvents include aliphatic hydrocarbon solvents such as n-hexane, n-heptane, n-octane, n-decane, and cyclohexane; aromatics such as toluene, xylene, cumene, cymene, cymene, pyridine, and lutidine. Solvents; ether solvents such as tetrahydrofuran, dioxane, dibutyl ether, cyclopentyl methyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like. Moreover, the raw material (meth) acrylate compound can be used excessively and used as a solvent. In addition, it can also react on the conditions on which the solvent and produced | generated alcohol do not azeotrope. Among these, a combination of methyl (meth) acrylate and n-hexane (azeotropic system of methanol and n-hexane) is preferable.

  The ratio of the solvent used varies depending on the type of alcohol produced and the ratio of the azeotropic composition when azeotroped with the solvent. The amount of the solvent that can be removed by azeotropic distillation based on the theoretical calculation amount when the reaction rate is 100% is required, and the weight ratio to the theoretical calculation amount is usually 1 to 10 times, preferably 1.1 times to 5 times. If the proportion of the solvent used is less than the above range, the resulting alcohol may not be sufficiently removed, and the reaction may not be completed. If it exceeds the above range, there is no effect and it is not practical.

  In addition, when removal of the generated alcohol becomes insufficient due to lack of azeotropic solvent, it is possible to add the solvent later, but the total amount of water contained in the additional solvent is reduced. Care must be taken because it needs to be considered. Alternatively, it is possible to sequentially add the required amount of solvent into the reaction system until the reaction is completed during the transesterification reaction, but this is included in the cumulative amount of solvent that is sequentially introduced into the reaction system. Care must be taken because it is necessary to take into account all the moisture contained.

  The solvent can also be used as a reaction solvent. By using the reaction solvent, the temperature and concentration of the reaction solution can be controlled, and polymerization and side reactions in the liquid phase can be suppressed. In particular, in the case of a water-insoluble reaction solvent, it is possible to expect effects such as promoting separation and acting as an extraction solvent when the organic layer and the aqueous layer are separated by post-treatment. When a large amount of an azeotropic solvent having a low boiling point is used, the temperature of the reaction system tends to decrease. Therefore, it is more preferable to use a combination of a plurality of azeotropic solvents and reaction solvents having higher boiling points. When combining an azeotropic solvent and a high-boiling reaction solvent, in consideration of the total amount of water in advance, an amount of azeotropic solvent that does not decrease the reaction temperature while maintaining azeotropy is sequentially introduced into the reaction system. The method is further preferred. As a combination of an azeotropic solvent and a reaction solvent, for example, a method of using toluene as a reaction solvent with respect to a combination of methyl (meth) acrylate and n-hexane (azeotropic system of methanol and n-hexane) can be mentioned. It is done.

  When a reaction solvent is used, a solvent as a reaction solvent component is required separately from the amount of solvent required for azeotropy, but the amount is usually as a volume ratio to the compound having a glycidyl group to be used. 0.5 to 20 times, preferably 1 to 5 times. When the proportion of the reaction solvent used is less than the above range, the effect as a reaction solvent cannot be expected so much, and when it is more than the above range, there is not only the effect but also the reaction rate decreases due to dilution. And there is a risk that control of moisture will be difficult due to the decrease in concentration relative to the total amount of moisture.

  The reaction temperature during the transesterification reaction is usually 50 to 130 ° C., preferably 60 to 120 ° C., although depending on the (meth) acrylate compound and the solvent used, and the reaction time is usually 1 to 24 hours. Preferably it is 3 to 12 hours. When the reaction temperature is low, the progress of the transesterification reaction is slow. Conversely, when the reaction temperature is too high, the risk of polymerization of the (meth) acryloyl group may be increased. In the transesterification reaction, the reaction time can be shortened by removing the generated alcohol as quickly as possible while maintaining the azeotropic temperature (azeotropic composition). In a reaction system in which a high-boiling alcohol is generated, a high temperature is required to remove the generated alcohol out of the reaction system, but the risk of polymerization of (meth) acryloyl groups increases as the reaction temperature increases. Therefore, the reaction can be carried out under reduced pressure and the reaction temperature can be lowered so as to be within the above reaction temperature range. Therefore, the pressure during the transesterification reaction is controlled to a desired reaction temperature according to the type of (meth) acrylate compound and solvent to be used, and any of normal pressure, reduced pressure, and pressurized pressure is selected. May be.

