GLYCIDYL (METH)ACRYLATE COMPOSITION

Abstract

Provided are a glycidyl (meth)acrylate composition, which includes a phenolic polymerization inhibitor that is unlikely to deteriorate such that the glycidyl (meth)acrylate composition can be stably stored for a long period of time, and a method for suppressing deactivation of a phenolic polymerization inhibitor in a glycidyl (meth)acrylate resin composition. More specifically, provided are: a glycidyl (meth)acrylate composition including a glycidyl (meth)acrylate, a quaternary ammonium salt, a strong acid salt, and a phenolic polymerization inhibitor; and a method for suppressing deactivation of a phenolic polymerization inhibitor in a glycidyl (meth)acrylate composition, the method including adjusting the content of a strong acid salt in the glycidyl (meth)acrylate composition to a certain amount relative to an amount of a quaternary ammonium salt by mole.

Claims

1. A method for suppressing deactivation of a phenolic polymerization inhibitor in a glycidyl (meth)acrylate composition, comprising adjusting a content of a strong acid salt in the glycidyl (meth)acrylate composition to 0.50 equivalents or more relative to an amount of a quaternary ammonium salt by mole.

2. The method according to claim 1, wherein the strong acid salt is selected from the group consisting of a sulfonate, a nitrate, and a phosphate.

3. The method according to claim 2, wherein the strong acid salt is alkyl benzene sulfonate or alkyl sulfonate.

4. The method according to claim 3, wherein the strong acid salt is sodium p-toluenesulfonate or sodium methanesulfonate.

5. The method according to claim 2, wherein the strong acid salt is sodium nitrate.

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

7. The method according to claim 6, wherein the quaternary ammonium salt is tetramethylammonium chloride or triethylmethylammonium chloride.

8. The method according to claim 1, wherein the phenolic polymerization inhibitor is p-methoxyphenol, hydroquinone, or Topanol A (2-(tert-butyl)-4,6-di methyl phenol).

9. The method according to claim 1, wherein the glycidyl (meth)acrylate composition comprises the strong acid salt in an amount of 0.50 equivalents or more relative to the amount of the quaternary ammonium salt by mole.

10. The method according to claim 1, wherein the glycidyl (meth)acrylate is glycidyl methacrylate.

11. A glycidyl (meth)acrylate composition comprising a glycidyl (meth)acrylate, a quaternary ammonium salt, a strong acid salt, and a phenolic polymerization inhibitor.

12. The glycidyl (meth)acrylate composition according to claim 11, wherein the strong acid salt is selected from the group consisting of a sulfonate, a nitrate, and a phosphate.

13. The glycidyl (meth)acrylate composition according to claim 12, wherein the strong acid salt is alkyl benzene sulfonate or alkyl sulfonate.

14. The glycidyl (meth)acrylate composition according to claim 13, wherein the strong acid salt is sodium p-toluenesulfonate or sodium methanesulfonate.

15. The glycidyl (meth)acrylate composition according to claim 12, wherein the strong acid salt is sodium nitrate.

16. The glycidyl (meth)acrylate composition according to claim 11, wherein the quaternary ammonium salt is tetraalkylammonium halogenide.

17. The glycidyl (meth)acrylate composition according to claim 16, wherein the quaternary ammonium salt is tetramethylammonium chloride or triethylmethylammonium chloride.

18. The glycidyl (meth)acrylate composition according to claim 11, wherein the phenolic polymerization inhibitor is p-methoxyphenol, hydroquinone, or Topanol A (2-(tert-butyl)-4,6-dimethylphenol).

19. The glycidyl (meth)acrylate composition according to claim 11, which comprises the strong acid salt in an amount of 0.50 equivalents or more relative to the amount of the quaternary ammonium salt by mole.

20. The glycidyl (meth)acrylate composition according to claim 11, wherein the glycidyl (meth)acrylate is glycidyl methacrylate.

Description

EXAMPLES

[0078] Hereinafter, the present invention will be specifically described with reference to the following examples. However, these examples are not intended to limit the present invention.

