KR20200004689A - Preparation method of thiol compound - Google Patents

Abstract

Embodiments relate to a method for manufacturing a thiol compound with high purity and high yield, which does not require cryogenic reaction conditions, does not require additional special equipment, and increases the amount of production per hour. The manufacturing method comprises following steps of: obtaining a sulfur-containing heterocyclic compound from a thioepoxy-based compound obtained by conducting a reaction of an epoxy-based compound with a sulfide; and conducting a reaction of the sulfur-containing heterocyclic compound with a thiolating agent.

Description

Manufacturing method of thiol compound for optical materials {PREPARATION METHOD OF THIOL COMPOUND}

Embodiments relate to a method for preparing a thiol compound that can be suitably used in the field of resins such as optical materials or polyurethane resins, high refractive index, high Abbe number and transparency, paints, coatings and the like. Moreover, it is related with the polymeric composition, molded object, and optical material containing the thiol compound obtained from the said manufacturing method.

Plastic optical materials are widely used in optical materials such as spectacle lenses, camera lenses, etc. because they are lighter than the optical materials including inorganic materials such as glass, are not easily broken, and have excellent dyeing properties. In recent years, high performance of optical materials such as high transparency, high refractive index, low specific gravity, high heat resistance and high impact resistance has been required.

Polythiourethane-based compounds among plastic optical materials have been widely used as optical materials because of their excellent optical properties and mechanical properties. The polythiourethane-based compound may be prepared by polymerizing a thiol compound and an isocyanate compound, and the physical properties of the thiol compound have a great influence on the physical properties of the polythiourethane to be produced.

The thiol compound having a sulfur-containing heterocyclic structure is a monomer for a urethane resin having excellent optical properties is disclosed in Japanese Patent Laid-Open No. 3-236386. As a preparation method, a method of obtaining a target product by reacting thiourea in 2,5-bis (bromomethyl) -1,4-dithi obtained by reacting diallyl disulfide with bromine is hydrolyzed with an aqueous sodium hydroxide solution.

In addition, Japanese Unexamined Patent Application Publication No. 6-25223 discloses the above-mentioned Japan by diolization of 2,5-bis (chloromethyl) -1,4-dithiane obtained by chlorination of diallyl disulfide, followed by purification such as distillation. Compared to the method described in Japanese Patent Laid-Open No. Hei 3-236386, the purpose of producing a desired product with high yield and high purity is described.

Further, Japanese Laid-Open Patent Publication No. 2003-206287 discloses by selecting an extraction solvent during the thiolation process without separating and purifying 2,5-bis (chloromethyl) -1,4-dithiane obtained by chlorinating diallyl disulfide. A method of selectively extracting 2,5-bis (mercaptomethyl) -1,4-dithianes and simultaneously removing impurities is described.

Japanese Patent Laid-Open No. 3-236386 Japanese Patent Laid-Open No. 6-25223 Japanese Patent Laid-Open No. 2003-206287

An embodiment is a method of manufacturing a thiol compound having a sulfur-containing heterocyclic structure for producing an optical material having high optical properties such as high refractive index, high Abbe number, heat resistance, and to provide a new manufacturing method with excellent economic efficiency.

According to the manufacturing method disclosed in the said patent documents 1-3, the thiol compound which has a sulfur containing heterocyclic structure can be manufactured and can be used as a monomer of an optical lens.

However, the production method described in Patent Document 1 may cause a decrease in yield by purification by crystallization of 2,5-bis (bromomethyl) -1,4-dithiane or purification by isothiouronium salt or the like, Since it generates a lot of impurities, the load in the distillation process can be increased. Therefore, the manufacturing method of the said patent document 1 has a problem in both the purity and the yield of a thiol compound.

Further, according to the production method described in Patent Document 2, since 2,5-bis (chloromethyl) -1,4-dithiane is highly toxic, safety problems may occur in the distillation step.

The said patent document 3 uses high purity 2, 5-bis (mercaptomethyl) -1, 4- dithiane by the selection of an extraction solvent, without isolate | separating and refine | purifying 2, 5-bis (chloromethyl) -1, 4- dithiane. Although the preparation method through the chlorination reaction of diallyl disulfide is prepared in the same manner as in Patent Document 2, a similar problem may be caused.

Furthermore, according to the production methods disclosed in Patent Documents 1 to 3, in the step of obtaining a sulfur-containing heterocyclic compound by brominating or chlorinating the diallyl disulfide, a reaction temperature of −15 ° C. or less is required. In addition, the bromination or chlorination reaction of the diallyl disulfide has a problem that the amount of by-products is increased when the broth or chlorination reaction is higher than -15 ° C, and the purity and yield are lowered. In addition, considering that the brominated or chlorinated reaction of diallyl disulfide is exothermic, when performing mass production on an industrial scale, enormous energy and special equipment for controlling the reaction temperature are required.

Embodiments do not require cryogenic reaction conditions, do not require additional special equipment, and are intended to provide a method for preparing high purity and high yield thiol compounds while increasing the amount produced per hour. In addition, another embodiment is to provide a polymerizable composition, a molded article and an optical material comprising a thiol compound obtained from the production method.

According to one or more exemplary embodiments, a method for preparing a thiol compound includes: obtaining a sulfur-containing heterocyclic compound from a thioepoxy compound obtained by reacting an epoxy compound with a sulfide; And reacting the sulfur-containing heterocyclic compound with a thiolating agent.

According to another embodiment, a polymerizable composition may include a step of obtaining a sulfur-containing heterocyclic compound from a thioepoxy compound obtained by reacting an epoxy compound with a sulfide, and reacting the sulfur-containing heterocyclic compound with a thiolating agent. Thiol compounds prepared by a compound preparation method; And an isocyanate compound.

A molded article according to another embodiment is obtained by curing the polymerizable composition.

According to another embodiment, an optical material includes the molded body.

According to the method for preparing a thiol compound according to the embodiment, there is no need for cryogenic reaction conditions, no additional special equipment, and a high purity and high yield of a thiol compound can be prepared while increasing the amount of production per hour.

The thiol compound prepared by the above production method has high refractive index, high Abbe number and high heat resistance physical properties, and the production cost per hour can be greatly reduced due to high production efficiency.

When the thiol compound is provided in a polymerizable composition including an isocyanate compound, it is useful in the manufacture of an optical material because it not only improves optical properties such as refractive index and Abbe's number, but also excellent mechanical properties such as heat resistance and impact resistance.

Hereinafter, the present invention will be described in detail through embodiments. The embodiments are not limited to the contents disclosed below and may be modified in various forms as long as the gist of the invention is not changed.

"Including" in the present specification means that it may further include other components unless otherwise specified.

In addition, all numbers and expressions indicating amounts of components, reaction conditions, and the like described herein are to be understood as being modified in all instances by the term "about" unless otherwise specified.

