Monoglycidyl isocyanurate compound and production method therefor

Abstract

There are provided a novel isocyanurate compound having a glycidyl group as a substituent to be bonded to a nitrogen atom. A monoglycidyl isocyanurate compound of the following Formula (1), (2), or (3). ##STR00001##
(wherein two R.sup.1s are each a C.sub.2-10 alkyl group, two R.sup.2s are each a C.sub.1-5 alkylene group, two R.sup.3s are each a C.sub.1-2 alkyl group, two R.sup.4s are each a C.sub.1-2 alkylene group, and two R.sup.5s are each a C.sub.1-2 alkyl group).

Claims

1. A monoglycidyl isocyanurate compound of Formula (3) below: ##STR00019## wherein two R.sup.2s are each a C.sub.1-5 alkylene group, two R.sup.4s are each a C.sub.1-2 alkylene group, and two R.sup.5s are each a C.sub.1-2 alkyl group.

2. The monoglycidyl isocyanurate compound according to claim 1, wherein the two R.sup.2s are each a C.sub.1-2 alkylene group.

3. The monoglycidyl isocyanurate compound according to claim 1, wherein the monoglycidyl isocyanurate compound of Formula (3) is liquid at normal temperature under normal pressure when the total number of carbon atoms and oxygen atoms of a R.sup.2OR.sup.4OR.sup.5 group in Formula (3) is four or more.

4. A method for producing the monoglycidyl isocyanurate compound according to claim 1 comprising the steps of obtaining a reaction intermediate of the following Formula (3): ##STR00020## wherein two R.sup.2s, two R.sup.4s, and two R.sup.5s each have the same definition as that in claim 1 from monoallyl isocyanuric acid, and reacting the reaction intermediate of Formula (3) with an oxidant.

5. The method for producing the monoglycidyl isocyanurate compound according to claim 4, wherein the reaction intermediate of Formula (3) is obtained by reacting the monoallyl isocyanuric acid with a compound of the following Formula (c): ##STR00021## wherein X is a chloro group, a bromo group, or an iodo group, and R.sup.2 is a C.sub.1-5 alkylene group, R.sup.4 is a C.sub.1-2 alkylene group, and R.sup.5 is a C.sub.1-2 alkyl group.

6. The method for producing the monoglycidyl isocyanurate compound according to claim 4, wherein the oxidant is m-chloroperbenzoic acid or hydrogen peroxide.

Description

MODES FOR CARRYING OUT THE INVENTION

(1) The monoglycidyl isocyanurate compound of the present invention is represented by Formula (1), (2), or (3) described above. In Formula (1), a C.sub.2-10 alkyl group of R.sup.1 may be a linear, branched, or cyclic group. Examples of the alkyl group include ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-pentyl group, n-nonyl group, n-decyl group, cyclohexylmethyl group, and cyclopentylmethyl group.

(2) Examples of C.sub.1-5 alkylene group of R.sup.2 in Formulae (2) and (3) include methylene group, ethylene group, propylene group, trimethylene group, butylene group, and pentylene group. In Formula (2), R.sup.3 is a C.sub.1-2 alkyl group. Examples of the C.sub.1-2 alkyl group include methyl group and ethyl group. Examples of C.sub.1-2 alkylene group of R.sup.4 in Formula (3) include methylene group and ethylene group. Examples of the C.sub.1-2 alkyl group of R.sup.5 in Formula (3) include methyl group and ethyl group.

(3) Examples of the monoglycidyl isocyanurate compound of the present invention include compounds of the following Formulae (1-1) to (1-13), (2-1) to (2-5), and (3-1) to (3-4).

(4) ##STR00005## ##STR00006##

EXAMPLES

(5) Hereinafter, the monoglycidyl isocyanurate compound according to the present invention will be described with reference to specific examples. However, the present invention is not necessarily limited to the specific examples described below.