Reference Example 1

[0079] Glycidyl methacrylate with a purity of 99.5% (hereinafter sometimes referred to as GMA) in an amount of 40.0 g was mixed with 10.0 g of pure water and stirred for 30 seconds with a vortex mixer, thereby dissolving the salt component in GMA in the aqueous phase. An aqueous phase was recovered from the mixture, and ion components in the aqueous phase were confirmed.

[0080] Specifically, measurements were carried out under the following conditions using cation ion chromatography and anion ion chromatography.

<Cation Ion Chromatography>

[0081] Column: Shodex IC YS-50 (inner diameter: 4.6 mm; length 125 mm)

[0082] Column temperature: 40? C.

[0083] Eluent: 0.2 mmol/L nitric acid aqueous solution

[0084] Flow rate: 0.8 mL/min

[0085] Detector: Electric conductivity detector

[0086] Sample injection volume: 100 ?L

<Anion Ion Chromatography>

[0087] Column: Tosoh TSKgel IC-Anion-PW (inner diameter: 4.6 mm; length: 50 mm)

[0088] Column temperature: 40? C.

[0089] Eluent: Tosoh TSKgel eluent IC-Anion-A

[0090] Flow rate: 0.8 mL/min

[0091] Detector: Electric conductivity detector

[0092] Sample injection volume: 100 ?L

[0093] Analysis by cation ion chromatography and anion ion chromatography showed no peaks detected, thereby confirming that the produced GMA did not contain a salt component such as a quaternary ammonium salt.

Reference Example 2

[0094] A predetermined amount of p-methoxyphenol (special grade reagent of FUJIFILM Wako Pure Chemical Corporation) was added to GMA of Reference Example 1 to prepare a test solution. The test solution was stored at 25? C. under ordinary pressure in the atmosphere to confirm the MQ concentration decrease. The concentration of p-methoxyphenol (MQ) in GMA was quantitatively determined using high-performance liquid chromatography.

<Quantitative Determination of p-Methoxyphenol (High-Performance Liquid Chromatography)>

[0095] Column: Tosoh TSKgel ODS-120T (particle diameter: 5 ?m; inner diameter: 4.6 mm; length: 25 cm)

[0096] Column temperature: 40? C.

[0097] Eluent: Acetonitrile/pure water/acetic acid=700/300/1 (volume ratio)

[0098] Flow rate: 0.8 mL/min

[0099] Detector: UV-visible spectrometer (wavelength: 285 nm)

[0100] Sample injection volume: 5 ?L

[0101] Retention time: MQ (4.5 min)

[0102] The MQ concentration at the start of testing was 102.4 ppm, while the MQ concentration after storage for 90 days was 102.1 ppm, showing substantially no deterioration (deactivation) of MQ.

Comparative Example 1

[0103] A predetermined amount of MQ and 5.00 ppm of triethylmethylammonium chloride (EMAC) were added to GMA of Reference Example 1 to prepare a test solution. The MQ concentration of the test solution was 101.8 ppm. The test solution was stored at 25? C. under ordinary pressure in the atmosphere. The MQ concentration was quantitatively determined in the same manner as Reference Example 2. Accordingly, the MQ concentrations after storage for 15 days, 34 days, 49 days, and 61 days were 92.4 ppm, 77.0 ppm, 65.8 ppm, and 58.2 ppm, respectively. The reaction rate constant calculated in the same manner as Example 3 was 9.32?10.sup.?3 day.sup.?1, and the time required for MQ to deteriorate by 10% was 11 days.

Example 1

[0104] To the test solution prepared in Comparative Example 1, sodium p-toluenesulfonate (special grade reagent of FUJIFILM Wako Pure Chemical Corporation, p-TSANa) was added in an amount of 0.50 equivalents relative to the amount of triethylmethylammonium chloride (EMAC) by mole and stored at 25? C. under ordinary pressure in the atmosphere. The MQ concentration was quantitatively determined in the same manner as Reference Example 2. Accordingly, the MQ concentration at the start of testing was 101.8 ppm, while the MQ concentrations after storage for 15 days, 34 days, 49 days, and 61 days were 97.6 ppm, 91.4 ppm, 86.5 ppm, and 82.7 ppm, respectively.