In addition, the term "substituted" in this specification, unless otherwise specified, deuterium, halogen group (-F, -Cl, -Br, -I), hydroxy group, cyano group, nitro group, amino group and substituted or unsubstituted It means substituted with one or more substituents selected from the group consisting of alkyl groups.

One embodiment does not require cryogenic reaction conditions, does not require additional special equipment, and provides a method for preparing high purity and high yield of thiol compounds while increasing the amount of production per hour.

According to one or more exemplary embodiments, a method for preparing a thiol compound includes obtaining a sulfur-containing heterocyclic compound from a thioepoxy compound obtained by reacting an epoxy compound with a sulfide (step 1); And reacting the sulfur-containing heterocyclic compound with a thiolating agent (step 2).

Obtaining the sulfur-containing heterocyclic compound (step 1), the step of obtaining a thioepoxy compound by the reaction of the epoxy compound and sulfide (step 1-1); And obtaining a sulfur-containing heterocyclic compound from the thioepoxy compound (step 1-2).

In order to perform the above steps 1-1 and 1-2, no special facility for maintaining cryogenic temperatures (-10 ° C. or lower) is required, and because the production efficiency per hour is high, it is useful as a manufacturing method on an industrial scale. In addition, the polythiourethane-based optical material prepared using the thiol compound prepared through the above process is excellent in physical properties such as high refractive index, high Abbe number, heat resistance and impact resistance.

In order to prepare a thiol compound according to the embodiment, first, a step (step 1-1) of obtaining a thioepoxy compound is carried out by reacting an epoxy compound with a sulfide.

The epoxy compound may be represented by Formula 1 below:

<Formula 1>

In Formula 1,

R ₁ to R ₄ are each independently selected from a group comprising hydrogen, deuterium, a halogen group, a hydroxyl group, a cyano group, a nitro group, an amino group, a -S- linking group and a substituted or unsubstituted C ₁ -C ₄ alkyl group; ,

At least one of R ₁ to R ₄ is selected from a halogen group, a hydroxy group, an alkyl group substituted with a halogen, and an alkyl group substituted with a hydroxy group.

In this case, the halogen group may be -F, -Cl, -Br or -I.

Specifically, in Formula 1, R ₁ to R ₄ are independently of each other, hydrogen, bromine, chlorine, hydroxy group, methyl group, ethyl group, 1-propyl group, isopropyl group, 1-butyl group, tert-butyl group, chloro Methyl group, chloroethyl group, 1-chloropropyl group, 2-chloropropyl group, 3-chloropropyl group, 1-chlorobutyl group, 2-chlorobutyl group, 3-chlorobutyl group, 4-chlorobutyl group, 1-chloro 2-methylbutyl group, 2-chloro-1-methylbutyl group, 1-methyl-3-chlorobutyl group, 2-methyl-3chlorobutyl group, bromomethyl group, bromoethyl group, 1-bromopropyl group , 2-bromopropyl group, 3-bromopropyl group, 1-bromobutyl group, 2-bromobutyl group, 3-bromobutyl group, 4-bromobutyl group, 1-bromo-2- Methylbutyl group, 2-bromo-1-methylbutyl group, 1-methyl-3-bromobutyl group, 2-methyl-3-bromobutyl group, hydroxymethyl group, hydroxyethyl group, 1-hydroxypropyl Group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy Hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, 1-hydroxy-2-methylbutyl group, 2-hydroxy-1-methylbutyl group, 1- Methyl-3-hydroxybutyl group, 2-methyl-3-hydroxybutyl group, and -CH ₂ -S-CH ₂ CH ₂ OH.

For example, the epoxy compound represented by Formula 1 may be epichlorohydrin, epibromohydrin, glycidol or 2-chloromethyl-2-methyloxylane, but is not limited thereto.

The sulfide means a sulfur containing compound.

Specifically, the sulfide may be sulfur, thiourea, potassium thiocyanate (KSCN), sodium thiocyanate, calcium thiocyanate, silver thiocyanate, or silver thiocyanate. ), Thiocarbanilide, mercury thiocyanate, copper thiocyanate, cobalt thiocyanate, methyl thiocyanate, 3-methylbenzothiane With 3-methylbenzothiazole-2-thione, guanidine thiocyanate, ammonium thiocyanate, dimethyl thioformamide and phosphine sulfide It may be one or more selected from the group consisting of, but is not limited thereto.

The reaction of the epoxy compound and the sulfide may proceed in the presence of an acid component.

In this case, the acid component may be at least one selected from the group consisting of organic acids, inorganic acids, Lewis acids, and phosphines.

Specifically, the organic acid may be acetic acid, acetic anhydride, oxalic acid, chloro acetic acid, dichloro acetic acid, succinic acid, maleic acid, glutaric acid, formic acid, lactic acid, butyric acid, salicylic acid, benzoic acid, propionic acid, chloropropionic acid, cinnamic acid, malonic acid, phthalic acid and Acrylic acid may be used, and the inorganic acid may be hydrochloric acid, sulfuric acid, nitric acid, (poly) phosphoric acid, and the like, and the Lewis acid may be dimethyl tin dichloride, dimethyl tin oxide, tetrachloro tin, monobutyl tin, dibutyl Tin dichloride, tributyl tin monochloride, tetrabutyl tin, dibutyl tin oxide, dibutyl tin dilaurate, dibutyl tin octanoate, tin stearate, zinc chloride, acetylacetone zinc, aluminum fluoride, aluminum chloride, tetra Butoxytitanium, tetrachlorotitanium, ruthenium chloride, bismuth chloride, beta-seed Rodextrin, calcium acetate, and the like can be used. Examples of the phosphines include trimethyl phosphine, triethyl phosphine, tricyclo hexyl phosphine, tribenzyl phosphine, triphenyl phosphine, and 1,2-bis (dimethylphosphono). Ethane, 1,2-bis (diphenylphosphino) ethane and the like can be used.

The acid added at this time may be used independently from the above-mentioned acids, and may mix and use 2 or more types.

The amount of the acid component added may range from 0.001 equivalents to 1.5 equivalents based on 1 equivalent of the epoxy compound. Specifically, the addition amount of the acid component may be in the range of 0.01 equivalents to 1.5 equivalents or 0.01 equivalents to 0.5 equivalents based on 1 equivalent of the epoxy compound, but is not limited thereto.

In addition, the reaction between the epoxy compound and the sulfide may proceed in an atmosphere in which the acid component is not present.

For example, thiourea can be produced from the epoxy-based compound under an atmosphere in which no acid component is present using thiourea as the sulfide.

In this case, the sulfide content may be 0.5 to 3.5 equivalents, specifically 0.7 to 3.0 equivalents, and more specifically 0.8 to 2.0 equivalents, based on 1 equivalent of the epoxy compound.

For example, the reaction between the epoxy compound and the sulfide may be performed according to the following mechanism, but is not limited thereto.

