KR101971110B1 - Method for preparing polythiol compound used in the manufacture of an optical material - Google Patents
Method for preparing polythiol compound used in the manufacture of an optical material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/02—Thiols having mercapto groups bound to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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Abstract
The present invention relates to a process for producing a polythiol compound for an optical material. According to the process for producing a polythiol compound according to the embodiment, a specific type of base is used in the hydrolysis process for producing the polythiol compound, The desired polythiol compound can be produced economically and efficiently by carrying out sufficient hydrolysis in a short time. Accordingly, the polythiourethane obtained from the polythiourethane is excellent in optical properties such as refractive index and hue, and thus can be usefully used in the production of various plastic optical materials such as spectacle lenses and camera lenses.
Description
The examples relate to a method for producing a polythiol compound used as a raw material for a polythiourethane-based optical material. The examples also relate to a polymerizable composition comprising a polythiol compound produced by the above production method and an optical material obtained therefrom.
Optical materials using plastics are lightweight, easily broken, and excellent in dyability compared with optical materials made of inorganic materials such as glass. Therefore, plastic materials of various resins are widely used as optical materials for spectacle lenses and camera lenses. Recently, as demand for higher performance and convenience has increased, research on optical materials having properties such as high transparency, high refractive index, low specific gravity, high heat resistance, and high impact resistance continues.
BACKGROUND ART Polythiourethane-based compounds are widely used as optical materials due to their excellent optical properties and mechanical properties. The polythiourethane compound can be prepared by reacting a polythiol compound with an isocyanate compound.
A method of producing a polythiol compound for an optical material is variously known. For example, a method of obtaining a polythiol compound through a step of introducing an SH group into a polyol compound followed by hydrolysis is known.
For example, Korean Patent Registration No. 10-1338568 discloses a method for producing a polythiol compound by reacting a polyol compound with thiourea to generate an isothiouronium salt and hydrolyzing the salt by using ammonia water. Specifically, , ≪ / RTI > 25% ammonia water. However, ammonia water has a disadvantage in that it is difficult to produce ammonia water at a concentration of 30% or more from the industrial viewpoint, and it takes a long time for hydrolysis and a large amount of waste water is generated. Furthermore, if the hydrolysis is insufficient, the isothiouronium salt may be present in the molecular structure of the product, and the product may migrate to the water layer during purification, resulting in a lower yield. In addition, since the color of the polythiol tends to deteriorate when the hydrolysis time is increased or the hydrolysis temperature is increased for sufficient hydrolysis, it is very important to appropriately control the degree and condition of hydrolysis.
Accordingly, the embodiment attempts to provide a method for economically and efficiently producing a desired polythiol compound by performing sufficient hydrolysis in a short time by suitably controlling the kind and concentration of a base used in hydrolysis.
The embodiment is a method for producing a polythiol compound by reacting a polyol compound with thiourea to produce an isothiouronium salt and then hydrolyzing the isothiouronium salt with a basic aqueous solution to prepare a polythiol compound, wherein the basic aqueous solution is diluted with distilled water to 100 mM wherein the basic aqueous solution contains a basic substance having a pH of 11 to 13 and a concentration of the basic aqueous solution is 35 to 60%.
Furthermore, the Examples provide a polymerizable composition comprising a polythiol compound and an isocyanate compound produced by the above production method.
Further, the embodiment provides a molded article obtained by curing the above-mentioned polymerizable composition.
Furthermore, the embodiment provides an optical material comprising the molded body.
According to the method for producing a polythiol compound according to the embodiment, sufficient hydrolysis can be carried out in a short time by appropriately controlling the concentration of the base by using a specific kind of base in the hydrolysis step in the production of the polythiol compound, Can be produced economically and efficiently. Accordingly, the polythiourethane obtained from the polythiourethane is excellent in optical properties such as refractive index and hue, and thus can be usefully used in the production of various plastic optical materials such as spectacle lenses and camera lenses.
The embodiment is a method for producing a polythiol compound by reacting a polyol compound with thiourea to produce an isothiouronium salt and then hydrolyzing the isothiouronium salt with a basic aqueous solution to prepare a polythiol compound, wherein the basic aqueous solution is diluted with distilled water to 100 mM wherein the basic aqueous solution contains a basic substance having a pH of 11 to 13 and a concentration of the basic aqueous solution is 35 to 60%.
