WO2021167256A1 - Composé épisulfure pour matériau optique, composition pour matériau optique à indice de réfraction élevé contenant celui-ci et procédé pour la fabrication de matériau optique - Google Patents

Composé épisulfure pour matériau optique, composition pour matériau optique à indice de réfraction élevé contenant celui-ci et procédé pour la fabrication de matériau optique Download PDF

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WO2021167256A1
WO2021167256A1 PCT/KR2021/000990 KR2021000990W WO2021167256A1 WO 2021167256 A1 WO2021167256 A1 WO 2021167256A1 KR 2021000990 W KR2021000990 W KR 2021000990W WO 2021167256 A1 WO2021167256 A1 WO 2021167256A1
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optical material
episulfide
compound
composition
bis
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PCT/KR2021/000990
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Korean (ko)
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장동규
노수균
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주식회사 케이오씨솔루션
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Publication of WO2021167256A1 publication Critical patent/WO2021167256A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D331/00—Heterocyclic compounds containing rings of less than five members, having one sulfur atom as the only ring hetero atom
    • C07D331/02—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/06—Polythioethers from cyclic thioethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • 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
    • 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
    • G02B1/041—Lenses

Definitions

  • the present invention relates to a method for producing an episulfide compound for an optical material, a composition for a high refractive optical material using the same, and a method for producing an optical material. It relates to a method for efficiently producing an episulfide compound for an optical material having good color and transparency by controlling the amount of hydrin added.
  • Plastic lenses are light, have good impact resistance, and are easy to color, so plastic lenses are used in most spectacle lenses in recent years.
  • Plastic spectacle lenses have been developed in the direction of increasing lightness, high transparency, low yellowness, heat resistance, light resistance, and strength.
  • Korean Patent No. 10-0681218 proposes an episulfide-based plastic lens.
  • Episulfide-based lenses have a high refractive index and high Abbe's number, but have many problems in terms of tensile strength, compressive strength, colorability, hard adhesion, productivity, and the like.
  • a method of copolymerizing two types of resins having different properties that is, a method of copolymerizing an episulfide compound and a polythiol compound or a polyisocyanate compound therewith, is disclosed in Korean Patent No. 10-0417985, Japanese Patent Laid-Open Patent Publication No. It was proposed in Hei 11-352302, etc.
  • Patent Document 1 Republic of Korea Patent Publication No. 10-0417985
  • Patent Document 2 Japanese Patent Application Laid-Open No. Hei 11-352302
  • Patent Document 3 Japanese Patent Laid-Open No. 2001-2783
  • Patent Document 4 Republic of Korea Patent Publication No. 10-2014-0122721
  • a method of producing an episulfide compound for an optical material that can precisely control the reaction rate by directly generating hydrogen sulfide gas and introducing it into the process and controlling the addition amount of hydrochloric acid and epichlorohydrin at a constant temperature and pressure.
  • Another object of the present invention is to provide an economical and mass-produced episulfide compound, a composition for a high refractive optical material using the same, and a method for manufacturing the optical material.
  • It provides a method for producing an episulfide compound for an optical material, characterized in that the reaction progress is controlled by adjusting the input amount of the acid and the epichlorohydrin.
  • n is an integer from 0 to 2.
  • the reactor (A) maintains the reactor (A) at a temperature of 5 °C ⁇ 30 °C, a pressure of 0.02kgf / cm 2 ⁇ 5kgf / cm 2
  • the reactor (B) is a pressure of 0.02kgf / cm 2 It is more preferable to maintain at ⁇ 5 kgf/cm 2 .
  • reaction control step in a preferred embodiment, when epichlorohydrin is detected by GC analysis of the reaction product of step (c), an acid is additionally added to the reactor (A), and 3-chloro-2-hydrogen When hydroxy-propane-1-thiol is detected, the progress of the reaction can be controlled by additionally adding epichlorohydrin to the reactor (B).
  • It provides a method for preparing a composition for an episulfide-based high refractive optical material, comprising the step of preparing a composition comprising the episulfide compound and a polymerization catalyst.
