JP2002308873A - Isocyanuric ester having epithiopropyl group and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an isocyanuric ester which has two or three epithiopropyl groups and can be suitably used as a raw material of a high-refractive-index optical material such as a plastic lens, an optical fiber, or a functional film. SOLUTION: This isocyanuric ester having epithiopropyl groups is represented by formula (1) (wherein X is O or S; and R is H or CH3 ).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound useful as a crosslinking agent or an additive for a reactive molecule or a reactive polymer, for example, a high refractive index optic such as a plastic lens, an optical fiber, and a functional film. The present invention relates to an isocyanuric acid ester having two or three epithiopropyl groups in a molecule, which can be suitably used as a raw material of an application material, and a method for producing the same.

[0002]

2. Description of the Related Art Organic polymer materials are widely used as optical materials such as plastic lenses, optical fibers, and functional films in recent years because they are lightweight and easy to process. Not only is the refractive index lower than that of the inorganic polymer material, but also the chromatic aberration represented by the Abbe number is large, so that there is a drawback that the range of use is limited.

[0003] On the other hand, inorganic polymer materials are superior to organic polymers in performance such as heat resistance, mechanical properties, chemical resistance and the like and high in refractive index, but have the disadvantage that they are heavy and cannot be easily molded. Have.

As a design of a conventional organic high refractive index material,
Introduction of an aromatic ring, halogen, and sulfur has been widely studied in order to achieve a high refractive index. However, it is known that when an aromatic ring is introduced into the skeleton, birefringence is likely to occur due to the high orientation of the aromatic ring, and transparency is impaired. Further, since the absorption wavelength of the aromatic ring is relatively close to the visible light portion, the Abbe number decreases and the chromatic aberration increases. This is due to the localization of the refractive index near the absorption wavelength called anomalous dispersion, and is generally well known. Therefore, it is necessary to design a molecule that does not contain an aromatic ring, but there are not so many organic materials having a high refractive index and no aromatic ring.

In general, the refractive index of an inorganic polymer material is 1.46 to 1.92, and the Abbe number is 25 to 80, which is a wide range of characteristics. However, the refractive index of an organic polymer material is around 1.65. Almost no large Abbe number exceeding 40 is known. Against this background, there is a growing demand for a variety of optical characteristics in terms of refractive index and Abbe number in organic high-refractive-index materials. For this reason, a new organic high-refractive-index material or its raw material is required from the market. .

Japanese Patent Application Laid-Open No. H11-189592 discloses 1,
Disclosed are 2,3-tris (β-epithiopropylthio) propanes, which react 1,2,3-trimercaptopropane with epihalohydrin, followed by thiourea,
It is described that it was produced by reacting a thiocyanate.

Japanese Patent Application Laid-Open No. Hei 9-71580 discloses a branched alkyl sulfide type episulfide compound.

Japanese Patent Application Laid-Open No. 9-110979 discloses a bis (epithiopropyl) sulfide compound as a straight alkyl sulfide type episulfide compound.

[0009]

SUMMARY OF THE INVENTION In order to satisfy the above-mentioned market demands, the present invention provides a raw material, a curing agent, or a polymer-modified organic high refractive index material having a high Abbe number without deteriorating transparency. The present invention provides a compound useful as an agent, and relates to an isocyanuric ester having two or three epithiopropyl groups in a molecule and a method for producing the same.

[0010]

According to a first aspect of the present invention, there is provided formula (1):

[0011]

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(Wherein X represents an oxygen atom or a sulfur atom, and R represents a hydrogen atom or a methyl group). An isocyanuric acid ester having an epithiopropyl group represented by the following formula: 1,3,5-tris- (2,3-epithiopropyl) wherein X is a sulfur atom and R is hydrogen
Isocyanurate, as a third aspect, 1,3,5-tris- wherein X in the formula (1) is a sulfur atom and R is a methyl group.
(2,3-epithio-2-methylpropyl) isocyanurate, as a fourth aspect, formula (2):

[0013]

