JPH093058A - Novel thiol derivative and its production - Google Patents

Abstract

PURPOSE: To obtain a novel thiol derivative which has high refractive index, gives cured products excellent in transparency and can be used as a raw material for optical materials, coating materials and adhesives. CONSTITUTION: This thiol derivative is shown by formula I. This compound is obtained by reaction of (A) bis(4-mercaptophenyl)sulfide with (B) an allyl halide such as allyl chloride in the presence of an alkali at 0-70 deg.C, preferably 10-40 deg.C. In this reaction, the component B is used in an amount of 1-1.5 equivalent amount, preferably 1-1.2 equivalent amount per 1 equivalent amount of the component A. In addition, this thiol derivative is shown by formula II. This thiol compound of formula II is prepared by reaction of (C) bus(4-(2,3- epoxypropylthio)phenyl)sulfide with (D) thiourea or a thiocyanate salt at 0-80 deg.C, preferably 10-60 deg.C where the amount of the component (D) is a 1-4, preferably 1-3 equivalent per one equivalent of the component (C).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel thiol derivative, more specifically, a plastic lens for glasses, a Fresnel lens, a lenticular lens, an optical disk substrate,
Plastic optical fiber, prism sheet for LCD,
The present invention relates to a novel thiol derivative that is extremely useful as a raw material for optical materials such as light guide plates and diffusion sheets, paints, adhesives, and sealants, especially optical materials, and a method for producing the same.

[0002]

2. Description of the Related Art Resins for organic optical materials have been widely used in recent years as various materials because they are lighter in weight and easier to handle than glass and the like. As such resins for organic optical materials, polystyrene resins, polymethylmethacrylate resins, polycarbonate resins, diethylene glycol diallyl carbonate resins, etc. have been widely used.

However, such conventional resins for organic optical materials have the drawbacks of low refractive index, large birefringence and high dispersibility, and are inferior in heat resistance and impact resistance, so that they are not always satisfactory. There wasn't.

Particularly, diethylene glycol diallyl carbonate resin (CR-) used as a material for lenses.
39) and the like have a low refractive index of 1.50, and thus when used as a lens, the edge thickness and the center thickness become thick, so that the appearance of the lens is deteriorated and the weight is increased. .

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

Japanese Examined Patent Publication (Kokoku) No. 4-15249 and Japanese Patent Laid-Open No. Sho 6
0-199016 discloses a technique for obtaining a resin by polymerizing an isocyanate compound and a polythiol. However, although this resin also has a large refractive index of 1.60, it 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 the heat during the polymerization. It had the drawback of large distortion.

[0007]

In view of the above situation, an object of the present invention is to provide a novel thiol derivative which is a monomer suitable for producing a transparent resin having a high refractive index, and a method for producing the same. That is the purpose.

[0008]

According to the present invention, there is provided the following formula (I):
Alternatively, it relates to a novel thiol derivative represented by the following formula (II) and a method for producing the same.

[0009]

Embedded image

The bis (4-allylthiophenyl) sulfide represented by the above formula (I) can be obtained by reacting bis (4-mercaptophenyl) sulfide and an allyl halide in the presence of an alkali as shown in the following formula (III). It can be produced by reacting in water or in a two-phase system of water and an organic solvent while stirring.

[0011]

[Chemical 6]

(In the formula, X represents a halogen atom.)

Examples of the allyl halide include allyl chloride, allyl bromide, and allyl iodide. The amount of allyl halide used is 1 to 1.5 equivalents based on bis (4-mercaptophenyl) sulfide. , Preferably 1
1.2 equivalents.

Examples of the alkali include metal hydroxides such as sodium hydroxide and potassium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, and tertiary amines such as triethylamine and tributylamine. Sodium hydroxide is the most preferable in terms of properties, and the amount used is 1 with respect to bis (4-mercaptophenyl) sulfide.
~ 1.5 equivalents, preferably 1-1.2 equivalents.

At this time, the reaction temperature is 0 to 70 ° C., preferably 10 to 40 ° C. As the organic solvent, it is preferable to use hydrocarbons such as n-hexane, n-heptane, cyclohexane, toluene and xylene, and halogenated hydrocarbons such as chlorobenzene and o-dichlorobenzene.

