CN104039860A - Polymeric composition for thioepoxy-based optical material and method of manufacturing thioepoxy-based optical material - Google Patents
Polymeric composition for thioepoxy-based optical material and method of manufacturing thioepoxy-based optical material Download PDFInfo
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- CN104039860A CN104039860A CN201380004719.6A CN201380004719A CN104039860A CN 104039860 A CN104039860 A CN 104039860A CN 201380004719 A CN201380004719 A CN 201380004719A CN 104039860 A CN104039860 A CN 104039860A
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/52—Polythioethers
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- 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
- C08K5/378—Thiols containing heterocyclic rings
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- 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
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
- C08K5/405—Thioureas; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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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
Abstract
The present invention relates to a polymeric composition for a thioepoxy-based optical material and a method of manufacturing a thioepoxy-based optical material, and more particularly, to providing a clear, transparent, and high quality thioepoxy-based optical material that resolves a color instability problem exhibited in thioepoxy-based optical materials. The present invention provides a thioepoxy-based polymeric composition comprising a thioepoxy compound having 1% or less by weight of epichlorohydrin. In the present invention, the color instability problem exhibited in thioepoxy-based optical materials can be resolved in an easy way by controlling the content of epichlorohydrin in a starting material, which synthesizes a thioepoxy compound, or the content of epichlorohydrin in a thioepoxy compound. According to the present invention, a clear, transparent, and high quality thioepoxy-based optical material can be easily manufactured at a high yield. The thioepoxy optical material thus manufactured according to the present invention can be widely used instead of a common optical material.
Description
Technical field
The present invention relates to sulfo-epoxy base system optical material polymerizability synthetics and sulfo-epoxy base system optical material manufacture method, especially solve the form and aspect instability problem that sulfo-epoxy base system optical material occurs, limpid, transparent high-quality sulfo-epoxy base system optical material is provided.
Background technology
No. 1993-0006918, communique of Korean Patent bulletin and 1992-0005708 etc. disclose that a kind of to allow poly-thiol compound react the sulphur urethane obtaining with polyisocyanate compounds be eyeglass.
Korean registered patent discloses a kind of sulfo-epoxy base system glass lens for No. 10-0681218.Sulphur urethane eyeglass refractive index is high, and shock strength is outstanding, but has lens surface difference of hardness, the problems such as central concave, and refractive index while uprising Abbe number sharply decline.Sulfo-epoxy base system eyeglass refractive index is high, and has high Abbe number, and performance is outstanding, but problem is easily fragmentation of eyeglass, not easy dyeing.
Be the problem points that eyeglass and sulfo-epoxy base system eyeglass exist in order to solve sulphur urethane, No. 10-0417985, Korean registered patent, Japanese Patent Publication communique Unexamined Patent 11-292950 and Unexamined Patent 11-352302 etc. disclose the method for two kinds of resins of different nature of polymerization, and polymerised sulphur is for the method for epoxy compounds and poly-thiol compound and polyisocyanate compounds.
But still there is the unsettled problem of form and aspect in the sulfo-epoxy base system eyeglass containing sulfo-epoxy group(ing).Korea S's publication is found out for No. 10-0681218 in sulfo-epoxy compounds manufacturing processed, epoxy compounds changes the purity in the process of sulfo-epoxy compounds into, be that the content of impurity sulfo-epoxy compounds producing due to side reaction in switching process is to affect eyeglass form and aspect, disclose a kind of polymerizability synthetics obtaining after this impurity sulfo-epoxy compounds content and method that reduces described content of reducing.
Summary of the invention
The problem of invention
The object of the invention is to, find out the more deciding factor exerting an influence to the form and aspect of sulfo-epoxy base system optical material, by controlling this factor, solve the form and aspect instability problem of sulfo-epoxy base system optical material.Especially, the object of the invention is to, by finding out the form and aspect labile factor that is more prone to control, provide the method for the as clear as crystal high-quality sulfo-epoxy base system optical material of a kind of easy manufacture and the polymerizability synthetics for the manufacture of it.
Technical solution of the present invention
Each contriver of the present invention chances on the Epicholorohydrin (epichlorohydrin) using as the material that sets out and continues to remain in reaction system, and changing epithio into is the principal element exerting an influence to the form and aspect of sulfo-epoxy base system optical material for chloroethanol (epithiochlorohydrin).; because the Epicholorohydrin using as the material that sets out continues to remain in reaction system; putting into thiocarbamide (thiourea), carry out the process of epithio (episulfide); it changes epithio into for chloroethanol, and this epithio produces conclusive impact for chloroethanol to the form and aspect of optical material.In addition, confirm through each contriver of the present invention, even if do not control separately the content of the impurity sulfo-epoxy compounds producing due to side reaction in sulfo-epoxy compounds manufacturing processed, as long as the epithio in Epicholorohydrin and sulfo-epoxy compounds that control is set out in material, for chloroethanol content, just can solve the form and aspect problem of sulfo-epoxy base system optical material.
The invention provides a kind of sulfo-epoxy base system polymerizability synthetics, it,, containing sulfo-epoxy compounds, is characterized in that: the epithio of described sulfo-epoxy compounds is below 1 % by weight for chloroethanol content.Described polymerizability synthetics can also comprise polyisocyanate compounds and/or poly-thiol compound.
Preferably, described sulfo-epoxy compounds can be synthetic with the method that comprises the steps, and reaction table chloropharin content is sulfide compound and thiocarbamide below 1 % by weight, the step of carrying out epithio.
The invention provides a kind of the manufacture method of the sulfo-epoxy base system optical material of described polymerizability synthetics polymerization.
The invention provides the sulfo-epoxy base system optical material obtaining with described manufacture method and the optical mirror slip forming with this optical material.
In the present invention, " sulfo-epoxy base system optical material ", in the situation that being not particularly limited, includes optical material that polymerised sulphur obtains for epoxy compounds and instrument sulfo-epoxy group(ing) and sulphur urethane and the optical material that obtains.
Invention effect
Epithio in the Epicholorohydrin content or the sulfo-epoxy compounds that set out in material when the synthetic sulfo-epoxy compounds of control of the present invention, for chloroethanol content, can solve the form and aspect instability problem that sulfo-epoxy base system optical material occurs by being easy to method.The present invention can be with very high yield, easily manufacture as clear as crystal high-quality sulfo-epoxy base system eyeglass.