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(Wherein R represents a hydrogen atom or a methyl group). An isocyanurate having an epoxy group represented by the formula (1) is reacted with an oxygen-sulfur conversion reagent. The fifth aspect is a method for producing an isocyanuric acid ester having an epithiopropyl group, and the fifth aspect, wherein the oxygen-sulfur conversion reagent is thiourea or a thiocyanate.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, an isocyanuric ester having an epithiopropyl group is represented by the formula (1) (where X represents an oxygen atom or a sulfur atom, and R represents a hydrogen or a methyl group). It is represented by

In the formula (1), when X is a sulfur atom and R is a hydrogen atom, it represents 1,3,5-tris- (2,3-epithiopropyl) isocyanurate; X is a sulfur atom; Is a methyl group, 1,3,5-tris-
Represents (2,3-epithio-2-methylpropyl) isocyanurate.

When X is an oxygen atom and R is a hydrogen atom,
1,3-bis- (2,3-epithiopropyl) -5-
Represents (2,3-epithiopropyl) isocyanurate.

It can be produced by using at least 2 moles, preferably 2 to 10 moles, more preferably 2 to 5 moles of oxygen-sulfur conversion agent per mole of isocyanuric acid ester having an epoxy group as a raw material.

The isocyanuric acid ester having an epoxy group used here is represented by the formula (2) (wherein, R represents a hydrogen atom or a methyl group). In the formula (2), when R is a hydrogen atom, it represents 1,3,5-tris- (2,3-epoxypropyl) isocyanurate, and when R is a methyl group, it is 1,3,5- Triss
Represents (2,3-epoxy-2-methylpropyl) isocyanurate.

When R is hydrogen in the formulas (1) and (2), triglycidyl isocyanurate, that is, 1,3,5-tris- (2,3-epoxypropyl) isocyanurate is used as a raw material. 1,3,5-tris- (2,3-epithiopropyl) isocyanurate or 1,3,5-tris- (2,3-epithiopropyl) isocyanurate and 1,3-bis- (2, A mixture of (3-epithiopropyl) -5- (2,3-epoxypropyl) isocyanurate is obtained.

When R is a methyl group in the formulas (1) and (2), (methyl) triglycidyl isocyanurate, that is, 1,3,5-tris- (2,3-
Using epoxy-2-methylpropyl) isocyanurate, 1,3,5-tris- (2,3-epithio-2
-Methylpropyl) isocyanurate or 1,
3,5-Tris- (2,3-epithio-2-methylpropyl) isocyanurate and 1,3-bis- (2,3-epithio-2-methylpropyl) -5- (2,3-epoxy-2 A mixture of (-methylpropyl) isocyanurates is obtained.

The triglycidyl isocyanurate used as a raw material is not particularly limited, but 1,3,5-tris- (2,3-epoxypropyl) isocyanurate (manufactured by Nissan Chemical Industries, Ltd.) Product name TEPI
C) can be easily obtained as a commercial product, and by using TEPIC-S which is commercially available as a high-purity product, 1,3,5-tris- (2,
(3-Epithiopropyl) isocyanurate is preferred because it is obtained.

Further, the raw materials are described in JP-A-11-315078.
No. 1,3,5-tris- (2,
By using (3-epoxypropyl) isocyanurate, optically active 1,3,5-tris- (2,3-epithiopropyl) isocyanurate can be produced.

For example, (2S, 2'S, 2 "S) -1,
When 3,5-tris- (2,3-epoxypropyl) isocyanurate is used as a raw material, (2S, 2 ′
(S, 2 "S) -1,3,5-tris- (2,3-epithiopropyl) isocyanurate is obtained.

Specific examples of the oxygen-sulfur conversion agent will be given below. As thioamide compounds, thiourea, dimethylaminothioformamide, N-methylbenzothiazoline-
2-thione, benzothiazoline-2-thione and the like. Examples of the thiocyanate include potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate. Examples of the phosphinethione compound include triphenylphosphinethione. The used amount thereof is 2 to 10 mol, particularly preferably 2 to 5 mol, per 1 mol of the isocyanuric acid ester having an epoxy group represented by the formula (2).