Specifically, the concentration of the basic aqueous solution may be 35 to 55%, more specifically 35 to 50%. If the concentration is within the above range, a sufficient hydrolysis reaction can be performed in a much shorter time than in the conventional method. The basic aqueous solution is a basic substance and includes a substance having a pH of 11 to 13 when diluted with distilled water to 100 mM. When a basic substance having a pH lower than 11 is used under the above conditions, hydrolysis is difficult to occur sufficiently. When a basic substance having a pH higher than 13 is used, the decomposition reaction occurs and the yield of the target polythiol compound is lowered and the product tends to be colored
Wherein the basic substance is potassium hydroxide (KOH), meta-sodium silicate (Na 2 SiO 3), calcium hydroxide (Ca (OH) 2), trisodium phosphate (Na 3 PO 4), potassium carbonate (K 2 CO 3), sodium carbonate ( Na 2 CO 3 ) and ammonium hydroxide (NH 4 OH). The basic materials exhibit a pH of about 12.88, about 12.62, about 12.46, about 12.12, about 11.36, about 11.26, and about 11.12 when measured at 25 ° C after dilution to 100 mM in distilled water.
The Examples can efficiently prepare various polythiol compounds from various polyol compounds by the above-mentioned production method. The polyol compound may be a compound having a sulfur atom. According to the production process according to the embodiment, trifunctional and tetrafunctional polythiol compounds can be efficiently produced from each of a triol compound having a sulfur atom and a tetraol compound.
Hereinafter, a method for producing trifunctional and quadrivalent polythiol compounds will be described in detail as an example.
Trifunctional
Polythiol
Preparation of compounds
According to one embodiment, a trifunctional polythiol compound represented by the following formula (1) can be prepared from a polyol compound (compound of formula (7)) obtained by reacting 2-mercaptoethanol with epihalohydrin 1).
Specifically, the compound of Formula 1 may be prepared by (1) reacting a compound of Formula 5 with 2-mercaptoethanol in the presence of a base catalyst to produce a compound of Formula 7; (2) reacting the compound of formula (7) with thiourea followed by hydrolysis in a basic aqueous solution. Wherein the compound of formula (6) is an intermediate product of the compound of formula (5) and 2-mercaptoethanol:
[Reaction Scheme 1]
In the above formula, X may be a halogen atom such as F, Cl, Br or I, and preferably Cl.
Specifically, in the step (1), the triol compound of the formula (7) can be prepared by reacting the compound of the formula (5) with 2-mercaptoethanol. The conditions such as the temperature and the time can be determined by a conventional method Can be used.
In step (2), the obtained triol compound is reacted with thiourea to obtain an isothiouronium salt, which is then hydrolyzed in a basic aqueous solution to prepare a compound of formula (1).
First, the compound of formula (7) and thiourea are mixed and refluxed under acidic conditions to obtain an isothiouronium salt. The thiourea may be used in an amount of 3 mol or more, specifically 3 mol to 6 mol, per 1 mol of the compound of the formula (7). In order to form the acid condition, an acid such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid or phosphoric acid can be used, and hydrochloric acid is preferable from the viewpoint of controlling the coloring of the product. Reflux can be carried out at 90 to 120 ° C, specifically at 100 to 110 ° C for 1 to 10 hours.
Thereafter, the obtained isothiouronium salt can be hydrolyzed in a basic aqueous solution to obtain a trifunctional polythiol compound of the formula (1). The basic aqueous solution may be used in an amount of 1 mol or more, specifically 1 mol to 3 mol, more specifically 1.1 mol to 2 mol, based on 1 mol of the acid. The reaction may be carried out at a temperature ranging from room temperature to the reflux temperature, and the temperature at the time of adding the basic aqueous solution may be 0 to 80 ° C or 0 to 50 ° C. Within the above range, the obtained polythiol compound is not colored well.
Four-sensory
Polythiol
Preparation of compounds
According to another embodiment, from the polyol compound (compound of formula 8) obtained by reacting a compound obtained by the reaction of 2-mercaptoethanol with epihalohydrin with a metal sulfide, the tetrafunctional A polythiol compound can be prepared (see Scheme 2).
Specifically, the tetrafunctional polythiol compounds represented by Formulas (2) to (4) can be prepared by (1) reacting a compound of Formula (5) with 2-mercaptoethanol in the presence of a base catalyst to prepare a compound of Formula (2) reacting a compound of formula (VI) with a metal sulfide to produce a compound of formula (VIII) (3) reacting the compound of formula (8) with thiourea followed by hydrolysis in a basic aqueous solution:
[Reaction Scheme 2]
In the above formula, X may be a halogen atom such as F, Cl, Br or I, and preferably Cl.
Specifically, in step (1), the diol compound of formula (6) can be prepared by reacting the compound of formula (5) with 2-mercaptoethanol. The conditions such as temperature and time can be measured by a conventional method .
In step (2), the tetraol compound of formula (8) can be prepared by reacting the diol compound of formula (6) with a metal sulfide in a solvent. The reaction may be carried out at a temperature of 10 to 50 ° C, specifically 20 to 40 ° C for 1 to 10 hours, 1 to 8 hours, or 1 To 5 hours. The metal sulfide may be, for example, sodium sulfide (Na 2 S). The metal sulfide may be used in the form of an aqueous solution or solid. The metal sulfide may be used in an amount of 0.4 to 0.6 mol, specifically 0.45 to 0.57 mol, more specifically 0.48 to 0.55 mol, based on 1 mol of the diol compound of the formula (6).