Embodiment
The contained sulfo-epoxy compounds of polymerizability synthetics of the present invention is the compound with more than one sulfo-epoxy group(ing).Epithio is that sulfo-epoxy compounds below 1 % by weight can be manufactured by several different methods for chloroethanol content.Preferably, sulfo-epoxy compounds is by allowing the Epicholorohydrin content be that sulfide compound below 1 % by weight reacts with thiocarbamide, and the step of carrying out epithio is synthetic.Such as, add Epicholorohydrin and hydrogen sulfide, manufacture after 1-chloro-3-sulfydryl-2-propyl alcohol (1-chloro-3-mercapto-2-propanol), again carry out addition reaction (addition reaction) with Epicholorohydrin, or first manufacture after the chloro-3-sulfydryl-2-of 1-propyl alcohol, again carry out addition reaction with Epicholorohydrin, or first manufacture after the chloro-3-sulfydryl-2-of 1-propyl alcohol, carry out self disulphide (disulphide) and change after reaction, manufacture epoxy compounds.In this process, be difficult to remove completely Epicholorohydrin, but by sustained reaction, its remaining quantity be controlled at below 1 % by weight, preferably, below 0.5 % by weight, manufacture sulfo-epoxy compounds.The sulfo-epoxy compounds of so manufacturing, can allow optical material have optimization form and aspect.
Described sulfo-epoxy compounds is such as can be two (2, 3-epithio is for propylthio) disulphide (bis (2, 3-epithiopropyl) disulfide), two (2, 3-epithio is for propylthio) sulfide (bis (2, 3-epithiopropyl) sulfide), 2, 3-epidithio is for propylthio (2, 3-epithio is for propylthio) disulphide (2, 3-epidithiopropyl (2, 3-epithiopropyl) disulfide), 2, 3-epidithio is for propylthio (2, 3-epithio is for propylthio) sulfide (2, 3-epidithiopropyl (2, 3-epithiopropyl) sulfide), 1, 3 and 1, 4-bis-(β-epithio is for propyl dithiocarbamate) hexanaphthene) (bis (β-epithiopropylthio) cyclo hexane), 1, 3 and 1, 4-bis-(β-epithio is for propyl dithiocarbamate methyl) hexanaphthene) (bis (β-epithiopropylthiomethyl) cyclo hexane), two [4-(β-epithio is for propyl dithiocarbamate) cyclohexyl] methane (bis[4-(β-epithiopropylthio) cyclo hexyl] methane), 2, 2-bis-[4-(β-epithio is for propyl dithiocarbamate) cyclohexyl] propane (2, 2-bis[4-(β-epithiopropylthio) cyclo hexyl] propane), two [4-(β-epithio is for propyl dithiocarbamate) cyclohexyl] sulfide (bis[4-(β-epithiopropylthio) cyclo hexyl] sulfide) etc. has the episulfide compound of alicyclic bone, 1, 3 and 1, 4-bis-(β-epithio is for propyl dithiocarbamate methyl) benzene bis (β-epithiopropylthiomethyl) benzene), two [4-(β-epithio is for propyl dithiocarbamate) phenyl] methane (bis[4-(β-epithiopropylthio) phenyl] methane), 2, 2-bis-[4-(β-epithio is for propyl dithiocarbamate) phenyl] propane (2, 2-bis[4-(β-epithiopropylthio) phenyl] propane), two [4-(β-epithio is for propyl dithiocarbamate) phenyl] sulfide (bis[4-(β-epithiopropylthio) phenyl] sulfide), two [4-(β-epithio is for propyl dithiocarbamate) phenyl] sulphur (bis[4-(β-epithiopropylthio) phenyl] sulfin), 4, 4-bis-(β-epithio is for propyl dithiocarbamate) phenylbenzene (4, 4-bis (β-epithiopropylthio) biphenyl) etc. there is the episulfide compound of aromatic series bone, 2, 5-bis-(β-epithio is for propyl dithiocarbamate methyl)-1, 4-dithiane (2, 5-bis (β-epithiopropylthiomethyl)-1, 4-dithiane), 2, 5-bis-(β-epithio is for propyl dithiocarbamate ethylenebis dithiocarbamate methyl)-1, 4-dithiane (2, 5-bis (β-epithiopropylthioethylthiomethyl)-1, 4-dithiane), 2, 5-bis-(β-epithio is for propyl dithiocarbamate ethyl group)-1, 4-dithiane (2, 5-bis (β-epithiopropylthioethyl)-1, 4-dithiane), 2, 3, 5-tri-(β-epithio is for propyl dithiocarbamate ethyl group)-1, 4-dithiane (2, 3, 5-tri (β-epithiopropylthioethyl)-1, 4-dithiane) etc. there is the episulfide compound of dithiane (dithiane) chain bone, 2-(2-β-epithio is for propyl dithiocarbamate ethylenebis dithiocarbamate)-1, 3-bis-(β-epithio is for propyl dithiocarbamate) propane (2-(2-β-epithiopropylthioethylthio)-1, 3-bis (β-epithiopropylthio) propane), 1, 2-bis-[(2-β-epithio is for propyl dithiocarbamate ethyl group) sulfo-]-3-(β-epithio is for propyl dithiocarbamate) propane (1, 2-bis[(2-β-epithiopropylthioethyl) thio]-3-(β-epithiopropylthio) propane), four (β-epithio is for propyl dithiocarbamate methyl) methane) (Tetrakis (β-epithiopropylthiomethyl) methane), 1, 1, 1-tri-(β-epithio is for propyl dithiocarbamate methyl) propane (1, 1, 1-tris (β-epithiopropylthiomethyl) propane), two-(β-epithio is for propyl group) sulfide (bis-(β-epithiopropyl) sulfide) etc. have episulfide (episulfide) compound of aliphatics bone.In addition, as sulfo-epoxy compounds, can also use the halogen family substitution product such as chlorine substitution product (substitution product), bromine substitution product, alkyl substitution product (alkyl substitution product), alkoxyl group substitution product (alkoxy substitution product), nitro substitution product (nitro substitution product) of the compound of band sulfuration (episulfide) base or prepolymer (prepolymer) the type denatured products (denaturant) with polythiol.