  After completion of the transesterification reaction, water is added to the reaction solution to deactivate the catalyst, and the insolubilized catalyst is removed by a method such as filtration. If the deactivation of the metal alcoholate is insufficient, the metal component derived from the catalyst that has not been filtered may remain or may cause problems such as clogging during filtration and a decrease in filterability. . When the metal component derived from the catalyst remains, there is a high risk of causing a polymerization or disproportionation reaction of the (meth) acryloyl group during heating in the subsequent steps.

  The amount of water added is usually 10 to 200 parts by weight, preferably 20 to 50 parts by weight, based on 1 part by weight of the catalyst used, although it depends on the molecular weight and amount of catalyst used. When the proportion of water used is less than the above range, the catalyst may be insufficiently hydrolyzed, or the separability when separating the organic layer and the aqueous layer may be deteriorated. Moreover, when there is more usage-amount of water than said range, there is no effect by it, and when the organic layer and an aqueous layer are isolate | separated on the contrary, the loss to the aqueous layer of an epoxy-group terminal (meth) acrylate increases. In addition, when removing the catalyst insolubilized by filtration, it is preferable to use filter aids, such as diatomaceous earth, for the purpose of improving filterability or preventing the mixture of the catalyst insolubilized due to leakage or the like.

  Since metal alcoholates easily react with water, usually adding a large excess of water causes hydrolysis, but it is preferable to deactivate the catalyst sufficiently for the above reasons, and water was added for this purpose. It is preferable to hydrolyze the reaction liquid later by heating. The hydrolysis conditions depend on the amount of the catalyst, but are 30 ° C. or higher, preferably 40 to 100 ° C., more preferably 50 to 80 ° C., and the hydrolysis time is usually 5 minutes to 24 hours, preferably 10 Minutes to 12 hours, more preferably 15 minutes to 6 hours. When the hydrolysis temperature is low or when the hydrolysis time is too short, there is a risk that the deactivation of the catalyst may be insufficient, and it takes a long time to sufficiently deactivate the catalyst at a low temperature. Conversely, when the hydrolysis temperature is too high, the epoxy group terminal (meth) acrylate itself may be hydrolyzed to reduce the yield, but the time required for hydrolysis of the catalyst is shortened.

  After completion of hydrolysis, an organic layer containing an epoxy group-terminated (meth) acrylate and an aqueous layer are separated. In practice, it is often difficult to separate the organic layer and the aqueous layer in a state where the catalyst is insolubilized and dispersed. Therefore, it is preferable to separate the organic layer and the aqueous layer after removing the insolubilized catalyst by filtration or the like. At this time, a water-insoluble solvent may be used to promote separation of the organic layer and the aqueous layer. The solvent used may be the same as or different from the solvent used in the transesterification reaction, but in general, an aromatic solvent such as toluene or xylene is preferred. These solvents can be used in advance from the stage of transesterification.

  When a solvent is used to promote separation of the organic layer and the aqueous layer, the use ratio is usually 0.1 to 10 times, preferably 0, as a volume ratio with respect to the organic layer containing an epoxy group-terminated (meth) acrylate. .2-5 times. Further, if necessary, the organic layer containing the separated epoxy group-terminated (meth) acrylate may be further subjected to extraction washing treatment by adding water. By adding this extraction and washing step, it is possible to substantially completely remove a hydrophilic compound such as an alcohol generated by a raw material or a reaction remaining in the organic layer.

  Concentrate the organic layer containing the above epoxy group-terminated (meth) acrylate, and remove by distillation the components having a lower boiling point than the epoxy group-terminated (meth) acrylate, such as solvent, residual raw material, residual alcohol, and residual moisture. Thus, an epoxy group-terminated (meth) acrylate crude product can be obtained as a distillation residue. Although it depends on the purity of the compound having a glycidyl group as a raw material, when the water is appropriately managed in the transesterification reaction and the reaction is performed in a high yield, the resulting epoxy group-terminated (meth) acrylate crude product The purity is usually 95% or more, and it can be used as a raw material for various applications as the target epoxy group-terminated (meth) acrylate. In addition, when further high-purity epoxy group-terminated (meth) acrylate is required or when a residue having a high boiling point is contained, it is purified to the desired purity by extraction washing by a generally performed method. You can also The concentration conditions depend on the type of solvent, but from the viewpoint of preventing polymerization of the (meth) acryloyl group, concentration under reduced pressure is performed at a temperature lower than the temperature during the transesterification reaction in the presence of a polymerization inhibitor. Is preferred.

