JPH0931047A - Novel xylylenedithiol derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new xylylenedithiol derivative useful as a raw material for resins used in optical lenses, etc., having good optical physical properties, etc. SOLUTION: This compound of formula I, i.e., 1,4-bis(mercaptopropylthiomethyl)benzene or a compound of formula II (R is H or methyl). p-Xylylenedithiol prepared by reacting p-xylylene dichloride with thiourea is converted into an alkaline salt with sodium hydroxide, etc. The resultant salt is then reacted with 1-bromo-3-chloropropane to afford S,S'-bis(chloropropyl)-p-xylylene dithioether, which is further reacted with thiourea in a solvent to provide the compound of formula 1. The resultant compound of formula I is reacted with acryloyl chloride, etc., in a solvent without reactivity with the raw material in the presence of a chlorine capturing agent (e.g. an aqueous solution of potassium hydroxide) to afford the compound of formula II.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to good optical properties,
The present invention relates to a novel xylylenedithiol derivative useful as a raw material for optical lens resins having a high refractive index and excellent scratch resistance.

[0002]

2. Description of the Related Art Plastic lenses are lighter and harder to break than inorganic lenses, and can be dyed. Therefore, plastic lenses have recently been rapidly used in optical elements such as spectacle lenses and camera lenses. Currently, resins widely used for these purposes include diethylene glycol bis (allyl carbonate)
Some are radically polymerized (hereinafter referred to as DAC). This resin has various characteristics such as excellent heat resistance, light weight, excellent dyeability, and good workability such as machinability and abrasivity. However, this resin has a smaller refractive index than inorganic glass, and in order to obtain optical characteristics equivalent to those of glass lenses, it is necessary to increase the center thickness, edge thickness, and curvature of the lens, and the overall thickness is increased. It cannot be avoided. Therefore, a resin for lenses having a higher refractive index has been desired.

Polyurethane lenses are known as lenses having a higher refractive index than DAC resin. For example, JP-A-63-46213 proposes a polyurethane lens composed of a xylylene diisocyanate compound and a polythiol compound. Further, JP-A-2-270859 proposes a polyurethane lens having a high refractive index, light weight, and excellent impact resistance by combining a specific polythiol compound and an isocyanate compound. However, lenses made of these resins have the drawbacks that the scratch resistance is not sufficient and the surface of the lens is easily scratched. Further, in order to obtain an optically uniform lens, the polymerization time becomes long and the workability may be complicated. Therefore, further improvement has been desired to solve these problems.

[0004]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a novel xylylenedithiol derivative useful as a raw material for an optical lens resin having good optical properties, high refractive index and excellent scratch resistance. It is a thing.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies in order to solve the above problems, and as a result, the present invention has been achieved. That is, the present invention provides a novel formula (1)
And a xylylenedithiol derivative represented by the formula (2)
The present invention relates to a xylylenedithiol derivative represented by (Chemical Formula 3).

[0006]

Embedded image (In the above formula, R represents a hydrogen atom or a methyl group)

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The xylylenedithiol derivative represented by the formula (1), that is, 1,4-bis (mercaptopropylthiomethyl) benzene is obtained by the following method. That is, first, p-xylylene dichloride and thiourea are added.
After reacting in a water solvent to obtain p-xylylenedithiol, and then converting p-xylylenedithiol into an alkali salt with sodium hydroxide, potassium hydroxide, etc., 1-bromo-3-chloropropane in a solvent To react with S,
By obtaining S′-bis (chloropropyl) -p-xylylenedithioether and reacting the obtained S, S′-bis (chloropropyl) -p-xylylenedithioether with thiourea in a solvent, A xylylenedithiol derivative represented by the formula (1) of the present application is obtained.

In the reaction, the amount of thiourea used is p
-2 to 2.5 mol, preferably 2 to 2.1 mol, relative to 1 mol of xylylene dichloride, and the amount of water used is
600 to 1 per mol of p-xylylene dichloride
It is 000 ml, preferably 700 to 900 ml. The reaction temperature is 100 to 105 ° C., and the reaction time is 4
~ 6 hours. After completion of the reaction, the product is dissolved in an organic solvent such as toluene or benzene, and the organic layer is washed well,
The solvent is distilled off to obtain the product. This product can be further purified by a known method, if necessary.