Preferably use two-(2 as sulfo-epoxy compounds, 3-epithio is for propyl group) sulfide (bis-(2, 3-epithiopropyl) sulfide), two-(2, 3-epithio is for propyl group) disulphide (bis-(2, 3-epithiopropyl) disulfide), 2, 3-epidithio is for propylthio (2, 3-epithio is for propylthio) sulfide, 2, 3-epidithio is for propylthio (2, 3-epithio is for propylthio) disulphide, 1, 3 and 1, 4-bis-(β-epithio is for propyl dithiocarbamate) hexanaphthene, 1, 3 and 1, 4-bis-(β-epithio is for propyl dithiocarbamate methyl) hexanaphthene, 2, 5-bis-(β-epithio is for propyl dithiocarbamate methyl)-1, 4-dithiane, 2, 5-bis-(β-epithio is for propyl dithiocarbamate ethylenebis dithiocarbamate methyl)-1, 4-dithiane, 2-(2-β-epithio is for propyl dithiocarbamate ethylenebis dithiocarbamate)-1, in 3-bis-(β-epithio is for propyl dithiocarbamate) propane more than a kind.
Described polymerizability synthetics can also comprise polyisocyanate compounds.Described polyisocyanate compounds is not particularly limited, can use at least with more than 1 isocyanato and/. or the compound of different thiocyanato.Such as, use more than a kind hexamethylene diisocyanate (hexa methylene diisocyanate), 2, 2-dimethylpentane vulcabond (2, 2-dimethyl pentane diisocyanate), 2, 2, 4-trimethyl cyclohexane vulcabond (2, 2, 4-trimethyl hexane diisocyanate), butene diisocyanate (butene diisocyanate), 1, 3-divinyl-1, 4-vulcabond (1, 3-butadiene-1, 4-diisocyanate), 2, 4, 4-trimethyl hexamethylene diisocyanate (2, 4, 4-trimethyl hexa methylene diisocyanate), 1, 6, 11-undecane triisocyanate (1, 6, 11-undecane triisocyanate), 1, 3, 6-hexa-methylene triisocyanate (1, 3, 6-hexa methylene triisocyanate), 1, 8-vulcabond-4-isocyanato methyloctane (1, 8-diisocyanate-4-isocyanato methyl octane), two (isocyanato ethyl) carbonic ether (bis (isocyanato ethyl) carbonate), the aliphatic isocyanates compounds (aliphatic isocyanate compounds) such as two (isocyanato ethyl) ether (bis (isocyanato ethyl) ether), isophorone diisocyanate (isophorone diisocyanate), 1, 2-bis-(isocyanato methyl) hexanaphthene (1, 2-bis (isocyanato methyl) cyclo hexane), 1, 3-bis-(isocyanato methyl) hexanaphthene (1, 3-bis (isocyanato methyl) cyclo hexane), 1, 4-bis-(isocyanato methyl) hexanaphthene (1, 4-bis (isocyanato methyl) cyclo hexane), dicyclohexyl methane diisocyanate (dicyclo hexyl methane diisocyanate), cyclohexyl diisocyanate (cyclo hexane diisocyanate), methylcyclohexane diisocyanate (methyl cyclo hexane diisocyanate), dicyclohexyl dimethylmethane isocyanic ester (dicyclo hexyl dimethyl methane isocyanate), 2, 2-dimethyl dicyclohexyl methyl hydride isocyanic ester (2, 2-dimethyl dicyclo hexyl methane isocyanate) etc. alicyclic isocyanate compound (Cycloaliphatic isocyanate compounds), two (isocyanato ethyl) benzene (bis (isocyanatoethyl) benzene), two (isocyanato propyl group) benzene (bis (isocyanato propyl) benzene), two (isocyanato butyl) benzene (bis (isocyanato butyl) benzene), two (isocyanato methyl) naphthalene (bis (isocyanato methyl) naphthalene), two (isocyanato methyl) phenylbenzene ether (bis (isocyanato methyl) diphenyl ether), phenylene vulcabond (phenylene diisocyanate), ethyl phenylene vulcabond (ethyl phenylene diisocyanate), sec.-propyl phenylene vulcabond (isopropyl phenylene diisocyanate), dimethyl phenylene vulcabond (dimethyl phenylene diisocyanate), diethyl phenylene vulcabond (diethyl phenylene diisocyanate), di-isopropyl phenylene vulcabond (diisopropyl phenylene diisocyanate), Three methyl Benzene triisocyanate (trimethyl benzene triisocyanate), benzene triisocyanate (benzene triisocyanate), biphenyl diisocyanate (biphenyl diisocyanate), Tolylamine vulcabond (toluidine diisocyanate), 4, 4'-diphenylmethanediisocyanate (4, 4'-diphenyl methane diisocyanate), tolylene diisocyanate (tolylene diisocyanate), eylylene diisocyanate (xylylene diisocyanate (XDI)), 3, 3'-dimethyl diphenylmethane-4, 4'-vulcabond (3, 3'-dimethyl diphenyl methane-4, 4'-diisocyanate), bibenzyl-4, 4'-vulcabond (bibenzyl-4, 4'-diisocyanate), two (isocyanato phenyl) ethene (bis (isocyanato phenyl) ethylene), 3, 3'-dimethoxy-biphenyl-4, 4'-vulcabond (3, 3'-dimethoxy biphenyl-4, 4'-diisocyanate), hexahydrobenzene vulcabond (hexa hydrobenzene diisocyanate), six diphenyl hydrogen methylmethane-4, 4'-vulcabond (hexa hydro diphenyl methane-4, the aromatic isocyanate compound (aromatic isocyanate compounds) such as 4'-diisocyanate), two (isocyanato ethyl) sulfide (bis (isocyanato ethyl) sulphide), two (isocyanato propyl group) sulfide (bis (isocyanato propyl) sulphide), two (isocyanato hexyl) sulfide (bis (isocyanato hexyl) sulphide), two (isocyanato methyl) sulphur (bis (isocyanato methyl) sulfone), two (isocyanato methyl) disulphide (bis (isocyanato methyl) disulphide), two (isocyanato propyl group) disulphide (bis (isocyanato propyl) disulphide), two (isocyanato methyl sulfo-) methane (bis (isocyanato methyl thio) methane), two (isocyanato ethylenebis dithiocarbamate) methane (bis (isocyanato ethyl thio) methane), two (isocyanato ethylenebis dithiocarbamate) ethane (bis (isocyanato ethyl thio) ethane), two (isocyanato methyl sulfo-) ethane (bis (isocyanato methyl thio) ethane), 1,5-bis-isocyanatos-2-isocyanato methyl-3-sulfo-pentane (1,5-diisocyanato-2-isocyanato methyl-3-thia pentane) etc. sulfur-bearing aliphatic isocyanates compound (sulfur aliphatic isocyanate compounds), diphenyl sulfide-2, 4-vulcabond (diphenyl sulphide-2, 4-diisocyanate), diphenyl sulfide-4, 4'-vulcabond (diphenyl sulphide-4, 4'-diisocyanate), 3, 3'-dimethoxy-4 ', 4'-bis-isocyanato diphenyl-methyl thio-ethers (3, 3'-dimethoxy-4, 4'-diisocyanato dibenzyl thio ether), two (4-isocyanato methylbenzene) sulfide (bis (4-isocyanato methyl benzene) sulphide), 4, 4-anisole sulfo-ethylene glycol-3, 3-vulcabond (4, 4-methoxy benzene thio ethylene glycol-3, 3-diisocyanate), Diphenyl disulfide compound-4, 4'-vulcabond (diphenyl disulphide-4, 4'-diisocyanate), 2, 2'-dimethyl diphenyl disulphide-5, 5'-vulcabond (2, 2'-dimethyl diphenyl disulphide-5, 5'-diisocyanate), 3, 3'-dimethyl diphenyl disulphide-5, 5'-vulcabond (3, 3'-dimethyl diphenyl disulphide-5, 5'-diisocyanate), 3, 3'-dimethyl diphenyl disulphide-6, 6'-vulcabond (3, 3'-dimethyl diphenyl disulphide-6, 6'-diisocyanate), 4, 4'-dimethyl diphenyl disulphide-5, 5'-vulcabond (4, 4'-dimethyl diphenyl disulphide-5, 5'-diisocyanate), 3, 3'-dimethoxy Diphenyl disulfide compound-4, 4'-vulcabond (3, 3'-dimethoxy diphenyl disulphide-4, 4'-diisocyanate), 4, 4'-dimethoxy Diphenyl disulfide compound-3, 3'-vulcabond (4, 4'-dimethoxy diphenyl disulphide-3, the sulfur-containing aromatic isocyanate compound (sulfur aromatic isocyanate compounds) such as 3'-diisocyanate), 2, 5-bis-isocyanato thiophene (2, 5-diisocyanato thiophene), 2, 5-bis-(isocyanato methyl) thiophene (2, 5-bis (isocyanato methyl) thiophene), 2, 5-bis-isocyanato tetramethylene sulfides (2, 5-diisocyanato Tetra hydrothiophene), 2, 5-bis-(isocyanato methyl) tetramethylene sulfide (2, 5-bis (isocyanato methyl) Tetra hydrothiophene), 3, 4-bis-(isocyanato methyl) tetramethylene sulfide (3, 4-bis (isocyanato methyl) Tetra hydrothiophene), 2, 5-bis-isocyanato-1, 4-dithiane (2, 5-diisocyanato-1, 4-dithiane), 2, 5-bis-(isocyanato methyl)-1, 4-dithiane (2, 5-bis (isocyanato methyl)-1, 4-dithiane), 4, 5-bis-isocyanato-1, 3-dithiolane (4, 5-diisocyanato-1, 3-dithiolane), 4, 5-bis-(isocyanato methyl)-1, 3-dithiolane (4, 5-bis (isocyanato methyl)-1, 3-dithiolane), 4, 5-bis-(isocyanato methyl)-2-methyl isophthalic acid, 3-dithiolane (4, 5-bis (isocyanato methyl)-2-methyl-1, the sulfur heterocyclic ring isocyanate compound (sulfur heterocyclic isocyanate compounds) such as 3-dithiolane).Can also use the chlorine substitution product (substitution product) of these compounds, the halogen family substitution products such as bromine substitution product, alkyl substitution product (alkyl substitution product), alkoxyl group substitution product (alkoxy substitution product), nitro substitution product (nitro substitution product) or with prepolymer (prepolymer) the type denatured products (denaturant) of multivalence alcohol or mercaptan, carbodiimide (carbodiimide) denatured products, urea (urea) denatured products, biuret (biuret) denatured products or dipolymer (dimer) are changed or trimer (trimer) is changed resultant of reaction etc.Preferably use and be selected from isophorone diisocyanate (IPDI) as polyisocyanate compounds, hexamethylene diisocyanate (HDI), cyclohexyl diisocyanate (H12MDI), eylylene diisocyanate, 3, 8-bis-(isocyanic acid methyl) three rings [5, 2, 1, 02, 6] decane (3, 8-bis (isocyanatemethyl) tri cyclo[5, 2, 1, 02, 6] decane), 3, 9-bis-(isocyanic acid methyl) three rings [5, 2, 1, 02, 6] decane (3, 9-bis (isocyanatemethyl) tri cyclo[5, 2, 1, 02, 6] decane), 4, 8-bis-(isocyanic acid methyl) three rings [5, 2, 1, 02, 6] decane (4, 8-bis (isocyanatemethyl) tri cyclo[5, 2, 1, 02, 6] decane), 2, 5-bis-(isocyanic acid methyl) two rings [2, 2, 1] heptane (2, 5-bis (isocyanatemethyl) bicyclo[2, 2, 1] heptane), 2, 6-bis-(isocyanic acid methyl) two rings [2, 2, 1] heptane (2, 6-bis (isocyanatemethyl) bicyclo[2, 2, 1] heptane) more than a kind.