In step (3), the obtained tetraol compound of the formula (8) is reacted with thiourea to obtain an isothiouronium salt, which is then hydrolyzed in a basic aqueous solution to prepare the compounds of the formulas (2) to .
First, the compound of formula (8) and thiourea are mixed and refluxed under acidic conditions to obtain an isothiouronium salt. The thiourea may be used in an amount of 3 mol or more, specifically 3 mol to 6 mol, per 1 mol of the compound of the formula (8). Reflux can be carried out at 90 to 120 ° C, specifically at 100 to 110 ° C for 1 to 10 hours.
Thereafter, the obtained isothiouronium salt may be hydrolyzed in a basic aqueous solution to obtain a tetrafunctional polythiol compound represented by any of formulas (2) to (3).
The reaction liquid containing the isothiouronium salt is added to the reaction solution for not more than 80 minutes, not more than 70 minutes, not more than 20 minutes, and more preferably not more than 20 minutes, while maintaining the reaction solution at a temperature of 20 to 60 ° C, specifically 25 to 55 ° C, A basic aqueous solution may be added for 60 minutes or 20 to 30 minutes. The addition time of the basic aqueous solution is preferably as short as possible, but is set within the above-mentioned time in consideration of the cooling facility, facility facilities, and the like.
The basic aqueous solution may be used in an amount of 1 mol or more, specifically 1 mol to 3 mol, more specifically 1.1 mol to 2 mol, per 1 mol of the acid. The reaction may be carried out at a temperature ranging from room temperature to the reflux temperature, and the temperature at the time of adding the basic aqueous solution may be 0 to 80 ° C or 0 to 50 ° C. Within the above range, the obtained polythiol compound is not colored well. After the basic aqueous solution is added, the hydrolysis reaction may be performed at room temperature to reflux temperature, specifically at 30 to 80 ° C for 1 to 8 hours.
An organic solvent may be added before adding the basic aqueous solution. The organic solvent can inhibit the formation of by-products. The organic solvent may be added in an amount of 0.1 to 3.0 times, particularly 0.2 to 2.0 times, the isothiouronium salt reaction solution. Examples of the organic solvent include toluene, xylene, chlorobenzene, and dichlorobenzene, and specifically may be toluene.
The above steps (1) to (3) may be carried out in air or under a nitrogen atmosphere, and it is preferable in terms of color to be carried out under a nitrogen atmosphere.
The obtained trifunctional and tetrafunctional polythiol compounds can be further purified.
For example, it is possible to perform a plurality of times of alkaline cleaning and a plurality of times of water cleaning. Impurities and the like remaining in the polythiol can be removed through the cleaning process, thereby improving the color of the polythiol and improving the color of the optical material obtained therefrom.
Thereafter, if necessary, the desired trifunctional and tetrafunctional polythiol compounds can be obtained by drying, filtration and the like.
An embodiment provides a polymerizable composition comprising a polythiol compound and an isocyanate compound produced by the method as described above.
Specifically, the polythiol compound may be a trifunctional polythiol compound represented by the general formula (1). The polythiol compound may be a tetrafunctional polythiol compound having at least one of the compounds represented by the above formulas (2) to (4).
The isocyanate-based compound may be a conventional one used for the synthesis of polythiourethane.
Specific examples include isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, Butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecatriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-di (Isocyanatoethyl) ether, 1,2-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) But are not limited to, bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane Sociane Bis (isocyanatoethyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatoethyl) sulfide, bis (Isocyanatoethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatoethylthio) Bis (isocyanatoethylthio) ethane, bis (isocyanatomethylthio) ethane, 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane, 2,5- Diisocyanatotetrahydrothiophene, 2,5-bis (isocyanatomethyl) tetrahydrothiophene, 3, 5-bis (isocyanatomethyl) thiophene, , 2,5-bis (isocyanatomethyl) -1,4-dithiene, 2,5-bis (isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanato- Diisocyanato-1,3-dithiolane, 4,5-bis (isocyanatomethyl) -1,3-dithiolane, 4,5-bis (isocyanatomethyl) 2-methyl-1,3-dithiolane, and the like; (Isocyanatoethyl) benzene, bis (isocyanatoethyl) benzene, bis (isocyanatoethyl) benzene, bis (isocyanatoethyl) Examples of the aromatic diisocyanate compound include aromatic diisocyanates such as phenyl ether, phenylenediisocyanate, ethylphenylenediisocyanate, isopropylphenylenediisocyanate, dimethylphenylenediisocyanate, diethylphenylenediisocyanate, diisopropylphenylenediisocyanate, trimethylbenzene triisocyanate, Toluene diisocyanate, 4,4-diphenylmethane diisocyanate, 3,3-dimethyldiphenylmethane-4,4-diisocyanate, bibenzyl-4,4-diisocyanate, bis (isocyanato Phenyl) ethylene, 3,3-dimethoxybiphenyl-4,4-diisocyanate, hexahydrobenzene diisocyanate, hexahydrate 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 -Isocyanatomethylbenzene) sulfide, 4,4-methoxybenzenethioethylene glycol-3,3-diisocyanate, diphenyldisulfide-4,4-diisocyanate, 2,2-dimethyl diphenyl disulfide Diisocyanate, 3,3-dimethyldiphenyldisulfide-5,5-diisocyanate, 3,3-dimethyldiphenyldisulfide-6,6-diisocyanate, 4,4- Diisocyanate, 5,5-diisocyanate, 3,3-dimethoxydiphenyl disulfide-4,4-diisocyanate, 4,4-dimethoxydiphenyl di From the aromatic group consisting of isocyanate-based compound, or the like feed-3,3-diisocyanate it can be used at least one member.