In the reaction, the amount of 1-bromo-3-chloropropane used is 2-2.5 mol, preferably 2-2.1 mol, per 1 mol of p-xylylenedithiol. The solvent used in the reaction may be any solvent that is not reactive with the raw materials and the like, and examples thereof include water, ethanol, and an aprotic solvent N, N-dimethylformamide. The amount of the solvent used is 300 to 3000 ml, preferably 800 to 1 mol, relative to 1 mol of p-xylylenedithiol.
It is 2000 ml. The reaction temperature is 5 to 120 ° C,
The temperature is preferably 30 to 100 ° C., and the reaction time is 1 to 20 hours, preferably 2 to 10 hours. At this time, a surfactant, a phase transfer catalyst, or the like may be used if necessary. After completion of the reaction, the product is dissolved in an organic solvent such as toluene and benzene, the organic layer is washed well, and then the solvent is distilled off to obtain the product. This product can be further purified by a known method, if necessary.

In the reaction, the amount of thiourea used is
The amount is 2-2.5 mol, preferably 2-2.1 mol, per 1 mol of S, S'-bis (chloropropyl) -p-xylylenedithioether. The solvent used in the reaction is
Any solvent may be used so long as it is not reactive with the raw materials such as water,
Examples thereof include ethanol, aprotic solvent N, N-dimethylformamide, dimethyl sulfoxide, and the like. The amount of the solvent used is S, S′-bis (chloropropyl) -p-
200 to 10 per mol of xylylene dithioether
It is 00 ml, preferably 600 to 900 ml. The reaction temperature is 30 to 120 ° C., preferably 60 to 90.
At C, the reaction time is 1 to 15 hours, preferably 2 to 5 hours. At this time, if necessary, a halogen displacing agent such as potassium iodide or potassium bromide, a surfactant, a phase transfer catalyst and the like may be used. After the reaction is completed, the product is toluene,
After dissolving in an organic solvent such as benzene and thoroughly washing the organic layer, the solvent is distilled off to obtain a product. This product can be further purified by a known method, if necessary.

The xylylenedithiol derivative represented by the formula (2), that is, the diester of 1,4-bis (mercaptopropylthiomethyl) benzene and (meth) acrylic acid, was obtained by the above method. A known method, that is, acrylic acid chloride or methacrylic acid chloride, is added to the dithiol represented by the formula (1) in a solvent which is not reactive with raw materials such as acetone, toluene and chloroform.
It is obtained by reacting in the presence of a hydrochloric acid scavenger.
The amount of acrylic acid chloride or methacrylic acid chloride used is 2 to 2.5 mol per 1 mol of the dithiol represented by the formula (1). The reaction temperature is kept at -10 to 35 ° C, and a hydrochloric acid aqueous solution, a sodium hydroxide aqueous solution, a hydrochloric acid scavenger such as triethylamine and pyridine is added to proceed the reaction. After completion of the reaction, the product is dissolved in an organic solvent such as toluene or benzene, and the organic layer is washed well,
The solvent is distilled off to obtain the product. This product can be further purified by a known method, if necessary.

[0012]

EXAMPLES Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. All parts shown in the examples are parts by weight. Example 1 Reaction: Synthesis of p-xylylene dithiol 78.5 parts of p-xylylene dichloride, thiourea 7
1.5 parts and 275 parts of water were mixed, and the reaction liquid temperature was kept at 102 ° C. and stirred for 5 hours. After completion of the reaction, the mixture was cooled, and under a nitrogen atmosphere, 144 parts of a 50 wt% sodium hydroxide aqueous solution was added, the reaction liquid temperature was kept at 100 ° C., and the mixture was stirred for 30 minutes. Then, the reaction solution was cooled to 40 ° C., 180 parts of concentrated hydrochloric acid was added,
It was stirred for 30 minutes as it was. After completion of the reaction, toluene 20
0 part was added, extraction was carried out, and the organic layer was separated. Organic layer with water 1
After washing with 50 parts, concentration and distillation were performed to obtain p-xylylenedithiol as a distillate. Colorless solid, yield 5
9 copies.

Reaction: Synthesis of S, S'-bis (chloropropyl) -p-xylylenedithioether 112 parts of 1-bromo-3-chloropropane and 130 parts of ethanol were added to 59 parts of p-xylylenedithiol obtained by the reaction. A solution obtained by reacting 47 parts of potassium hydroxide with 300 parts of ethanol was added dropwise over 1.5 hours while maintaining the reaction solution temperature at 60 to 70 ° C. After dropping, 3 under reflux
The reaction was performed for 0 minutes. After the reaction was completed, 460 parts of water and 4 parts of toluene
00 parts was added and extracted, and the organic layer was separated. The organic layer was washed with 350 parts of water and then concentrated. The concentrate was purified by a chromatographic method to give a pale red syrupy S, S'-bis (chloropropyl) -p-xylylenedithioether 8
One part was obtained.

