(meth)acrylate glycidyl composition

Abstract

Provided are a glycidyl (meth)acrylate composition wherein a phenolic polymerization inhibitor included therein does not readily deteriorate and the glycidyl (meth)acrylate composition can be stably preserved for a long time period, as well as a method for suppressing deactivation of a phenolic polymerization inhibitor in a glycidyl (meth)acrylate resin composition. Specifically, provided are a glycidyl (meth)acrylate composition including glycidyl (meth)acrylate, a quaternary ammonium salt, and a phenolic polymerization inhibitor, wherein the quaternary ammonium salt content is less than or equal to 1.00 ppm, as well as a method for suppressing deactivation of a phenolic polymerization inhibitor in a glycidyl (meth)acrylate composition, said method including adjusting the quaternary ammonium salt content in the glycidyl (meth)acrylate composition to be less than or equal to 1.00 ppm.

Description

[Technical Field]

[0001] The present invention relates to a glycidyl (meth)acrylate composition. More specifically, the present invention relates to a glycidyl (meth)acrylate composition in which the phenolic polymerization inhibitor contained therein is less likely to deteriorate and can be stored stably for a long period of time. The present invention also provides a method for suppressing the deactivation of the phenolic polymerization inhibitor in a glycidyl (meth)acrylate resin composition. [Background technology]

[0002] (Meth)acrylate glycidyl compositions are widely used as raw materials for various industrial applications, including resin modifiers, thermosetting paints, adhesives, fiber treatment agents, antistatic agents, and ion exchange resins. In this technical field, (meth)acrylate glycidyl refers to glycidyl acrylate or glycidyl methacrylate.

[0003] A typical method for synthesizing glycidyl (meth)acrylate is the method using epichlorohydrin as a raw material. This method can be broadly classified into the following two types.

[0004] The first method involves reacting epichlorohydrin with an alkali metal salt of (meth)acrylic acid in the presence of a catalyst to synthesize glycidyl (meth)acrylate (Patent Documents 1 and 2). The second method involves reacting epichlorohydrin with (meth)acrylic acid in the presence of a catalyst, followed by a ring-closing reaction with an alkaline aqueous solution to synthesize glycidyl (meth)acrylate (Patent Document 3). In both methods, a quaternary ammonium salt is used as the catalyst.

[0005] Furthermore, 1,3-dichloropropanol is a reaction by-product during the synthesis of glycidyl (meth)acrylate. Since 1,3-dichloropropanol has a boiling point close to that of glycidyl methacrylate and is difficult to separate by distillation, reduction treatment using a quaternary ammonium salt as a catalyst is sometimes performed (Patent Document 4).

[0006] As described above, quaternary ammonium salts are widely used in the manufacturing process of glycidyl (meth)acrylate.

[0007] On the other hand, Non-Patent Literature 1 describes that the addition reaction of phenol to epoxy groups proceeds in the presence of quaternary ammonium salts. Generally, phenolic polymerization inhibitors such as p-methoxyphenol are used as polymerization inhibitors for glycidyl (meth)acrylate. Therefore, if quaternary ammonium salts used in the manufacturing process are mixed into the product, there is a concern that the amount of phenolic polymerization inhibitor present in the glycidyl (meth)acrylate composition may decrease over time due to the reaction of the phenolic polymerization inhibitor with the epoxy groups of glycidyl (meth)acrylate during storage, or that unintended polymerization may occur. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 7-2818 [Patent Document 2] Japanese Patent Application Publication No. 9-59268 [Patent Document 3] Japanese Patent Application Publication No. 7-118251 [Patent Document 4] Patent No. 4666139 [Non-patent literature]

[0009] [Non-Patent Document 1] Chem.Commun.,2015,51,15133-15136 [Overview of the initiative] [Problems that the invention aims to solve]

[0010] Therefore, the present invention provides a glycidyl (meth)acrylate composition in which the phenolic polymerization inhibitor contained in the glycidyl (meth)acrylate composition is less likely to deteriorate (deactivate) and can be stored stably for a long period of time. The present invention also provides a method for suppressing the deactivation of the phenolic polymerization inhibitor in the glycidyl (meth)acrylate resin composition.

Means for Solving the Problems

[0011] The present inventors conducted intensive studies to solve the above problems. As a result, it was found that the above problems can be solved by adjusting the quaternary ammonium salt concentration in the glycidyl (meth)acrylate composition, and the present invention has been completed. That is, the present invention is as follows, for example.