Specifically, the isocyanate compound may be 1,3-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, or the like.
The polymerizable composition may further contain an additive such as an internal mold release agent, a heat stabilizer, a reaction catalyst, an ultraviolet absorber, and a blueing agent, depending on the purpose.
Examples of the ultraviolet absorber include benzophenone, benzotriazole, salicylate, cyanoacrylate, oxanilide, and the like.
Examples of the internal release agent include a fluorine-based nonionic surfactant having a perfluoroalkyl group, a hydroxyalkyl group or a phosphate ester group; A silicone-based nonionic surfactant having a dimethylpolysiloxane group, a hydroxyalkyl group or a phosphate ester group; Alkyl quaternary ammonium salts such as trimethylcetylammonium salt, trimethylstearyl, dimethylethylcetylammonium salt, triethyldodecylammonium salt, trioctylmethylammonium salt, diethylcyclohexadecylammonium salt and the like; And acidic phosphate esters may be used singly or in combination of two or more.
As the reaction catalyst, a known reaction catalyst used in the production of a polythiourethane resin may be appropriately added. Dialkyltin halide systems such as dibutyltin dichloride and dimethyltin dichloride; Dialkyltin dicarboxylates such as dimethyltin diacetate, dibutyltin dioctanoate and dibutyltin dilaurate; Dialkyltin dialkoxides such as dibutyltin dibutoxide and dioctyltin dibutoxide; Dialkyltin dithioalkoxide systems such as dibutyltin di (thiobutoxide); Dialkyltin oxides such as di (2-ethylhexyl) tin oxide, dioctyltin oxide, and bis (butoxy dibutyltin) oxide; And a dialkyltin sulfide system such as dibutyltin sulfide feed. Specifically, it may be selected from the group consisting of dialkyltin halide systems such as dibutyltin dichloride, dimethyltin dichloride and the like.
Examples of the thermal stabilizer include a metal fatty acid salt, phosphorus, lead, and an organosilicate.
The bluing agent has an absorption band in the wavelength range from orange to yellow in the visible light region and has a function of adjusting the color of the optical material made of the resin. Specifically, the bluing agent may include a material that exhibits blue to violet, but is not particularly limited. Examples of the bluing agent include dyes, fluorescent whitening agents, fluorescent pigments, and inorganic pigments, but they can be appropriately selected in accordance with physical properties and resin color required for the produced optical component. These bluing agents may be used alone or in combination of two or more. From the viewpoints of the solubility in the polymerizable composition and the transparency of the resulting optical material, dyes are preferred as the bluing agent. In view of the absorption wavelength, the dye may specifically be a dye having a maximum absorption wavelength of 520 to 600 nm, and more specifically, a dye having a maximum absorption wavelength of 540 to 580 nm. Further, from the viewpoint of the structure of the compound, an anthraquinone-based dye is preferable as the dye. The method of adding the bluing agent is not particularly limited and may be added to the monomer system in advance. Specifically, the method of adding the bluing agent may be a method of dissolving the monomer in a monomer, or a method of preparing a master solution containing a high concentration of a bluing agent and diluting the monomer solution or other additives using the master solution and adding You can use branching methods.
The examples provide polythiourethane-based compounds obtained from the polymerizable composition as described above. The polythiourethane compound is prepared by polymerizing (and curing) the polythiol compound and the isocyanate compound. The reaction mole ratio of the SH group / NCO group in the polymerization reaction may be 0.5 to 3.0, specifically 0.6 to 2.0, more specifically 0.8 to 1.3. Within this range, the refractive index, heat resistance And the balance and the like can be improved. Further, in order to control the reaction rate, the above-mentioned reaction catalyst which is conventionally used for the production of polythiourethane may be added.
The embodiment provides a molded article obtained by curing the polymerizable composition and an optical material comprising the molded article. The optical material may be prepared by polymerizing and molding the polymerizable composition.