  • Preparing the composition may further include any one or more of sulfur, a polythiol compound, and a polyisocyanate compound in the composition.
  • composition for an optical material comprising the episulfide compound and a polymerization catalyst
  • It provides a method for producing an episulfide-based high refractive optical material, comprising the step of polymerizing the composition for an optical material.
  • Preparing the composition may further include any one or more of sulfur, a polythiol compound, and a polyisocyanate compound in the composition.
  • the reaction rate can be precisely controlled by directly generating hydrogen sulfide gas and injecting it into the process and adjusting the addition amounts of hydrochloric acid and epichlorohydrin at a constant temperature and pressure. have.
  • a compound with high purity and uniformity can be prepared in the process of reacting hydrogen sulfide gas, and an episulfide compound, which is a monomer capable of forming an optical material with high transparency and no fog during polymerization, can be prepared.
  • an episulfide compound having high transparency can be obtained in an economical manner because there is no haze during polymerization, and mass production is possible.
  • 'high refractive index' includes all of 1.67 or more to 1.71 or more, commonly referred to as ultra-high refractive index. Although not limited, the refractive index is usually in the range of 1.67 to 1.77.
  • the method for producing an episulfide compound for an optical material of the present invention comprises the steps of generating hydrogen sulfide gas; reacting epichlorohydrin with hydrogen sulfide to prepare bis((3-chloro-2-hydroxypropyl)sulfide; and reacting bis((3-chloro-2-hydroxypropyl)sulfide with thiourea to produce epi It includes the step of preparing a sulfide compound, and at this time, the overall reaction progress is controlled and controlled by adjusting the input amounts of the hydrochloric acid and the epichlorohydrin.
  • each step will be described in detail.
  • Sulfide is put into the reactor (A) and acid is added to react to generate hydrogen sulfide gas.
  • acid preferably concentrated hydrochloric acid can be used. It is also possible to use dilute hydrochloric acid instead of concentrated hydrochloric acid, but since a relatively large amount of residual hydrogen sulfide gas remains in the reactor, there is a disadvantage in that the production is reduced.
  • the reactor (A) reacts with the sulfide and acid while maintaining the temperature 1 °C ⁇ 50 °C, pressure 0.001kgf / cm 2 ⁇ 10kgf / cm 2 range, more preferably temperature 5 °C ⁇ 30 °C, pressure 0.02kgf / cm 2 ⁇ 5kgf / cm 2
  • the reaction is maintained while maintaining.
  • a temperature 5 °C ⁇ 20 °C is allowed to react while maintaining the pressure 0.02kgf / cm 2 ⁇ 3kgf / cm 2.
  • the reaction must be saturated with hydrogen sulfide, and the reaction can proceed at a constant rate by controlling the temperature and pressure. If the above conditions are not maintained, that is, if the temperature of the reactor rises to 30° C. or higher or the pressure exceeds the above range, the reaction proceeds irregularly and impurities are generated, affecting the episulfide compound, the product of the next step, and finally During polymerization, a haze phenomenon appears in the optical lens.
  • the overall reaction progress can be controlled by adjusting the amounts of acid and epichlorohydrin in the above step. That is, the amount of acid input to the reactor (A) in the hydrogen sulfide gas generation step and epichlorohydrin input to the reactor (B) in the production step of bis((3-chloro-2-hydroxypropyl)sulfide By adjusting the amount, the overall reaction progress can be controlled.
  • epichlorohydrin when epichlorohydrin is detected by GC analysis of the reaction product generated in the preparation step of the episulfide compound, hydrochloric acid is further added to the reactor (A), and 3-chloro-2-hydroxy- When propane-1-thiol is detected, epichlorohydrin is additionally added to the reactor (B) to control the reaction progress.
  • the starting material remaining without participating in the reaction may become an unintended impurity due to various reactions in the subsequent reaction system and may be incorporated into the final desired product.
  • the reaction progress can be precisely controlled to minimize the remaining starting materials and to react almost completely, so that it is possible to produce a high-purity episulfide compound in a simple and easy way.
  • composition comprising the episulfide compound and a polymerization catalyst.