[0012] <1> A method for suppressing the deactivation of a phenolic polymerization inhibitor in a glycidyl (meth)acrylate composition, comprising adjusting the content of the quaternary ammonium salt in the glycidyl (meth)acrylate composition to 1.00 ppm or less. <2> The method according to <1>, wherein the quaternary ammonium salt is a tetraalkylammonium halide. <3> The method according to <2>, wherein the quaternary ammonium salt is tetramethylammonium chloride or triethylmethylammonium chloride. <4> The method according to any one of <1> to <3>, wherein the phenolic polymerization inhibitor is p-methoxyphenol, hydroquinone, or topanol A (2-(tert-butyl)-4,6-dimethylphenol). <5> The method according to any one of <1> to <4>, wherein the glycidyl (meth)acrylate is glycidyl methacrylate. <6> (Meta) glycidyl acrylate composition containing glycidyl (meta) acrylate, a quaternary ammonium salt, and a phenolic polymerization inhibitor, wherein the content of the quaternary ammonium salt is 1.00 ppm or less. <7> The glycidyl (meta) acrylate composition according to <6>, wherein the quaternary ammonium salt is tetraalkylammonium halide. <8> The glycidyl (meta) acrylate composition according to <7>, wherein the quaternary ammonium salt is tetramethylammonium chloride or triethylmethylammonium chloride. <9> The glycidyl (meta) acrylate composition according to any one of <6> to <8>, wherein the phenolic polymerization inhibitor is p-methoxyphenol, hydroquinone, or topanol A (2-(tert-butyl)-4,6-dimethylphenol). <10> The glycidyl (meta) acrylate composition according to any one of <6> to <9>, wherein the glycidyl (meta) acrylate is glycidyl methacrylate.

Advantages of the Invention

[0013] According to the present invention, it is possible to provide a glycidyl (meta) acrylate composition in which the phenolic polymerization inhibitor contained in the glycidyl (meta) acrylate composition is less likely to deteriorate (deactivate) and can be stored stably for a long period of time.

Embodiments for Carrying Out the Invention

[0014] 1. (Meth)acrylate glycidyl composition The glycidyl (meta) acrylate composition of the present invention contains glycidyl (meta) acrylate, a quaternary ammonium salt, and a phenolic polymerization inhibitor. Hereinafter, each component will be described.

[0015] 1.1 Glycidyl (meth)acrylate (Meth)acrylate glycidyl refers to glycidyl acrylate and glycidyl methacrylate. In one embodiment of the present invention, (meth)acrylate glycidyl may be glycidyl acrylate. In another embodiment of the present invention, (meth)acrylate glycidyl may be glycidyl methacrylate. In a preferred embodiment of the present invention, (meth)acrylate glycidyl is glycidyl methacrylate.

[0016] Glycidyl (meth)acrylate can be produced by known methods. As mentioned above, typical methods for producing glycidyl (meth)acrylate include those using epichlorohydrin (hereinafter sometimes referred to as "EpCH") as a raw material. These methods can be broadly classified into two types: one in which epichlorohydrin is reacted with an alkali metal salt of (meth)acrylic acid in the presence of a catalyst to synthesize glycidyl (meth)acrylate (Patent Documents 1 and 2); and another in which epichlorohydrin is reacted with (meth)acrylic acid in the presence of a catalyst, and then a ring-closing reaction is carried out with an alkaline aqueous solution to synthesize glycidyl (meth)acrylate (Patent Document 3). In these methods, a quaternary ammonium salt is used as a catalyst.

[0017] In these manufacturing methods, known substances can be used as quaternary ammonium salts, but examples include tetraalkylammonium halogens such as tetramethylammonium chloride (hereinafter also called "TMAC"), trimethylethylammonium chloride, dimethyldiethylammonium chloride, triethylmethylammonium chloride (hereinafter also called "EMAC"), and tetraethylammonium chloride; and trialkylbenzylammonium halogens such as trimethylbenzylammonium chloride and triethylbenzylammonium chloride. The quaternary ammonium salt may be one of the above, or any combination of two or more may be used, but among the above, tetramethylammonium chloride, triethylmethylammonium chloride, tetraethylammonium chloride, triethylbenzylammonium chloride, and trimethylbenzylammonium chloride are preferably used. The amount of catalyst used is usually 0.01 to 1.5 mol% relative to (meth)acrylic acid.