Described polymerizability synthetics can also comprise poly-thiol compound.Described poly-thiol compound is not particularly limited, and as long as having the compound of more than 1 thiol group, can be used alone or mixes two or more use.Such as, can use two (2-mercaptoethyl) sulfide (bis (2-mercapto ethyl) sulfide), 4-mercapto methyl-1, 8-dimercapto-3, 6-dithio octane (4-mercapto methyl-1, 8-dimercapto-3, 6-dithia octane), 2, 3-bis-(2-mercaptoethyl sulfo-) propane-1-mercaptan (2, 3-bis (2-mercapto ethyl thio) propane-1-thiol), 2, 2-bis-(mercapto methyl)-1, 3-propane two mercaptan (2, 2-bis (mercapto methyl)-1, 3-propane dithiol), four (mercapto methyl) methane (Tetrakis (mercapto methyl) methane), 2-(2-mercaptoethyl sulfo-) propane-1, 3-bis-mercaptan (2-(2-mercapto ethyl thio) propane-1, 3-dithiol), 2-(2, 3-bis-(2-mercaptoethyl sulfo-) propyl dithiocarbamate) ethane mercaptan (2-(2, 3-bis (2-mercapto ethyl thio) propyl thio) ethane thiol), two (2, 3-dimercaprol dimercaptopropanol) sulfide (bis (2, 3-dimercapto propanol) sulfide), two (2, 3-dimercaprol dimercaptopropanol) disulphide (bis (2, 3-dimercapto propanol) disulfide), 1, 2-bis-(2-mercaptoethyl sulfo-)-3-sulfydryl propane (1, 2-bis (2-mercapto ethyl thio)-3-mercapto propane), 1, 2-bis-(2-(2-mercaptoethyl sulfo-)-3-sulfydryl propyl dithiocarbamate) ethane (1, 2-bis (2-(2-mercapto ethyl thio)-3-mercapto propyl thio) ethane), two (2-(2-mercaptoethyl sulfo-)-3-sulfydryl propyl group) sulfide (bis (2-(2-mercapto ethyl thio)-3-mercapto propyl) sulfide), two (2-(2-mercaptoethyl sulfo-)-3-sulfydryl propyl group) disulphide (bis (2-(2-mercapto ethyl thio)-3-mercapto propyl) disulfide), 2-(2-mercaptoethyl sulfo-)-3-2-sulfydryl-3-[3-sulfydryl-2-(2-mercaptoethyl sulfo-)-propyl dithiocarbamate] propyl dithiocarbamate-propane-1-mercaptan (2-(2-mercapto ethyl thio)-3-2-mercapto-3-[3-mercapto-2-(2-mercapto ethyl thio)-propyl thio] propyl thio-propane-1-thiol), 2, 2-bis--(3-sulfydryl-propionyl oxygen methyl)-butyl ester (2, 2-bis-(3-mercapto-propionyl oxymethyl)-butyl ester), 2-(2-mercaptoethyl sulfo-)-3-(2-(2-[3-sulfydryl-2-(2-mercaptoethyl sulfo-)-propyl dithiocarbamate] ethylenebis dithiocarbamate) ethylenebis dithiocarbamate) propane-1-mercaptan (2-(2-mercapto ethyl thio)-3-(2-(2-[3-mercapto-2-(2-mercapto ethyl thio)-propyl thio] ethyl thio) ethyl thio) propane-1-thiol), (4R, 11S)-4, 11-bis-(mercapto methyl)-3, 6, 9, 12-tetrathio four decane-1, 14-bis-mercaptan ((4R, 11S)-4, 11-bis (mercapto methyl)-3, 6, 9, 12-Tetra thia Tetra decane-1, 14-dithiol), (S)-3-((R-2, 3-dimercapto propyl group) sulfo-) propane-1, 2-bis-mercaptan ((S)-3-((R-2, 3-dimercapto propyl) thio) propane-1, 2-dithiol), (4R, 14R)-4, 14-bis-(mercapto methyl)-3, 6, 9, 12, 15-five sulfo-heptane-1, 17-bis-mercaptan ((4R, 14R)-4, 14-bis (mercapto methyl)-3, 6, 9, 12, 15-Penta thia heptane-1, 17-dithiol), (S)-3-((R-3-sulfydryl-2-((2-mercaptoethyl) sulfo-) propyl group) sulfo-) propyl group) sulfo-)-2-((2-mercaptoethyl) sulfo-) propane-1-mercaptan ((S)-3-((R-3-mercapto-2-((2-mercapto ethyl) thio) propyl) thio) propyl) thio)-2-((2-mercapto ethyl) thio) propane-1-thiol), 3, 3'-dithio two (propane-1, 2-bis-mercaptan) (3, 3'-dithio bis (propane-1, 2-dithiol)), (7R, 11S)-7, 11-bis-(mercapto methyl)-3, 6, 9, 12, 15-five sulfo-heptadecane 100 alkane-1, 17-bis-mercaptan ((7R, 11S)-7, 11-bis (mercapto methyl)-3, 6, 9, 12, 15-Penta thia heptadecane-1, 17-dithiol), (7R, 12S)-7, 12-bis-(mercapto methyl)-3, 6, 9, 10, 13, 16-six sulfo-octadecane-1, 18-bis-mercaptan ((7R, 12S)-7, 12-bis (mercapto methyl)-3, 6, 9, 10, 13, 16-hexa thia octadecane-1, 18-dithiol), 5, 7-dimercapto methyl-1, 11-dimercapto-3, 6, 9-trithio undecane (5, 7-dimercapto methyl-1, 11-dimercapto-3, 6, 9-trithia undecane), 4, 7-dimercapto methyl-1, 11-dimercapto-3, 6, 9-trithio undecane (4, 7-dimercapto methyl-1, 11-dimercapto-3, 6, 9-trithia undecane), 4, 8-dimercapto methyl-1, 11-dimercapto-3, 6, 9-trithio undecane (4, 8-dimercapto methyl-1, 11-dimercapto-3, 6, 9-trithia undecane), tetramethylolmethane four (3-mercaptopropionic acid ester) (Penta erythritol Tetrakis (3-mercapto propionate)), three methylol propane three (3-mercaptopropionic acid ester) (trimethylol propane tris (3-mercapto propionate)), tetramethylolmethane four (2-thioglycolate) (Pentaerythritol Tetrakis (2-mercapto acetate)), Dipentaerythritol-ether-phenylpropyl alcohol tin (3-mercaptopropionic acid ester) (bispenta erythritol-ether-hexakis (3-mercapto propionate)), 1, 1, 3, 3-tetra-(mercapto methyl sulfo-) propane (1, 1, 3, 3-Tetrakis (mercapto methyl thio) propane), 1, 1, 2, 2-tetra-(mercapto methyl sulfo-) ethane (1, 1, 2, 2-Tetrakis (mercapto methyl thio) ethane), 4, 6-bis-(mercapto methyl sulfo-)-1, 3-dithiane (4, 6-bis (mercapto methyl thio)-1, 3-dithiane) and 2-(2, 2-bis-(sulfydryl dimethyl sulphide generation) ethyl)-1, 3-dithiane (2-(2, 2-bis (mercapto dimethyl thio) ethyl)-1, 3-dithiane) etc.Outside, as long as thering is the compound of more than 1 thiol group, can use one or be mixed with two or more.In addition, also can use to poly-thiol compound and add isocyanic ester or sulfo-epoxy compounds, sulfuration cyclopropane (Thietane) or the compound with unsaturated combination with modifier use, the polymerization denatured products obtaining by prepolymerization.Preferably mixing more than a kind other poly-thiol compounds to two (2-mercaptoethyl) sulfide or two (2-mercaptoethyl) sulfide as poly-thiol compound uses.