According to the mechanism, a base catalyst may be used in the reaction of the epoxy compound and the sulfide. The base catalyst used may be at least one selected from the group consisting of triethylamine, sodium hydroxide, piperidine, aniline, potassium hydroxide, methoxide hydroxide, ethoxide hydroxide and lithium hydroxide, but is not limited thereto.

The reaction between the epoxy compound and the sulfide may proceed without a solvent. However, the reaction is exothermic and usually takes place under polar solvents such as alcohols, esters, ketones and ethers in consideration of the purity and yield of the product.

When an acid component is used in this reaction, water added to dilute the acid component is also included in the category of the polar solvent.

Specifically, the alcohol polar solvent is methanol, ethanol, isopropanol, propanol, n-butanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, pentanol, n-hexanol, methyl amino alcohol, 2-ethyl butanol, n-heptanol, n-octanol, 2-octanol, 3-octanol, 2-ethyl hexanol, 3,5,5-trimethyl hexanol, nonar, n-decanol, unde Canol, n-dodecanol, hepta decanol, cyclohexanol, benzyl alcohol, 2-methylcyclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol and the like can be used, the ester The polar solvents are methyl acetate, ethyl acetate, butyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-amyl acetate, and methyl isoamyl acetate. Sodium Wheat, Methoxybutyl Acetate, sec-ethylbutyl acetate, 2-ethyl hexanol acetate, Iclohexyl, methylcyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, propionic acid-n-butyl, isopropyl propionate, methyl butyrate, ethyl butyrate, butyrate-n-butyl, isoamyl butyrate, butyl stearate, amyl stearate , Methyl acetoacetate, ethyl acetoacetate, ethyl lactate, methyl lactate, lactate-n-butyl, amyl lactate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, benzyl benzoate, methyl cinnamic acid, ethyl cinnamic acid, salicylic acid Methyl, ethyl salicylate, diethyl oxalate, dibutyl oxalate, diamyl oxalate, diethyl malonate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, and the like may be used. The solvent is acetone, methyl acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, Methyl-n-amyl ketone, methyl-n-hexyl ketone, diethyl ketone, ethyl-n-butyl ketone, di-n-propyl ketone, diisobutyl ketone, acetonyl acetone, mesityloxide, isophorone, cyclohexa Paddy, o-cyclohexanone, acetophenone and the like can be used, and the ether polar solvent is isopropylethyl ether, ethyl ether, dichloroethyl ether, isobutyl ether, n-butyl ether, propyl ether, isopropyl ether, Isoamyl ether, diisoamyl ether, methylphenyl ether, n-hexyl ether, n-butylphenyl ether, amyl phenyl ether, benzyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol Isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, ethylene glycol isoamyl ether, ethylene glycol monophenyl ether, Ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol monoethyl ether, triethylene glycol diethyl ether and propylene glycol mono Ethyl ether and the like can be used.

The polar solvents may be used alone or in combination.

The reaction temperature of the said process 1-1 is -10-50 degreeC. Specifically, the reaction temperature of step 1-1 may be 0 to 40 ℃, more specifically 10 to 30 ℃. In addition, the reaction time of the process 1-1 may be 0.1 hours to 12 hours, specifically 0.5 hours to 8 hours, more specifically 1 hour to 3 hours.

When the reaction temperature and the reaction time of the step 1-1 satisfy the above range, the yield and purity of the product can be improved.

In addition, whether or not the thioepoxy compound production reaction is terminated under the above conditions can be confirmed by the result of gas chromatography-mass spectrometry, and the product containing the thioepoxy compound may be used after separation and purification, It is industrially preferable to proceed.

The thioepoxy compound produced by Step 1-1 may be represented by the following Formula 2:

<Formula 2>

In Formula 2,

R ₅ to R ₈ are each independently selected from hydrogen, deuterium, a halogen group, a hydroxyl group, a cyano group, a nitro group, an amino group, a group comprising an -S- linking group and a substituted or unsubstituted C ₁ -C ₄ alkyl group; ,

At least one of R ₅ to R ₈ is selected from a halogen group, a hydroxy group, an alkyl group substituted with a halogen, and an alkyl group substituted with a hydroxy group.

Specifically, the thioepoxy compound produced by the process 1-1 may be 2-chloromethyl tyrane, 2-bromomethyl tyrein or 2-hydroxymethyl tyrein, but is not limited thereto.

Next, to obtain a sulfur-containing heterocyclic compound from the thioepoxy compound (step 1-2);

The thioepoxy clock compound is converted into a sulfur-containing heterocyclic compound through an intermolecular dimerization in the presence of a perchloric acid compound or an aluminum silicate.

Specifically, the perchlorate-based compound may be at least one selected from the group consisting of sodium perchlorate, copper perchlorate, ammonium perchlorate, lithium perchlorate, potassium perchlorate, calcium perchlorate, cesium perchlorate and silver perchlorate, but is not limited thereto.

In addition, the aluminum silicates (aluminosilicates) may be a compound having a chemical formula of Al _x SiO _y . X and y are integers of 1 or more.

The intermolecular dimerization reaction may be performed according to the following mechanism, but is not limited thereto.

In addition, a co-catalyst may be further used in the dimerization reaction.

An acid catalyst may be mainly used as the cocatalyst, but is not limited thereto.

Specifically, the promoter is acetic acid, p-toluenesulfonic acid, trifluoroacetic acid, formic acid (formic acid), phosphoric acid, fumaric acid, lactic acid, citric acid, malic acid, butyric acid, propionic acid, ethyltrifluoroacetate, methyltrifluoro It may be at least one selected from the group consisting of acetate and benzoic acid. More specifically, the promoter may be acetic acid or p-toluenesulfonic acid.

The content of the perchloric acid compound used in the dimerization reaction is 0.1 to 8.0 equivalents based on 1 equivalent of the thioepoxy compound. Specifically, the content of the perchloric acid compound used in the dimerization reaction may be 0.1 to 6.0 equivalents or 0.5 to 4.5 equivalents based on 1 equivalent of the thioepoxy compound.

In addition, the content of the promoter used in the dimerization reaction is 0.001 to 10 equivalents based on 1 equivalent of the thioepoxy compound. Specifically, the content of the promoter used in the dimerization reaction may be 0.01 to 8 equivalents, more specifically 0.1 to 4 equivalents based on 1 equivalent of the thioepoxy compound.

The perchlorate compound and the cocatalyst are added to a product solution containing the thioepoxy compound obtained in Step 1-1, and then reflux reaction is performed. Thus, the intermolecular dimerization reaction temperature is in the range of (boiling point ± 10 ° C of the solvent used in Step 1-1 above).

Whether or not the dimerization reaction is terminated can be confirmed by the result of a gas chromatography-mass spectrometer, and is usually terminated in the range of 0.1 to 48 hours, specifically 1 to 20 hours, after the perchlorate compound and the promoter are added. do.