  The polymerization inhibitor used at the time of concentration can be selected from a group of polymerization inhibitors that can be used during the transesterification reaction, and may be the same as or different from the polymerization inhibitor used during the transesterification reaction. A sufficient amount and type of polymerization inhibitor can be added in advance to prevent polymerization of the (meth) acryloyl group at the time of concentration at a time prior to concentration, such as transesterification. Moreover, you may use a polymerization inhibitor in combination of 2 or more types. Depending on the type of the polymerization inhibitor, there may be obtained a higher polymerization prevention effect by introducing oxygen into the concentrated distillation system. In this case, it is preferable to introduce oxygen gas diluted with an inert gas into the reaction system so that the concentrated distillation system does not enter the explosion range, and it is introduced by blowing it into the concentrated liquid. Is more preferable.

  When using a polymerization inhibitor, the use ratio is usually 0.01 to 5 parts by weight, preferably 0.1 to 1 part per 100 parts by weight of the epoxy group-terminated (meth) acrylate contained in the organic layer to be concentrated. Parts by weight.

  By the above method, the content of the metal component derived from the metal alcoholate is usually 5 ppm or less without performing recovery as a distillate by distillation purification that may cause polymerization and loss, and the end of the epoxy group having a purity that can withstand practical use ( (Meth) acrylate can be obtained in high yield.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded.

Example 1:
In a 500 ml four-necked flask equipped with a distillation apparatus, thermometer, and stirring apparatus, 100.0 g of 1,4-butanediol monoglycidyl ether (purity: 98.3%, 0.67 mol in terms of purity), methyl acrylate 87 .6 g, toluene 70.3 g, n-hexane 128.4 g, and MEHQ 0.03 g were added to prepare a raw material mixture (total 386.3 g). It was 840 ppm when the water | moisture content of this raw material liquid mixture was measured with the Karl Fischer moisture meter. Therefore, the total amount of moisture contained in this raw material mixture is 0.32 g (0.018 mol).

  When TBT 4.6g (0.014mol) was added to said raw material liquid mixture and it heated and heated under normal pressure and stirring, the azeotropic reflux of methanol / n-hexane began immediately from the reaction liquid temperature vicinity of 72 degreeC. . The gas temperature was 50-52 ° C. While maintaining this azeotropic temperature (azeotropic composition), an azeotropic liquid of methanol / n-hexane was extracted. In addition, since the amount of methanol produced decreased from the time when the reaction was almost finished and the azeotropic temperature (azeotropic composition) was difficult to maintain, the gas temperature rose to 64 ° C., but the extraction was continued as it was. . Finally, 128.8 g of a methanol / n-hexane mixed fraction was withdrawn in 8 hours, the reaction was terminated at a reaction liquid temperature of 92 ° C., and the reaction liquid was cooled to 258. 4HBAGE (49.4 wt%). 5 g was obtained. The quantitative yield of 4HBAGE is 94.8%. The molar ratio of the total amount of water in this reaction system is 1.3 times the TBT used.

  135.7 g of water was added to the above reaction solution, heated to 60 ° C. under normal pressure and stirring, and then subjected to heat hydrolysis at 60 ° C. for 30 minutes. The reaction solution was cooled and suction filtered using a filter covered with celite to remove insoluble catalyst. The filtrate was separated into an organic layer and an aqueous layer to obtain 255.5 g of an organic layer containing 4HBAGE (47.6% by weight). The quantitative yield of 4HBAGE is 90.4%.

  The organic layer containing 4HBAGE was concentrated under reduced pressure using a rotary evaporator to obtain 123.6 g of a 4HBAGE crude product (purity 97.7%). The quantitative conversion yield of 4HBAGE in terms of purity is 90.1%. This 4HBAGE crude product was a transparent liquid with almost no coloration, and the TBT-derived titanium content used as a catalyst was below the detection limit (2 ppm). This 4HBAGE crude product is of a quality that can be sufficiently used as a raw material for various uses.

Comparative Example 1:
Reaction similar to Example 1 was performed and the same reaction result was obtained. Thereafter, 135.7 g of water was added to the reaction solution, and hydrolysis was performed at room temperature (20 ° C.) for 30 minutes with stirring. The reaction solution was subjected to suction filtration using a filter covered with celite to remove insoluble catalyst. The filtrate was separated into an organic layer and an aqueous layer to obtain 251.9 g of an organic layer containing 4HBAGE (47.0% by weight). The quantitative yield of 4HBAGE is 88.5%.

