JPH01226870A - Novel thiolcarboxylic acid ester - Google Patents

Abstract

NEW MATERIAL:A thiolcarboxyic acid ester of formula I. USE:Useful as a raw material for optical plastics. The compound of formula I can be homopolymerized by itself or copolymerized with various olefinic double bond-containing compounds to provide a polymer or oligomer. The produced resin containing the compound as a main component has a high refractive index and excellent transparency. The polymer and oligomer are also useful as an adhesion improver to metals and glass. PREPARATION:The compound of formula I is prepared by reacting phenylthioethanethiol with a methacrylic acid derivative as represented in the reaction equation (X is Cl, Br, OH, 1-4C alkoxy).

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel thiol carboxylic acid ester represented by the following formula (1) and useful as a raw material for optical plastics.

<Conventional technology> As a material to replace inorganic optical lenses, resin for high refractive index lenses made of transparent synthetic resin is used as a raw material for plastic lenses due to its light weight, impact resistance, moldability, and dyeability. The field of application is expanding.

Conventionally, as resins used as glass lens materials, diethylene glycol bisallyl carbonate resin, polymethyl methacrylate, and polycarbonate are generally used, but diethylene glycol bisallyl carbonate resin and polymethyl methacrylate have a low refractive index. Since it is as small as 1.49 to 1.50, when these resins are molded into glass lenses, there is a drawback that the center thickness, edge thickness, and curvature become larger than inorganic optical glass lenses. Further, although polycarbonate has a high refractive index of 1.58 to 1.59, it tends to cause birefringence during molding, and has a drawback in terms of chemical uniformity.

In addition, vinylnaphthalene and vinyl carbazole provide resin gold with a high refractive index, but the resulting resins have large dispersion and significant coloring, and are not satisfactory as resins for optical plastic lenses. Problems with Problems> As explained above, conventional optical plastic materials have various drawbacks, and improvements are desired. Therefore, an object of the present invention is to provide a monomer that provides a resin with a high refractive index and excellent transparency that is useful as an optical plastic material.

Means for Solving the Problems> In order to achieve the above object, the present inventors conducted repeated studies and arrived at the present invention. That is, the present invention provides a novel thiol cardanic acid ester represented by the following formula (1), which has not been described in any literature.

Further, the compound (1) of the present invention can be produced by reacting phenylthioethanethiol and a methacrylic acid salt conductor (see formula (n) below).

(However, in the formula, X is CL, Br, OH or C1
~C4 alkoxy group. ) <Effects of the Invention> The novel thiolcarboxylic acid Nisterha represented by the above-described (1) provided by the present invention can be polymerized by itself or copolymerized with various compounds having an olefinic double bond. Polymers and oligomers can be obtained by this process. The resin containing the novel compound of the present invention as a main component has a high refractive index and excellent transparency.

Furthermore, these polymers and oligomers can also be used as adhesion improvers with metals and glass.

<Example> Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 In a 500-volume glass flask equipped with a stirrer, a thermometer, a Dimroth condenser, and a dropping funnel, 68% of phenylthioethanethiol was added. IIi, 13% by weight hydroxide) I
Jium aqueous solution 209#, methylene chloride 901R1,4-
Methoxyphenol 23.8μ was charged. Next, the temperature inside the reaction vessel was maintained at t-10° C. or below, and 54.4 F of methacrylic acid chloride e2 was added dropwise over 50 minutes while stirring the system. After the dropwise addition was completed, stirring was further continued for 1 hour at the same temperature, and then the reaction solution was separated into two layers. 5% by weight methylene chloride layer
After washing with an aqueous sodium hydroxide solution and then twice with water, it was dried over anhydrous sodium sulfate. After removing sodium sulfate by filtration, methylene chloride was distilled off using an evaporator, and the resulting colorless concentrated reaction solution was distilled under reduced pressure to obtain a novel thiol cardanic acid ester of the formula (21.3). !9 (yield 44.7%) was obtained.

Next, we will show the results of the analysis of the structure of this new substance.

0 boiling point 123-126℃/0.0.6T
orr19゜0Refractive index no 1.5970 0 Elemental analysis value C (%) H (%) S (%) Theoretical value 60
．． 47 5.92 26.90 Analysis value 60.3
9 5.90 27.040 Mass spectrometry spectral EI m/e-239 (M+1) 6'H-NMR (solvent: CDC43, internal standard substance: TMS) = 3.10 ppm (multi
pl@t 4H-S-CHJ -CHJ -S -)
=5.57 ppm (singL@t IHCHJ
-=6. O7ppm (singl*t IHCH,
--7,14~7.41 ppm (multipl@
t 5H benzene nucleus H) and infrared absorption spectrum (N
aC2 plate) 1660m (thioester νCm,
) The 1H-NMR spectrum of this new substance (1) is shown in Figure 1, and the infrared absorption spectrum is shown in Figure 2.

Reference Example New thioester (1) obtained in Example 1 10.0F K
2. A solution containing 2'-asohysu(2,4-dimethylvaleronitrile) 301119 was poured into a mold made of two glass plates and a silicone rubber socket, and heated at 50°C for 6 hours and at 60°C for 16 hours. The mixture was further heated at 90°C for 2 hours to polymerize. The obtained resin was colorless and transparent. When the refractive index and Atsube number of this resin piece were measured using an Atsube refractometer, the refractive index n was 1.6492 and the Atsube number was 27.8.

[Brief explanation of the drawing]

Figure 1 shows 1H-Tox4 in deuterated chloroform solvent according to the 7MS standard of the new substance (1) obtained in Example 1.
This is a vector diagram. Figure 2 shows the new substance (1) NaC obtained in Example 1.
It is an infrared absorption spectrum diagram on an L plate.

Claims (1)

[Claims] (1) A novel thiol carboxylic acid ester represented by the following formula. ▲Contains mathematical formulas, chemical formulas, tables, etc.▼