The resulting sulfur-containing heterocyclic compound is a compound that is thermally sufficiently stable and can be purified by conventional methods such as distillation and chromatography, but is highly toxic. Therefore, proceeding immediately to the next reaction without a separate purification process increases the work stability, industrially preferred.

Then, the step of reacting the sulfur-containing heterocyclic compound and the thiolating agent (step 2).

The sulfur-containing heterocyclic compound produced through Step 1 includes a halogen group or a hydroxy group.

Reacting the sulfur-containing heterocyclic compound and the thiolating agent is specifically, It may be a step of converting a halogen group or a hydroxyl group contained in the sulfur-containing heterocyclic compound to a thiol group.

Specifically, a method in which a halogen group contained in the sulfur-containing heterocyclic compound is reacted with thiourea, a thiolating agent, to produce an isothiouronium salt, and then hydrolyzed with a base to thiolate may be used. For example, the process 2 may be performed according to the following mechanism, but is not limited thereto.

Alternatively, the hydroxy group contained in the sulfur-containing heterocyclic compound may be reacted with thiourea, a thiolating agent, in the presence of hydrogen chloride to generate isothiouronium salt, and then hydrolyzed with a base to thiolate. .

In addition to the above-described methods, a method of reacting a halogen group in a molecule with sodium thiosulfate to produce bunte salt (BRS salt -RSSO 3-), decomposing it into an acid and thiolating, and the like is not limited thereto.

The thiolating agent may include thiourea or sodium thiosulfate, but is not limited thereto.

Specifically, the use of thiourea as the thiolating agent is advantageous for improving the production yield while lowering the production cost.

The process of using thiourea as the thiolating agent will be described in detail below.

The step of reacting the halogen group contained in the sulfur-containing heterocyclic compound with thiourea to convert to isothiouronium salt is carried out in a conventional polar solvent. As the polar solvent, water, alcohols (methyl alcohol, ethyl alcohol and the like), dimethyl sulfoxide, N, N-dimethylformamide and the like can be used, but preferably water, alcohols or a mixed solvent thereof.

At this time, the content of thiourea may be 0.5 to 3 equivalents, specifically 1 to 2 equivalents, based on 1 equivalent of the halogen group contained in the sulfur-containing heterocyclic compound.

In this case, the reaction temperature is not particularly limited, and may be in the range from room temperature to reflux temperature, specifically, reflux temperature ± 10 ° C, in consideration of the reaction proceeding under heating reflux. In addition, the reaction time may be 0.5 to 24 hours.

The hydroxy group contained in the sulfur-containing heterocyclic compound is reacted with thiourea to convert to isothiouronium salt in the presence of hydrogen chloride.

At this time, the content of thiourea may be 0.5 to 3 equivalents, specifically 1 to 2 equivalents, based on 1 equivalent of the hydroxyl group contained in the sulfur-containing heterocyclic compound. In addition, the content of hydrogen chloride may be 0.1 to 4 equivalents, specifically 0.5 to 2 equivalents, based on 1 equivalent of the hydroxyl group contained in the sulfur-containing heterocyclic compound.

In this case, the reaction temperature may range from room temperature to reflux temperature, specifically, 80 to 120 ° C., and the reaction time may be 1 to 10 hours.

As described above, since the isothiouronium salt obtained by reacting a halogen group or a hydroxy group contained in a sulfur-containing heterocyclic compound with thiourea is precipitated, there are a method of fractionating it and a method of not separating it.

In the case of an embodiment, in order to increase the purity of the final thiol compound, an aliquot is washed several times with alcohols (methyl alcohol or ethyl alcohol) and dried for 2 to 24 hours in a temperature range of 25 to 60 ° C.

After producing the isothiouronium salt, it is hydrolyzed to prepare a sulfur-containing heterocyclic compound (thiol compound) containing a thiol group.

The organic solvent may be added before the hydrolysis of the isothiouronium salt. By adding an organic solvent, generation of by-products can be suppressed.

The addition amount of the organic solvent may be appropriately added depending on the type of solvent, and may be added in an amount of 0.1 to 3.0 times, specifically 0.2 to 2.0 times, based on the reaction solution containing isothiouronium salt.

Toluene, xylene, chlorobenzene, dichlorobenzene and the like can be used as the organic solvent. Specifically, toluene may be used as the organic solvent.

A thiol compound is prepared by hydrolyzing the isothiouronium salt by adding a base to the reaction solution containing the isothiouronium salt.

Specifically, ammonia water or sodium hydroxide solution is added while maintaining the reaction solution containing the isothiouronium salt in a temperature range of 20 to 60 ° C, 25 to 55 ° C or 25 to 50 ° C. The time to which the ammonia water or the sodium hydroxide solution is added is not particularly limited, and is 0.1 hours to 5 hours, and is set in consideration of facilities such as cooling capacity.

The ammonia water has a content of ammonia (NH ₃ ) of 1 mol or more, specifically 1 mol to 3 mol, more specifically 1.1 mol to 2 mol, based on 1 mol of hydrogen chloride, the concentration is 10 to 25% It is suitable to use.

Alternatively, the sodium hydroxide solution has a content of sodium hydroxide (NaOH) of 1 mol or more, specifically 1 mol to 3 mol, more specifically 1.1 mol to 2 mol, based on 1 mol of hydrogen chloride, and the concentration is 5 to It is suitable to use 50%.

Subsequently, after adding the aqueous ammonia solution or sodium hydroxide solution, the hydrolysis reaction is continued for 1 hour to 8 hours in the room temperature to reflux temperature range.

Benzene, toluene, xylene and the like are suitable as extraction solvents of the thiol compound obtained through the hydrolysis process, and after several pickling and washing with water, the solvent is removed and then filtered to obtain a final product. The obtained product may be further purified by distillation or chromatography, but may be used as it is. In addition, the above-described processes may be reacted by exposure in air, but it is advantageous to proceed with the overall process under nitrogen atmosphere to prevent discoloration.

According to another embodiment, a polymerizable composition may include a step of obtaining a sulfur-containing heterocyclic compound from a thioepoxy compound obtained by reacting an epoxy compound with a sulfide, and reacting the sulfur-containing heterocyclic compound with a thiolating agent. Thiol compounds prepared by a compound preparation method; And an isocyanate compound.

That is, the polymerizable composition is a thiol compound obtained by the method for producing a thiol compound described above; And an isocyanate compound.

In addition, the polymerizable composition may further include a thiol compound different from the thiol compound.