[0018] In all manufacturing methods, the synthesis solution contains a large amount of solid matter, including a quaternary ammonium salt (the catalyst) and alkali chloride in an amount nearly equimolar to the generated glycidyl (meth)acrylate. Furthermore, the synthesis reaction is carried out in excess EpCH to improve yield. Therefore, after the synthesis is complete, the solid matter is usually removed from the synthesis solution by methods such as filtration or washing with water. Then, the unreacted excess EpCH is recovered by distillation, followed by the recovery of glycidyl (meth)acrylate by distillation. The EpCH recovered by distillation is recycled as a raw material for synthesis. Hereinafter, the process up to the removal of solid matter from the synthesis solution will be called the synthesis process, the solution obtained after removing the solid matter from the synthesis solution will be called the mother liquor, and the process after the removal of solid matter will be called the distillation process.

[0019] The distillation process can be batch or continuous, and can be carried out by combining simple distillation, rectification, thin-film distillation, etc. as appropriate. The synthesis process is preferably carried out in the presence of a suitable polymerization inhibitor, and known inhibitors such as phenolic compounds, phenothiazine compounds, N-oxyl compounds, amines, phosphorus compounds, sulfur compounds, and transition metal compounds can be used, and it is preferable to use these in the distillation process as well. Furthermore, polymerization can be further prevented by supplying molecular oxygen as needed. As mentioned above, generally, phenolic polymerization inhibitors such as p-methoxyphenol are used as polymerization inhibitors for glycidyl (meth)acrylate.

[0020] In all of the above methods, EpCH is used as a raw material, so the resulting glycidyl (meth)acrylate contains 1,3-dichloropropanol (hereinafter sometimes referred to as "1,3-DCP") as an impurity. Since the boiling point of 1,3-DCP is very similar to that of glycidyl (meth)acrylate, separation by distillation is impractical. In other words, if EpCH is recovered in the distillation process as described above, and then glycidyl (meth)acrylate is recovered, almost all of the 1,3-DCP produced in the synthesis process will be recovered together with the glycidyl (meth)acrylate.

[0021] For example, in the purification process of glycidyl methacrylate (hereinafter also referred to as "GMA"), when a quaternary ammonium salt is added to crude GMA containing 1,3-DCP, the equilibrium reaction shown in Formula 1 below proceeds, producing EpCH and 3-chloro-2-hydroxypropyl methacrylate (hereinafter sometimes referred to as "MACE"). The resulting EpCH is a low-boiling point component relative to GMA, while MACE has a sufficiently high boiling point relative to GMA. (Formula 1) 1,3-DCP + GMA → EpCH + MACE

[0022] Examples of quaternary ammonium salts added in the purification process include tetraalkylammonium halogens such as tetramethylammonium chloride, trimethylethylammonium chloride, dimethyldiethylammonium chloride, triethylmethylammonium chloride, and tetraethylammonium chloride; and trialkylbenzylammonium halogens such as trimethylbenzylammonium chloride and triethylbenzylammonium chloride. Only one type of quaternary ammonium salt may be used, or two or more may be used in combination. Among the above, tetramethylammonium chloride, triethylmethylammonium chloride, tetraethylammonium chloride, triethylbenzylammonium chloride, and trimethylbenzylammonium chloride are preferred. Furthermore, the quaternary ammonium salt added may be the same as or different from the one used in the synthesis. The amount of quaternary ammonium salt used is 0.001 to 1%, preferably 0.01 to 0.5%, and more preferably 0.02 to 0.4%, relative to crude (meth)acrylate glycidyl. If the response is lower than this, the response will be slow, and if it is higher, it will be economically disadvantageous.

[0023] The form of the quaternary ammonium salt used in the synthesis and purification processes is not particularly limited. It may be in powder or granular solid form, or in the case of the purification process, it may be dispersed as a slurry in an aqueous solution or glycidyl (meth)acrylate. Granular or powder form is usually used.

[0024] There are no particular limitations on the method of adding the quaternary ammonium salt. In the case of a solid, it may be added to the reactor using a hopper or the like, or in the case of a purification process, it may be added by flushing it with crude (meth)acrylate glycidyl or the like. It may be added in several stages, but it is usually added all at once.