  • any one or more of sulfur, a polythiol compound, and a polyisocyanate compound may be further included in the composition.
  • the episulfide compound is represented by Formula 1 above, for example, bis(2,3-epithiopropyl)sulfide, bis(2,3-epithiopropyl)disulfide, 1,3 and 1,4-bis( ⁇ ).
  • the episulfide compound may be a chlorine substituent of a compound having an episulfide group, a halogen substituent such as a bromine substituent, an alkyl substituent, an alkoxy substituent, a nitro substituent, or a prepolymer-type modified product with polythiol.
  • a halogen substituent such as a bromine substituent, an alkyl substituent, an alkoxy substituent, a nitro substituent, or a prepolymer-type modified product with polythiol.
  • the episulfide compound represented by Formula 1 is preferably bis(2,3-epithiopropyl)sulfide, bis(2,3-epithiopropyl)disulfide, 1,3 and 1,4-bis( ⁇ -epi).
  • thiopropylthio)cyclohexane 1,3 and 1,4-bis( ⁇ -epithiopropylthiomethyl)cyclohexane, 2,5-bis( ⁇ -epithiopropylthiomethyl)-1,4-dithiane; 2,5-bis( ⁇ -epithiopropylthioethylthiomethyl)-1,4-dithiane, 2-(2- ⁇ -epithiopropylthioethylthio)-1,3-bis( ⁇ -epithiopropyl thio) propane.
  • a 2,3-epoxypropyl (2,3-epithiopropyl) sulfide compound as in the product of Scheme 3 may be further included in the episulfide compound as a final product.
  • the 2,3-epoxypropyl (2,3-epithiopropyl) sulfide compound increases the polymerizability of the composition to facilitate polymerization.
  • the 2,3-epoxypropyl (2,3-epithiopropyl) sulfide compound is contained in an amount of 0.3 to 15 wt%, more preferably 0.5 to 13 wt%.
  • the 2,3-epoxypropyl (2,3-epithiopropyl) sulfide compound is particularly preferably used in an amount of 0.5 to 5% by weight in the episulfide compound. Included.
  • the polythiol compound is not particularly limited, and as long as it is a compound having at least one thiol group, one type or a mixture of two or more types may be used.
  • a compound having one or more thiol groups one type or a mixture of two or more types may be used.
  • a polymerization modified product obtained by prepolymerization with an isocyanate, an episulfide compound, a thietane compound, or a compound having an unsaturated bond as a resin modifier to the polythiol compound can also be used.
  • polythiol compound particularly preferably, bis(2-mercaptoethyl)sulfide or 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane or another polythiol compound is added thereto to 1 It can be used by mixing more than one species.
  • the polythiol may preferably be included in the composition for an optical material in an amount of 1 to 15% by weight, more preferably 4 to 13% by weight, and still more preferably 5 to 11% by weight.
  • the polyisocyanate compound is not particularly limited, and a compound having at least one isocyanate group and/or an isothiocyanate group may be used.
  • a compound having at least one isocyanate group and/or an isothiocyanate group may be used.
  • aromatic isocyanate compounds 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(isocyanatomethyl) sulfur-containing aliphatic isocyanate compounds such as thio)ethane and 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane; Diphenylsulfide-2,4-diisocyanate, diphenylsulfide-4,4'-diisocyanate, 3,3'-d
  • halogen substituents such as chlorine substituents and bromine substituents, alkyl substituents, alkoxy substituents, nitro substituents, polyhydric alcohols or thiols of these isocyanate compounds, carbodiimide modified products, urea modified products, and biuret modified products Alternatively, dimerization or trimerization reaction products may also be used.
  • isophorone diisocyanate IPDI
  • HDI hexamethylene diisocyanate
  • H12MDI dicyclohexylmethane diisocyanate
  • XDI xylylene diisocyanate
  • NBDI norborane diisocyanate
  • At least one selected from among ,6-bis(isocyanatomethyl)bicyclo[2,2,1]heptane may be used.
  • the isocyanate compound is included in an amount of 0.01 to 20% by weight of the composition for an optical material, and more preferably, may be included in an amount of 0.05 to 10% by weight.