  The organic layer containing 4HBAGE was concentrated under reduced pressure using a rotary evaporator to obtain 121.0 g of a 4HBAGE crude product (purity 97.2%). The quantitative conversion yield of 4HBAGE in terms of purity is 87.8%. The recovered 4HBAGE contained 70 ppm of TBT-derived titanium used as a catalyst. When such a titanium-rich 4HBAGE is used, it is expected that a coating film having a problem in weather resistance is generated, and storage stability is also adversely affected.

Example 2:
1,4-butanediol monoglycidyl ether (hereinafter abbreviated as “14BDMGE”) 100.0 g (purity: 93.7%, converted to purity) in a 500 ml four-necked flask equipped with a distillation apparatus, thermometer, and stirring apparatus 0.64 mol), 125.1 g (0.96 mol) of 2-methoxyethyl acrylate, 200.0 g of o-xylene, and 0.03 g of MEHQ were added to prepare a raw material mixed solution (total 425.1 g). When the water content of this raw material mixture was measured with a Karl Fischer moisture meter, it was 503 ppm, and the total amount of water contained was 0.21 g (0.012 mol).

  4.4 g (0.013 mol) of TBT was added to the above raw material mixture, and the temperature was raised with stirring while reducing the pressure to 100 hPa, while o-xylene and 2-methoxyethanol produced were distilled out of the reaction system. The transesterification was performed at a reaction solution temperature of 80 ° C to 90 ° C. The temperature of the distillate gas was 57-74 ° C. Finally, 169.9 g of a fraction was withdrawn in 6 hours to complete the reaction, and 255.2 g of a reaction solution containing 4HBAGE (46.3% by weight) was obtained. The quantitative conversion yield of 4HBAGE in terms of purity is 92.0%, and the molar ratio of the total amount of water in this reaction system is 0.9 times the TBT used.

  140.0 g of water was added to the reaction solution, heated to 60 ° C. under normal pressure and stirring, and subjected to heat hydrolysis at 60 ° C. for 1 hour. The reaction solution was cooled and suction filtered using a filter covered with celite to remove insoluble catalyst. The filtrate was separated into an organic layer and an aqueous layer. The organic layer containing 4HBAGE was concentrated under reduced pressure using a rotary evaporator to obtain 130.8 g of a 4HBAGE crude product (purity 94.0%). The purity conversion quantitative yield of 4HBAGE was 95.8%, and the TBT-derived titanium content used as a catalyst was 2 ppm or less. The purity of the raw 14BDMGE was originally slightly lower (93.7%), so that the purity of the obtained 4HBAGE crude product was 94.0%. It can also be purified to purity. Alternatively, as in Example 1, higher-purity 14BDMGE can be used as a raw material from the beginning.

Example 3:
In a 500 ml four-necked flask equipped with a distillation apparatus, thermometer, and stirrer, 14BDDMGE 100.0 g (purity: 93.7%, 0.64 mol in terms of purity), tetrahydrofurfuryl acrylate 150.1 g (0.96 mol) P-cymene 200.0 g and MEHQ 0.03 g were added to adjust the raw material mixture (total 450.1 g). When the water content of this raw material mixture was measured with a Karl Fischer moisture meter, it was 547 ppm, and the total amount of water contained was 0.25 g (0.014 mol).

  4.4 g (0.013 mol) of TBT was added to the above raw material mixture, and the temperature was raised while stirring while reducing the pressure to 40 hPa, while p-cymene and the resulting tetrahydrofurfuryl alcohol were being distilled out of the reaction system. The transesterification was carried out at a reaction solution temperature of 89 ° C. to 102 ° C. The temperature of the distillate gas was 69-78 ° C. Finally, 196.6 g of a fraction was withdrawn in 11 hours to complete the reaction, and 252.2 g of a reaction solution containing 4HBAGE (43.2% by weight) was obtained. The quantitative conversion yield of 4HBAGE in terms of purity is 84.9%, and the molar ratio of the total amount of moisture in this reaction system is 1.1 times the TBT used.

  140.0 g of water and 100.0 g of additional p-cymene were added to the reaction solution, heated to 60 ° C. under normal pressure and stirring, and subjected to heat hydrolysis at 60 ° C. for 1 hour. The reaction solution was cooled and suction filtered using a filter covered with celite to remove insoluble catalyst. The filtrate was separated into an organic layer and an aqueous layer. The organic layer containing 4HBAGE was concentrated under reduced pressure using a rotary evaporator to obtain 124.0 g of a 4HBAGE crude product (purity 88.2%). The purity conversion quantitative yield of 4HBAGE was 85.2%, and the content of titanium derived from TBT used as a catalyst was 2 ppm or less. The purity of the raw 14BDMGE was originally slightly low (93.7%), and a relatively small amount remained because the boiling point of the raw tetrahydrofurfuryl acrylate was relatively high. The purity of the resulting 4HBAGE crude product was 88 Although it was 2%, it can be further purified to a desired purity by extraction washing if necessary. Alternatively, as in Example 1, higher-purity 14BDMGE can be used as a raw material from the beginning.