[0105] When ln([MQ]/[MQ].sub.n) was plotted against time for the obtained results, a linear relationship was obtained. From the above, the deterioration of MQ was a primary reaction, and the reaction rate constant was 3.43?10.sup.?3 day.sup.?1. From the calculated reaction rate constant, the time required for MQ to deteriorate by 10% was calculated, resulting in 31 days. The addition of sodium p-toluenesulfonate caused the rate of deterioration of MQ to decrease. [MQ]0 is the molar concentration of MQ at the start of testing, and [MQ] is the molar concentration of MQ at the time of measurement.

Example 2

[0106] To the test solution prepared in Comparative Example 1, sodium p-toluenesulfonate (special grade reagent of FUJIFILM Wako Pure Chemical Corporation, p-TSANa) was added in an amount of 0.75 equivalents relative to the amount of triethylmethylammonium chloride (EMAC) by mole and stored at 25? C. under ordinary pressure in the atmosphere. The MQ concentration was quantitatively determined in the same manner as Reference Example 2. Accordingly, the MQ concentration at the start of testing was 101.8 ppm, while the MQ concentrations after storage for 15 days, 34 days, 49 days, and 61 days were 99.7 ppm, 97.2 ppm, 95.9 ppm, and 94.8 ppm, respectively. The reaction rate constant calculated in the same manner as Example 3 was 1.18?10.sup.?3 day.sup.?1, and the time required for MQ to deteriorate by 10% was 89 days. The addition of sodium p-toluenesulfonate caused the rate of deterioration of MQ to decrease.

Example 3

[0107] To the test solution prepared in Comparative Example 1, sodium p-toluenesulfonate (special grade reagent of FUJIFILM Wako Pure Chemical Corporation, p-TSANa) was added in an amount of 1.00 equivalent relative to the amount of triethylmethylammonium chloride (EMAC) by mole and stored at 25? C. under ordinary pressure in the atmosphere. The MQ concentration was quantitatively determined in the same manner as Reference Example 2. Accordingly, the MQ concentration at the start of testing was 101.8 ppm, while the MQ concentrations after storage for 15 days, 34 days, 49 days, and 61 days were 100.4 ppm, 99.1 ppm, 99.0 ppm, and 99.2 ppm, respectively. The reaction rate constant calculated in the same manner as Example 3 was 4.36?10.sup.?4 day.sup.?1, and the time required for MQ to deteriorate by 10% was 242 days. The addition of sodium p-toluenesulfonate caused the rate of deterioration of MQ to decrease.

Example 4

[0108] To the test solution prepared in Comparative Example 1, sodium p-toluenesulfonate (special grade reagent of FUJIFILM Wako Pure Chemical Corporation, p-TSANa) was added in an amount of 1.25 equivalents relative to the amount of triethylmethylammonium chloride (EMAC) by mole and stored at 25? C. under ordinary pressure in the atmosphere. The MQ concentration was quantitatively determined in the same manner as Reference Example 2. Accordingly, the MQ concentration at the start of testing was 101.8 ppm, while the MQ concentrations after storage for 15 days, 34 days, 49 days, and 61 days were 101.3 ppm, 100.3 ppm, 100.3 ppm, and 100.6 ppm, respectively. The reaction rate constant calculated in the same manner as Example 3 was 2.39?10.sup.?4 day.sup.?1, and the time required for MQ to deteriorate by 10% was 442 days. The addition of sodium p-toluenesulfonate caused the rate of deterioration of MQ to decrease.

Example 5

[0109] To the test solution prepared in Comparative Example 1, sodium p-toluenesulfonate (special grade reagent of FUJIFILM Wako Pure Chemical Corporation, p-TSANa) was added in an amount of 1.50 equivalents relative to the amount of triethylmethylammonium chloride (EMAC) by mole and stored at 25? C. under ordinary pressure in the atmosphere. The MQ concentration was quantitatively determined in the same manner as Reference Example 2. Accordingly, the MQ concentration at the start of testing was 101.8 ppm, while the MQ concentrations after storage for 15 days, 34 days, 49 days, and 61 days were 101.3 ppm, 100.4 ppm, 100.4 ppm, and 100.8 ppm, respectively. The reaction rate constant calculated in the same manner as Example 3 was 2.05?10.sup.?4 day.sup.?1, and the time required for MQ to deteriorate by 10% was 515 days. The addition of sodium p-toluenesulfonate caused the rate of deterioration of MQ to decrease.