Synthesis Example 1

(6) ##STR00007##

(7) 25.00 g of monoallyl isocyanuric acid (product name: MA-IC, available from Shikoku Chemicals Corporation), 51.07 g of potassium carbonate, and 125.00 g of N-methylpyrrolidone were mixed and stirred at 25 C. To the mixture, 40.27 g of bromoethane (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropwise addition, the mixture was stirred at 25 C. for 5.5 hours to obtain a reaction solution. To the reaction solution, 250.00 g of toluene was added, and the solution was filtered. A cake was washed with 25.00 g of toluene twice. After washing, 250.00 g of water was added to the obtained solution, resulting in separation. This separation operation was repeated three times. From the organic phase, a solvent was distilled off under reduced pressure, and the residue was then dried at 40 C. under reduced pressure. 30.16 g of diethyl monoallyl isocyanurate of Formula (4) above was obtained as a liquid (yield: 90.6%). This compound was subjected to .sup.1H NMR measurement (500 MHz, CDCl.sub.3). 5.88 (ddt, 1H), 5.31 (dd, 1H), 5.23 (dd, 1H), 4.48 (d, 2H), 3.95 (q, 4H), 1.24 (t, 6H)

(8) In the specification, a NMR apparatus used in .sup.1H NMR measurement was JNM-ECA500 manufactured by JEOL Ltd.

Synthesis Example 2

(9) ##STR00008##

(10) 25.00 g of monoallyl isocyanuric acid (product name: MA-IC, available from Shikoku Chemicals Corporation), 51.07 g of potassium carbonate, and 125.00 g of N-methylpyrrolidone were mixed and stirred at 25 C. To the mixture, 45.45 g of bromopropane (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropwise addition, the temperature was increased to 60 C., and the mixture was stirred for 4 hours to obtain a reaction solution. The reaction solution was cooled to room temperature. To the reaction solution, 250.00 g of toluene was added, and the solution was filtered. A cake was washed with 25.00 g of toluene twice. After washing, 250.00 g of water was added to the obtained solution, resulting in separation. This separation operation was repeated three times. From the organic phase, a solvent was distilled off under reduced pressure, and the residue was then dried at 40 C. under reduced pressure. 36.35 g of dipropyl monoallyl isocyanurate of Formula (5) above was obtained as a liquid (yield: 97.1%). This compound was subjected to .sup.1H NMR measurement (500 MHz, CDCl.sub.3). 5.88 (1H, ddt), 5.29 (1H, dd), 5.23 (1H, dd), 4.48 (2H, d), 3.85 (4H, t), 1.67 (4H, qt), 0.94 (6H, t)

Synthesis Example 3

(11) ##STR00009##

(12) 30.00 g of monoallyl isocyanuric acid (product name: MA-IC, available from Shikoku Chemicals Corporation), 61.29 g of potassium carbonate, and 150.00 g of N-methylpyrrolidone were mixed. To the mixture, 35.70 g of chloromethyl methyl ether (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise with stirring at 25 C. After completion of dropwise addition, a reaction solution was obtained. To the reaction solution, 300.00 g of ethyl acetate was added, and the solution was filtered. A cake was washed with 30.00 g of ethyl acetate twice. After washing, 300.00 g of water was added to the obtained solution, resulting in separation. This separation operation was repeated three times. From the organic phase, a solvent was distilled off under reduced pressure, and the residue was then dried at 40 C. under reduced pressure. 30.63 g of dimethoxymethyl monoallyl isocyanurate of Formula (6) above was obtained as a liquid (yield: 67.1%). This compound was subjected to .sup.1H NMR measurement (500 MHz, CDCl.sub.3). 5.88 (ddt, 1H), 5.34-5.20 (m, 6H), 4.51 (d, 2H), 3.45 (s, 6H)

Synthesis Example 4

(13) ##STR00010##

(14) 20.00 g of monoallyl isocyanuric acid (product name: MA-IC, available from Shikoku Chemicals Corporation), 40.86 g of potassium carbonate, and 100.00 g of N-methylpyrrolidone were mixed. To the mixture, 38.76 g of 2-methoxyethoxymethyl chloride (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise with stirring at 25 C. After completion of dropwise addition, a reaction solution was obtained. To the reaction solution, 300.00 g of toluene was added, and the solution was filtered. A cake was washed with 30.00 g of toluene twice. After washing, 300.00 g of water was added to the obtained solution, resulting in separation. This separation operation was repeated three times. From the organic phase, a solvent was distilled off under reduced pressure, and the residue was then dried at 40 C. under reduced pressure. 20.36 g of dimethoxyethoxymethyl monoallyl isocyanurate of Formula (7) above was obtained as a liquid (yield: 49.9%). This compound was subjected to .sup.1H NMR measurement (500 MHz, CDCl.sub.3). 5.87 (ddt, 1H), 5.43 (s, 4H), 5.34 (dd, 1H), 5.24 (dd, 1H), 4.50 (d, 2H), 3.81 (t, 4H), 3.51 (t, 4H), 3.34 (s, 6H)