Example 4:
In a 500 ml four-necked flask equipped with a distillation apparatus, thermometer and stirring apparatus, 10BD g of 14BDDMGE (purity: 93.7%, 0.64 mol in terms of purity), 109.7 g (0.96 mol) of ethyl methacrylate, cyclopentyl 200.0 g of methyl ether (hereinafter abbreviated as “CPME”) and 0.03 g of MEHQ were added to prepare a raw material mixture (total of 409.7 g). When the water content of this raw material mixture was measured with a Karl Fischer moisture meter, it was 1372 ppm, and the total amount of water contained was 0.56 g (0.031 mol).

  TBT 6.5 g (0.019 mol) was added to the above raw material mixture, and the temperature was raised with stirring while reducing the pressure to 400 hPa. The transesterification reaction was carried out for 6 hours while distilling CPME and the ethanol produced out of the reaction system. However, the reaction progressed slightly slower, so an additional 4.4 g (0.013 mol) of TBT and 150.0 g of additional CPME (moisture was 56 ppm, and the increase in water was 0.01 g). Was added, followed by a transesterification reaction for 5 hours. The temperature of the reaction solution was 84 ° C to 95 ° C, and the temperature of the distillate gas was 57 to 77 ° C. Finally, 223.3 g of a fraction was withdrawn in 11 hours to complete the reaction, and 342.2 g of a reaction solution containing 4-hydroxybutyl methacrylate glycidyl ether (hereinafter abbreviated as “4HBMAGE”) (28.0 wt%). Got. The purity conversion quantitative yield of 4HBMAGE is 69.8%. The molar ratio of the total amount of water in this reaction system was 1.6 times the TBT used at the beginning of the transesterification reaction, but since TBT and CPME were added during the transesterification reaction, the final water content was The total amount of TBT was 0.57 g (0.032 mol), and the total amount of TBT finally used was 10.9 g (0.032 mol), and finally 1.0 times the TBT used.

  Water 220.0g was added to said reaction liquid, and it heated and heated to 60 degreeC under normal pressure and stirring, and heat-hydrolyzed as it was at 60 degreeC for 1 hour. The reaction solution was cooled and suction filtered using a filter covered with celite to remove insoluble catalyst. The filtrate was separated into an organic layer and an aqueous layer. The organic layer containing 4HBMAGE was concentrated under reduced pressure using a rotary evaporator to obtain 110.3 g of a 4HBMAGE crude product (purity 91.8%). The purity conversion quantitative yield of 4HBMAGE was 73.7%, and the content of titanium derived from TBT used as a catalyst was 2 ppm or less. The purity of the raw 14BDMGE was originally slightly lower (93.7%), so that the purity of the obtained 4HBAGE crude product was 91.8%. It can also be purified to purity. Alternatively, as in Example 1, higher-purity 14BDMGE can be used as a raw material from the beginning.

Example 5:
In a 500 ml four-necked flask equipped with a distillation apparatus, thermometer and stirring apparatus, 10BD g of 14BDDMGE (purity: 93.7%, 0.64 mol in terms of purity), 77.0 g (0.77 mol) of methyl methacrylate, methyl ethyl ketone 100.0 g, 100.0 g of toluene, and 0.03 g of MEHQ were added to prepare a raw material mixture (total 377.0 g). When the water content of this raw material mixture was measured with a Karl Fischer moisture meter, it was 453 ppm, and the total amount of water contained was 0.17 g (0.009 mol).

