JPH1112273A - Episulfide compound and its compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful as a polymerization raw material for optical materials such as plastic lens for glasses, a coating material, etc., suitable as a monomer for producing a resin having a high refractive index and excellent transparency. SOLUTION: This compound is shown by formula I ((n) is 0-5) such as 4,4'bis(2,3-epithiopropylthiomethyl)phenyl sulfide. The compound of formula I is obtained by reacting (A) an epoxy compound of formula II with (B) (i) thiourea and/or (ii) a thiocyanate in the molar ratio of the component B to the component A of generally, 2-8 times, preferably 2-6 times in (C) an organic solvent generally at a tepmerature of 0-80 deg.C, preferably 10-60 deg.C generally for 1-15 hours. Potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, etc., may be cited as the component (ii). Methylene chloride, toluene, chlorobenzene, methanol, ethanol, etc., are preferably used as the component C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an episulfide compound and a method for producing the same. More specifically, plastic lenses for eyeglasses, Fresnel lenses, lenticure lenses, optical disc substrates, plastic optical fibers, optical materials such as LCD prism sheets, light guide plates, diffusion sheets, etc., and raw materials for polymerization such as paints, adhesives, sealing materials, etc. The present invention relates to an episulfide compound which is useful as a (monomer), and particularly extremely useful as a raw material (monomer) for polymerization of an optical material, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, resins for organic optical materials are widely used as various materials in recent years because they are lightweight and easy to handle as compared with glass and the like. Desired characteristics of the resin for optical materials include a high refractive index, a low birefringence, a low specific gravity, a low dispersibility and the like. Various attempts have been made to produce a resin having such characteristics. It has been done.

[0003] As a resin for organic optical materials, conventionally,
Polystyrene resins, polymethyl methacrylate resins, polycarbonate resins, diethylene glycol diallyl carbonate resins and the like are widely used.

However, such conventional resins for organic optical materials have drawbacks such as low refractive index, large birefringence, and high dispersibility, and are inferior in heat resistance and impact resistance. Was not.

[0005] Particularly, diethylene glycol diallyl carbonate resin (CR-
39) and the like have the drawback that when used as a lens, the edge thickness and the center thickness are increased, the appearance of the lens is deteriorated, and the weight is increased because the refractive index is as low as 1.50.

[0006] In order to solve these drawbacks, various methods for mainly improving the refractive index have been studied. For example, Japanese Patent Publication No. 5-4404 discloses a resin in which halogen is introduced into an aromatic ring. However, although the resin obtained by this technique has a high refractive index of 1.60, it has a high specific gravity of 1.37 and is not satisfactory in terms of the lightness of the lens, which is a characteristic of plastic lenses.

Further, Japanese Patent Application Laid-Open Nos. Hei 2-27059 and Hei 5-208950 disclose a method of increasing the content of sulfur atoms in monomer molecules of a resin raw material in order to increase the refractive index of a resin. Is disclosed. Here, a mercapto compound is generally used to increase the content of sulfur atoms. As this mercapto compound, for example, low-molecular-weight mercapto compounds such as methanethiol, ethanethiol, and ethanedithiol are widely known. However, these low-molecular-weight mercapto compounds have a specific mercapto odor based on thiol groups, and the amount used is restricted by the composition ratio with other resin raw materials used for curing the resin. There is.

Therefore, instead of these low-molecular-weight mercapto compounds, trimethylolpropane tris- (thioglycolate) and pentaerythritol tetrakis-
Use of a polyfunctional mercapto compound having a large molecular weight, which is used as an epoxy resin curing agent such as (thioglycolate), has been considered. However, this type of mercapto compound has the advantage of low odor due to its high molecular weight and good handleability.However, since the content of sulfur atoms in the molecule is low, the content of sulfur atoms in the resin is reduced. There is a disadvantage that it is difficult to obtain a desired refractive index by increasing it ideally.

Further, Japanese Patent Publication No. 4-15249 and Japanese Patent Application Laid-Open No. 60-199016 disclose a technique for obtaining a resin by polymerization of an isocyanate compound and a polythiol. However, this resin also has a refractive index as large as 1.60, but has a specific gravity of 1.30 or more, a relatively low polymerization temperature, and a high polymerization rate, which makes it difficult to control heat during polymerization. There is a disadvantage that optical distortion is large.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin having a high refractive index, which is a characteristic of an optical material desired, and excellent in transparency in view of the above-mentioned prior art. It is to provide an episulfide compound which is a monomer. Another object of the present invention is to provide a method for producing the episulfide compound.

