JPH0791262B2 - Novel sulfur-containing aliphatic (meth) acrylate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel sulfur-containing aliphatic (meth) acrylate useful as a raw material for an acrylic resin or a methacrylic resin.

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

(Problems to be Solved by the Invention) The present inventors have been studying the use of acrylic resins and methacrylic resins as resins for optical components such as lenses, but ethylene glycol was used as a bifunctional monomer. When diacrylate or diethylene glycol dimethacrylate is used, a high refractive index cannot be expected, and the resin obtained by copolymerizing benzenethiol acrylate and β-naphthalenethiol methacrylate as monofunctional monomers with other bifunctional monomers is in the visible light range. The dispersion of the refractive index is large (the Abbe number is small) and the utility value is small.

(Means for Solving the Problems) The present inventors have earnestly studied a sulfur-containing bifunctional monomer in order to obtain a resin having a high refractive index while keeping the dispersion small.

As a result, they have found that this object can be achieved by using a sulfur-containing aliphatic (meth) acrylate, and have reached the present invention.

That is, the present invention provides a novel sulfur-containing aliphatic (meth) acrylate represented by the general formula (I), which is useful as a raw material for an acrylic resin or a methacrylic resin.

(In the formula, A represents oxygen or sulfur, R represents hydrogen or a methyl group, m is 1 or 2, and n is an integer of 0 or 1. However, when R is a methyl group, m is 2, n. Is an integer of 0).

The novel sulfur-containing aliphatic (meth) acrylate of the present invention is specifically ethanedithiol diacrylate, 2,2'-
Examples thereof include oxydiethanethiol diacrylate, 2,2'-thiodiethanethiol diacrylate, 1,4-butanedithiol diacrylate and 1,4-butanedithiol dimethacrylate.

These compounds are ethanedithiol, 2,2'-oxydiethanethiol, 2,2'-thiodiethanethiol or
It is obtained by carrying out an esterification reaction of 1,4-butanedithiol and acrylic acid chloride or methacrylic acid chloride in a solvent in the presence of a hydrochloric acid scavenger.

That is, the synthesis reaction is carried out in a solvent such as hexane, benzene, toluene, chloroform and the like which has no reactivity with the raw materials, ethanedithiol raw material, 2,2'-
Acrylic acid chloride or methacrylic acid chloride 2 to 2.5 per mol of oxydiethanethiol, 2,2'-thiodiethanethiol or 1,4-butanedithiol
The reaction solution temperature is -10 ° C to 30 ° C, preferably -10 ° C to
Keep the temperature at 10 ° C and add a hydrochloric acid scavenger such as triethylamine to proceed the reaction. After the completion of the reaction, the reaction solution is washed with a dilute alkaline aqueous solution and then with water to remove the solvent to obtain the sulfur-containing aliphatic (meth) acrylate of the present invention.

(Operation) The sulfur-containing aliphatic (meth) acrylate of the present invention is used alone or together with an unsaturated carboxylic acid ester such as diethylene glycol dimethacrylate or ethylene glycol dimethacrylate to heat-polymerize a conventional diethylene glycol diacrylate or ethylene glycol diacrylate. It is possible to obtain a sulfur-containing acrylic resin or a sulfur-containing methacrylic resin having a high refractive index while maintaining a high Abbe number as compared with the resin using, and it is useful for optical parts.

(Examples) Examples will be shown below, but parts in the examples represent parts by weight.

Example 1 9 parts of 2,2'-oxydiethanethiol, chloroform 200
And 13.6 parts of acrylic acid chloride were mixed, and the reaction solution temperature was -5.
15.4 parts of triethylamine was added dropwise over 35 minutes while maintaining the temperature at ℃. After completion of the dropping, the solution was washed with a 5% sodium hydrogen carbonate aqueous solution and then with water, and the chloroform layer was concentrated. The concentrate was purified by chromatogram method to give colorless syrup.
3 parts of 2,2'-oxydiethanethiol diacrylate were obtained.

C H S Elemental analysis value (%) 48.42 6.03 25.45 Calculated value (%) 48.76 5.73 26.03 (as C ₁₀ H ₁₄ O ₃ S ₂ ) Example 2 9 parts of 2,2'-thiodiethanethiol, chloroform 200
And 12.2 parts of acrylic acid chloride were mixed, and the reaction solution temperature was -5.
13.8 parts of triethylamine was added dropwise over 30 minutes while maintaining the temperature at 0 ° C to 0 ° C. After completion of the dropping, the solution was washed with a 5% sodium hydrogen carbonate aqueous solution and then with water, and the chloroform layer was concentrated. The concentrate was purified by a chromatogram method to obtain a colorless syrup-like 2,2'-thiodiethanethiol diacrylate.
I got 3.6 copies.