[0025] The glycidyl (meth)acrylate used in the present invention preferably has a purity of 97% or higher, more preferably 98% or higher, even more preferably 99% or higher, and even more preferably 99.5% or higher. The purity of glycidyl (meth)acrylate can be measured by conventional methods, for example, by gas chromatography (GC).

[0026] 1.2 Quaternary Ammonium Salts Quaternary ammonium salts may be present in the (meth)acrylate glycidyl composition because those used as reaction catalysts in the manufacturing process of (meth)acrylate glycidyl and those added in the purification process may remain in the (meth)acrylate glycidyl composition.

[0027] Examples of quaternary ammonium salts that may be present in the (meth)acrylate glycidyl composition include tetraalkylammonium halogens such as tetramethylammonium chloride, trimethylethylammonium chloride, dimethyldiethylammonium chloride, triethylmethylammonium chloride, and tetraethylammonium chloride; and trialkylbenzylammonium halogens such as trimethylbenzylammonium chloride and triethylbenzylammonium chloride. The quaternary ammonium salt that may be present in the (meth)acrylate glycidyl composition may be one of the above, or any combination of two or more. Among the above, the quaternary ammonium salts that may be present in the (meth)acrylate glycidyl composition are preferably tetramethylammonium chloride, triethylmethylammonium chloride, tetraethylammonium chloride, triethylbenzylammonium chloride, and trimethylbenzylammonium chloride. In a preferred embodiment, the quaternary ammonium salt that may be present in the (meth)acrylate glycidyl composition is a tetraalkylammonium halogen. In a more preferred embodiment, the quaternary ammonium salt that may be present in the (meth)acrylate glycidyl composition is tetramethylammonium chloride or triethylmethylammonium chloride.

[0028] The inventors have found that quaternary ammonium salts that may remain in (meth)acrylate glycidyl compositions or (meth)acrylate glycidyl products react with phenolic polymerization inhibitors present in the (meth)acrylate glycidyl compositions, reducing the amount of phenolic polymerization inhibitors in the system, which impairs the long-term storage stability of the (meth)acrylate glycidyl compositions. Therefore, the present invention aims to ensure the long-term storage stability of (meth)acrylate glycidyl compositions by adjusting the content of quaternary ammonium salts in the (meth)acrylate glycidyl compositions.

[0029] The content of the quaternary ammonium salt present in the (meth)acrylate glycidyl composition of the present invention is preferably 1.00 ppm or less, more preferably 0.75 ppm or less, and even more preferably 0.50 ppm or less. If the content of the quaternary ammonium salt present in the (meth)acrylate glycidyl composition of the present invention is within the above range, the reaction between the quaternary ammonium salt and the phenolic polymerization inhibitor can be appropriately suppressed.

[0030] 1.3 Phenolic polymerization inhibitors Phenolic polymerization inhibitors are commonly used polymerization inhibitors in the production of glycidyl (meth)acrylate and are present in the manufactured glycidyl (meth)acrylate composition.

[0031] Examples of phenolic polymerization inhibitors used in the production of glycidyl (meth)acrylate of the present invention include, but are not limited to, p-methoxyphenol (hereinafter sometimes referred to as "MQ"), hydroquinone, 2,6-di-tert-butyl-4-methylphenol, 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), and topanol A (2-(tert-butyl)-4,6-dimethylphenol). In embodiments of the present invention, the phenolic polymerization inhibitor is preferably p-methoxyphenol, hydroquinone, or topanol A (2-(tert-butyl)-4,6-dimethylphenol), more preferably p-methoxyphenol or hydroquinone, and most preferably p-methoxyphenol.

[0032] The phenolic polymerization inhibitor used in the production of glycidyl (meth)acrylate is usually added in an amount ranging from 0.0005 to 0.01 equivalents relative to the amount of (meth)acryloyl group. The content of the phenolic polymerization inhibitor present in the produced glycidyl (meth)acrylate composition is in the range of 20 to 200 ppm, preferably in the range of 20 to 150 ppm.