  • the composition for an episulfide-based optical material may further include sulfur.
  • sulfur When sulfur is included, the refractive index may be increased to an ultra-high refractive index of 1.71 or more.
  • the sulfur included in the composition is preferably 98% or more pure. In the case of less than 98%, the transparency of the optical material may be deteriorated due to the influence of impurities.
  • the purity of the sulfur is more preferably 99.0% or more, and particularly preferably 99.5% or more.
  • commercially available sulfur is classified by differences in shape or refining method, and there are fine powder, colloidal sulfur, precipitated sulfur, crystalline sulfur, sublimated sulfur, and the like. In the present invention, any sulfur can be used as long as the purity is 98% or more.
  • fine powder of fine particles that are easily dissolved may be used in the preparation of the composition for an optical material.
  • sulfur is preferably contained in an amount of 1 to 40 wt%, more preferably 2 to 30 wt%, and most preferably 3 to 22 wt%.
  • the polymerization catalyst is preferably at least one selected from among amines, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, and phosphine compounds. More preferably, at least one selected from a quaternary ammonium salt, a quaternary phosphonium salt, and a phosphine compound may be used.
  • quaternary ammonium salt for example, tetra-n-butylammonium bromide, tetraphenylammonium bromide, triethylbenzylammonium chloride, cetyldimethylbenzylammonium chloride, 1-n-dodecylpyridinium chloride, etc. can be used.
  • a quaternary phosphonium salt tetra-n-butylphosphonium bromide, tetraphenylphosphonium bromide, etc. can be used, for example.
  • phosphine compound triphenylphosphine or the like can be used.
  • the polymerization catalyst is a quaternary phosphonium salt, and includes any one of tetra-n-butylphosphonium bromide and tetraphenylphosphonium bromide. These polymerization catalysts can be used individually or in mixture of 2 or more types.
  • the composition for an episulfide-based optical material may further include a tin halogen compound as a polymerization regulator.
  • the tin halogen compound is preferably any one of dibutyl tin dichloride and dimethyl tin dichloride, or one in which monomethyl tin trichloride is included in a small amount may be used. More preferably, monomethyl tin trichloride may be included in an amount of 0.1 to 3.5 wt%.
  • the polymerization regulator is preferably used in an amount of 0.01 to 5% by weight based on the total weight of the composition for an optical material.
  • the polymerization rate can be controlled to suppress a sudden increase in viscosity, and as a result, the polymerization yield is increased, and the generation of bubbles is also eliminated.
  • composition for an episulfide-based optical material When sulfur is included in the composition for an episulfide-based optical material, it is preferable to polymerize after forming the prepolymer. have.
  • Said alkylimidazole particularly preferably comprises 2-mercapto-1-methylimidazole.
  • 2-Mercapto-1-methylimidazole is preferably used with a purity of 98% or more.
  • the composition for an optical material may preferably contain 0.01 to 5% by weight, more preferably 0.1 to 3% by weight, and still more preferably 0.15 to 1% by weight.
  • the composition for an optical material of the present invention may further include an internal release agent.
  • an internal release agent Preferably, it may include a phosphate ester compound as an internal mold release agent.
  • Phosphoric acid ester compound is prepared by adding 2 to 3 moles of an alcohol compound to phosphorus pentoxide (P 2 O 5 ). At this time, various types of phosphoric acid ester compounds can be obtained depending on the type of alcohol used. Representative examples are those in which ethylene oxide or propylene oxide is added to an aliphatic alcohol or ethylene oxide or propylene oxide is added to a nonylphenyl group or the like.