Synthesis Example 5

(15) ##STR00011##

(16) 22.00 g of monoallyl isocyanuric acid (product name: MA-IC, available from Shikoku Chemicals Corporation), 47.58 g of potassium carbonate, and 110.00 g of N-methylpyrrolidone were mixed and stirred at 25 C. To the mixture, 47.57 g of 2-bromoethyl methyl ether (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropwise addition, a reaction solution was obtained. To the reaction solution, 220.00 g of toluene was added, and the solution was filtered. A cake was washed with 22.00 g of toluene twice. After washing, 220.00 g of water was added to the obtained solution, resulting in separation. This separation operation was repeated three times. From the organic phase, a solvent was distilled off under reduced pressure, and the residue was then dried at 40 C. under reduced pressure. 30.93 g of dimethoxyethyl monoallyl isocyanurate of Formula (8) above was obtained as a liquid (yield: 83.3%). This compound was subjected to .sup.1H NMR measurement (500 MHz, CDCl.sub.3). 5.87 (1H, ddt), 5.29 (1H, dd), 5.23 (1H, dd) 4.49 (2H, d), 4.12 (4H, t) 3.62 (4H, t) 3.35 (6H, s)

Synthesis Example 6

(17) ##STR00012##

(18) 40.00 g of monoallyl isocyanuric acid (product name: MA-IC, available from Shikoku Chemicals Corporation), 81.73 g of potassium carbonate, and 200.00 g of N-methylpyrrolidone were mixed and stirred at 25 C. To the mixture, 83.92 g of iodomethane (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropwise addition, the temperature was increased to 105 C., and the mixture was stirred for 2 hours to obtain a reaction solution. To the reaction solution, 400.00 g of toluene was added, and the solution was filtered. A cake was washed with 40.00 g of toluene twice. After washing, 400.00 g of water was added to the obtained solution, resulting in separation. This separation operation was repeated three times. From the organic phase, a solvent was distilled off under reduced pressure, and the residue was then dried at 40 C. under reduced pressure. 39.70 g of dimethyl monoallyl isocyanurate of Formula (9) above was obtained as a white solid (yield: 85.1%).

Example 1

(19) ##STR00013##

(20) 30.00 g of diethyl monoallyl isocyanurate obtained in Synthesis Example 1 and 225.00 g of chloroform were mixed and stirred at 25 C. To the mixture, 42.43 g of m-chloroperbenzoic acid (available from Tokyo Chemical Industry Co., Ltd.) was added. The mixture was stirred at 25 C. for 85.5 hours to obtain a reaction solution. To the reaction solution, 300.00 g of chloroform was added. With stirring, 600.00 g of 5 wt % NaHCO.sub.3 was added dropwise, and separation was carried out. To the obtained organic phase, 300.00 g of 10 wt % Na.sub.2CO.sub.3 was then added, resulting in separation. To the organic phase, 600.00 g of 5 wt % NaHCO.sub.3 was added, resulting in separation. To the organic phase, 300.00 g of water was added, resulting in separation. This separation operation was repeated twice. From the organic phase, a solvent was distilled off under reduced pressure, and the residue was then dried at 40 C. under reduced pressure. 30.77 g of diethyl monoglycidyl isocyanurate of Formula (1-1) above was obtained as a white solid (yield: 95.8%). This compound was subjected to .sup.1H NMR measurement (500 MHz, CDCl.sub.3). 4.16 (dd, 1H), 3.99 (dd, 1H), 3.96 (q, 4H), 3.26 (dddd, 1H), 2.82 (dd, 1H), 2.70 (dd, 1H), 1.25 (t, 6H)