[0011]

That is, the gist of the present invention is as follows: (1) The general formula (I):

[0012]

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(Wherein, n represents an integer of 0 to 5;
N may be the same or different), and (2) a general formula (II):

[0014]

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(Wherein, n represents an integer of 0 to 5;
N may be the same or different), and reacting an epoxy compound represented by the formula (1) with thiourea and / or thiocyanate in an organic solvent.
(I):

[0016]

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(Wherein, n represents an integer of 0 to 5;
Two n's may be the same or different), and (3) one kind in which the thiocyanate is selected from the group consisting of potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate (4) The method according to (2), wherein the organic solvent is at least one selected from the group consisting of methylene chloride, toluene, chlorobenzene, methanol, ethanol, and isopropanol. , Concerning.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The episulfide compound of the present invention has the general formula
(I):

[0020]

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(Wherein, n represents an integer of 0 to 5;
N may be the same or different). In the present invention, from the viewpoints of the refractive index, specific gravity, and the like, it is particularly preferable that two n are the same and are 0 to 2.

The episulfide compound represented by the above general formula (I) of the present invention can be suitably produced by the production method of the present invention described below, but the present invention is limited to a compound obtained only by such a production method. It is not limited. Hereinafter, the production method of the present invention will be described in detail.

The episulfide compound represented by the above general formula (I) of the present invention has the general formula (II):

[0024]

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(Wherein, n represents an integer of 0 to 5.
Two n's may be the same or different), and a thiourea and / or thiocyanate in an organic solvent.

Here, the method for producing the epoxy compound represented by the general formula (II), which is a raw material, is not particularly limited, but it can be easily prepared, for example, according to the method described in WO 97/08139. Can be manufactured. Specifically, general formula (III):

[0027]

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(Wherein, n represents an integer of 0 to 5;
The two n's may be the same or different) can be obtained by a method in which dithiol and epichlorohydrin are reacted in the presence of an alkali.

The thiocyanate used for the reaction with the epoxy compound represented by the general formula (II) includes, for example,
Thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate can be mentioned. Preferably, it is potassium thiocyanate or sodium thiocyanate. The amount of thiourea and / or thiocyanate used is usually 2 to 8 times the molar ratio of the epoxy compound represented by the general formula (II),
Preferably it is 2 to 6 times. If the molar ratio of the amount of thiourea and / or thiocyanate used is less than twice, unreacted epoxy compound remains, which is not preferable.
Even if it is used more than twice, the effect corresponding to the amount used is not obtained and it is not economical.

The organic solvent used in the reaction of the epoxy compound represented by the general formula (II) with thiourea and / or thiocyanate includes methylene chloride, 1,2
-Dichloroethane, chlorobenzene, halogenated hydrocarbons such as o-dichlorobenzene, n-hexane, n-heptane, aliphatic hydrocarbons such as cyclohexane, toluene,
Aromatic hydrocarbons such as xylene, tetrahydrofuran,
Cyclic ethers such as 1,4-dioxane, methanol,
Examples include alcohols such as ethanol and isopropanol. Preferably, methylene chloride, toluene, chlorobenzene, methanol, ethanol and isopropanol are used. These organic solvents can be used alone or
A mixture of more than one species is used.

The reaction temperature is usually 0 to 80 ° C, preferably 10 to 60 ° C. If the reaction temperature is lower than 0 ° C., the progress of the reaction will be slow. The reaction time varies depending on the reaction temperature, but is usually 1 to 15 hours.

After completion of the reaction, water is added to the reaction solution to separate an organic layer and an aqueous layer, and the obtained organic layer is washed with water. An episulfide compound can be obtained. Further, if necessary, it can be purified by column chromatography.

The episulfide compound represented by the general formula (I) of the present invention can obtain a polymer used for an optical material, a paint, an adhesive, a sealing material, or the like by homopolymerization or copolymerization.

In the present invention, the compound copolymerizable with the episulfide compound represented by the general formula (I) includes:
Although not particularly limited, for example, a monomer having an epoxy group, an oligomer having an epoxy group, a monomer having a polymerizable unsaturated bond, an oligomer having a polymerizable unsaturated bond, a monomer having a thiol group, an oligomer having a thiol group, and an isocyanate Examples include a monomer having a nate group, a monomer having an amino group, and the like. Depending on the purpose of use, not only a monofunctional compound but also a polyfunctional compound can be selected. The above may be used in combination.

Examples of the monomer having an epoxy group and the oligomer having an epoxy group include phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl ether of bisphenol A, glycidyl acrylate, glycidyl methacrylate, and 4,4 ′.
-Bis (2,3-epoxypropylthio) phenyl sulfide and the like.

The monomer having a polymerizable unsaturated bond and the oligomer having a polymerizable unsaturated bond are not particularly restricted but include, for example, styrene, divinylbenzene, bis (4-vinylthiophenyl) sulfide, 4,4'- Bis (vinylthiomethyl) phenyl sulfide, bis (4
-Methacryloylthiophenyl) sulfide, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, diethylene glycol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, glycidyl acrylate, glycidyl methacrylate and the like.