  • the composition of the present invention is an internal mold release agent, preferably 4-PENPP [polyoxyethylene nonylphenyl ether phosphate (5 wt% of ethylene oxide added by 5 moles, 80 wt% of 4 moles added, 3 moles added) 10% by weight, 5% by mole of added)], 8-PENPP [polyoxyethylene nonylphenyl ether phosphate (3% by weight of added 9 moles of ethylene oxide, 80% by weight of 8 moles added) 5 wt% of molar addition, 6 wt% of 7 molar addition, 6 wt% of 6 molar addition)], 12-PENPP [polyoxyethylene nonylphenyl ether phosphate (3 wt% of ethylene oxide added by 13 moles) , 80
  • the composition for an optical material of the present invention may further include an olefin compound as a reactive resin modifier for the purpose of controlling impact resistance, specific gravity, monomer viscosity, etc. in order to improve optical properties of the optical material.
  • an olefin compound that can be added as the resin modifier include benzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2 -Hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, phenoxy ethyl acrylate, phenoxy ethyl methacrylate, phenyl methacrylate, ethylene glycol di Acrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol di
  • the composition for an optical material of the present invention may further include an ultraviolet absorber, if necessary.
  • the ultraviolet absorber is used for improving the light resistance of the optical material and blocking ultraviolet rays, and a known ultraviolet absorber used for the optical material may be used without limitation.
  • ethyl-2-cyano-3,3-diphenylacrylate 2-(2'-hydroxy-5-methylphenyl)-2H-benzotriazole; 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chloro-2H-benzotriazole; 2-(2′-hydroxy-3′-t-butyl-5′-methylphenyl)-5-chloro-2H-benzotriazole; 2-(2'-hydroxy-3',5'-di-t-amylphenyl)-2H-benzotriazole; 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-2H-benzotriazole; 2-(2'-hydroxy-5
  • 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5 which has good ultraviolet absorption ability in the wavelength range of 400 nm or less and has good solubility in the composition of this invention -Chloro-2H-benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)-2H-benzotriazole, etc. can be used.
  • Such a UV absorber can block 400 nm or more when used in an amount of 0.6 g or more with respect to 100 g of the composition for optical materials.
  • composition for an optical material of the present invention may further include various additives such as a chain extender, a crosslinking agent, a light stabilizer, an antioxidant, a color inhibitor, an organic dye, a filler, and an adhesion improver, if necessary.
  • additives such as a chain extender, a crosslinking agent, a light stabilizer, an antioxidant, a color inhibitor, an organic dye, a filler, and an adhesion improver, if necessary.
  • composition for an optical material of the present invention composed as described above, after polymerization, has a solid-state refractive index (Ne) of 1.67 to 1.70 when sulfur is not included, and 1.71 to 1.77 when sulfur is included.
  • composition for an optical material comprising the episulfide compound and a polymerization catalyst
  • an episulfide-based high refractive optical material can be obtained.
  • a more detailed description is as follows.
  • the polymerizable composition of the present invention is injected between the molding molds held by gaskets or tapes.
  • a degassing treatment under reduced pressure or a filtration treatment such as pressurization or reduced pressure depending on the physical properties required for the obtained optical material and if necessary.
  • the polymerization conditions are not limited because conditions vary greatly depending on the polymerizable composition, the type and amount of catalyst used, the shape of the mold, and the like, but it is carried out at a temperature of about -50 to 130° C. for 1 to 50 hours. In some cases, it is preferable to maintain or gradually increase the temperature in a temperature range of 10 to 130° C. and harden in 1 to 48 hours.
  • the episulfide compound-based optical material obtained by curing may be subjected to treatment such as annealing, if necessary.
  • the treatment temperature is usually 50 to 130°C, and preferably 90 to 120°C.
  • the optical material of the present invention can be obtained as a molded article having various shapes by changing the mold during casting polymerization, it can be used as various optical materials such as spectacle lenses, camera lenses, and light emitting diodes (LEDs).
  • it is suitable as an optical material and an optical element, such as a spectacle lens, a camera lens, and a light emitting diode.
  • the episulfide-based high-refractive optical material obtained according to the present invention has excellent hard adhesion and can be hard coated without a primer, can be easily coated, and has excellent coating stability.
  • the plastic optical lens obtained according to the present invention can be used by forming various coating layers on one side or both sides, if necessary.
  • a primer layer, a hard coating layer, an anti-reflection film layer, an anti-fogging coating film layer, an anti-fouling layer, a water-repellent layer, etc. are all possible, and these coating layers may be used alone or in multiple coating layers.