Example 6

[0110] To the test solution prepared in Comparative Example 1, sodium methanesulfonate (special grade reagent of FUJIFILM Wako Pure Chemical Corporation, Me-SO.sub.3Na) was added in an amount of 1.00 equivalent relative to the amount of triethylmethylammonium chloride (EMAC) by mole and stored at 25? C. under ordinary pressure in the atmosphere. The MQ concentration was quantitatively determined in the same manner as Reference Example 2. Accordingly, the MQ concentration at the start of testing was 101.8 ppm, while the MQ concentrations after storage for 15 days, 34 days, 49 days, and 61 days were 96.1 ppm, 88.5 ppm, 83.9 ppm, and 81.1 ppm, respectively. The reaction rate constant calculated in the same manner as Example 3 was 3.81?10.sup.?3 day.sup.?1, and the time required for MQ to deteriorate by 10% was 28 days. The addition of sodium methanesulfonate caused the rate of deterioration of MQ to decrease.

Example 7

[0111] To the test solution prepared in Comparative Example 1, sodium nitrate (special grade reagent of FUJIFILM Wako Pure Chemical Corporation, NaNO.sub.3) was added in an amount of 1.00 equivalent relative to the amount of triethylmethylammonium chloride (EMAC) by mole and stored at 25? C. under ordinary pressure in the atmosphere. The MQ concentration was quantitatively determined in the same manner as Reference Example 2. Accordingly, the MQ concentration at the start of testing was 101.8 ppm, while the MQ concentrations after storage for 15 days, 34 days, 49 days, and 61 days were 94.2 ppm, 84.0 ppm, 78.2 ppm, and 74.9 ppm, respectively. The reaction rate constant calculated in the same manner as Example 3 was 5.16?10.sup.?3 day.sup.?1, and the time required for MQ to deteriorate by 10% was 20 days. The addition of sodium nitrate caused the rate of deterioration of MQ to decrease.

Comparative Example 2

[0112] To the test solution prepared in Comparative Example 1, sodium acetate (special grade reagent of FUJIFILM Wako Pure Chemical Corporation, AcONa) was added in an amount of 1.00 equivalent relative to the amount of triethylmethylammonium chloride (EMAC) by mole and stored at 25? C. under ordinary pressure in the atmosphere. The MQ concentration was quantitatively determined in the same manner as Reference Example 2. Accordingly, the MQ concentration at the start of testing was 101.8 ppm, while the MQ concentrations after storage for 15 days, 34 days, 49 days, and 61 days were 92.9 ppm, 78.4 ppm, 67.9 ppm, and 60.6 ppm, respectively. The reaction rate constant calculated in the same manner as Example 3 was 8.63?10.sup.?3 day.sup.?1, and the time required for MQ to deteriorate by 10% was 12 days. Even the addition of sodium nitrate did not substantially cause the rate of deterioration of MQ to change.

Example 8

[0113] To GMA of Reference Example 1, a predetermined amount of MQ and 1.00 ppm of triethylmethylammonium chloride (EMAC) were added. Then, sodium p-toluenesulfonate (special grade reagent of FUJIFILM Wako Pure Chemical Corporation, p-TSANa) was added in an amount of 0.50 equivalents relative to the amount of triethylmethylammonium chloride (EMAC) by mole and stored at 25? C. under ordinary pressure in the atmosphere. The MQ concentration was quantitatively determined in the same manner as Reference Example 2. Accordingly, the MQ concentration at the start of testing was 99.3 ppm, while the MQ concentrations after storage for 10 days, 21 days, 32 days, 46 days, and 65 days were 98.2 ppm, 97.5 ppm, 96.7 ppm, 95.3 ppm, and 94.2 ppm, respectively. The reaction rate constant calculated in the same manner as Example 3 was 8.15?10.sup.?4 day.sup.?1, and the time required for MQ to deteriorate by 10% was 129 days. The addition of sodium p-toluenesulfonate caused the rate of deterioration of MQ to decrease.