After the reaction, the organic layer and the aqueous layer are separated, the organic layer is washed with water, and then the solvent is distilled off to obtain the bis (4-allylthiophenyl) sulfide of the present invention.

The bis (4- (2,3-epithiopropylthio) phenyl) sulfide represented by the above formula (II) of the present invention is bis (4-) as shown in the following formula (IV).
It can be produced by reacting (2,3-epoxypropylthio) phenyl) sulfide with thiourea or thiocyanate in an organic solvent.

[0018]

[Chemical 7]

The method for producing the raw material bis (4- (2,3-epoxypropylthio) phenyl) sulfide is not particularly limited, and examples thereof include bis (4-mercaptophenyl).
After addition reaction of epichlorohydrin with sulfide,
Method for carrying out ring closure reaction (J. Appl. Poly. Sc
i. 39, 1623 (1990), US Patent No. 2
No. 731437).

As the thiocyanate, thiocyanates such as potassium thiocyanate and ammonium thiocyanate can be used. The amount of thiourea or thiocyanate used is 1 to 4 equivalents, preferably 1 to 3 equivalents, relative to bis (4- (2,3-epoxypropylthio) phenyl) sulfide.

Examples of the organic solvent used include halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chlorobenzene and o-dichlorobenzene, and hydrocarbons such as n-hexane, n-heptane, cyclohexane, toluene and xylene. , Tetrahydrofuran, ethers such as 1,4-dioxane, methanol, ethanol, is
Examples thereof include alcohols such as o-propanol.

The reaction temperature is 0 to 80 ° C., preferably 10
６０60 ° C. After the reaction, water is added to separate the organic layer from the aqueous layer, the organic layer is washed with water, and then the solvent is distilled off to give bis (4- (2,3-epithiopropylthio)) of the present invention.
Phenyl) sulfide can be obtained.

The novel thiol derivative of the present invention can be copolymerized by blending a copolymerizable compound depending on the purpose of use and the like. Examples of the compound copolymerizable with the novel thiol derivative of the present invention include a monomer having a vinyl group, an oligomer having a vinyl group, a monomer having an epoxy group, an oligomer having an epoxy group, a monomer having a thiol group, and a thiol group. Examples thereof include oligomers and the like, and not only a monofunctional compound but also a polyfunctional compound can be selected according to the purpose of use, and two or more kinds of these compounds can be used in combination. Further, a composition containing the novel thiol derivative of the present invention and a copolymerizable compound,
It can be copolymerized by heat, light or the like by a usual method.

[0024]

The present invention will be described below in more detail with reference to examples.

Example 1 300 m equipped with stirrer, thermometer, Dimroth type cooling tube
In a four-necked 1-liter flask, 50.1 g (0.20 mol) of bis (4-mercaptophenyl) sulfide and 4 parts of water were added.
0 g was charged, and 0.038 g of sodium borohydride prepared separately while keeping the reaction temperature at 20 to 30 ° C.
59.3 g (0.40 mol) of a 27% aqueous sodium hydroxide solution containing (0.001 mol) was added dropwise over 1 hour. After the dropping was completed, the mixture was further stirred at 75 to 80 ° C. for 1.5 hours and then cooled to 20 ° C. Next, 50.0 g (0.416 mol) of allyl bromide was added to a 1-liter four-necked flask equipped with a stirrer, a thermometer, and a Dimroth-type condenser prepared separately.
Then, 300 g of toluene and 1.61 g (0.005 mol) of tetra-n-butylammonium bromide were charged, and the aqueous solution obtained by the above reaction was added dropwise over 45 minutes while maintaining the reaction temperature at 20 ° C or lower. Furthermore, after stirring at 20 ° C. for 1 hour, the reaction solution was separated. The organic layer was washed twice with 100 g of water and then dehydrated with anhydrous sodium sulfate, and toluene was distilled off to obtain a pale yellow liquid. By purifying this liquid by column chromatography, a colorless transparent liquid was obtained.