Example 2

(21) ##STR00014##

(22) 36.00 g of dipropyl monoallyl isocyanurate obtained in Synthesis Example 2 and 270.00 g of chloroform were mixed and stirred at 25 C. To the mixture, 45.28 g of m-chloroperbenzoic acid (available from Tokyo Chemical Industry Co., Ltd.) was added. The mixture was stirred at 25 C. for 134 hours to obtain a reaction solution. To the reaction solution, 360.00 g of chloroform was added. With stirring, 720.00 g of 5 wt % NaHCO.sub.3 was added dropwise, and separation was carried out. To the resulting organic phase, 360.00 g of 10 wt % Na.sub.2SO.sub.3 was added, resulting in separation. To the organic phase, 720.00 g of 5 wt % NaHCO.sub.3 was added, resulting in separation. To the organic phase, 360.00 g of water was added, resulting in separation. This separation operation was repeated twice. From the organic phase, a solvent was distilled off under reduced pressure, and the residue was then dried at 40 C. under reduced pressure. 37.93 g of dipropyl monoglycidyl isocyanurate of Formula (1-2) above was obtained as a white solid (yield: 98.0%). This compound was subjected to .sup.1H NMR measurement (500 MHz, CDCl.sub.3). 4.17 (1H, dd), 4.00 (1H, dd), 3.86 (4H, t), 3.25 (1H, dddd), 2.81 (1H, dd), 2.69 (1H, dd), 1.68 (4H, tq), 0.95 (6H, t)

Example 3

(23) ##STR00015##

(24) 30.00 g of dimethoxymethyl monoallyl isocyanurate obtained in Synthesis Example 3 and 225.00 g of chloroform were mixed and stirred at 25 C. To the mixture, 37.16 g of m-chloroperbenzoic acid (available from Tokyo Chemical Industry Co., Ltd.) was added. The mixture was stirred at 25 C. for 172 hours to obtain a reaction solution. To the reaction solution, 300.00 g of chloroform was added. With stirring, 600.00 g of 5 wt % NaHCO.sub.3 was added dropwise, and separation was carried out. To the resulting organic phase, 300.00 g of 10 wt % Na.sub.2SO.sub.3 was added, resulting in separation. To the organic phase, 600.00 g of 5 wt % NaHCO.sub.3 was added, resulting in separation. To the organic phase, 300.00 g of water was added, resulting in separation. This separation operation was repeated twice. From the organic phase, a solvent was distilled off under reduced pressure, and the residue was then dried at 40 C. under reduced pressure. 29.23 g of dimethoxymethyl monoglycidyl isocyanurate of Formula (2-1) above was obtained as a white solid (yield: 91.7%). This compound was subjected to .sup.1H NMR measurement (500 MHz, CDCl.sub.3). 5.35 (s, 4H), 4.35 (dd, 1H), 4.19 (dd, 1H), 4.67 (s, 6H), 3.28 (dddd, 1H), 2.82 (dd, 1H), 2.71 (dd, 1H)

Example 4

(25) ##STR00016##

(26) 20.00 g of dimethoxyethoxymethyl monoallyl isocyanurate obtained in Synthesis Example 4 and 150.00 g of chloroform were mixed and stirred at 25 C. To the mixture, 18.45 g of m-chloroperbenzoic acid (available from Tokyo Chemical Industry Co., Ltd.) was added. The mixture was stirred at 25 C. for 152 hours to obtain a reaction solution. To the reaction solution, 200.00 g of chloroform was added. With stirring, 400.00 g of 5 wt % NaHCO.sub.3 was added dropwise, and separation was carried out. To the resulting organic phase, 200.00 g of 10 wt % Na.sub.2SO.sub.3 was then added, resulting in separation. To the organic phase, 400.00 g of 5 wt % NaHCO.sub.3 was added, resulting in separation. To the organic phase, 200.00 g of water was added, resulting in separation. This separation operation was repeated twice. From the organic phase, a solvent was distilled off under reduced pressure, and the residue was then dried at 40 C. under reduced pressure. 18.34 g of dimethoxyethoxymethyl monoglycidyl isocyanurate of Formula (3-1) above was obtained as a liquid (yield: 87.6%). This compound was subjected to .sup.1H NMR measurement (500 MHz, CDCl.sub.3). 5.42 (s, 4H), 4.18 (dd, 1H), 4.00 (dd, 1H), 3.82 (t, 4H), 3.52 (t, 4H), 3.34 (s, 6H), 3.25 (dddd, 1H), 2.82 (dd, 1H), 2.71 (dd, 1H)