The monomer having a thiol group and the oligomer having a thiol group are not particularly limited. For example, 1,3-benzenedithiol, 1,4-benzenedithiol, bis (4-mercaptophenyl) sulfide, 1,2 -Ethanedithiol, pentaerythritol tetrakismercaptopropionate, 4,4'-bis (mercaptomethyl) phenyl sulfide, 4,4'-
Bis (4-mercapto-2-thiabutyl) phenyl sulfide, 4,4′-bis (7-mercapto-2,5-dithiaheptyl) phenyl sulfide and the like can be mentioned.

The monomer having an isocyanate group is not particularly limited, and examples thereof include xylylene diisocyanate, dichlorodiphenyl diisocyanate, hexamethylene diisocyanate, and bis (isocyanatomethyl) cyclohexane.

The monomer having an amino group is not particularly restricted but includes isophoronediamine, cyclohexanediamine, xylylenediamine, tolylenediamine and the like.

The episulfide compound of the present invention represented by the general formula (I) can be homopolymerized by a conventional method such as heating. The episulfide compound represented by the general formula (I) and a compound copolymerizable with the compound can be copolymerized by heat, light, or the like by an ordinary method.

The episulfide compound of the present invention represented by the general formula (I) has a refractive index of 1.65 or more.
A cured product having a high refractive index of 1.65 or more can be obtained by homopolymerization, and a cured product obtained by copolymerization can be obtained by appropriately selecting a partner monomer or the like.
Those having a high refractive index of 65 or more are obtained. Further, these cured products are excellent in transparency because they are uniform polymers.

[0042]

The present invention will be described in more detail with reference to the following Examples and Reference Examples, but the present invention is not limited by these Examples and the like.

Example 1 Production example of 4,4'-bis (2,3-epithiopropylthiomethyl) phenyl sulfide (compound of the general formula (I) wherein n is 0) Stirrer, thermometer, condenser In a 1-liter four-necked flask equipped with, 128.9 g of 4,4'-bis (2,3-epoxypropylthiomethyl) phenyl sulfide
(0.33 mol), 300 g of methylene chloride, 250 g of methanol, and 100.7 g (1.32 mol) of thiourea were charged, and the mixture was stirred for 4 hours while maintaining the reaction temperature at 40 to 45 ° C. to carry out a reaction. After completion of the reaction, the reaction solution was cooled to room temperature, 250 g of water was added to the reaction solution, and then separated into an organic layer and an aqueous layer,
The obtained organic layer was washed twice with 200 g of water. Thereafter, the solvent of the washed organic layer was distilled off, and the residue was purified by column chromatography to obtain a white solid. Analysis was performed to determine the structure of this compound. The results are shown below.

Molecular weight 422.7 Melting point 56.5-57.5 ° C. Refractive index (60 ° C.) n _D = 1.666 Elemental analysis Theoretical value (%) C: 56.83, H: 5.25, S: 37 .93 Analytical value (%) C: 56.72, H: 5.35, S: 37.85 Infrared absorption spectrum (KBrcm ^-1 ) 2910, 2848, 1899, 1592, 1488,
1434, 1400 1350, 1307, 1240, 1197, 1149,
1085, 1049 1045, 1016, 925, 892, 863, 82
7,744,613 520,505 ¹ H-nuclear magnetic resonance spectrum (CDCl ₃ solvent, TMS
Reference) δ (ppm) 7.32 (S , 8H, -C 6 H 4 -) 3.78 (S, 4H, -SC H 2 C 6 H 4 -)

[0045]

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The refractive index was measured by Abago refractometer 4T manufactured by Atago.
It was measured using a mold. The same applies to the following embodiments.

From the above analysis results, the white solid was 4,4 ′.
-Bis (2,3-epithiopropylthiomethyl) phenyl sulfide (a compound of the formula (I) wherein n is 0). The yield was 129.7 g, and the yield was 4,
93.0% based on 4'-bis (2,3-epoxypropylthiomethyl) phenyl sulfide.

Example 2 4,4'-bis (4- (2,3-epithiopropylthio) -2-thiabutyl) phenyl sulfide (general formula
Production Example of (I) wherein n is 1) In Example 1, 4,4'-bis (2,3-epoxypropylthiomethyl) phenyl sulfide 12
8.9 g (0.33 mol) of 4,4'-bis (4-
(2,3-epoxypropylthio) -2-thiabutyl)
The reaction was carried out in the same manner as in Example 1 except that phenylsulfide was changed to 168.5 g (0.33 mol), and purification was carried out to obtain a white solid. Analysis was performed to determine the structure of this compound. The results are shown below.