Reaction: Synthesis of dithiol represented by formula (1) S, S'-bis (chloropropyl) -obtained by reaction
19.5 parts of p-xylylene dithioether, 9.5 parts of thiourea, and 35 parts of N, N-dimethylformamide were kept at a liquid temperature of 80 to 85 ° C. and stirred for 5 hours to cause a reaction. After the reaction was completed, 300 parts of a 10 wt% sodium hydroxide aqueous solution was added, and the mixture was stirred at room temperature for 30 minutes. Next, 10 wt%
250 parts of hydrochloric acid was added, and the mixture was stirred at room temperature for 30 minutes. Then, 160 parts of toluene was added and extraction was carried out to separate the organic layer. The organic layer was washed with 250 parts of water and then concentrated. The concentrate was purified by a chromatographic method to obtain 8 parts of dithiol represented by the following formula (1) (formula 4) in the form of a colorless syrup.

[0015]

Embedded image

Example 2 Synthesis of dimethacrylate Dithiol 8 represented by the formula (1) obtained in Example 1
Parts, acetone 40 parts, 20 wt% sodium hydroxide 1
1.6 parts were mixed, and 5.7 parts of methacrylic acid chloride was added dropwise while maintaining the reaction solution temperature at 10 to 20 ° C. After the completion of dropping, the mixture was stirred for 30 minutes. Next, 200 parts of water and 80 parts of toluene were added and extracted, and the organic layer was separated. The organic layer is 100 parts of a 5 wt% sodium hydrogen carbonate aqueous solution and 15 parts of water.
After washing with 0 part, it was concentrated. The concentrate was purified by a chromatographic method to obtain 1.6 parts of a colorless syrupy dimethacrylate represented by the following formula (3) (formula 5).

[0017]

Embedded image

Example 3 Synthesis of diacrylate The procedure of Example 2 was repeated except that 5.7 parts of methacrylic acid chloride of Example 2 was replaced with 5.0 parts of acrylic acid chloride and the reaction temperature was 5 ° C. 0.5 parts of a colorless syrupy diacrylate represented by the following formula (4) (formula 6) was obtained.

[0019]

[Chemical 6]

Reference Example 1 With respect to 35 parts of the dimethacrylate obtained in Example 2,
T-butylperoxy-2- as a radical polymerization initiator
35 mg of ethyl hexanoate was added and mixed well. After sufficiently defoaming this, it was poured into a mold composed of a glass mold and a gasket. The temperature was raised to 30 to 120 ° C over 1 hour, and further heated at 120 ° C for 1 hour. After the completion of the polymerization, the mixture was gradually cooled and the molded product was taken out of the mold. The obtained molded product was colorless and transparent, and had a refractive index n _d = 1.63 and an Abbe number ν _d = 40. The scratch resistance was also very good, and the evaluation was good. The refractive index, Abbe number, scratch resistance, appearance and impact resistance were evaluated by the following test methods. * Refractive index, Abbe number: 20 using Pulfrich refractometer
Measured in ° C. * Scratch resistance: The surface of the resin was rubbed with # 0000 steel wool to examine the scratch resistance of the surface, and judged as follows. ◯: No scratch even if strongly rubbed Δ: Slightly scratched if strongly rubbed ×: Damaged even if weakly rubbed * Appearance: visually observed. * Impact resistance: Height 127 cm at the center of the manufactured lens
The impact resistance was evaluated by dropping an iron ball from the.

Reference Example 2 With respect to 35 parts of the diacrylate obtained in Example 3, 17.5 mg of t-butylperoxy-2-ethylhexanoate was used as a radical polymerization initiator, and 2-hydroxy- was used as a sensitizer. 35 mg of 2-methyl-1-phenylpropan-1-one were added and mixed well. After sufficiently defoaming this, it was poured into a mold composed of a glass mold and a gasket. After irradiating with ultraviolet rays for 5 minutes while cooling, the temperature was raised to 30 to 120 ° C. over 1 hour, and further 1
Heated at 20 ° C. for 1 hour. After the completion of polymerization, gradually cool,
The molded body was taken out of the mold. The obtained molded body is
Colorless and transparent, refractive index n _d = 1.64, Abbe number ν _d
= 35. The scratch resistance was very good, and the evaluation was good.