[0033] 2. Method for suppressing the deactivation of phenolic polymerization inhibitors in (meth)acrylate glycidyl compositions. As described above, the inventors have found that quaternary ammonium salts that may remain in (meth)acrylate glycidyl composition or (meth)acrylate glycidyl product react with phenolic polymerization inhibitors present in (meth)acrylate glycidyl composition, thereby reducing the amount of phenolic polymerization inhibitors in the system. Based on these discoveries, the present invention also provides a method for suppressing the deactivation of phenolic polymerization inhibitors in (meth)acrylate glycidyl composition, which includes adjusting the content of quaternary ammonium salts in the (meth)acrylate glycidyl composition.

[0034] In a method for suppressing the deactivation of a phenolic polymerization inhibitor in a (meth)acrylate glycidyl composition of the present invention, the content of the quaternary ammonium salt in the (meth)acrylate glycidyl composition is preferably adjusted to 1.00 ppm or less, more preferably to 0.75 ppm or less, and even more preferably to 0.50 ppm or less. By adjusting the content of the quaternary ammonium salt present in the (meth)acrylate glycidyl composition of the present invention to the above range, the reaction between the quaternary ammonium salt and the phenolic polymerization inhibitor can be appropriately suppressed, thereby ensuring the long-term storage stability of the (meth)acrylate glycidyl composition. In a preferred embodiment of the present invention, a method for suppressing the deactivation of a phenolic polymerization inhibitor in a (meth)acrylate glycidyl composition is provided, which includes adjusting the content of the quaternary ammonium salt in the (meth)acrylate glycidyl composition to 1.00 ppm or less. A more preferred embodiment of the present invention provides a method for suppressing the deactivation of a phenolic polymerization inhibitor in a (meth)acrylate glycidyl composition, comprising adjusting the content of a quaternary ammonium salt in the (meth)acrylate glycidyl composition to 0.75 ppm or less. A still more preferred embodiment of the present invention provides a method for suppressing the deactivation of a phenolic polymerization inhibitor in a (meth)acrylate glycidyl composition, comprising adjusting the content of a quaternary ammonium salt in the (meth)acrylate glycidyl composition to 0.50 ppm or less.

[0035] The quaternary ammonium salts are as described above. Specifically, in the method for suppressing the deactivation of phenolic polymerization inhibitors in the (meth)acrylate glycidyl composition of the present invention, examples of quaternary ammonium salts include tetraalkylammonium halogens such as tetramethylammonium chloride, trimethylethylammonium chloride, dimethyldiethylammonium chloride, triethylmethylammonium chloride, and tetraethylammonium chloride; and trialkylbenzylammonium halogens such as trimethylbenzylammonium chloride and triethylbenzylammonium chloride. There may be only one quaternary ammonium salt or two or more, but among the above, tetramethylammonium chloride, triethylmethylammonium chloride, tetraethylammonium chloride, triethylbenzylammonium chloride, and trimethylbenzylammonium chloride are preferred. In a preferred embodiment of the method of the present invention, the quaternary ammonium salt that may be present in the (meth)acrylate glycidyl composition is a tetraalkylammonium halogen. In a more preferred embodiment of the method of the present invention, the quaternary ammonium salt that may be present in the (meth)acrylate glycidyl composition is tetramethylammonium chloride or triethylmethylammonium chloride.

[0036] The phenolic polymerization inhibitors are as described above. Specifically, in the method for suppressing the deactivation of the phenolic polymerization inhibitor in the (meth)acrylate glycidyl composition of the present invention, examples of the phenolic polymerization inhibitor include, but are not limited to, p-methoxyphenol ("MQ"), hydroquinone, 2,6-di-tert-butyl-4-methylphenol, 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), and topanol A (2-(tert-butyl)-4,6-dimethylphenol). In embodiments of the present invention, the phenolic polymerization inhibitor is preferably p-methoxyphenol, hydroquinone, or topanol A (2-(tert-butyl)-4,6-dimethylphenol), more preferably p-methoxyphenol or hydroquinone, and most preferably p-methoxyphenol.

[0037] The phenolic polymerization inhibitor used in the production of glycidyl (meth)acrylate is usually added in an amount ranging from 0.0005 to 0.01 equivalents relative to the amount of (meth)acryloyl group. The content of the phenolic polymerization inhibitor present in the produced glycidyl (meth)acrylate composition is in the range of 20 to 200 ppm, preferably in the range of 20 to 150 ppm.

[0038] In the present invention, a method for suppressing the deactivation of a phenolic polymerization inhibitor in a glycidyl (meth)acrylate composition, the reaction between the quaternary ammonium salt and the phenolic polymerization inhibitor can be appropriately suppressed by adjusting the content of the quaternary ammonium salt present in the glycidyl (meth)acrylate composition to a certain range as described above.