The thiol compound different from the thiol compound is not particularly limited, but bis (2- (2-mercaptoethylthio) -3-mercaptopropyl) sulfide, 4-mercaptomethyl-3,6-dithia-1,8 -Octane thiol, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,3-bis (2-mercaptoethylthio) propane-1-thiol, 2,2-bis (Mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) sulfide, tetrakis (mercaptomethyl) methane, 2- (2-mercaptoethylthio) propane-1,3-diti Ol, 2- (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol, bis (2,3-dimercaptopropaneyl) sulfide, bis (2,3-dimercaptopropaneyl) Disulfide, 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, 1,2-bis (2- (2-mercaptoethylthio) -3-mercaptopropylthio) ethane, 2- (2-mercaptoethylthio) -3-2-mercapto-3- [3-mercapto-2- (2-mercaptoethylthio) -propylthio] propylthio-propane- 1-thiol, 2,2-bis- (3-mercapto-propionyloxymethyl) -butyl ester, 2- (2-mercaptoethylthio) -3- (2- (2- [3-mercapto- 2- (2-mercaptoethylthio) -propylthio] ethylthio) ethylthio) propane-1-thiol, (4R, 11S) -4,11-bis (mercaptomethyl) -3,6,9,12 Tetrathiatetradecane-1,14-dithiol, (S) -3-((R-2,3-dimercaptopropyl) thio) propane-1,2-dithiol, (4R, 14R) -4 , 14-bis (mercaptomethyl) -3,6,9,12,15-pentathiaheptan-1,17-dithiol, (S) -3-((R-3-mercapto-2-(( 2-mercaptoethyl) thio) propylthio) propylthio) -2-((2-mercaptoethyl) thio) propane-1-thiol, 3,3'-dithiobis (propane-1,2-dithiol) , (7R, 11S) -7,11-bis (mercaptomethyl) -3,6,9,12,15-pentathiaheptadecane-1,17-dithiol, (7R, 12S) -7,12- Bis (mercaptomethyl) -3,6,9,10,13,16-hexathiaoctadecane-1,18-dithiol, 5,7-dimercaptomethyl-1,11-dimercapto-3, 6,9-trithiaoundecan, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9- Lithiaundane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundane, pentaerythritol tetrakis (3-mercaptopropionate), trimethylol Propane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), bispentaerythritol ether hexakis (3-mercaptopropionate), trimetholpropane tris (thioglycol) Rate), trimetholpropane tris (3-mercaptopropionate), 1,4-butanediolbis (thioglycolate), 1,4-butanediolbis (3-mercaptopropionate), 1,1, 3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane Or 2- (2,2-bis (mercaptodimethylthio) ethyl) -1,3-dithiane and the like.

Specifically, the thiol compound different from the thiol compound is 4-mercaptomethyl-3,6-dithia-1,8-octane thiol, 1,2-bis [(2-mercaptoethyl) thio] -3-mer Captopropane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan, 4,7-dimercaptomethyl-1,11-dimercapto-3, 6,9-trithiaundane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundane, pentaerythritol tetrakis (3-mercaptopropionate ), Pentaerythritol tetrakis (2-mercaptoacetate), trimetholpropane tris (thioglycolate), trimetholpropane tris (3-mercaptopropionate), 1,4-butanediolbis (thioglycol) Rate) and 1,4-butanediolbis (3-mercaptopropionate).

The isocyanate compound may be a conventional one used in the synthesis of polythiourethane.

For example, the isocyanate compound is isophorone diisocyanate, dicyclohexyl methane-4,4-diisocyanate, hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, Butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undectriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,2-bis (isocyanatomethyl) cyclohexane , 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, dicyclohexyl methane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicy Cle Hexyldimethylmethane isocyanate, 2,2-dimethyldicyclohexylmethane isocyanate, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (Isocyanatomethyl) sulfone, bis (isocyanatomethyl) disulfide, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) Methane, bis (isocyanatoethylthio) ethane, bis (isocyanatomethylthio) ethane, 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane, 2,5 Diisocyanatothiophene, 2,5-bis (isocyanatomethyl) thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis (isocyanatomethyl) tetrahydroti Offen, 3,4-bis (isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-bis ( Socyanatomethyl) -1,4-dithiane, 4,5-diisocyanato-1,3-dithiolan, 4,5-bis (isocyanatomethyl) -1,3-dithiolan, 4 , 5-bis (isocyanatomethyl) -2-methyl-1,3-dithiolan, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, bis (isocyanatobutyl ) Benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, phenylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate , Diisopropylphenylene diisocyanate, trimethylbenzenetriisocyanate, benzenetriisocyanate, biphenyl diisocyanate, toluene diisocyanate, toluidine diisocyanate, 4,4-diphenylmethane diisocyanate, 3,3-dimethyldiphenylmethane-4 , 4-diisocia Hite, bibenzyl-4,4-diisocyanate, bis (isocyanatophenyl) ethylene, 3,3-dimethoxybiphenyl-4,4-diisocyanate, hexahydrobenzenediisocyanate, hexahydrodiphenylmethane- 4,4-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, xylene diisocyanate, X- xylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, Diphenylsulfide-2,4-diisocyanate, diphenylsulfide-4,4-diisocyanate, 3,3-dimethoxy-4,4-diisocyanatodibenzylthioether, bis (4-isocyane Itomethylbenzene) sulfide, 4,4-methoxybenzenethioethylene glycol-3,3-diisocyanate, diphenyldisulfide-4,4-diisocyanate, 2,2-dimethyldiphenyldisulfide-5,5 -Diisocyanate, 3,3-dimethyldiphenyldisulfide-5,5-diisocyanate, 3,3-dimethyldipe Disulfide-6,6-diisocyanate, 4,4-dimethyldiphenyldisulfide-5,5-diisocyanate, 3,3-dimethoxydiphenyldisulfide-4,4-diisocyanate and 4,4-di It may be one or more compounds selected from the group consisting of methoxydiphenyldisulfide-3,3-diisocyanate.

Specifically, as the isocyanate compound, 1,3-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate and the like can be used.

The polymerizable composition may further include additives such as an internal mold release agent, a heat stabilizer, a reaction catalyst, and a blueing agent according to the purpose.

The internal mold release agent includes a fluorine-based nonionic surfactant having a perfluoroalkyl group, a hydroxyalkyl group or a phosphate ester group; Silicone-based nonionic surfactants having a dimethylpolysiloxane group, a hydroxyalkyl group or a phosphate ester group; Alkyl quaternary ammonium salts such as trimethylcetyl ammonium salt, trimethylstearyl, dimethylethylcetyl ammonium salt, triethyldodecyl ammonium salt, trioctylmethylammonium salt, diethylcyclohexadodecyl ammonium salt and the like; And components selected from acidic phosphate esters may be used alone or in combination of two or more thereof.

As the heat stabilizer, metal fatty acid salts, phosphorus salts, lead salts, organotin salts, or the like may be used alone or in combination of two or more.