Polymerizability synthetics of the present invention can comprise internal mold release, and internal mold release preferably comprises acid phosphoesterase compound.Acid phosphoesterase compound passes through to Vanadium Pentoxide in FLAKES (P
2o
5) add the alkylol cpd manufacture of 2～3 moles.Here by the alcohol kind using, can obtain various ways phosphate compound.Representational oriented fatty alcohol adds oxyethane or propylene oxide, or adds the kind of oxyethane or propylene oxide to nonylphenol (nonylphenol) base etc.When polymerizability synthetics of the present invention uses as internal mold release the phosphate compound that adds oxyethane or propylene oxide, can obtain the optical material that release property is good, of fine qualities.As internal mold release, preferably use from 4-PENPP[polyoxyethylene nonylphenol ether phosphate (poly oxy ethylene nonyl phenol ether phosphate) and (add 5 % by weight of 5 moles, oxyethane, add 80 % by weight of 4 moles, add 10 % by weight of 3 moles, add 5 % by weight of 1 mole)], 8-PENPP[polyoxyethylene nonylphenol ether phosphate (adds 3 % by weight of 9 moles, oxyethane, add 80 % by weight of 8 moles, add 5 % by weight of 9 moles, add 6 % by weight of 7 moles, add 6 % by weight of 6 moles)], 12-PENPP[polyoxyethylene nonylphenol ether phosphate (adds 3 % by weight of 13 moles, oxyethane, add 80 % by weight of 12 moles, add 8 % by weight of 11 moles, add 3 % by weight of 9 moles, add 6 % by weight of 4 moles)], 16-PENPP[polyoxyethylene nonylphenol ether phosphate (adds 3 % by weight of 17 moles, oxyethane, add 79 % by weight of 16 moles, add 10 % by weight of 15 moles, add 4 % by weight of 14 moles, add 4 % by weight of 13 moles)], 20-PENPP[polyoxyethylene nonylphenol ether phosphate (adds 5 % by weight of 21 moles, oxyethane, add 76 % by weight of 20 moles, add 7 % by weight of 19 moles, add 6 % by weight of 18 moles, add 4 % by weight of 17 moles)], 4-PPNPP[polyoxytrimethylene nonylphenol ether phosphate (poly oxy propylene nonyl phenol ether phosphate) (adds 5 % by weight of 5 moles of propylene oxide, add 80 % by weight of 4 moles, add 10 % by weight of 3 moles, add 5 % by weight of 1 mole)], 8-PPNPP[polyoxytrimethylene nonylphenol ether phosphate (adds 3 % by weight of 9 moles of propylene oxide, add 80 % by weight of 8 moles, add 5 % by weight of 9 moles, add 6 % by weight of 7 moles, add 6 % by weight of 6 moles)], 12-PPNPP[polyoxytrimethylene nonylphenol ether phosphate (adds 3 % by weight of 13 moles of propylene oxide, add 80 % by weight of 12 moles, add 8 % by weight of 11 moles, add 3 % by weight of 9 moles, add 6 % by weight of 4 moles)], 16-PPNPP[polyoxytrimethylene nonylphenol ether phosphate (adds 3 % by weight of 17 moles of propylene oxide, add 79 % by weight of 16 moles, add 10 % by weight of 15 moles, add 4 % by weight of 14 moles, add 4 % by weight of 13 moles)], 20-PPNPP[polyoxytrimethylene nonylphenol ether phosphate (adds 5 % by weight of 21 moles of propylene oxide, add 76 % by weight of 20 moles, add 7 % by weight of 19 moles, add 6 % by weight of 18 moles, add 4 % by weight of 17 moles)], Zelec UN
tMmore than one phosphate compounds of middle selection.Under equal object, also can use halogen family substituent and various other substituents of this phosphate compound.
Polymerizability synthetics of the present invention, in order to improve the optics physical property of optical material, to regulate impact resistance, proportion and monomer (monomer) viscosity etc. as object, can additionally add olefin(e) compound as modifier.Can be used as alkene (olefin) compound that reaction resin properties-correcting agent adds, such as there being vinylformic acid benzyl ester (benzylacrylate), benzyl methacrylate (benzylmethacrylate), butoxy ethyl group CALCIUM ACRYLATE (butoxy ethylacrylate), butoxymethyl methacrylate (butoxy methyl methacrylate), cyclohexyl CALCIUM ACRYLATE (cyclo hexyl acrylate), cyclohexyl methyl CALCIUM ACRYLATE (cyclo hexyl methacrylate), 2-hydroxyl ethane base CALCIUM ACRYLATE (2-hydroxyl ethylacrylate), 2-methylol methacrylate (2-hydroxyl methyl methacrylate), epoxypropyl CALCIUM ACRYLATE (glycidyl acrylate), epoxypropyl methacrylate (glycidyl methacrylate), phenoxy group ethyl group CALCIUM ACRYLATE (phenoxy ethylacrylate), phenoxy group ethyl group methacrylate (phenoxy ethylmethacrylate), phenyl methyl CALCIUM ACRYLATE (phenylmethacrylate), ethylene glycol diacrylate fat (ethylene glycol diacrylate), ethylene glycol dimethacrylate fat (ethylene glycol dimethacrylate), divinyl ethylene glycol bisthioglycolate CALCIUM ACRYLATE (diethylene glycol diacrylate), divinyl ethyleneglycol dimethacrylate fat (diethylene glycol dimethacrylate), tri-ethylene glycol diacrylate fat (triethylene glycol diacrylate), tri-ethylene glycol dimethacrylate fat (triethylene glycol dimethacrylate), tetrem allyl diglycol diacrylate fat (tetra ethylene glycol diacrylate), tetrem allyl diglycol dimethacrylate fat (tetra ethylene glycol dimethacrylate), polyethylene glycol diacrylate fat (polyethylene glycol diacrylate), polyethylene glycol dimethacrylate fat (polyethylene glycol dimethacrylate), neo-pentyl ethylene glycol bisthioglycolate CALCIUM ACRYLATE (neopentyl glycol diacrylate), neo-pentyl ethyleneglycol dimethacrylate fat (neopentyl glycol dimethacrylate), ethylene glycol diepoxy propyl group CALCIUM ACRYLATE (ethylene glycol bisglycidyl acrylate), ethylene glycol diepoxy propyl methyl acid fat (ethylene glycol bisglycidyl methacrylate), biphenol A diacrylate fat (bisphenol A diacrylate), biphenol A dimethacrylate fat (bisphenol A dimethacrylate), 2, 2-bis-(4-allyl oxygen ethoxyl phenenyl) propane (2, 2-bis (4-acryloxy ethoxy phenyl) propane), 2, 2-bis-(4-methyl allyl oxygen ethoxyl phenenyl) propane (2, 2-bis (4-methacryloxy ethoxy phenyl) propane), 2, 2-bis-(4-allyl oxygen diethoxy phenyl) propane (2, 2-bis (4-acryloxy diethoxy phenyl) propane), 2, 2-bis-(4-methyl ethoxy diethoxy phenyl) propane (2, 2-bis (4-methacryloxydiethoxy phenyl) propane), biphenol F diacrylate fat (bisphenol F diacrylate), biphenol F dimethacrylate fat (bisphenol F dimethacrylate), 1, 1-bis-(4-allyl oxygen ethoxyl phenenyl) methane (1, 1-bis (4-acryloxy ethoxy phenyl) methane), 1, 1-bis-(4-methyl allyl oxygen ethoxyl phenenyl) methane (1, 1-bis (4-methacryloxy ethoxy phenyl) methane), 1, 1-bis-(4-allyl oxygen diethoxy phenyl) methane (1, 1-bis (4-acryloxy diethoxy phenyl) methane), 1, 1-bis-(4-methyl ethoxy diethoxy phenyl) methane (1, 1-bis (4-methacryloxydiethoxy phenyl) methane), dihydroxymethyl three tristane diacrylate fat (dimethylol tricyclo decane diacrylate), trimethylolpropane triacrylate (trimethylol propane triacrylate), trimethylol propane trimethyl CALCIUM ACRYLATE (trimethylol propane trimethacrylate), glycerol diacrylate fat (glycerol diacrylate), glycerol dimethacrylate fat (glycerol dimethacrylate), five erythritol three CALCIUM ACRYLATE (Penta erythritol triacrylate), five erythritol tetrapropylene acid fat (Penta erythritol tetra acrylate), five erythritol tetramethyl-CALCIUM ACRYLATE (Penta erythritol tetra methacrylate), methyl sulfo-CALCIUM ACRYLATE (methyl thio acrylate), methylthiomethyl CALCIUM ACRYLATE (methyl thio methacrylate), phenyl sulfo-CALCIUM ACRYLATE (phenylthio acrylate), dibenzylsulfide is for methacrylate (benzylthio methacrylate), xylylene two mercaptan diacrylate fat (xylylene dithiol diacrylate), xylylene two mercaptan dimethacrylate fat (xylylene dithiol dimethacrylate), ethane thiol base sulfide diacrylate fat (mercapto ethylsulfide diacrylate), (methyl) CALCIUM ACRYLATE ((meth) acrylate) compounds such as ethane thiol base sulfide dimethacrylate fat (mercapto ethylsulfide dimethacrylate) and, allyl group glycidyl ethers (allyl glycidyl ether), diallyl phthalate (diallyl phthalate), diallyl terephthalic acid's ester (diallyl terephthalate), diallyl isophthalic ester (diallyl isophthalate), diallyl carbonic ether (diallyl carbonate), allyl group (allyl) compounds such as divinyl ethylene glycol bisthioglycolate allyl carbonate (diethylene glycol bisallyl carbonate), vinylbenzene (styrene), chloro-styrene (chlorostyrene), vinyl toluene (methyl styrene), bromostyrene (bromostyrene), dibromo-benzene ethene (dibromostyrene), Vinylstyrene (divinyl benzene), 3, 9-divinyl spiral shell two (m-diepoxide for example) (3, 9-divinyl Spiro bi (m-dioxane)) etc. vinyl (vinyl) compound, but spendable compound is not limited to the compound of example above.These alkene (olefin) compound can separately or mix two or more use.
Optical material of the present invention obtains by injection molding polymerization.That is, polymer composition is injected between the mould of being sealed by sealing member or adhesive tape, carry out polyreaction.Here according to the physical property that requires of glass lens, can carry out on demand the filtration treatment such as vacuum deaerator or pressurization, decompression.Polymerizing condition is pressed kind and the consumption of polymerizability synthetics, catalyzer, and the shape of mould presents very big difference, does not therefore limit, but at approximately-50～150 DEG C of temperature, carries out through 1～50 hour.Sometimes according to circumstances, under 10～150 DEG C of temperature ranges, maintain or heat up gradually, being hardened to suitable through 1～48 hour.
The sulfo-epoxy compounds obtaining by sclerosis and isocyanate compound and mercaptan compound interpolymer, the processing such as can anneal as required.Treatment temp is generally 50～150 DEG C, preferably 90～140 DEG C.
In addition, polymerizability synthetics of the present invention is by known forming method, can comprise various additives, such as various additives such as chainextender (chain extender), linking agent (cross linking agent), polymerization starter (polymerization initiator), internal mold release, photostabilizer, thermo-stabilizer, oxidation inhibitor, UV light absorber, painted preventing agent, pigment dyestuff, mineral dye, weighting agent, binding property tougheners.Polymerization starter (catalyzer) plays an important role to sclerosis.The kind of catalyzer is used epoxy curing agent conventionally, but strong amine can allow isocyanic ester vigorous reaction, should add to note when use.The present invention mainly uses Barbiturates, phosphonium salt (phosphonium salt) class, phosphuret-(t)ed hydrogen (phosphine) class of amine and is with the tertiary amine class of electron withdrawing group (electron withdrawing group), Lewis acid (Lewis acid) class, radical initiator (radical initiators) etc., and the kind of catalyzer and usage quantity can be different.
Copolymer resin of the present invention, the mould when changing injection molding polymerization, can obtain the formed body of various shape, can be used as the various optical materials such as glasses lens, camera eyeglass, photodiode (LED) and uses.Especially, resin of the present invention is as clear as crystal, is suitable as the uses such as correcting lens, sunglasses eyeglass, fashion eyeglass, color-changing lens, camera eyeglass, Optical devices eyeglass.
The optical mirror slip obtaining by the present invention, can form coating as required on two sides.There are priming paint (primer) layer, [Dan, anti-reflection layer, anti-fog layer, anti-contamination layer, waterproof layer as coating.These coatings can be distinguished formation separately, or multilayer forms multiple coatings.While implementing coating on two sides, two sides forms respectively different coatings or identical coating.