[0039] (meth)acrylate glycidyl compositions are generally prepared by purifying a reaction mixture obtained by the reaction of epichlorohydrin with (meth)acrylate or a metal salt of (meth)acrylate by distillation. The quaternary ammonium salt content in the (meth)acrylate glycidyl composition is adjusted by the amount of quaternary ammonium salt used during preparation and the distillation method and conditions when distilling and recovering (meth)acrylate glycidyl.

[0040] The amount of quaternary ammonium salt added during manufacturing is preferably 0.0001 to 0.01 equivalents relative to the amount of (meth)acryloyl group.

[0041] Examples of distillation methods include simple distillation and rectification, with a reflux ratio of 0.1 to 3.0 being preferred in rectification. Examples of distillation conditions include temperature and pressure, with a temperature of 40 to 120°C and a pressure of 0.05 to 10 kPaA being preferred.

[0042] To suppress the deactivation of phenolic polymerization inhibitors, indicators such as "the number of days required for 10% deterioration of the phenolic polymerization inhibitor" and "the reaction rate constant" can be used.

[0043] The term "number of days required for 10% degradation of the phenolic polymerization inhibitor" (unit: day) refers to the number of days required for 10% of the phenolic polymerization inhibitor present in the manufactured (meth)acrylate glycidyl composition to become inactive. In the method of the present invention, the "number of days required for 10% degradation of the phenolic polymerization inhibitor" is preferably 20 days or more, more preferably 50 days or more, even more preferably 60 days or more, and most preferably 90 days or more. If the "number of days required for 10% degradation of the phenolic polymerization inhibitor" is within the above range, it can be said that the inactivation of the phenolic polymerization inhibitor in the (meth)acrylate glycidyl composition is appropriately suppressed.

[0044] "Reaction rate constant" (unit: day) -1 ) is the rate constant for the alteration of phenolic polymerization inhibitors, and refers to k in the following equation (1). -d[I] / dt = k[I] ···(1) Here, [I] is the concentration of the phenolic polymerization inhibitor. Since the deterioration of the phenolic polymerization inhibitor is due to the reaction with glycidyl (meth)acrylate, the concentration of glycidyl (meth)acrylate should originally be considered when calculating the reaction rate. However, since the glycidyl (meth)acrylate contained in the glycidyl (meth)acrylate composition is in excess with respect to the phenolic polymerization inhibitor, the concentration of glycidyl (meth)acrylate was assumed to be constant. In the method of the present invention, the "reaction rate constant" is preferably 5.3×10 -3 day -1 or less, more preferably 2.1×10 -3 day -1 or less, still more preferably 1.8×10 -3 day -1 or less, and most preferably 1.2×10 -3 day -1 or less. If the "reaction rate constant" is within the above range, it can be said that the deactivation of the phenolic polymerization inhibitor in the glycidyl (meth)acrylate composition is appropriately suppressed.

Examples

[0045] Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[0046] [Reference Example 1] 40.0 g of glycidyl methacrylate with a purity of 99.5% (hereinafter sometimes referred to as "GMA") and 10.0 g of pure water were mixed and stirred with a vortex mixer for 30 seconds to dissolve the salt components in GMA in the aqueous phase. The aqueous phase was recovered from the mixture, and the ionic components in the aqueous phase were confirmed.

[0047] Specifically, measurements were carried out under the following conditions using cation ion chromatography and anion ion chromatography.

[0048] <Cation Ion Chromatography> Column: Shodex IC YS-50 (inner diameter 4.6 mm, length 125 mm) Column temperature: 40 °C Eluent: 0.2 mmol / L nitric acid aqueous solution Flow rate: 0.8 mL / min Detector: Conductivity detector Sample injection volume: 100 μL

[0049] <Anion ion chromatography> Column: Tosoh TSKgel IC-Anion-PW (inner diameter 4.6 mm, length 50 mm) Column temperature: 40 °C Eluent: Tosoh TSKgel eluent IC-Anion-A Flow rate: 0.8 mL / min Detector: Conductivity detector Sample injection volume: 100 μL

[0050] In the analysis by cation ion chromatography and anion ion chromatography, since no peak was detected, it was confirmed that the produced GMA does not contain salt components such as quaternary ammonium salts.