As said reaction catalyst, the well-known reaction catalyst used for manufacture of a polythiourethane type resin can be added suitably. For example, Dialkyl tin halide system, such as dibutyl tin dichloride and dimethyl tin dichloride; Dialkyl tin dicarboxylates such as dimethyl tin diacetate, dibutyl tin dioctanoate and dibutyl tin dilaurate; Dialkyl tin dialkoxides such as dibutyl tin dibutoxide and dioctyl tin dibutoxide; Dialkyl tin dithio alkoxides such as dibutyl tin di (thiobutoxide); Dialkyl tin oxides such as di (2-ethylhexyl) tin oxide, dioctyltin oxide and bis (butoxydibutyltin) oxide; Dialkyl tin sulfides such as dibutyl tin sulfide; and the like. Specifically, it may be selected from the group consisting of dialkyl tin halides such as dibutyltin dichloride and dimethyltin dichloride.

The bluing agent has an absorption band in the wavelength range of orange to yellow in the visible light region, and has a function of adjusting the color of the optical material made of resin. The bluing agent may include, but is not particularly limited to, a substance which shows, specifically, “blue to purple”. In addition, examples of the bluing agent include dyes, fluorescent brighteners, fluorescent pigments, inorganic pigments, and the like, but may be appropriately selected according to physical properties, resin colors, and the like required for optical components to be manufactured. The said bluing agent can be used individually or in mixture of 2 or more types, respectively.

In view of the solubility in the polymerizable composition and the transparency of the optical material obtained, the bluing agent is suitably a dye. The dye may be, in terms of absorption wavelength, specifically, a dye having a maximum absorption wavelength of 520 to 600 nm. More specifically, the dye may be a dye having a maximum absorption wavelength of 540 to 580 nm. From the viewpoint of the structure of the compound, the dye is preferably an anthraquinone dye. The addition method of a bluing agent is not specifically limited, It can add to a preliminary monomer. Specifically, the method for adding the bluing agent may be dissolved in a monomer, or a master solution containing a high concentration of bluing agent is prepared, and the method is diluted with a monomer or another additive using the master solution. Can be used.

According to one embodiment, a molded article obtained by curing the polymerizable composition as described above is provided.

Specifically, the present invention provides a method for producing a polythiourethane-based plastic lens obtained by heat curing the polymerizable composition in a mold, and further provides a polythiourethane-based plastic lens obtained by the production method.

The polymerizable composition is degassed under reduced pressure and then injected into a lens molding mold. Such degassing and mold injection can be carried out, for example, in a temperature range of 20 to 40 ° C. After injection into the mold, polymerization is usually carried out by gradually heating from low to high temperatures. The temperature of the polymerization reaction may be, for example, 20 to 150 ℃, specifically may be 25 to 120 ℃. The polythiourethane-based plastic lens is then separated from the mold. The polythiourethane-based plastic lens can be manufactured in various shapes by changing the mold of the mold used in manufacturing. Specifically, the lens may be in the form of an eyeglass lens, a camera lens, or the like.

In the polymerization reaction, the SH value may be 104 to 108 g / eq, specifically 105 to 107 g / eq, more specifically 106 to 107 g / eq.

The plastic lens may have a solid-state refractive index (nd 20) of 1.55 to 1.70, 1.55 to 1.66, 1.57 to 1.65, or 1.58 to 1.62 at a temperature of 20 ° C., and may be 30 to 50, 35 to 48, 38 to 45 or 38 It may have an Abbe number of 40 to 40.

The plastic lens may have a heat deflection temperature (Tg) of 100 to 115 ° C, 102 to 112 ° C, 105 to 110 ° C, or 106 to 108 ° C.

According to another embodiment, an optical material including the molded body is provided.

[ Example ]

The above content is described in more detail by the following examples. However, the following examples are only for illustrating the present invention, and the scope of the examples is not limited thereto.

Example  1-1

In a reactor, 95 parts by weight of thiourea was added to 300 parts by weight of ethyl alcohol, and the temperature was lowered to -5 to 5 ° C. Then, 100 parts by weight of epichlorohydrin was added dropwise while maintaining the temperature over 1 hour, followed by stirring for 1 hour. Was carried out. The temperature was then raised to 20 ° C. over 30 minutes, followed by further stirring for 3 hours. The gas chromatography-mass spectrometry (GC / MS) confirmed that epichlorohydrin reacted and decreased, and 2-chloromethylthiirane was produced and increased. 300 parts by weight of chloroform was added to the resulting 2-chloromethyl styrene reaction solution, washed three times with 200 parts by weight of water, and the solvent was removed at 20 ° C. under reduced pressure. 100 parts by weight of ethyl acetate was added to the obtained 2-chloromethyl silane reaction solution, 10 parts by weight of lithium perchlorate and 5 parts by weight of acetic acid were charged, and stirred at 20 ° C. for 12 hours to carry out a heterocyclic reaction. After confirming that the reaction was terminated through a gas chromatography-mass spectrometer (GC / MS), three times washing with 200 parts by weight of water was carried out to remove the solvent through a reduced pressure at 20 ℃. 300 weight part of ethyl alcohol and 80 weight part of thioureas were dripped at the obtained heterocyclic compound, and it heated up to 85 degreeC again, and stirred for 3 hours under reflux. 2,2 '-((1,4-dithiane-2,5-diyl) bis (methylene)) diisothiouronium (2,2'-((1,4-dithiane-) produced after stirring for 3 hours 2,5-diyl) bis (methylene)) diisothiouronium) solid powder was removed from the solvent through a filter, washed three times with ethanol at 5 to 15 ℃ and dried at 25 to 60 ℃ conditions. Dried 2,2 '-((1,4-dithiane-2,5-diyl) bis (methylene)) diisothiouronium (2,2'-((1,4-dithiane-2,5- Charge 250 parts by weight of degassed water (dissolved oxygen concentration 2 ppm), 250 parts by weight of toluene and 120 parts by weight of 50% sodium hydroxide over 25 minutes at 25 ° C. in diyl) bis (methylene)) diisothiouronium) salt, and at 42-48 ° C. It stirred for 3 hours and obtained the toluene solution of the thiol compound which has 2, 5-bis (mercaptomethyl) -1, 4- dithiane as a main component. 80 weight part of 36% hydrochloric acid was added to this toluene solution, and acid washing was performed once at 30-40 degreeC for 30 minutes. 200 parts by weight of degassed water (dissolved oxygen concentration of 2 ppm) was added, and washing was performed four times at 30 to 40 ° C for 30 minutes. Toluene and traces of water were removed under reduced pressure under heating, and impurities were removed by fractional distillation at 180 ° C. under 1 torr. The obtained product was filtered under reduced pressure with a PTFE type membrane filter to obtain a thiol compound having a GPC purity of 99.9% having a main component of 2,5-bis (mercaptomethyl) -1,4-dithiane in 40% yield.

Example  1-2

Except for using potassium thiocyanate (KSCN) instead of thiourea was carried out in the same manner as in Example 1-1, GPC purity of 99.9% of 2,5-bis (mercaptomethyl) -1,4-dithiane as a main component The thiol compound was obtained in 35% yield.