Example 5

(27) ##STR00017##

(28) 31.00 g of dimethoxyethyl monoallyl isocyanurate obtained in Synthesis Example 5 and 232.50 g of chloroform were mixed and stirred at 25 C. To the mixture, 34.62 g of m-chloroperbenzoic acid (available from Tokyo Chemical Industry Co., Ltd.) was added. The mixture was stirred at 25 C. for 152 hours to obtain a reaction solution. To the reaction solution, 310.00 g of chloroform was added. With stirring, 620.00 g of 5 wt % NaHCO.sub.3 was added dropwise, and separation was carried out. To the resulting organic phase, 310.00 g of 10 wt % Na.sub.2SO.sub.3 was then added, resulting in separation. To the organic phase, 620.00 g of 5 wt % NaHCO.sub.3 was added, resulting in separation. To the organic phase, 310.00 g of water was added, resulting in separation. This separation operation was repeated twice. From the organic phase, a solvent was distilled off under reduced pressure, and the residue was then dried at 40 C. under reduced pressure. 30.44 g of dimethoxyethyl monoglycidyl isocyanurate of Formula (2-2) above was obtained as a liquid (yield: 93.0%). This compound was subjected to .sup.1H NMR measurement (500 MHz, CDCl.sub.3). 4.19-4.12 (5H, m), 4.01 (1H, dd), 3.62 (4H, t), 3.35 (6H, s), 3.25 (1H, dddd), 2.81 (1H, dd), 2.69 (1H, dd)

Comparative Example 1

(29) ##STR00018##

(30) 30.00 g of dimethyl monoallyl isocyanurate obtained in Synthesis Example 6 and 300.00 g of dichloromethane were mixed and stirred at 25 C. To the mixture, 56.51 g of m-chloroperbenzoic acid (available from Tokyo Chemical Industry Co., Ltd.) was added. The mixture was stirred at 25 C. for 64.5 hours to obtain a reaction solution. To the reaction solution, 300.00 g of chloroform was added. With stirring, 600.00 g of 5 wt % NaHCO.sub.3 was added dropwise, and separation was carried out. To the organic phase, 600.00 g of 10 wt % Na.sub.2SO.sub.3 was added, resulting in separation. To the organic phase, 600.00 g of 5 wt % NaHCO.sub.3 was added, resulting in separation. To the organic phase, 600.00 g of water was added, resulting in separation. This separation operation was repeated twice. From the organic phase, a solvent was distilled off under reduced pressure, and the residue was then dried at 40 C. under reduced pressure. 27.64 g of dimethyl monoglycidyl isocyanurate of Formula (10) above was obtained as a white solid (yield: 73.1%).

(31) [Evaluation of Solubility in Solvent]

(32) To 0.1 g of the compound obtained in each of Examples 1 to 5 and Comparative Example 1, 0.4 g of propylene glycol monomethyl ether was added to obtain a 20 wt % solution. The solution was stirred at 25 C. for 10 minutes. The solubility of the solution was visually confirmed. As shown in Table 1, the solubility of all the compounds synthesized in Examples 1 to 5 was improved as compared with the compound obtained in Comparative Example 1. In Table 1, x represents a clouded solution, and represents a clear solution in which a precipitate is not produced.

(33) TABLE-US-00001 TABLE 1 Comparative Exam- Exam- Exam- Exam- Exam- Example 1 ple 1 ple 2 ple 3 ple 4 ple 5 Solubility X

INDUSTRIAL APPLICABILITY

(34) For example, the monoglycidyl isocyanurate compound of the present invention can be applied to an anti-reflective coating-forming composition for lithography, a resist underlayer film-forming composition, a resist upper layer film-forming composition, a photocurable resin composition, a thermosetting resin composition, a flattened film-forming composition, an adhesives composition, and other compositions. The monoglycidyl isocyanurate compound of the present invention can be used as a raw material compound in synthesis of an oligomer or polymer used for the composition.