JPH0477467A - New sulfur-containing aromatic acrylate - Google Patents

Abstract

NEW MATERIAL:4,4'-Dimercaptodiphenylsulfide diacrylate expressed by the formula. USE:Useful as a raw material for resins having a high refractive index and effectively used in optical parts. PREPARATION:4,4'-Thiobis-benzenethiol is made to react with 2-2.5mol beta- chloropropionyl chloride in the presence of pyridine or sodium hydroxide in an amount of 2-5mol based on 1mol raw materials in a solvent, e.g. acetone, hexane or toluene without any reactivity with the raw materials at -10 to +20 deg.C, and 2-2.5 mol triethylamine is further added thereto at-10 to +20 deg.C. After completing the reaction, water is added to the reaction solution and extraction is subsequently carried out using hydrocarbons, especially n-hexane as an extracting solvent to afford the objective compound expressed by the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel sulfur-containing aromatic acrylate useful as a raw material for a resin having a high refractive index.

C. Prior Art Ethylene glycol diacrylate and diethylene glycol dimethacrylate are used for modifying, that is, crosslinking, polyacrylate and polymethacrylate resins.

[Problem to be solved by the invention]

The present inventors have been researching the use of acrylic resins and methacrylic resins as resins for optical components such as lenses.

When using ethylene glycol diacrylate or diethylene glycol dimethacrylate, which are known (meth)acrylic resins, as raw materials, the refractive index of the resulting resin is 1.
．． It is about 50. On the other hand, the present applicant has previously proposed JP-A-63316766 and JP-A No. 63-188666 as a g-containing (meth)acrylate monomer having a high refractive index.
proposed. However, the refractive index of resins obtained from these sulfur-containing acrylate monomers is about 1.65 at most, and further improvement has been desired.

[Means for Solving the Problems] In order to obtain a resin with a high refractive index, the present inventors conducted extensive research on sulfur-containing bifunctional monomers, and as a result, by using sulfur-containing aromatic acrylates, this The inventors have discovered that the object can be achieved and have developed the present invention.

That is, the present invention provides a novel sulfur-containing aromatic acrylate represented by formula (I) that is useful as a raw material for resins having a high refractive index.

The synthetic aromatic acrylate of the present invention can be prepared by mixing 4,4'-thiobis-benzenethiol in a solvent such as acetone, hexane, toluene, chloroform, etc., which has no reactivity with the raw materials. At a temperature of 20°C, 2 to 2.5 mol of β-chloropropionyl chloride is reacted with 1 mol of raw materials in the presence of 2 to 5 mol of pyridine or sodium hydroxide, and further at -10 to 20°C.
Add 2 to 2.5 moles of triethylamine, and after the reaction is complete, water is added to the reaction solution, and hydrocarbons, especially n-
It can be obtained by extraction using hexane as an extraction solvent.

[Effect]

The synthetic aromatic acrylate of the present invention can be thermally polymerized alone or together with unsaturated carboxylic acid esters such as diethylene glycol diacrylate or ethylene glycol diacrylate, thereby making it more effective than resins using conventional diethylene glycol diacrylate or ethylene glycol diacrylate. , a synthetic acrylic resin with a high refractive index can be obtained. Furthermore, by reacting the mirror aromatic acrylate of the present invention with trifunctional or higher functional polythiols, a polysulfide resin having a high refractive index can be obtained, which is effective for optical parts.

〔Example〕

Examples will be shown below, and parts in the examples indicate parts by weight.

Example 1 In 200 parts of chloroform, 25.0 parts (0.10 mol) of 4,4'-thiobisuhensenthiol was dissolved, and while stirring, 31.6 parts (0.40 mol) of pyridine was added in total. Ta. At this time, the content liquid was cooled to maintain it at 10°C.

Next, while maintaining the content at 10°C, 26.7 parts (0.21 mol) of β-chloropropionyl chloride was added dropwise over an hour. After the reaction is complete, while continuing to stir,
4.200 parts of sodium chloride water (mW) was added to separate the chloroform solution layer. After repeating this three times, water 20
0 parts was added and washed with water. This chloroform solution layer was
Concentration at ~38"C gave crystals.

Next, 22.0 parts (0.05 mol) of these crystals were dissolved in 100 parts of acetone, the content was kept at 10°C, and 11.4 parts (0.11 mol) of triethylamine was added with stirring for 1 hour. After the completion of the dropwise reaction, 600 parts of n-hexane and 400 parts of water were added while stirring, and the beef san solution layer was separated into n-hexane. After repeating this several times, the n-hexane layer was concentrated at 30°C and recrystallized to obtain the desired needle-like crystals 4,4゛-dimercapto diphenyl sulfide diacrylate 5.2 I got the department.

Elemental analysis value (as C+J+aOzS3) H3 Measured value (%) 60.04 4.12 26.2
7 Calculated value (%) 60.31 3.94 26.
83 parts MR (δc++cL3) δ=5.79 (m, 2H, -CJL=)6.42
(m, 4H, Cf1z=-) Melting point 52-53°C Reference example 1 50 parts of 4.4゛-dimercapto diphenyl sulfide diacrylate and 0.10 parts of lauroyl peroxide
The mixture was mixed and the homogeneous solution was poured into a mold consisting of a glass mold and a gasket made of ethylene-vinyl acetate copolymer. Next, polymerization was initially started at 30°C, and the temperature was gradually raised to 70'C after 6 hours. Further, after double indirect polymerization at 80° C., the polymer was taken out from the gasket and mold. The polymer was further subjected to double indirect polymerization at 90''C. This polymer had a refractive index of 1.71, was colorless and transparent, and had good processability.

Reference Example 2 30 parts of 4.4'-dimercapto diphenyl sulfide diacrylate and 14.4 parts of 1,2-bis[(2-mercaptoethyl)1,000]3-mercaptopropane were mixed and a homogeneous solution was prepared. The mixture was poured into a mold consisting of a glass mold and a gas container made of ethylene-vinyl acetate copolymer. Next, polymerization was initially started at 30'C, and the temperature was gradually raised to 70C after 6 hours. Further, after double indirect polymerization at 80°C, the polymer was taken out from the gasket and mold. The polymer was further double-indirectly polymerized at 90°C. This polymer has a refractive index of 1
．． 69, it was colorless and transparent and had good workability.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1) Sulfur-containing aromatic acrylate represented by formula (I)▲There are mathematical formulas, chemical formulas, tables, etc.▼(I)