CH S elemental analysis value (%) 45.26 5.62 37.11 calculated value (%) 45.77 5.38 36.66 (as C ₁₀ H ₁₄ O ₂ S ₃ ) Example 3 A colorless syrupy ethanedithiol diacrylate was prepared in the same manner as in Example 1 except that 9 parts of 2,2'-oxydiethanethiol in Example 1 was replaced with 6.1 parts of ethanedithiol.
I got 2.5 copies.

C H S Elemental analysis value (%) 47.79 5.02 31.59 Calculated value (%) 47.50 4.98 31.70 (as C ₈ H ₁₀ O ₂ S ₂ ) NMR δ (CDCl ₃ ) δ = 3.50 (s, 4H, −SCH ₂ CH ₂ S −) 5.70 (m, 2H, CH ₂ ＝ CH
−) 6.30 (m, 4H, CH ₂ ═CH−) Example 4 9 parts of 2,2′-oxydiethanethiol of Example 1 was added to 1,4-
Butanedithiol 7.9 parts, acrylic acid chloride 13.6
The same procedure as in Example 1 was carried out except that 14.1 parts of methacrylic acid chloride was used in place to obtain 3.1 parts of colorless syrup-like 1,4-butanedithiol dimethacrylate.

C H S Elemental analysis value (%) 55.50 7.13 24.95 Calculated value (%) 55.78 7.02 24.82 (as C ₁₂ H ₁₈ O ₂ S ₂ ) Reference Example 1 2,2'-oxydiethanethiol diacrylate 54 parts,
A uniform solution prepared by mixing 6 parts of diethylene glycol dimethacrylate and 0.01 part of lauroyl peroxide was poured into a mold composed of a glass mold and a gasket made of an ethylene-vinyl acetate copolymer. Then, the polymerization was first started at 30 ° C., and after 6 hours, the temperature was gradually raised to 70 ° C. After further polymerizing at 80 ° C. for 2 hours, the polymer was taken out from the gasket and the mold. The polymer was further polymerized at 90 ° C. for 2 hours. This polymer has a refractive index of 1.
It was 58 and Abbe number 37, and was colorless and transparent, and had good workability and impact resistance.

The refractive index and Abbe's number are 20 ° C in the Prurich type.
It was measured at. In addition, the workability is good (○) if it is ground with a ball-shaving machine for eyeglass lens processing and the ground surface is good, and if it cannot be ground due to clogging, it is bad (×). A steel ball drop test was carried out in accordance with FDA standards using a flat plate having a size of 2 mm, and those that did not crack were rated as good (○).

Reference Example 2 A mixture of 40 parts of 2,2'-thiodiethanethiol diacrylate, 10 parts of ethylene glycol dimethacrylate and 0.01 part of dicumyl peroxide and homogenized is a glass mold and an ethylene-vinyl acetate copolymer. It was poured into a mold composed of a gasket. Then, the polymerization was first started at 30 ° C., and after 6 hours, the temperature was gradually raised to 70 ° C. After further polymerizing at 80 ° C. for 2 hours, the polymer was taken out from the gasket and the mold. The polymer was further polymerized at 90 ° C. for 2 hours. This polymer has a refractive index of 1.61,
It had an Abbe number of 36, was colorless and transparent, and had good workability and impact resistance.

Reference Examples 3 to 4 Reference is made except that 54 parts of 2,2′-oxydiethanethiol diacrylate of Reference Example 1 is replaced with 54 parts of 1,4-butanedithiol diacrylate or 54 parts of 1,4-butanedithiol dimethacrylate. A polymer was obtained in the same manner as in Example 1.

Reference Example 5 A polymer was obtained in the same manner as in Reference Example 2 except that 40 parts of 2,2'-thiodiethanethiol diacrylate of Reference Example 2 was replaced with 40 parts of ethanedithiol diacrylate.

Comparative Example 1 A polymer was obtained in the same manner as in Reference Example 1, except that 54 parts of 2,2'-oxydiethanediacrylate and 6 parts of diethylene glycol dimethacrylate of Reference Example 1 were replaced with 60 parts of diethylene glycol diacrylate alone.

Comparative Example 2 Similar to Reference Example 2 except that 40 parts of 2,2′-thiodiethanethiol diacrylate and 10 parts of ethylene glycol dimethacrylate of Reference Example 2 were replaced with 30 parts of benzenethiol acrylate and 30 parts of ethylene glycol diacrylate. A polymer was obtained. The refractive index of these polymers, the Abbe number,
Table 1 shows the test results of workability and impact resistance.

Claims (1)

[Claims] 1. A sulfur-containing aliphatic (meth) acrylate represented by the general formula (I). (In the formula, A represents oxygen or sulfur, R represents hydrogen or a methyl group, m is 1 or 2, and n is an integer of 0 or 1. However, when R is a methyl group, m is 2, n. Is an integer of 0)