Molecular weight 543.0 Melting point 46.0-47.0 ° C. Refractive index (60 ° C.) n _D = 1.664 Elemental analysis Theoretical value (%) C: 53.09, H: 5.57, S: 41 .34 Analytical value (%) C: 53.15, H: 5.45, S: 41.19 Infrared absorption spectrum (KBrcm ^-1 ) 2912, 2846, 1594, 1490, 1419,
1402, 1400 1270, 1240, 1195, 1124, 1083,
1043, 1014 887, 827, 734, 686, 661, 613, 5
22,499 ¹ H-nuclear magnetic resonance spectrum (CDCl ₃ solvent, TMS
Reference) δ (ppm) 7.26 (S , 8H, -C 6 H 4 -) 3.72 (S, 4H, -SC H 2 C 6 H 4 -)

[0050]

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From the above analysis results, the white solid was 4,4 ′.
-Bis (4- (2,3-epithiopropylthio) -2-
Thiabutyl) phenyl sulfide (compound having the general formula (I) wherein n is 1). The yield is 164.4g,
The yield was 91.8% based on the raw material 4,4'-bis (4- (2,3-epoxypropylthio) -2-thiabutyl) phenyl sulfide.

Example 3 Preparation of 4,4'-bis (7- (2,3-epithiopropylthio) -2,5-dithiaheptyl) phenyl sulfide (compound of general formula (I) wherein n is 2) Example In Example 1, 128.9 g of 4,4′-bis (2,3-epoxypropylthiomethyl) phenyl sulfide
(0.33 mol) was added to 208.3 g (0.33 mol) of 4,4′-bis (7- (2,3-epoxypropylthio) -2,5-dithiaheptyl) phenyl sulfide and 100.7 g of thiourea (1.32 mol) was replaced with 128.3 g (1.32 mol) of potassium thiocyanate. Analysis was performed to determine the structure of this compound. The results are shown below.

Molecular weight 663.2 Melting point 47.0-48.0 ° C. Refractive index (60 ° C.) n _D = 1.663 Elemental analysis Theoretical value (%) C: 50.71, H: 5.78, S: 43 .52 analysis value (%) C: 50.63, H: 5.85, S: 43.39 Infrared absorption spectrum (KBrcm ^-1 ) 2911, 2847, 1594, 1490, 1422,
1402, 1400 1272, 1240, 1194, 1122, 1085,
1043, 1013 826, 735, 688, 660, 612, 521, 5
00 ¹ H-nuclear magnetic resonance spectrum (CDCl ₃ solvent, TMS
Reference) δ (ppm) 7.25 (S , 8H, -C 6 H 4 -) 3.71 (S, 4H, -SC H 2 C 6 H 4 -)

[0054]

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From the above analysis results, the white solid was 4,4 ′.
-Bis (7- (2,3-epithiopropylthio) -2,
5-dithiaheptyl) phenyl sulfide (general formula (I)
And n was 2). The yield was 198.
0 g, and the yield was 4,4′-bis (7- (2,3-
90.5% based on epoxypropylthio) -2,5-dithiaheptyl) phenyl sulfide.

Reference Example 20 g of 4,4′-bis (2,3-epithiopropylthiomethyl) phenyl sulfide (compound of the general formula (I), in which n is 0) obtained in Example 1
A solution of I-60 (cationic polymerization initiator manufactured by Sanshin Chemical Co., Ltd.) / Diethylene glycol dimethyl ether = 1/2 was added to 0.1%.
After adding 6 g, sufficiently stirring and degassing, the mixture was poured into a glass mold having a diameter of 5 cm and a thickness of 3 mm, and the temperature was reduced from 50 ° C. to 130
The temperature was raised to 6 ° C. over 6 hours, the temperature was maintained at 130 ° C. for 3 hours, and the mold was removed. The resulting resin is uniform, colorless and transparent,
The refractive index was n _D ²⁰ = 1.698.

[0057]

According to the present invention, the episulfide compound of the present invention is homopolymerized by itself or is copolymerized with various copolymerizable compounds to obtain a cured product having a high refractive index and excellent transparency. be able to. Therefore, the episulfide compound of the present invention is a very useful monomer that provides an optical material, a paint, an adhesive, a sealing material, and the like having excellent physical properties.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Michio Suzuki 346 Miyanishi, Harima-cho, Kako-gun, Hyogo Pref.

Claims (4)

[Claims] [Claim 1] General formula (I): (Where n represents an integer of 0 to 5; two n's may be the same or different). 2. A compound of the general formula (II): (Wherein n represents an integer of 0 to 5; two n's may be the same or different), and a thiourea and / or thiocyanate are reacted in an organic solvent. General formula (I) characterized by the following: (Wherein, n represents an integer of 0 to 5; two n's may be the same or different). 3. The thiocyanate is at least one selected from the group consisting of potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate.
The manufacturing method as described. 4. The method according to claim 2, wherein the organic solvent is at least one selected from the group consisting of methylene chloride, toluene, chlorobenzene, methanol, ethanol and isopropanol.