Example 9

[0114] To GMA of Reference Example 1, a predetermined amount of MQ and 0.75 ppm of triethylmethylammonium chloride (EMAC) were added. Then, sodium p-toluenesulfonate (special grade reagent of FUJIFILM Wako Pure Chemical Corporation, p-TSANa) was added in an amount of 1.00 equivalent relative to the amount of triethylmethylammonium chloride (EMAC) by mole and stored at 25? C. under ordinary pressure in the atmosphere. The MQ concentration was quantitatively determined in the same manner as Reference Example 2. Accordingly, the MQ concentration at the start of testing was 99.3 ppm, while the MQ concentrations after storage for 10 days, 21 days, 32 days, 46 days, and 65 days were 98.8 ppm, 98.5 ppm, 98.1 ppm, 98.0 ppm, and 97.2 ppm, respectively. The reaction rate constant calculated in the same manner as Example 3 was 3.08?10.sup.?4 day.sup.?1, and the time required for MQ to deteriorate by 10% was 342 days. The addition of sodium p-toluenesulfonate caused the rate of deterioration of MQ to decrease.

Example 10

[0115] To GMA of Reference Example 1, a predetermined amount of MQ and 1.00 ppm of triethylmethylammonium chloride (EMAC) were added. Then, sodium p-toluenesulfonate (special grade reagent of FUJIFILM Wako Pure Chemical Corporation, p-TSANa) was added in an amount of 1.00 equivalent relative to the amount of triethylmethylammonium chloride (EMAC) by mole and stored at 25? C. under ordinary pressure in the atmosphere. The MQ concentration was quantitatively determined in the same manner as Reference Example 2. Accordingly, the MQ concentration at the start of testing was 99.3 ppm, while the MQ concentrations after storage for 10 days, 21 days, 32 days, 46 days, and 65 days were 98.2 ppm, 97.5 ppm, 96.7 ppm, 95.3 ppm, and 94.2 ppm, respectively. The reaction rate constant calculated in the same manner as Example 3 was 1.35?10.sup.?4 day.sup.?1, and the time required for MQ to deteriorate by 10% was 781 days. The addition of sodium p-toluenesulfonate caused the rate of deterioration of MQ to decrease.

Example 11

[0116] To the test solution prepared in Comparative Example 3, sodium p-toluenesulfonate (special grade reagent of FUJIFILM Wako Pure Chemical Corporation, p-TSANa) was added in an amount of 1.00 equivalent relative to the amount of tetramethylammonium chloride (TMAC) by mole and stored at 25? C. under ordinary pressure in the atmosphere. The MQ concentration was quantitatively determined in the same manner as Reference Example 2. Accordingly, the MQ concentration at the start of testing was 99.6 ppm, while the MQ concentrations after storage for 10 days, 21 days, 32 days, 46 days, and 65 days were 99.4 ppm, 99.3 ppm, 99.1 ppm, 99.1 ppm, and 98.8 ppm, respectively. The reaction rate constant calculated in the same manner as Example 3 was 1.11?10.sup.?4 day.sup.?1, and the time required for MQ to deteriorate by 10% was 948 days. The addition of sodium p-toluenesulfonate caused the rate of deterioration of MQ to decrease.

Example 12

[0117] To the test solution prepared in Comparative Example 4, sodium p-toluenesulfonate (special grade reagent of FUJIFILM Wako Pure Chemical Corporation, p-TSANa) was added in an amount of 1.00 equivalents relative to the amount of triethylmethylammonium chloride (EMAC) by mole and stored at 25? C. under ordinary pressure in the atmosphere. The MQ concentration was quantitatively determined in the same manner as Reference Example 2. Accordingly, the MQ concentration at the start of testing was 50.1 ppm, while the MQ concentrations after storage for 10 days, 21 days, 32 days, 46 days, and 65 days were 49.9 ppm, 49.9 ppm, 49.6 ppm, 49.4 ppm, and 49.1 ppm, respectively. The reaction rate constant calculated in the same manner as Example 3 was 3.04?10.sup.?4 day.sup.?1, and the time required for MQ to deteriorate by 10% was 347 days. The addition of sodium p-toluenesulfonate caused the rate of deterioration of MQ to decrease.