Example  1-3

The same procedure as in Example 1-1 was carried out except for using para-toluenesulfonic acid instead of acetic acid, and the purity of GPC containing 9,4-bis (mercaptomethyl) -1,4-dithiane was 99.9. % Thiol compound was obtained in 32% yield.

Example  1-4

Potassium thiocyanate (KSCN) was used instead of thiourea, and para-toluenesulfonic acid was used in place of acetic acid, and was carried out in the same manner as in Example 1-1, and 2,5-bis (mercaptomethyl A thiol compound having a GPC purity of 99.9% based on) -1,4-dithiane as a main component was obtained in a yield of 35%.

Example  1-5

In a reactor, 95 parts by weight of thiourea was added to 300 parts by weight of ethyl alcohol, and the temperature was lowered to -5 to 5 ° C. Then, 100 parts by weight of glycidol was added dropwise while maintaining the temperature over 1 hour, followed by 1 hour. Stirring was carried out. The temperature was then raised to 20 ° C. over 30 minutes, followed by further stirring for 3 hours. The gas chromatography-mass spectrometry (GC / MS) confirmed that glycidol reacted and decreased, and 2-hydroxymethylthiirane was produced and increased. 300 parts by weight of chloroform was added to the resulting 2-hydroxymethyltyrene reaction solution, and washed three times with 200 parts by weight of water, and then the solvent was removed at 20 ° C. under reduced pressure. 100 parts by weight of ethyl acetate was added to the obtained 2-hydroxymethyl styrene reaction solution, 10 parts by weight of lithium perchlorate and 5 parts by weight of acetic acid were charged, and stirred at 20 ° C. for 12 hours to carry out a heterocyclic reaction. After confirming that the reaction was terminated through a gas chromatography-mass spectrometer (GC / MS), three times washing with 200 parts by weight of water was carried out to remove the solvent through a reduced pressure at 20 ℃. 300 parts by weight of ethyl alcohol, 80 parts by weight of thiourea, and 100 parts by weight of 36% hydrochloric acid were added dropwise to the obtained heterocyclic compound, and the temperature was further raised to 85 ° C, followed by stirring for 3 hours under reflux. 2,2 '-((1,4-dithiane-2,5-diyl) bis (methylene)) diisothiouronium (2,2'-((1,4-dithiane-) produced after stirring for 3 hours 2,5-diyl) bis (methylene)) diisothiouronium) solid powder was removed from the solvent through a filter, washed three times with ethanol at 5 to 15 ℃ and dried at 25 to 60 ℃ conditions. Dried 2,2 '-((1,4-dithiane-2,5-diyl) bis (methylene)) diisothiouronium (2,2'-((1,4-dithiane-2,5- Charge 250 parts by weight of degassed water (dissolved oxygen concentration 2 ppm), 250 parts by weight of toluene and 120 parts by weight of 50% sodium hydroxide over 25 minutes at 25 ° C. in diyl) bis (methylene)) diisothiouronium) salt, and at 42-48 ° C. It stirred for 3 hours and obtained the toluene solution of the thiol compound which has 2, 5-bis (mercaptomethyl) -1, 4- dithiane as a main component. 80 weight part of 36% hydrochloric acid was added to this toluene solution, and acid washing was performed once at 30-40 degreeC for 30 minutes. 200 parts by weight of degassed water (dissolved oxygen concentration of 2 ppm) was added, and washing was performed four times at 30 to 40 ° C for 30 minutes. Toluene and traces of water were removed under reduced pressure under heating, and impurities were removed by fractional distillation at 180 ° C. under 1 torr. The obtained product was filtered under reduced pressure with a PTFE type membrane filter to obtain a thiol compound having a GPC purity of 99.9% having a 2,5-bis (mercaptomethyl) -1,4-dithiane as a main component in a yield of 28%.

Comparative example  1-1

In the reactor, 300 parts by weight of sodium sulfide hemihydrate and 310 parts by weight of degassed water (dissolved oxygen concentration of 2 ppm) were stirred at 20-25 ° C. for 1 hour, followed by adding 4 parts by weight of sulfur 40 and PEG 400 and stirring at 50 ° C. for 2 hours. Na ₂ S ₂ was prepared. After cooling the reaction solution to 25 ℃ 191 parts by weight of allyl chloride (allylchloride) was slowly added dropwise at 25 ℃. After completion of the dropwise addition, the temperature was raised to 50 ° C and stirred for 2 hours. After cooling to 25 ° C., the reaction and water layers were separated and the aqueous layer was discarded. 2000 parts by weight of MC (methylene chloride) was added dropwise, the temperature was cooled to -15 ° C, and SO ₂ Cl ₂ was slowly added dropwise at -15 to -10 ° C. After stirring at −15 ° C. for 2 hours, the remaining SO ₂ and Cl ₂ gases were removed through nitrogen (N ₂ ) gas bubbling, and the solvent was removed by heating and depressurizing after heating to 30 ° C. 400 parts by weight of methyl alcohol (MeOH) and 200 parts by weight of thiourea were added dropwise to the reaction product from which the solvent was removed, followed by refluxing for 2 hours by heating up to 65 ° C. Resulting 2,2 '-((1,4-dithiane-2,5-diyl) bis (methylene)) diisothiouronium (2,2'-((1,4-dithiane-2,5- diyl) bis (methylene)) diisothiouronium) solid powder was removed through a filter, washed three times with 5 to 15 ℃ ethanol and dried at 40 to 60 ℃ conditions. A toluene solution of a thiol compound containing 2,5-bis (mercaptomethyl) -1,4-dithiane as a main component was obtained. 80 weight part of 36% hydrochloric acid was added to this toluene solution, and acid washing was performed once at 30-40 degreeC for 30 minutes. 200 parts by weight of degassed water (dissolved oxygen concentration of 2 ppm) was added, and washing was performed four times at 30 to 40 ° C for 30 minutes. Toluene and traces of water were removed under reduced pressure under heating, and impurities were removed by fractional distillation at 180 ° C. and 1 torr. The obtained product was filtered under reduced pressure with a PTFE type membrane filter to obtain a thiol compound having a GPC purity of 99.9% having a main component of 2,5-bis (mercaptomethyl) -1,4-dithiane in 40% yield.

Example  2-1 to 2-5 and Comparative example  2-1

29.6 parts by weight of the thiol compound prepared in Examples 1-1 to 1-5 and Comparative Example 1-1, 19.7 parts by weight of pentaerythritol tetrakis (2-mercaptoacetate), 1,4-bis (isocyanatomethyl 50.7 parts by weight of cyclohexane, 0.01 parts by weight of dibutyl tin chloride, 0.1 parts by weight of a phosphate ester releasing agent (ZELEC® UN Stepan) was uniformly mixed, followed by a defoaming process at 600 Pa for 1 hour, followed by 3 μm Teflon. The resin composition filtered by the filter was inject | poured into the mold mold which consists of a glass mold and a tape. This mold mold was slowly heated up at a rate of 5 ° C per minute from 25 ° C to 120 ° C, and polymerization was carried out at 120 ° C for 18 hours. After mold release in the mold, the physical properties of the specimen further cured at 120 ° C for 4 hours were measured.