Analysis was performed to determine the structure of this novel thiol derivative. The results are shown below. Refractive index (n ²⁵ _D ) 1.666 Elemental analysis value Theoretical value (%) C: 65.41 H: 5.49
S: 29.10 Analytical value (%) C: 65.47 H: 5.53
S: 29.00 Infrared absorption spectrum (NaCl cm ^-1 ) 3080, 1635, 1575, 1473, 1425,
1388, 1228, 1099, 1076, 1010,
987,924 ¹ H-nuclear magnetic resonance spectrum (CDCl ₃ solvent, tetramethylsilane standard) δ (ppm) 7.23 (S, 8H, aromatic ring hydrogen), 6.1 to 5.6.
(M, 2H, -CH = C-), 5.4 to 5.0 (2d,
_{4H, CH 2 = C -)} , 3.52 (d, 4H, -SCH
₂ −)

From the above analysis results, the colorless transparent liquid was identified as bis (4-allylthiophenyl) sulfide.
The yield was 62.3 g, which was 94.2% based on the raw material bis (4-mercaptophenyl) sulfide.

Example 2 72.6 g (0.2 mol) of bis (4- (2,3-epoxypropylthio) phenyl) sulfide in a 1 liter four-necked flask equipped with a stirrer, thermometer and Dimroth condenser. 200 g of methylene chloride and 160 g of methanol were charged and the temperature was raised to 40 ° C. Then the reaction temperature is 40-
While maintaining the temperature at 45 ° C, 61 g (0.8 mol) of thiourea was added, and the mixture was stirred at the same temperature for 4 hours. Then, it cooled to room temperature, added 200 g of water, and stirred for 30 minutes. After separating the organic layer and the aqueous layer, the organic layer was washed twice with 200 g of water, the solvent was distilled off, and the residue was recrystallized with a mixed solvent of toluene / n-hexane to obtain white crystals.

Analysis was performed to determine the structure of this novel thiol derivative. The results are shown below. Melting point 41.5 to 43.0 ° C Refractive index (n ⁴⁵ _D ) 1.703 Elemental analysis value Theoretical value (%) C: 54.78 H: 4.60
S: 40.62 Analytical value (%) C: 54.80 H: 4.55
S: 40.65 Infrared absorption spectrum (KBrcm ^-1 ) 2923, 1473, 1388, 1099, 1008,
806 ¹ H-nuclear magnetic resonance spectrum (CDCl ₃ solvent, tetramethylsilane standard) δ (ppm) 7.5 to 7.2 (m, 8H, aromatic ring hydrogen), 3.6 to
2.1 (m, 10H, epithiopropylthiohydrogen)

From the above analysis results, white crystals are bis (4
-(2,3-Epithiopropylthio) phenyl) sulfide. The yield was 73.8 g, and the yield was 93.5% with respect to the raw material bis (4- (2,3-epoxypropylthio) phenyl) sulfide.

[0031]

INDUSTRIAL APPLICABILITY The novel thiol derivative of the present invention is polymerized 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 novel thiol derivative of the present invention has excellent physical properties in optical materials, paints, and
It is a very useful monomer that provides adhesives, encapsulants, etc.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Michio Suzuki 1 346 Miyanishi, Harima-cho, Kako-gun, Hyogo Prefecture Sumitomo Seika Co., Ltd. 1st research institute (72) Inventor Kazuo Sakiyama Irifune-cho, Shimaki-ku, Himeji-shi, Hyogo No. 1 Sumitomo Seika Chemical Co., Ltd. Second Research Center

Claims (4)

[Claims] 1. A novel thiol derivative represented by the following formula (I): Embedded image 2. A process for producing a novel thiol derivative represented by the following formula (I), which comprises reacting bis (4-mercaptophenyl) sulfide with an allyl halide in the presence of an alkali. Embedded image 3. A novel thiol derivative represented by the following formula (II). Embedded image 4. A novel thiol derivative represented by the following formula (II), which comprises reacting bis (4- (2,3-epoxypropylthio) phenyl) sulfide with thiourea or thiocyanate. Production method. Embedded image