In the present invention, when an isocyanuric acid ester having an epoxy group is reacted with an oxygen-sulfur converting agent, an isocyanuric acid ester having an epithiopropyl group is efficiently produced by using a catalyst if necessary. be able to.

Examples of the catalyst include Lewis acids such as titanium tetraisopropoxide, oxidizing agents such as cerium nitrate ammonium and ruthenium chloride, inorganic acids such as sulfuric acid, and organic acids such as formic acid, acetic acid, trifluoroacetic acid and picric acid. . Particularly, inorganic acids and organic acids are preferable because they also have an effect as a polymerization inhibitor.

The catalyst may be used in combination of two or more kinds.
It can be used in an amount of from 0.001 to 0.3 mol, particularly preferably from 0.01 to 0.05 mol, per mol.

The solvent used in the present invention may be any solvent as long as it is inert to the reaction. Typical solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like. Amides, sulfur compounds such as dimethyl sulfoxide and sulfolane, methanol, ethanol, isopropanol, t-
Alcohols such as butanol, 2-methoxyethanol, and 2-ethoxyethanol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile; esters such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; , Chloroform, halogenated hydrocarbons such as dichloroethane, nitromethane, nitro compounds such as nitrobenzene, benzene, aromatic hydrocarbons such as toluene,
Organic acids such as formic acid and acetic acid, water or a mixture thereof are used.

The reaction temperature used in the present invention can be between -78 ° C and the boiling point of the solvent.
Preferably 0 ° C to 60 ° C, more preferably 0 ° C to 3 ° C
It can be performed in the range of 0 ° C.

The isocyanuric acid ester having an epithiopropyl group obtained by the present invention can be used as an additive to other material systems to obtain a highly refractive organic material. Further, a 2,3-epithiopropyl group or a 2,3-epithio-2-methylpropyl group, which is a functional group site of the isocyanuric acid ester, shows reactivity. For example, other epithio compounds, or epoxy compounds, or mercapto compounds, mercaptocarboxylic acids, carboxylic acids, carboxylic anhydrides, amines,
Reacts with reactive compounds such as phenols, olefins, acrylates, and methacrylates.

The isocyanuric acid ester having an epithiopropyl group of the present invention has a high sulfur content per unit weight when used as a curing agent or an additive as well as the properties of the compound itself. Therefore, it has a feature of being an organic material having a high refractive index.

Further, it is also possible to carry out polymerization alone using a basic substance as a catalyst. And it can also be used as a crosslinking agent for a reactive compound or a reactive polymer.

The isocyanuric acid ester having an epithiopropyl group according to the present invention, which has no benzene ring in its skeleton itself, has a low ultraviolet absorption in a long wavelength region, has a relatively large Abbe number, and has a small chromatic aberration and excellent optical properties. Material. Further, when used as a curing agent, the resulting structure has a three-dimensional crosslinked structure and thus is excellent in isotropy, and therefore has low birefringence and provides excellent transparency.

[0035]

EXAMPLE 1 4.8 g of 1,3,5-tris- (2,3-epoxypropyl) isocyanurate (trade name: TEPIC, manufactured by Nissan Chemical Industries, Ltd.), 4.0 g of thiourea and 1 g of ethanol
20 ml was added, and the mixture was stirred and reacted at room temperature for 24 hours.
After completion of the reaction, the resulting insolubles were filtered, concentrated at 30 ° C. or lower, and extracted with chloroform. The solvent was distilled off to obtain 4.0 g of the objective 1,3,5-tris- (2,3-epithiopropyl) isocyanurate as white crystals.