[ Evaluation example ]

The following physical properties of the thiol compound according to Examples 1-1 to 1-5 and Comparative Example 1-1 and the specimen (lens) according to Examples 2-1 to 2-5 and Comparative Example 2-1 Measured and evaluated. The results are shown in Table 1 below.

Evaluation example  One: SH value  Measure

About 0.1 g of the sample was weighed into a beaker, 40 mL of chloroform was added thereto, stirred for 10 minutes, and 20 mL of IPA was added thereto, followed by further stirring for 10 minutes. The solution was titrated using 0.1 N iodine standard solution.

       SH value (g / eq.) = Sample weight (g) / {0.1x amount of iodine consumed (L)}

Evaluation example  2: liquid refractive index measurement

Measurement was carried out at 25 ° C. using Kyoto Refractometer RA-600.

Evaluation example  3: GPC  Purity measurement

GPC (Model Waters APC system).

The mobile phase was THF and measured for 10 minutes at a flow rate of 0.5 mL / min after a 10 μl injector. The column used is APC XT Column (45A (4.6 * 150mm) x 2) and the detector is RID.

Evaluation example  4: solid state refractive index ( nd20 ) And Abbesu  Measure

It measured at 20 degreeC using the Abbe refractometer DR-M4. In addition, it measured in accordance with JIS K 0071-1.

Specifically, the APHA color was determined by comparing a standard solution dilution with a concentration equal to the color of the sample using a standard solution prepared by dissolving platinum and cobalt reagents. The sample was dissolved in 1.245 g K ₂ PtCl ₆ and 1.00 g CoCl ₂ 6H ₂ O in 100 ml concentrated hydrochloric acid (gr 1.19) and diluted with water to a final volume of 500 mL (25 ° C.). (Manufacturer: WAKO). The smaller the frequency, the better the color.

Evaluation example  5: heat deflection temperature measurement

TA TMA Q400 was used to measure the glass transition temperature (Tg) in the penetration method (50g load, pin wire 0.5mmф, temperature increase rate 10 degrees / min).

Thiol Compound Physical Properties Item EXAMPLE
1-1 EXAMPLE
1-2 EXAMPLE
1-3 EXAMPLE
1-4 EXAMPLE
1-5 Comparative example
1-1 SH value (g / eq) 106.6 106.6 106.8 106.6 106.7 106.8 Refractive Index (25 ℃) 1.645 1.645 1.644 1.644 1.647 1.647 GPC Purity (%) 99.9 99.9 99.9 99.9 99.9 99.9 Specimen (Lens) Properties Item EXAMPLE
2-1 EXAMPLE
2-2 EXAMPLE
2-3 EXAMPLE
2-4 EXAMPLE
2-5 Comparative example
2-1 Refractive Index (20 ℃) 1.60 1.60 1.60 1.60 1.60 1.60 Abbesu 40 38 39 40 38 40 Heat deflection temperature (℃) 108 106 108 107 106 106

As can be seen in Table 1, in the case of the embodiment does not require the cryogenic reaction conditions, do not require additional special equipment, while increasing the amount of production per hour, it is excellent in the properties of the thiol compound and physical properties after lens processing Could confirm.

Claims (11)

Obtaining a sulfur-containing heterocyclic compound from a thioepoxy compound obtained by reacting an epoxy compound with a sulfide; And
Comprising; reacting the sulfur-containing heterocyclic compound with a thiolating agent;
Method for preparing thiol compound.
The method of claim 1,
The epoxy compound is represented by the following formula (1),
Process for preparing thiol compound:
<Formula 1>

In Formula 1,
R ₁ to R ₄ are each independently selected from a group comprising hydrogen, deuterium, a halogen group, a hydroxyl group, a cyano group, a nitro group, an amino group, a -S- linking group and a substituted or unsubstituted C ₁ -C ₄ alkyl group; ,
At least one of R ₁ to R ₄ is selected from a halogen group, a hydroxy group, an alkyl group substituted with a halogen, and an alkyl group substituted with a hydroxy group.
The method of claim 1,
The sulfide is sulfur, thiourea (thiourea), potassium thiocyanate (KSCN), sodium thiocyanate, calcium thiocyanate, silver thiocyanate, silver thiocyanate Occaranilide (thiocarbanilide), mercury thiocyanate, copper thiocyanate, cobalt thiocyanate, methyl thiocyanate, 3-methylbenzothiazole-2 -Thione (3-methylbenzothiazole-2-thione), guanidine thiocyanate, ammonium thiocyanate, dimethyl thioformamide and phosphine sulfide One or more selected
Method for preparing thiol compound.
The method of claim 1,
The step of obtaining a sulfur-containing heterocyclic compound from the thioepoxy compound obtained by the reaction of the epoxy compound and the sulfide proceeds in the presence of a perchloric acid compound or an aluminum silicate,
Method for preparing thiol compound.
The method of claim 4, wherein
The perchlorate-based compound is at least one selected from the group consisting of sodium perchlorate, copper perchlorate, ammonium perchlorate, lithium perchlorate, potassium perchlorate, calcium perchlorate, cesium perchlorate and silver perchlorate,
Method for preparing thiol compound.
The method of claim 4, wherein
In the step of obtaining a sulfur-containing heterocyclic compound from the thioepoxy compound obtained by the reaction of the epoxy compound and the sulfide, further using a co-catalyst,
Method for preparing thiol compound.
The method of claim 6,
The promoter is acetic acid, p-toluenesulfonic acid, trifluoroacetic acid, formic acid (formic acid), phosphoric acid, fumaric acid, lactic acid, citric acid, malic acid, butyric acid, propionic acid, ethyltrifluoroacetate, methyltrifluoroacetate and benzo At least one selected from the group consisting of Iksan,
Method for preparing thiol compound.
A thiol compound prepared by a method for preparing a thiol compound comprising the step of obtaining a sulfur-containing heterocyclic compound from a thioepoxy compound obtained by the reaction of an epoxy compound with a sulfide and reacting the sulfur-containing heterocyclic compound with a thiolating agent. ; And
Isocyanate compound; containing,
Polymerizable composition.
The method of claim 8,
The polymerizable composition is 4-mercaptomethyl-3,6-dithia-1,8-octane thiol, 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, 5,7 -Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithia Undecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundane, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetra Keith (2-mercaptoacetate), trimetholpropane tris (thioglycolate), trimetholpropane tris (3-mercaptopropionate), 1,4-butanediolbis (thioglycolate) and 1,4 -Further comprising at least one compound selected from the group consisting of butanediolbis (3-mercaptopropionate),
Polymerizable composition.
The molded object obtained by hardening | curing the polymeric composition of Claim 8.
An optical material comprising the molded article of claim 10.