  • the coating layer is formed on both surfaces, it is possible to form the same coating layer on each surface or to form different coating layers.
  • Epichlorohydrin (11126 g, 120.25 mol) and methanol (5000 g) were added to a GL reactor that can be used up to 12 kgf/cm 2 , and the reaction temperature was adjusted to 6 ° C. When the reaction temperature reached 6 ° C, caustic soda (50% ( aq), 10 g, 0.125 mol) was added.
  • Epichlorohydrin (11126 g, 120.25 mol) and methanol (5000 g) were added to a GL reactor that can be used up to 12 kgf/cm 2 , and the reaction temperature was adjusted to 6 ° C. When the reaction temperature reached 6 ° C, caustic soda (50% ( aq), 10 g, 0.125 mol) was added.
  • the reaction was carried out while maintaining /cm 2 , and the reactor in which epichlorohydrin and hydrogen sulfide reacted was reacted while maintaining an internal temperature of 10.0° C. and an internal pressure of 0.00 kgf/cm 2.
  • the completion of the reaction was completed by GC analysis of the final product to be epichlorohydrin.
  • the reaction was terminated at the point when the dry and 3-chloro-2-hydroxy-propane-1-thiol compounds were completely eliminated and bis(3-chloro-2-hydrocypropyl)sulfide was produced.
  • BCPS - 11 bis(3-chloro-2-hydroxypropyl)sulfide
  • BCPS- 1 (1070.48 g, 4.88 mol), 1300 g toluene, and 800 g of methanol were put in a 10 liter reaction vessel, and the external reaction temperature was adjusted to 30 °C while stirring. When it reached 25°C, NaOH (50% (aq), 783.08 g, 9.78 mol) was slowly added dropwise, and the reaction temperature was maintained at 25-30°C during the reaction. The dropwise addition was carried out within 1 hour, and the aging was carried out at 37° C. for 30 minutes. When the aging was completed, 2000 g of toluene was added, stirred for about 10 minutes, the layers were separated, the water layer was removed, and the organic solution as the supernatant was washed twice with water.
  • Episulfide compounds BEPS-2 to BEPS-10 were prepared using the starting materials BCPS- 2 to BCPS- 10 shown in Table 2 in the same manner as in Synthesis Example 1.
  • BCPS- 11 (1070.48g, 4.88 mol), 1300g toluene, and 800g methanol were put in a 10 liter reaction vessel, and the reaction temperature was adjusted to 30°C while stirring. When it reached 25°C, NaOH (50% (aq), 783.08 g, 9.78 mol) was slowly added dropwise, and the reaction temperature was maintained at 35-37°C during the reaction. The dropwise addition was carried out within 1 hour, and the aging was carried out at 37° C. for 30 minutes. When the aging was completed, 2000 g of toluene was added, stirred for about 10 minutes, the layers were separated, the water layer was removed, and the organic solution as the supernatant was washed twice with water.
  • BEPS- 1 Bis(2,3-epithiopropyl)sulfide ( BEPS- 1 ) 89g as thioepoxy compound, isophorone diisocyanate 5g as isocyanate compound, bis(2-mercaptoethyl)sulfide 6g as thiol compound, phosphate ester as internal mold release agent Phosphorus 8-PENPP [polyoxyethylene nonylphenyl ether phosphate (3 wt% of ethylene oxide added by 9 moles, 80 wt% of 8 moles added, 5 wt% of 9 moles added, 6 wt% of 7 moles added) %, 6% by weight of 6 mol added)] 0.15 g, tetrabutylphosphonium bromide 0.2g, triphenylphosphine 0.1g, organic dye HTAQ (20ppm) and PRD (10ppm), UV absorber 2-(2'- 1.5 g of hydroxy-5'-t-octylphen
  • This mixed solution was defoamed at 400 Pa for 1 hour. After that, it was filtered with a 1 ⁇ m PTFE filter, and injected into a mold made of a glass mold and a tape. This mold was put into a polymerization oven, and the temperature was gradually increased from 25°C to 130°C over 21 hours for polymerization. After completion of polymerization, the mold was taken out of the oven and demolded to obtain an optical lens. The releasability from the mold was good. The obtained optical lens was further annealed at 100°C for 4 hours. The obtained optical lens had a refractive index (nE) of 1.699 and an Abbe's number of 35. The melted state before injection into the mold was visually observed, and after demolding, physical properties and defects were checked.