First, the polymerizable composition is degassed under reduced pressure, and then injected into a mold for optical material molding. Such degassing and mold injection can be performed, for example, at a temperature range of 20 to 40 캜. After injection into the mold, the polymerization is usually carried out by gradually heating from a low temperature to a high temperature.
The temperature of the polymerization reaction may be, for example, 20 to 150 ° C, and specifically 25 to 120 ° C. In order to control the reaction rate, a reaction catalyst which is usually used in the production of polythiourethane may be added, and specific examples thereof are as exemplified above.
Then, the polythiourethane-based optical material is separated from the mold.
The optical material may be in various shapes by changing the mold of the mold used in the production. Specifically, it may be in the form of a spectacle lens, a camera lens, a light emitting diode (LED), or the like.
The optical material may have a refractive index of 1.65 to 1.75 or 1.65 to 1.70.
The optical material may be an optical lens, specifically a plastic optical lens. The optical lens can be used for surface polishing, antistatic treatment, hard coat treatment, anti-reflection coat treatment, anti-reflection treatment, anti-reflection treatment, anti- A dyeing treatment, a dimming treatment, and the like.
As described above, according to the method for producing a polythiol compound according to the embodiment, by using a specific type of base in the hydrolysis step during the production of the polythiol compound and appropriately controlling the concentration of the base, sufficient hydrolysis can be performed in a short time To thereby produce a desired polythiol compound economically and efficiently. Accordingly, the polythiourethane obtained from the polythiourethane is excellent in optical properties such as refractive index and hue, and thus can be usefully used in the production of various plastic optical materials such as spectacle lenses and camera lenses.
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended to illustrate the present invention, but the scope of the present invention is not limited thereto.
[
Example
]
Trifunctional Polythiol Preparation of compounds
Example One
169 parts by weight (2.16 mol) of 2-mercaptoethanol and 76.0 parts by weight of water were introduced into a 2-liter four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen purge tube and a thermometer under nitrogen, 91.9 parts by weight (1.08 mol) of a 47% by weight aqueous sodium hydroxide solution was added dropwise over 30 minutes. Next, 99.9 parts by weight (1.08 mol) of epichlorohydrin was added dropwise at the same temperature over 3 hours, and then aged for 1 hour. Next, 450 parts by weight (4.32 mol) of 35% hydrochloric acid and 246.9 parts by weight (3.24 mol) of thiourea having a purity of 99.9% were added and the reaction solution was reacted with thiouronium chloride for 3 hours while refluxing at 110 DEG C .
After the reaction solution was cooled to 60 캜, 450.0 parts by weight of toluene and 545.3 parts by weight (4.86 mol) of 50% potassium hydroxide aqueous solution were added and hydrolysis was carried out for 1 hour to obtain a reaction solution.
After the toluene portion of the reaction solution was separated, 59.4 parts by weight of 36% hydrochloric acid was added to the toluene and mixed. After 30 minutes, the water portion was removed using a separating funnel at 36 ° C (acid washing step). The pickling step was repeated twice. Then, 118.7 parts by weight of distilled water was added to the reaction solution which had been acid-cleaned and mixed. After 30 minutes, the distilled water was washed 5 times at 36 캜 by using a separating funnel to remove water.
Thereafter, toluene and a small amount of water were completely removed through a heating and depressurizing process, and then the mixture was filtered with a Teflon filter having a thickness of 1 mu m to obtain 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane ≪ / RTI >
Example 2
Except that 549.3 parts by weight (4.86 mol) of 50% calcium hydroxide was used instead of 545.3 parts by weight of 50% aqueous solution of potassium hydroxide and the hydrolysis was conducted for 2 hours instead of 1 hour, -Bis [(2-mercaptoethyl) thio] -3-mercaptopropane.
Example 3
Except that 324 parts by weight (4.86 mol) of 60% sodium hydroxide instead of 545.3 parts by weight of a 50% aqueous solution of potassium hydroxide was used in place of 1,2-bis [(2-mercaptoethyl) Thio] -3-mercaptopropane.
Example 4
Except that 856.7 parts by weight (4.86 mol) of 35% calcium hydroxide aqueous solution was used instead of 545.3 parts by weight of the 50% aqueous solution of potassium hydroxide and the hydrolysis was conducted for 2 hours instead of 1 hour, 2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane.
Example 5
The procedure of Example 1 was repeated except that 1030.3 parts by weight (4.86 mol) of a 50% sodium carbonate aqueous solution was used instead of 545.3 parts by weight of 50% potassium hydroxide aqueous solution, and hydrolysis was performed for 2 hours instead of 1 hour, 2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane.