Nuclear magnetic resonance spectrum (NMR, 300M
Hz, JEOL-ECP300, CD manufactured by JEOL Ltd.
Cl3) ^{is, 1 H-NMR (σ,} ppm): 2.46
(Dd, J = 6 Hz, 1 Hz, 3H), 2.51 (d,
J = 6 Hz, 3H), 3.20 (m, 3H), 3.88
(Dd, J = 14 Hz, 7 Hz, 3H), 4.38 (d
d, J = 14 Hz, 5 Hz, 3H) 13 C-NMR (σ, ppm): 24.79, 30.3
1, 47.69, 148.74 Melting point: 119 to 123 ° C (measured by TG / DTA320U, manufactured by Seiko Instruments Inc.) MASS (EI, M +): 345 Example 2 1,3,5-Tris- (2 , 3-Epoxypropyl) isocyanurate (TEPIC, manufactured by Nissan Chemical Industries, Ltd.) 4.8 g, thiourea 3.6 g and ethanol 1
20 ml was added, and the mixture was stirred and reacted at room temperature for 24 hours.
After completion of the reaction, the resulting insolubles were filtered, concentrated at 30 ° C. or lower, and extracted with chloroform. The solvent is distilled off, and the desired 1,3,5-tris- (2,3-epithiopropyl) isocyanurate and 1,3-bis- (2,3-epithiopropyl) -5- (2 , 3-epoxypropyl)
3.9 g of a mixture with isocyanurate were obtained as white crystals. 1,3,5-tris- (2,3-epithiopropyl) isocyanurate and 1,3-bis- (2,3-epithiopropyl) -5- (2,3-epoxypropyl)
The weight ratio of isocyanurate was 93: 7.

Nuclear magnetic resonance spectrum (NMR, 300M
Hz, JEOL-ECP300, C, manufactured by JEOL Ltd.
DCL3) has a < ¹ > H-NMR ([sigma], ppm): 2.47.
(D, J = 5 Hz) +2.71 (dd, J = 5 Hz, 3
Hz) (3H), 2.51 (d, J = 6 Hz) +2.8.
4 (dd, J = 4.5 Hz) (3H), 3.20
(M) +3.28 (m) (3H), 3.88 (dd, J
= 14 Hz, 7 Hz) +4.05 (dd, J = 14H)
z, 4 Hz) (3H), 4.17 (dd, J = 14H)
z, 5 Hz) +4.38 (dd, J = 14 Hz, 5H
z) (3H) 13C-NMR (σ, ppm): 24.87, 30.3
7, 44.88, 46.33, 47.75, 48.6
0,148.79 MASS (EI, M +): 345,329

[0038]

According to the present invention, an isocyanuric acid ester having two or three epithio rings in the molecule has been found.

An isocyanuric acid ester having two or three epithio rings in a molecule can be used as an additive to other material systems to obtain an organic material having a high refractive index. Further, a 2,3-epithiopropyl group or 2,2 which is a functional group site of the isocyanuric acid ester
The 3-epithio-2-methylpropyl group shows reactivity.
For example, reactive compounds such as other epithio compounds, or epoxy compounds, or mercapto compounds, mercaptocarboxylic acids, carboxylic acids, carboxylic anhydrides, amines, phenols, olefins, acrylates, methacrylates, etc. Reacts with.

The isocyanuric acid ester of the present invention has a high refractive index because it has a high sulfur content per unit weight even when used as a curing agent or an additive in addition to the properties of the compound itself. It has the feature of being an organic material. Further, it can be polymerized singly using a basic substance as a catalyst, and can be used as a crosslinking agent for a reactive compound or a reactive polymer.

Claims (5)

[Claims] (1) Formula (1): (In the formula, X represents an oxygen atom or a sulfur atom, and R represents a hydrogen atom or a methyl group.) An isocyanurate having an epithiopropyl group represented by the formula: 2. A 1,3,5-tris- (2,3-epithiopropyl) of the formula (1) wherein X is a sulfur atom and R is hydrogen.
Isocyanurate. 3. A 1,3,5-tris- (2,3-epithio-2-yl) of the formula (1) wherein X is a sulfur atom and R is a methyl group.
Methylpropyl) isocyanurate. 4. Formula (2): (Wherein, R represents a hydrogen atom or a methyl group) and an isocyanurate having an epoxy group represented by the formula:
A method for producing an isocyanuric ester having an epithiopropyl group represented by the formula (1), which comprises reacting a sulfur conversion reagent. 5. The method according to claim 4, wherein the oxygen-sulfur conversion reagent is thiourea or thiocyanate.