[0051] [Reference Example 2] A predetermined amount of p-methoxyphenol (Fuji Film Wako Pure Chemical Special Grade Reagent) was added to the GMA of Reference Example 1 to obtain a test solution. The test solution was stored at 25 °C in an atmospheric air atmosphere under normal pressure, and the decrease in MQ concentration was confirmed. The concentration of p-methoxyphenol (MQ) in GMA was quantified using a high performance liquid chromatograph under the following conditions.

[0052] <Quantification of p-methoxyphenol (high performance liquid chromatograph)> Column: Tosoh TSKgel ODS-120T (particle size 5 μm, inner diameter 4.6 mm, length 25 cm) Column temperature: 40 °C Eluent: Acetonitrile / water / acetic acid = 700 / 300 / 1 (volume ratio) Flow rate: 0.8 mL / min Detector: Ultraviolet-Vis spectroscopic detector (wavelength: 285 nm) Sample injection volume: 5 μL Holding time: MQ (4.5min)

[0053] If the MQ concentration at the start of the test was 102.4 ppm, the MQ concentration after 90 days of storage was 102.1 ppm, indicating that the MQ had hardly deteriorated (become inactive).

[0054] [Example 1] The test solution prepared in Reference Example 2 was mixed with 0.25 ppm of triethylmethylammonium chloride ("EMAC") and stored at 25°C under atmospheric pressure. When the MQ concentration was quantified using the same method as in Reference Example 2, the MQ concentration at the start of the test was 102.4 ppm, while the MQ concentrations after 14, 35, 56, 75, and 90 days of storage were 102.3 ppm, 101.7 ppm, 101.3 ppm, 100.2 ppm, and 100.0 ppm, respectively.

[0055] When the relationship between ln([MQ] / [MQ]0) and time was plotted based on the obtained results, a linear relationship was found. From the above, it can be concluded that the transformation of MQ is a first-order reaction, and its reaction rate constant is 2.78 × 10⁻⁶. -4 day -1 The result was calculated as follows: From the calculated reaction rate constant, the time required for MQ to change by 10% was calculated to be 379 days. Note that [MQ]0 is the molar concentration of MQ at the start of the test, and [MQ] is the molar concentration of MQ at the time of measurement.

[0056] [Example 2] 0.50 ppm of triethylmethylammonium chloride ("EMAC") was added to the test solution prepared in Reference Example 2, and the solution was stored at 25°C under atmospheric pressure. The MQ concentration was quantified using the same method as in Reference Example 2. The MQ concentration at the start of the test was 102.4 ppm, while the MQ concentrations after 14, 35, 56, 75, and 90 days of storage were 102.0 ppm, 101.0 ppm, 99.7 ppm, 97.6 ppm, and 96.7 ppm, respectively. The reaction rate constant, calculated using the same method as in Example 1, was 6.59 × 10⁻⁶. -4day -1 The time required for MQ to deteriorate by 10% was 160 days.

[0057] [Example 3] The test solution prepared in Reference Example 2 was mixed with 0.75 ppm of triethylmethylammonium chloride ("EMAC") and stored at 25°C under atmospheric pressure. The MQ concentration was quantified using the same method as in Reference Example 2. The MQ concentration at the start of the test was 102.4 ppm, while the MQ concentrations after 14, 35, 56, 75, and 90 days of storage were 101.5 ppm, 99.3 ppm, 96.5 ppm, 92.7 ppm, and 90.0 ppm, respectively. The reaction rate constant, calculated using the same method as in Example 1, was 1.44 × 10⁻⁶. -3 day -1 The time required for MQ to deteriorate by 10% was 73 days.

[0058] [Example 4] Triethylmethylammonium chloride ("EMAC") was added to the test solution prepared in Reference Example 2 and stored at 25°C under atmospheric pressure. The MQ concentration was quantified using the same method as in Reference Example 2. The MQ concentration at the start of the test was 102.4 ppm, while the MQ concentrations after 14, 35, 56, 75, and 90 days were 100.9 ppm, 97.9 ppm, 93.5 ppm, 88.5 ppm, and 84.9 ppm, respectively. The reaction rate constant, calculated using the same method as in Example 1, was 2.11 × 10⁻⁶. -3 day -1 The time required for MQ to deteriorate by 10% was 50 days.

