JPH0676370B2 - Sulfur-containing acrylic compound - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a novel sulfur-containing acrylic compound which gives a castable, high refractive index cured product.

2. Description of the Related Art In recent years, organic glass lenses have started to spread in place of inorganic glass. Organic glass has advantages such as light weight, safety, processability, and dyeability that are not possessed by inorganic glass, and polymethyl methacrylate, polydiethylene glycol bisallyl carbonate, polycarbonate, polystyrene and the like have already been used. However, cast-moldable organic glass generally has a low refractive index (n _D ≈1.50) and has a drawback that when molded into a lens, it has a larger wall thickness than inorganic glass. Polycarbonate and polystyrene have a relatively high refractive index of 1.59, but their surface hardness is small,
It is inferior in heat resistance, solvent resistance, weather resistance, and dyeability is poor, so it is difficult to use. In addition, since cast molding is difficult, it is not suitable for multi-product production such as spectacle lenses. Also,
Although organic glass such as polyvinylcarbazole and polyvinylnaphthalene can obtain a high refractive index, coloring is remarkable,
At present, it cannot be used due to poor impact resistance and weather resistance.

Problems to be Solved by the Invention An object of the present invention is to provide a resin having a high refractive index of 1.55 or more and giving a transparent cured product.

Means for Solving the Problems This object is achieved by a sulfur-containing acrylic compound represented by the following general formula (I).

[In the formula, R ¹ is H or CH ₃ , and R ² and R ³ are each 1 to 1 carbon atoms.
3 is an alkylene group, X is a halogen atom other than fluorine, and n is an integer of 0-4. Specific examples of the sulfur-containing acrylic compound represented by the formula (I) include the following (meth) acrylate compounds. For example, p-bis (β-methacryloyloxyethylthio) xylylene, p-bis (acryloyloxyethylthio) xylylene, m-bis (β-methacryloyloxyethylthio) xylylene, m-bis (acryloyloxyethylthio) xylylene, p -Bis (β-methacryloyloxyethylthio) tetrabromoxylylene and the like.

Such a novel sulfur-containing acrylic compound of the present invention can be produced by reacting a sulfur-containing polyol represented by the following formula (II) with an acylating agent represented by the formula (III).

[In the formula, R ² , R ³ , X, and n are the same as those in the above formula (I)] [In the formula, R ¹ represents H or CH ₃ , and X ¹ represents halogen or OH. (Sulfur-Containing Polyol) The sulfur-containing polyol represented by the above formula (II) is obtained by reacting a polyhalogen compound represented by the following formula (IV) with a hydroxyl group-containing aliphatic mercaptan compound. (Reference: Organic Sulfur Compounds N Karash (N.Kh)
arasch), Vol. 1, Ch. 11, pp. 97-111, U.S. Pat. No. 3,824,293.
No. specification etc. ) [In the formula, X ² represents C 1 or Br, and R ³ , X and n are the same as those in the above formula (I). Examples of the polyhalogen compound include, for example, polyhalogen compounds such as p-dichloroxylylene, p-dibromoxylylene, m-dichloroxylylene, m-dibromoxylylene, o-dichloroxylylene, and o-dibromoxylylene. But,
Used alone or as a mixture.

The hydroxyl group-containing aliphatic mercaptan compound is represented by the following formula (V) HO-R ² -SH (V) [In the formula, R ² represents an alkylene group having 1 to 3 carbon atoms. ] A compound represented by the following, for example, 2-mercaptoethanol, 3-mercaptopropanol, 2-mercapto-1-methylethanol and the like.

(Production of Sulfur-Containing Acrylic Compound) The novel sulfur-containing acryl compound of the present invention uses a carboxylic acid as an acylating agent represented by the above formula (III) with respect to 1 mol of the sulfur-containing polyol of the formula (II). A catalyst, for example, a mineral acid such as sulfuric acid or hydrochloric acid, 0.01 to 0.5 mol of an aromatic sulfonic acid such as p-toluenesulfonic acid, and 2-3 mol of methacrylic acid or acrylic acid as an acylating agent, and a solvent such as benzene, It is obtained by reacting with 500 to 1000 ml of toluene or the like, and removing the produced water outside the system by azeotropic distillation.

When an acid halide is used as the acylating agent represented by the formula (III), a nitrogen-containing organic base such as triethylamine, tributylamine, diisopropylamine, is added to 1 mol of the sulfur-containing polyol of the formula (II).
2-3 moles of pyridine and the like, and 2-3 moles of methacrylic acid chloride or acrylic acid chloride as an acylating agent.
React using moles. The reaction temperature is -10 for a system prepared by blending a sulfur-containing polyol compound with a nitrogen-containing organic base.
The temperature is maintained at + 50 ° C, preferably -10-30 ° C, and the acylating agent is added dropwise. Although the above reaction can be carried out without using a solvent, preferably a solvent having no reactivity, for example, a ketone solvent such as acetone and methyl ethyl ketone, a chlorine solvent such as chloroform and dichloromethane, and tetrahydrofuran, dioxane and the like. It is preferable to use an ether solvent.

The post-treatment is carried out by using a carboxylic acid and an acid halide as the acylating agent, washing the reaction solution with dilute hydrochloric acid or a dilute aqueous alkali solution after completion of the reaction, and distilling off the solvent when a solvent is used. A new sulfur-containing acrylic compound can be obtained.