[0118] The results obtained in the Reference Examples, Examples, and Comparative Examples are shown in Tables 1 and 2 below.

TABLE-US-00001 TABLE 1 Reference Comparative Example 2 Example 1 Example 1 Example 2 Example 3 Example 4 Quaternary ammonium salt EMAC EMAC EMAC EMAC EMAC (ppm) 0 5.00 5.00 5.00 5.00 5.00 Strong acid salt p-TSANa p-TSANa p-TSANa p-TSANa Strong acid salt/Quaternary 0 0 0.50 0.75 1.00 1.25 ammonium salt (mol/mol) Initial concentration of phenolic MQ MQ MQ MQ MQ MQ polymerization inhibitor (ppm) 102.4 101.8 101.8 101.8 101.8 101.8 Reaction rate constant (day.sup.?1) 5.97E?05 9.32E?03 3.43E?03 1.18E?03 4.36E?04 2.39E?04 Number of days required for 1764 11 31 89 242 442 phenolic polymerization inhibitor to deteriorate (day) Comparative Example 5 Example 6 Example 7 Example 2 Quaternary ammonium salt EMAC EMAC EMAC EMAC (ppm) 5.00 5.00 5.00 5.00 Strong acid salt p-TSANa MeSO.sub.3Na NaNO.sub.3 AcONa Strong acid salt/Quaternary 1.50 1.00 1.00 1.00 ammonium salt (mol/mol) Initial concentration of phenolic MQ MQ MQ MQ polymerization inhibitor (ppm) 101.8 101.8 101.8 101.8 Reaction rate constant (day.sup.?1) 2.05E?04 3.81E?03 5.16E?03 8.63E?03 Number of days required for 515 28 20 12 phenolic polymerization inhibitor to deteriorate (day)

TABLE-US-00002 TABLE 2 Example 8 Example 9 Example 10 Example 11 Example 12 Quaternary ammonium salt EMAC EMAC EMAC TMAC EMAC (ppm) 1.00 1.00 1.00 1.00 1.00 Strong acid salt p-TSANa p-TSANa p-TSANa p-TSANa p-TSANa Strong acid salt/Quaternary 0.50 0.75 1.00 1.00 1.00 ammonium salt (mol/mol) Initial concentration of phenolic MQ MQ MQ MQ MQ polymerization inhibitor (ppm) 99.3 99.3 99.3 99.6 50.1 Reaction rate constant (day.sup.?1) 8.15E?04 3.08E?04 1.35E?04 1.11E?04 3.04E?04 Number of days required for 129 342 781 948 347 phenolic polymerization inhibitor to deteriorate (day)

[0119] Abbreviations in the table are as follows:

[0120] EMAC: Triethylmethylammonium chloride

[0121] TMAC: Tetramethylammonium chloride

[0122] MQ: p-Methoxyphenol

[0123] p-TSANa: Sodium p-toluenesulfonate

[0124] Me-SO.sub.3Na: Sodium methanesulfonate

[0125] NaNO.sub.3: Sodium nitrate

[0126] AcONa: Sodium acetate

[0127] As described above, each example of the glycidyl (meth)acrylate composition of the present invention is a glycidyl (meth)acrylate composition, which includes a phenolic polymerization inhibitor that is unlikely to deteriorate such that the glycidyl (meth)acrylate composition can be stably stored for a long period of time. In addition, it is possible to appropriately suppress the deterioration (deactivation) of a phenolic polymerization inhibitor contained in a glycidyl (meth)acrylate composition using the method of the present invention. The glycidyl (meth)acrylate composition and the method of the present invention can contribute to ensuring the long-term storage stability of a glycidyl (meth)acrylate composition.