[0059] [Example 5] To the test solution prepared in Reference Example 1, a predetermined amount of p-methoxyphenol (Fujifilm Wako Pure Chemical Industries Special Grade Reagent) and 1.00 ppm of tetramethylammonium chloride ("TMAC") were added and stored at 25°C under atmospheric pressure. When the MQ concentration was quantified using the same method as in Reference Example 2, the MQ concentration at the start of the test was 99.6 ppm, while the MQ concentrations after 10, 21, 32, 46, and 65 days of storage were 98.4 ppm, 97.7 ppm, 96.6 ppm, 95.2 ppm, and 94.2 ppm, respectively. The reaction rate constant calculated using the same method as in Example 1 was 8.62 × 10⁻⁶. -4 day -1 The time required for MQ to deteriorate by 10% was 122 days.

[0060] [Example 6] A predetermined amount of p-methoxyphenol (Fujifilm Wako Pure Chemical Industries Special Grade Reagent) was added to the GMA of Reference Example 1 to prepare the test solution. 1.00 ppm of triethylmethylammonium chloride ("EMAC") was added to this test solution, and it was stored at 25°C under atmospheric pressure. The MQ concentration was quantified using the same method as in Reference Example 2. The MQ concentration at the start of the test was 50.1 ppm, while the MQ concentrations after 10, 21, 32, 46, and 65 days of storage were 48.7 ppm, 48.0 ppm, 46.8 ppm, 45.0 ppm, and 43.1 ppm, respectively. The reaction rate constant, calculated using the same method as in Example 1, was 2.30 × 10⁻⁶. -3 day -1 The time required for MQ to deteriorate by 10% was 46 days.

[0061] [Comparative Example 1] To the test solution prepared in Reference Example 1, a predetermined amount of p-methoxyphenol (Fujifilm Wako Pure Chemical Industries Special Grade Reagent) and 5.00 ppm of triethylmethylammonium chloride ("EMAC") were added and stored at 25°C under atmospheric pressure. When the MQ concentration was quantified using the same method as in Reference Example 2, the MQ concentration at the start of the test was 101.8 ppm, while the MQ concentrations after 15, 34, 49, and 61 days of storage were 92.4 ppm, 77.0 ppm, 65.8 ppm, and 58.2 ppm, respectively. The reaction rate constant calculated using the same method as in Example 1 was 9.32 × 10⁻⁶. -3 day -1 The time required for MQ to deteriorate by 10% was 11 days.

[0062] The results obtained from the reference examples, examples, and comparative examples are shown in Table 1 below.

[0063] [Table 1]

[0064] The abbreviations used in the table are as follows: EMAC: Triethylmethylammonium chloride TMAC: Tetramethylammonium Chloride MQ:p-methoxyphenol

[0065] As described above, all of the glycidyl (meth)acrylate compositions of the present invention are glycidyl (meth)acrylate compositions that are less susceptible to deterioration of the phenolic polymerization inhibitor contained in the glycidyl (meth)acrylate composition and can be stored stably for a long period of time. Furthermore, by using the method of the present invention, deterioration (deactivation) of the phenolic polymerization inhibitor contained in the glycidyl (meth)acrylate composition can be appropriately suppressed. The glycidyl (meth)acrylate composition and method of the present invention contribute to ensuring the long-term storage stability of the glycidyl (meth)acrylate composition.

Claims

1. This includes adjusting the content of quaternary ammonium salts in the (meth)acrylate glycidyl composition to 1.00 ppm or less. The (meth)acrylate glycidyl composition is produced by a method comprising the step of purifying crude (meth)acrylate glycidyl containing 1,3-dichloropropanol by adding a quaternary ammonium salt, and is a method for suppressing the deactivation of phenolic polymerization inhibitors in a (meth)acrylate glycidyl composition.

2. The method according to claim 1, wherein the quaternary ammonium salt is a tetraalkylammonium halogenide.

3. The method according to claim 2, wherein the quaternary ammonium salt is tetramethylammonium chloride or triethylmethylammonium chloride.

4. The method according to any one of claims 1 to 3, wherein the phenolic polymerization inhibitor is p-methoxyphenol, hydroquinone, or topanol A (2-(tert-butyl)-4,6-dimethylphenol).

5. The method according to any one of claims 1 to 4, wherein (meth)acrylate glycidyl is methacrylate glycidyl.

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