Four-sensory Polythiol Preparation of compounds
Example 6
51.7 parts by weight (0.66 mol) of 2-mercaptoethanol and 0.2 part by weight of triethylamine were fed into the reactor, 61.8 parts by weight (0.67 mol) of epichlorohydrin was added dropwise over 4 hours while maintaining the temperature at 8 DEG C, Lt; / RTI > for 1 hour to conduct the first reaction. Subsequently, 53.0 parts (0.34 mol) of a 50% aqueous solution of sodium sulfide was added dropwise at 22 DEG C over 5.5 hours, and stirring was carried out for 120 minutes. Then, 278.4 parts by weight (2.74 mol) of 36% hydrochloric acid was added. Then, 124.5 parts by weight (1.6 mol) of thiourea was added thereto and then thiouronium chloride was reacted for 3 hours while refluxing at 110 DEG C to obtain a reaction solution Respectively.
The reaction solution was cooled to 45 DEG C, 214.0 parts by weight of toluene was added, and the mixture was cooled to 26 DEG C and 317.5 parts by weight (2.83 mol) of 50% potassium hydroxide aqueous solution was added at 38 DEG C for 30 minutes, The reaction solution was further subjected to a hydrolysis process.
After the toluene portion of the reaction solution was separated, 59.4 parts by weight of 36% hydrochloric acid was added to the toluene and mixed. After 30 minutes, the water portion was removed using a separating funnel at 36 ° C (acid washing step). The pickling step was repeated twice. Then, 118.7 parts by weight of distilled water was added to the reaction solution which had been acid-cleaned and mixed. After 30 minutes, the distilled water was washed 5 times at 36 캜 by using a separating funnel to remove water.
Thereafter, toluene and a small amount of water were completely removed through a heating and depressurizing process, and then the solution was filtered with a Teflon filter having a thickness of 1 m to obtain 4,8-dimercaptomethyl-1,11-dimercapto- 9-trithiandecane (Formula 2), 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (Formula 3), and 5,7- 115.9 parts by weight of a polythiol compound containing, as a main component, captomethyl-1,11-dimercapto-3,6,9-trithiaundecane (Formula 4) (mole ratio -> Formula 2: Formula 4: 85: 5: 10).
Example 7
Except that 418.8 parts by weight (2.83 mol) of 50% calcium hydroxide aqueous solution was used instead of 317.5 parts by weight of 50% potassium hydroxide aqueous solution and hydrolysis was carried out for 2 hours instead of 1 hour, Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (Formula 2), 4,7-dimercaptomethyl-1,11-dimercapto-3,6 , 9-trithiane undecane (Formula 3), and 5, 7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (Formula 4) 115.9 parts by weight of a compound.
Example 8
The same procedure as in Example 6 was carried out except that 188.7 parts by weight (2.83 mol) of a 60% sodium hydroxide aqueous solution was used instead of 317.5 parts by weight of 50% potassium hydroxide aqueous solution to prepare 4,8-dimercaptomethyl-1,11 -Dimercapto-3,6,9-trithiandecane (Formula 2), 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (Formula 3 ) And 115.9 parts by weight of a polythiol compound containing, as a main component, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (Formula 4).
Example 9
The procedure of Example 6 was repeated except that 453.6 parts by weight (2.83 mol) of 35% calcium hydroxide aqueous solution was used instead of 317.5 parts by weight of 50% potassium hydroxide aqueous solution and hydrolysis was performed for 2 hours instead of 1 hour, Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (Formula 2), 4,7-dimercaptomethyl-1,11-dimercapto-3,6 , 9-trithiane undecane (Formula 3), and 5, 7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (Formula 4) 115.9 parts by weight of a compound.
Example 10
The procedure of Example 6 was repeated except that 600 parts by weight (2.83 mol) of a 50% sodium carbonate aqueous solution was used instead of 317.5 parts by weight of 50% potassium hydroxide aqueous solution and hydrolysis was conducted for 2 hours instead of 1 hour, Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (Formula 2), 4,7-dimercaptomethyl-1,11-dimercapto-3,6 , 9-trithiane undecane (Formula 3), and 5, 7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (Formula 4) 115.9 parts by weight of a compound.
Comparative Example One
Except that 331.1 parts by weight (4.86 mol) of 25% aqueous ammonia solution was used instead of 545.3 parts by weight of 50% potassium hydroxide aqueous solution and hydrolysis was carried out for 6 hours instead of 1 hour. 2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane.
Comparative Example 2
Except that 331.1 parts by weight (4.86 mol) of 25% aqueous ammonia solution was used instead of 545.3 parts by weight of 50% potassium hydroxide aqueous solution and hydrolysis was carried out for 2 hours instead of 1 hour, 2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane.
Comparative Example 3
Except that 953.9 parts by weight (4.86 mol) of a 50% potassium acetate aqueous solution was used instead of 545.3 parts by weight of 50% potassium hydroxide aqueous solution and the hydrolysis was conducted for 2 hours instead of 1 hour to obtain 1 , 2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane.