  TBT 2.2g (0.006mol) was added to said raw material liquid mixture, and it heated and heated under normal pressure and stirring, and while distilling methyl ethyl ketone and the produced | generated methanol out of a reaction system, reaction liquid temperature 98 degreeC- The transesterification was carried out at 111 ° C. for 5 hours. The temperature of the distillate gas was 74 to 81 ° C. 14BDMGE as a raw material still remains in this reaction solution (GC analysis of the reaction solution revealed that the area ratio of 14BDMGE was 24.7% when the total area value of 14BDMGE and 4HBMAGAGE was 100%. However, in this example, the reaction was terminated at this point in order to more clearly demonstrate the effect of the extraction washing in the latter stage. Finally, 96.5 g of a fraction was withdrawn in 5 hours to complete the reaction, and 278.8 g of a reaction solution containing 4HBMAGE (29.2% by weight) was obtained. The purity conversion quantitative yield of 4HBMAGE is 59.2%, and the molar ratio of the total amount of water in this reaction system is 1.5 times the TBT used.

  140.0 g of water was added to the reaction solution, heated to 60 ° C. under normal pressure and stirring, and subjected to heat hydrolysis at 60 ° C. for 1 hour. The reaction solution was cooled and suction filtered using a filter covered with celite to remove insoluble catalyst. The filtrate was separated into an organic layer and an aqueous layer. When the organic layer containing 4HBMAGE was subjected to GC analysis, the area ratio of 14BDMGE was 5.4% when the total area value of 14BDMGE and 4HBMAGE was 100%. If this is the case, the purity of the target 4HBMAGE will decrease, so 100.0 g of water was added to the organic layer containing 4HBMAGE and washed to separate it into an organic layer and an aqueous layer. When the washed organic layer containing 4HBMAGE was subjected to GC analysis again, the area ratio of 14BDMGE was reduced to 1.2% when the total area value of 14BDMGE and 4HBMAGE was 100%. The washed organic layer containing 4HBMAGE was concentrated under reduced pressure using a rotary evaporator to obtain 93.0 g of a 4HBMAGE crude product (purity 92.4%). The purity conversion quantitative yield of 4HBMAGE was 62.6%, and the content of titanium derived from TBT used as a catalyst was 2 ppm or less. The 14BDMGE content in this 4HBMAGE crude product was 1.3%. The purity of the raw 14BDMGE was originally slightly lower (93.7%), so that the purity of the obtained 4HBAGE crude product was 92.4%. It can also be purified to purity. Alternatively, as in Example 1, higher-purity 14BDMGE can be used as a raw material from the beginning.

  Incidentally, the results of a storage stability test for 1 year at room temperature for each 4HBAGE obtained in Example 1 and Comparative Example 1 were as follows. That is, the purity (97.7%) of 4HBAGE in Example 1 was 97.7% without any change, whereas the purity (97.2%) of 4HBAGE in Comparative Example 1 was 94.6%. Declined.

  The boiling points of the raw materials used in Examples 1 to 5 and Comparative Example 1 are as shown in Table 1 below.

Claims (6)

In the presence of a metal alcoholate, the compound having a glycidyl group represented by the following general formula (2) and a (meth) acrylate compound are transesterified while removing the generated alcohol and solvent out of the reaction system by distillation. By this, it is the method of manufacturing the epoxy group terminal (meth) acrylate represented by following General formula (1), Comprising: After obtaining an epoxy group terminal (meth) acrylate, water is added and it heats to 30 degreeC or more Then, after removing the hydrolyzate derived from the metal alcoholate, a component having a boiling point lower than that of the epoxy group-terminated (meth) acrylate containing at least one of the solvent, the remaining raw material, the remaining alcohol, and the remaining water is retained. A method for producing an epoxy group-terminated (meth) acrylate, characterized by comprising leaving.
.

(In the general formulas (1) and (2), Y represents a saturated hydrocarbon group having 2 to 8 carbon atoms. In the general formula (1), R represents a hydrogen atom or a methyl group. In 2), Z represents a hydrogen atom, a hydroxyl-protecting group or a metal atom, and n represents a number equal to the valence of the corresponding metal ion when Z is a metal atom.)   The process according to claim 1, wherein the metal alcoholate is a titanium alcoholate.   The method according to claim 1 or 2, wherein the aqueous layer is separated after adding water and heated, and the organic layer containing an epoxy group-terminated (meth) acrylate is extracted and washed.   Claims using a (meth) acrylate compound selected from the group of compounds in which the boiling point of an alcohol produced from a (meth) acrylate compound is lower than the boiling point of a compound having a glycidyl group used in the transesterification reaction Item 4. The production method according to any one of Items 1 to 3.   The epoxy group terminal (meth) acrylate is 4-glycidyloxybutyl acrylate in which Y in the general formula (1) is a linear alkylene group having 4 carbon atoms and R is a hydrogen atom. The manufacturing method in any one of.   The manufacturing method in any one of Claims 1-5 which perform transesterification under reduced pressure.