(Application) The novel sulfur-containing acrylic compound of the present invention can be polymerized alone or in combination with another radically polymerizable monomer. The radical polymerizable monomer, for example, styrene, vinyltoluene, methoxystyrene, chlorostyrene, bromostyrene, dichlorostyrene, trichlorostyrene, divinylbenzene, vinylnaphthalene, vinyl acetate, vinyl compounds such as vinyl chloride, methyl methacrylate, phenyl methacrylate, Acrylic or methacrylic compounds such as phenyl acrylate, chlorophenyl methacrylate, bromophenyl methacrylate, dichlorophenyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, trimethylolpropane triacrylate, epoxy acrylate, etc., diethylene glycol bisallyl carbonate, diallyl phthalate, epoxy amber Acid diallyl, allylfe Rushiran a radical polymerizable monomer allyl compounds such known, such as diallyl dimethyl silane.

Further, the radical initiator used in the polymerization thereof is not particularly limited, for example, benzoyl peroxide, diisopropyl peroxycarbonate, tert-butyl peroxyisopropyl carbonate, peroxides such as ditertiary butyl peroxide, azo. Azo compounds such as bisisobutyronitrile, photosensitizers such as benzophenone, benzoin, benzoin ethyl ether, benzyl, acetophenone, anthracene, α-chloromethylnaphthalene, diphenyl sulfide, thiocarbamate, and other radical initiators such as known radical initiators Is.

(Experimental Example) In order to better describe the present invention, an example will be specifically described below. The parts in the production examples, examples and applied examples are parts by weight.

Production example (sulfur-containing polyol) 2000 equipped with stirrer, thermometer, dropping funnel, cooling tube
In a ml four-necked flask, 206 parts of p-dichloroxylene, 450 parts of potassium carbonate, and 1000 parts of methyl ethyl ketone were charged, and while maintaining the temperature of the solution at 80 ° C or lower with stirring, 2-
216 parts of mercaptoethanol was added dropwise. After the dropping is completed,
Refluxed for 5 hours. Then, the reaction solution was heated, and after cooling, the precipitated crystals were separated. This was recrystallized from methanol to obtain p-bis (2-hydroxyethylthio) xylylene.

Example 1 48.3 parts of p-bis (2-hydroxyethylthio) xylylene, 60 parts of pyridine and 240 parts of dichloromethane were charged into a 500 ml four-necked flask equipped with a stirrer, a thermometer and a cooling tube, and the solution was stirred. Was cooled to 0 to 5 ° C., and 43.3 parts of methacrylic acid chloride was added dropwise while maintaining the temperature. After completion of dropping, stirring was continued for 1 hour.

Then, the reaction solution was separated, poured into a separating funnel, washed with a sodium hydrogencarbonate aqueous solution and a 5% hydrochloric acid aqueous solution, and then washed with water until it became neutral. This was dehydrated with magnesium sulfate, decolorized with activated carbon, and the solvent was removed under reduced pressure to obtain p-bis (β-methacryloyloxyethylthio) xylylene.

The infrared absorption spectrum and the nuclear magnetic resonance spectrum of this product are shown in FIG. 1 and FIG. 2, respectively.

Example 2 The same procedure as in Example 1 was carried out except that 48.3 parts of m-bis (2-hydroxyethylthio) xylylene was used instead of 48.3 parts of p-bis (2-hydroxyethylthio) xylylene of Example 1, m -Bis (β-methacryloyloxyethylthio) xylylene was obtained. The infrared absorption spectrum and nuclear magnetic resonance spectrum of this product are shown in FIGS. 3 and 4, respectively.

Application Example 1 A mixture obtained by adding 100 parts of p-bis (β-methacryloyloxyethylthio) xylylene obtained in Example 1 and 0.5 part of benzoyl peroxide was composed of a glass mold for lens molding and a silicone rubber gasket. The mixture was poured into a mold and heated from 60 ° C. to 100 ° C. for 14 hours to carry out polymerization.

The lens obtained by removing the cured product from the mold has good translucency and hardness, and the refractive index measured with an Abbe refractometer is
It had 1.593 and an Abbe number of 36.4.

Application Example 2 The mixture obtained by adding 100 parts of m-bis (β-methacryloyloxyethylthio) xylylene obtained in Example 2 and 0.5 part of benzoyl peroxide was polymerized in the same manner as in Application Example 1.

The obtained lens had a refractive index of 1.588 and an Abbe number of 35.9.

[Brief description of drawings]

1 and 2 are infrared absorption spectra of the sulfur-containing acrylic compound obtained according to Example 1 of the present invention (see FIG.
Fig.) And a nuclear magnetic resonance spectrum (Fig. 2) are shown. or,
3 and 4 show the infrared absorption spectrum (FIG. 3) and the nuclear magnetic resonance spectrum (FIG. 4) of the sulfur-containing acrylic compound of Example 2.

Claims (1)

[Claims] 1. A sulfur-containing acrylic compound represented by the following general formula: [In the formula, R ¹ is H or CH ₃ , and R ² and R ³ are each 1 to 1 carbon atoms.
3 is an alkylene group, X is a halogen atom other than fluorine, n is an integer of 0-4. ]