Comparative Example 4
Except that 1665 parts by weight (4.86 mol) of 50% aqueous barium hydroxide solution was used instead of 545.3 parts by weight of 50% aqueous potassium hydroxide solution to prepare 1,2-bis [(2-mercaptoethyl ) Thio] -3-mercaptopropane.
Comparative Example 5
The procedure of Example 6 was repeated except that 192.7 parts by weight (2.83 mol) of 25% aqueous ammonia solution was used instead of 317.5 parts by weight of 50% potassium hydroxide aqueous solution and hydrolysis was conducted for 6 hours instead of 1 hour, Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (Formula 2), 4,7-dimercaptomethyl-1,11-dimercapto-3,6 , 9-trithiane undecane (Formula 3), and 5, 7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (Formula 4) 115.9 parts by weight of a compound.
Comparative Example 6
The procedure of Example 6 was repeated except that 192.7 parts by weight (2.83 mol) of 25% aqueous ammonia solution was used instead of 317.5 parts by weight of 50% potassium hydroxide aqueous solution and hydrolysis was conducted for 2 hours instead of 1 hour, Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (Formula 2), 4,7-dimercaptomethyl-1,11-dimercapto-3,6 , 9-trithiane undecane (Formula 3), and 5, 7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (Formula 4) 115.9 parts by weight of a compound.
Comparative Example 7
The same procedure as in Example 6 was carried out except that 555.5 parts by weight (2.83 mol) of a 50% potassium acetate aqueous solution was used instead of 317.5 parts by weight of 50% potassium hydroxide aqueous solution and hydrolysis was performed for 2 hours instead of 1 hour to obtain 4 , 8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (2), 4,7-dimercaptomethyl-1,11-dimercapto- 6,9-trithiandecane (Formula 3), and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (Formula 4) 115.9 parts by weight of a thiol compound were obtained.
Comparative Example 8
The same procedure as in Example 6 was conducted, except that 969.5 parts by weight (2.83 mol) of a 50% aqueous solution of barium hydroxide was used instead of 317.5 parts by weight of a 50% aqueous solution of potassium hydroxide to prepare 4,8-dimercaptomethyl-1,11 -Dimercapto-3,6,9-trithiandecane (Formula 2), 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (Formula 3 ) And 115.9 parts by weight of a polythiol compound containing, as a main component, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (Formula 4).
Polymerizable Preparation of composition
Example 11
59.3 parts by weight of the polythiol compound prepared in Example 1 was uniformly mixed with 40.7 parts by weight of xylene diisocyanate (Takenate (R) 500). 0.01 part by weight of dibutyltin dichloride as a polymerization catalyst, 0.05 parts by weight of Zelec (R) UN 0.1 and UV stabilizer CYASORB (R) UV-5411 were added as polymerization catalysts and uniformly mixed to prepare a polymerizable composition.
Example 12 to 15 and Comparative Example 9-12
Polymerizable compositions were prepared in the same manner as in Example 11 except that the polythiol compounds of Examples 2 to 5 and Comparative Examples 1 to 4 were respectively used.
Example 16
49.3 parts by weight of the polythiol compound prepared in Example 6 was uniformly mixed with 50.7 parts by weight of xylene diisocyanate (Takenate (R) 500). Then, 0.01 part by weight of dibutyltin dichloride as a polymerization catalyst and 0.1 part by weight of Zelec (R) UN as an internal phase were added and uniformly mixed to prepare a polymerizable composition.
Example 17 to 20 and Comparative Example 13 to 16
Polymerizable compositions were prepared in the same manner as in Example 16 except that the polythiol compounds of Examples 7 to 10 and Comparative Examples 5 to 8 were respectively used.
Experimental Example : Property check
The properties of the polythiol compounds prepared in Examples 1 to 10 and Comparative Examples 1 to 8 and the polymerizable compositions prepared in Examples 11 to 20 and Comparative Examples 9 to 16 were measured as described below and measured The results are shown in Tables 1 and 2 below.
(1) Yield
The yields of the polythiol compounds prepared in Examples 1 to 10 and Comparative Examples 1 to 8 were calculated by the following formula (1).
In this case, the theoretical yield is calculated by the formula of "moles of introduced epichlorohydrin x molecular weight of formula 1 (about 274)" in the case of the compound of formula 1, and in the case of the compounds of formulas 2 to 4, "the amount of added epichlorohydrin (Molar number of formula (2) x mole number of formula (2) x mole number of formula (3) x mole number of formula (3) + mole number of formula (4) x molecular weight of formula (4) (about 366)
[Equation 1]
Yield (%) = (actual gain / theoretical gain) x100.
(2) SH value
After adding about 0.1 g each of the polythiol compounds prepared in Examples 1 to 10 and Comparative Examples 1 to 8 to the beaker, 40 mL of chloroform was further added, and the mixture was stirred for 10 minutes. Then, 20 mL of isopropyl alcohol was further added, Lt; / RTI > The solution was titrated with a 0.1N iodine standard solution, and the SH value was calculated by applying the following equation (2) (theoretical value = 91.3):
&Quot; (2) "
SH value (g / eq.) = Sample weight (g) / {0.1 X amount of iodine consumed (L)}.