  • nE refractive index
  • Refractive index and Abbe's number It was measured using an Abbe refractometer, a DR-M4 model of Atago Corporation.
  • An optical lens was manufactured with the composition shown in Table 2 in the same manner as in Example 1.
  • Bis(2,3-epithiopropyl)sulfide ( BEPS- 11 ) 89g as thioepoxy compound, isophorone diisocyanate 5g as isocyanate compound, bis(2-mercaptoethyl)sulfide 6g as thiol compound, phosphoric acid ester as internal mold release agent Phosphorus 8-PENPP [polyoxyethylene nonylphenyl ether phosphate (3 wt% of ethylene oxide added by 9 moles, 80 wt% of 8 moles added, 5 wt% of 9 moles added, 6 wt% of 7 moles added) %, 6% by weight of 6 mol added)] 0.15 g, tetrabutylphosphonium bromide 0.2g, triphenylphosphine 0.1g, organic dye HTAQ (20ppm) and PRD (10ppm), UV absorber 2-(2'- 1.5 g of hydroxy-5'-t-octylphenyl)
  • This mixed solution was defoamed at 400 Pa for 1 hour. After that, it was filtered with a 1 ⁇ m PTFE filter, and injected into a mold made of a glass mold and a tape. This mold was put into a polymerization oven, and the temperature was gradually increased from 25°C to 130°C over 21 hours for polymerization. After the polymerization was completed, the mold was taken out of the oven, and the releasability from the mold was good. The obtained lens was further annealed at 100 degreeC for 4 hours. The physical properties of the obtained lens were a refractive index (nE) of 1.699 and an Abbe's number of 35. The results of the physical properties are shown in Table 2 .
  • nE refractive index
  • the method for producing an episulfide compound for an optical material of the present invention can produce a high-purity episulfide compound by precisely controlling the reaction progress in a simple way, so it can be used in various fields requiring an episulfide compound by replacing the existing production method In particular, it can be used in the field of high refractive optical materials requiring a high purity episulfide compound.
  • the episulfide-based high refractive optical material obtained according to the present invention has a good color and is clear and transparent, it can be usefully used for corrective sunglasses, fashion lenses, color-changing lenses, camera lenses, lenses for optical devices, and the like.

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Abstract

La présente invention concerne une composition pour un matériau optique dans laquelle un phénomène de durcissement rapide qui se produit pendant la polymérisation dans un matériau optique à indice de réfraction élevé à base d'épisulfure est supprimé et un procédé pour la fabrication d'un matériau optique utilisant celle-ci. La composition pour un matériau optique à indice de réfraction élevé à base d'épisulfure selon la présente invention comprend un composé épisulfure représenté par la formule 1, un composé sulfure de 2,3-époxypropyle (2,3-épithiopropyle), un composé de catéchol et un sel de phosphonium quaternaire en tant que catalyseur de polymérisation. La composition selon la présente invention permet d'empêcher une soudaine augmentation de la viscosité pendant la polymérisation dans un matériau optique à indice de réfraction élevé à base d'épisulfure et de maintenir une vitesse de durcissement constante et peut ainsi être utilisée en tant que matériau de lentille de haute qualité exempt de problèmes de déséquilibre de polymérisation.
PCT/KR2021/000990 2020-02-18 2021-01-26 Composé épisulfure pour matériau optique, composition pour matériau optique à indice de réfraction élevé contenant celui-ci et procédé pour la fabrication de matériau optique WO2021167256A1 (fr)

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KR1020200019911A KR20210105219A (ko) 2020-02-18 2020-02-18 광학재료용 에피설파이드 화합물, 이를 포함하는 고굴절 광학재료용 조성물 및 광학재료의 제조방법

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