Reference Example 3 With respect to 32 parts of dimethacrylate obtained in Example 2,
8 g of polyethylene glycol dimethacrylate [n = 9, manufactured by Shin-Nakamura Chemical Co., Ltd .: NK ester 9G], 17.5 mg of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator, 2 as a sensitizer 70 mg of -hydroxy-2-methyl-1-phenylpropan-1-one were added and mixed well. After sufficiently defoaming this, it was poured into a mold composed of a glass mold and a gasket. After irradiating with ultraviolet rays for 5 minutes while cooling,
The temperature is raised to 30 to 120 ° C over 1 hour, and further 120
Heated at 0 ° C. for 1 hour. After the completion of the polymerization, the mixture was gradually cooled and the molded product was taken out of the mold. The obtained molded body is colorless and transparent, has a refractive index n _d = 1.59, and an Abbe number ν _d = 4.
It was 2. The scratch resistance was very good, and the evaluation was good. Furthermore, the impact resistance was higher than that of the molded body obtained in Reference Example 1.

Reference Example 4 To 35 parts of the diacrylate obtained in Example 3, 15 g of polyethylene glycol dimethacrylate [n = 9, manufactured by Shin-Nakamura Chemical Co., Ltd .: NK ester 9G] was used as a radical polymerization initiator. 17.5 mg of t-butylperoxy-2-ethylhexanoate and 70 mg of 2-hydroxy-2-methyl-1-phenylpropan-1-one as a sensitizer were added and mixed well. After sufficiently defoaming this, it was poured into a mold composed of a glass mold and a gasket. After irradiating with ultraviolet rays for 5 minutes while cooling,
The temperature is raised to 30 to 120 ° C over 1 hour, and further 120
Heated at 0 ° C. for 1 hour. After the completion of the polymerization, the mixture was gradually cooled and the molded product was taken out of the mold. The obtained molded product is colorless and transparent, has a refractive index n _d = 1.60 and an Abbe number ν _d = 4.
It was 0. The scratch resistance was very good, and the evaluation was good. Furthermore, the impact resistance was higher than that of the molded product obtained in Reference Example 2.

Reference Comparative Example 1 Dimethacrylate 35 represented by the following formula (5)
To the parts, 35 mg of t-butylperoxy-2-ethylhexanoate was added as a radical polymerization initiator and mixed well. After sufficiently defoaming this, it was poured into a mold composed of a glass mold and a gasket. 30-1
The temperature was raised to 20 ° C over 1 hour, and further heated at 120 ° C for 1 hour. After the completion of the polymerization, the mixture was gradually cooled and the molded product was taken out of the mold. The obtained molded product was colorless and transparent, had a refractive index n _d = 1.63, an Abbe number ν _d = 34, and had a scratch resistance evaluation of Δ.

[0025]

[Chemical 7]

Reference Comparative Example 2 With respect to 35 parts of p-benzenedithiol dimethacrylate, t-butylperoxy- was used as a radical polymerization initiator.
35 mg of 2-ethylhexanoate was added and mixed well. After sufficiently defoaming this, it was poured into a mold composed of a glass mold and a gasket. The temperature was raised to 30 to 120 ° C over 1 hour, and further heated at 120 ° C for 1 hour. After the completion of the polymerization, the mixture was gradually cooled and the molded product was taken out of the mold. The obtained molded product was colorless and transparent, had a refractive index n _d = 1.66, an Abbe number ν _d = 24, and was rated x for scratch resistance.

[0027]

INDUSTRIAL APPLICABILITY The dithiol represented by the formula (1) and the di (meth) acrylate represented by the formula (2) of the present invention are optical materials having good optical properties, high refractive index and excellent scratch resistance. Lens resin can be provided.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Seiichi Kobayashi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Katsuyoshi Sasagawa 1190, Kasama-cho, Sakae-ku, Yokohama, Kanagawa Chemicals Co., Ltd. (72) Inventor Kenichi Fujii 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemicals Co., Ltd.

Claims (2)

[Claims] 1. A xylylenedithiol derivative represented by formula (1) (formula 1). Embedded image 2. A xylylenedithiol derivative represented by formula (2) (formula 2). Embedded image (In the formula, R represents a hydrogen atom or a methyl group)