(3) American Public Health Association APHA ) color
The polythiol compound prepared in Examples 1 to 10 and Comparative Examples 1 to 8 was placed in a quartz cell having a transmission length of 1 cm and APHA color was measured using a ColorQuest XE instrument manufactured by Hunterlab. At this time, the concentration of the standard solution prepared by dissolving the reagent of platinum and cobalt was data, and the APHA value obtained by the comparison between the program and the sample solution was determined as a frequency (frequency). The smaller the measured value, the better the color.
(4) liquid refractive index
The refractive indexes of the polymerizable compositions prepared in Examples 11 to 20 and Comparative Examples 9 to 16 were measured at 25 占 폚 using a liquid refractometer Refractometer RA-600 (manufactured by Kyoto Electronics Co., Ltd.).
(5) Solid-state refractive index
The polymerizable compositions prepared in Examples 11 to 20 and Comparative Examples 9 to 16 were degassed at 600 Pa for 1 hour and then filtered through a Teflon filter of 3 占 퐉. The filtered polymerizable composition was injected into a glass mold template assembled by tape. The mold was heated from 25 캜 to 120 캜 at a rate of 5 캜 / min and polymerization was carried out at 120 캜 for 18 hours. The cured resin in the glass mold mold was further cured at 130 캜 for 4 hours, and then the molded body was released from the glass mold mold. The molded article was a circular lens (optical material) having a center thickness of 1.2 mm (deviation: -5.00) and a diameter of 72 mm. The lens was impregnated with ST11TN-8H hard coating solution (FINE COAT) and thermally cured to coat the lens.
The refractive index of the lens was measured at 20 ° C using an Abbe refractometer DR-M4 (Atago Co.).
(6) Light fastness (yellow before and after light exposure) Exponential Difference ; △ YI )
Using the polymerizable composition prepared in Examples 11 to 20 and Comparative Examples 9 to 16, a molded article was prepared in the same manner as in item (5), except that a circular lens having a thickness of 9 mm and a diameter of 75 mm ). At this time, no coating was performed. The chromaticity coordinates x and y of the optical material were measured using a chrominometer CM-5 manufactured by Minolta Co., and the measured values were applied to the following equation (3) to calculate an initial yellow index (YI). Then, the optical material was exposed to a QUV / Spray model (5w) of Q-Pannel lad product for 200 hours, and the yellow index was measured in the same manner as described above. The difference between the initial YI value (difference between YI values before and after light exposure) was calculated and expressed as the light resistance (? YI)
&Quot; (3) "
YI = (234x + 106y + 106) / y.
As shown in Tables 1 and 2, according to the hydrolysis process of Examples 1 to 10, the polythiol compound can be produced in a high yield in a much shorter time than the process of Comparative Examples 1 to 8, The APHA color value (frequency) of the compound is also excellent. Furthermore, the compositions of Examples 11 to 20 exhibit excellent refractive indexes before and after curing as well as excellent light resistance due to small chromaticity differences as compared with the compositions of Comparative Examples 9 to 16. Thus, it is expected that the optical lens manufactured in the examples is excellent in refractive index and light resistance and can be usefully used as an optical material.
Claims (13)
Wherein the basic aqueous solution comprises a basic substance having a pH of 11 to 13 upon dilution with distilled water to 100 mM, the concentration of the basic aqueous solution is 35 to 55%
Wherein the basic substance does not contain an amine base and is at least one selected from the group consisting of potassium hydroxide, calcium hydroxide, sodium hydroxide and sodium carbonate,
The SH value of the polythiol compound is 92.8 to 98.1 g / eq.
Wherein the difference (? YI) of the yellow index values before and after light exposure of the optical material according to the following formula (3) is 1.4 to 1.8:
&Quot; (3) "
YI = (234x + 106y + 106) / y.
Wherein the polyol compound is a compound having a sulfur atom.
Wherein the polyol compound is a compound obtained by reacting 2-mercaptoethanol with epihalohydrin.
Wherein the polyol compound is a compound represented by the following general formula (7)
(7)
Wherein the polyol compound is obtained by reacting a compound obtained by the reaction of 2-mercaptoethanol and epihalohydrin with a metal sulfide.
Wherein the polyol compound is a compound represented by the following general formula (8)
[Chemical Formula 8]
Wherein the polythiol compound is a compound represented by the following Formula 1:
[Chemical Formula 1]
Wherein the polythiol compound is at least one or more compounds represented by the following general formulas (2) to (4)
(2)
(3)
[Chemical Formula 4]
Wherein the optical material has a refractive index of 1.65 to 1.75.
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