[embodiment]
For making object, technical scheme and the advantage of the embodiment of the present invention clearer, below in conjunction with the accompanying drawing in the embodiment of the present invention, technical scheme in the embodiment of the present invention is carried out to clear, complete description, obviously, described embodiment is the present invention's part embodiment, instead of whole embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
test and evaluation method
Form and aspect: the YI value of the resin detecting with colour-difference meter is the embodiment 1 of 0.01 % by weight with respect to epithio for chloroethanol content, are recorded as when present ± 1 above gap " X ", not enough ± within 1 o'clock, to be recorded as " O ".
Refractive index and Abbe number: used IT and the DR-M4 model Abbe dioptrometer of Atago company, at 20 DEG C, detected.
(BCP-1) synthetic of [synthesis example 1] two (the chloro-2-hydroxypropyl of 3-) sulfide (bis (3-chloro-2-hydroxylpropyl) sulfide)
Add Epicholorohydrin (epichlorohydrin) (5563g to 10 liters of reactors, 60.12mol) and after methyl alcohol (2500g), temperature of reaction is adjusted to 6, in the time that arriving 6, temperature of reaction adds caustic soda (caustic soda) (50%aq, 5g).In another 10 liters of reactors, add NaSH.xH
2o (70%NaSH, 3660g, 45.75mol), methyl alcohol (1000g) and water (500g), by stirring after thawing completely, slowly drip hydrochloric acid, the hydrogen sulfide generating is added to Epicholorohydrin solution, obtained two (the chloro-2-hydroxypropyl of 3-) sulfide.The end point of reaction is to confirm end product by GC, Epicholorohydrin and the completely dissolve of 3-chlorine-2-hydroxyl-propyl-1-mercaptan compound, the time point that two (the chloro-2-hydroxypropyl of 3-) sulfide generates.In order to remove excessive 3-chlorine-2-hydroxyl-propyl-1-mercaptan, calculate relative integral than content by GC, add Epicholorohydrin.Analyze two (the chloro-2-hydroxypropyl of 3-) sulfide (BCP-1) (6388.73g, 58.31mol97%) that to have synthesized Epicholorohydrin content be 2.2% by GC.
Synthesizing of [synthesis example 2] two (the chloro-2-hydroxypropyl of 3-) sulfide (BCP-2)
Add Epicholorohydrin (epichlorohydrin) (5563g to 10 liters of reactors, 60.12mol) and after methyl alcohol (2500g), temperature of reaction is adjusted to 6, in the time that arriving 6, temperature of reaction adds caustic soda (caustic soda) (50%aq, 5g).In another 10 liters of reactors, add NaSH.xH
2o (70%NaSH, 3660g, 45.75mol), methyl alcohol (1000g) and water (500g), by stirring after thawing completely, slowly drip hydrochloric acid, the hydrogen sulfide generating is added to Epicholorohydrin solution, obtained two (the chloro-2-hydroxypropyl of 3-) sulfide.Two (the chloro-2-hydroxypropyl of the 3-) sulfide that is 2.2 % by weight to Epicholorohydrin content adds hydrogen sulfide, analyze by GC, having synthesized Epicholorohydrin content is two (the chloro-2-hydroxypropyl of 3-) sulfide (BCP-2) (6456.11g of 0.2 % by weight, 58.92mol, 98%).
Synthesizing of [synthesis example 3] two (the chloro-2-hydroxypropyl of 3-) sulfide (BCP-3)
Add Epicholorohydrin (epichlorohydrin) (5563g to 10 liters of reactors, 60.12mol) and after methyl alcohol (2500g), temperature of reaction is adjusted to 6, in the time that arriving 6, temperature of reaction adds caustic soda (caustic soda) (50%aq, 5g).In another 10 liters of reactors, add NaSH.xH
2o (70%NaSH, 3660g, 45.75mol), methyl alcohol (1000g) and water (500g), by stirring after thawing completely, slowly drip hydrochloric acid, the hydrogen sulfide generating is added to Epicholorohydrin solution, obtained two (the chloro-2-hydroxypropyl of 3-) sulfide.The end point of reaction is for to confirm by GC, as there is 3-chlorine-2-hydroxyl-propyl-1-mercaptan, calculate relative integral ratio by GC, add Epicholorohydrin, having synthesized Epicholorohydrin content is two (the chloro-2-hydroxypropyl of 3-) sulfide (BCP-3) (6455g of 0.7 % by weight, 58.91mol, 98%).
Synthesizing of [synthesis example 4] two (the chloro-2-hydroxypropyl of 3-) sulfide (BCP-4)
Add Epicholorohydrin (epichlorohydrin) (5563g to 10 liters of reactors, 60.12mol) and after methyl alcohol (2500g), temperature of reaction is adjusted to 6, in the time that arriving 6, temperature of reaction adds caustic soda (caustic soda) (50%aq, 5g).In another 10 liters of reactors, add NaSH.xH
2o (70%NaSH, 3660g, 45.75mol), methyl alcohol (1000g) and water (500g), by stirring after thawing completely, slowly drip hydrochloric acid, the hydrogen sulfide generating is added to Epicholorohydrin solution, obtained two (the chloro-2-hydroxypropyl of 3-) sulfide.Two (the chloro-2-hydroxypropyl of the 3-) sulfide that is 2.2 % by weight to Epicholorohydrin content adds hydrogen sulfide, having synthesized Epicholorohydrin content is two (the chloro-2-hydroxypropyl of 3-) sulfide (BCP-4) (6521.11g of 0.5 % by weight, 59.51mol, 99%).
Synthesizing of [synthesis example 5] two (2,3 epithios are for propyl group) sulfide (EPS-1)
Adding the synthetic Epicholorohydrin content of synthesis example 2 to 10 liters of reaction vessels is two (the chloro-2-hydroxypropyl of 3-) sulfide (BCP-2) (1072.48g of 0.2 % by weight, 4.89mol), toluene (toluene) 1300g, methyl alcohol 800g, stir, temperature of reaction is transferred to 30.Arrive at 25 o'clock, drip NaOH (50%aq., 783.08g, 9.78mol), temperature of reaction when dropping is carried out 35～37, holding temperature, reacts.Dropping was carried out in 1 hour, under 37 conditions, place afterwards fermentation in approximately 30 minutes, after fermentation ends, add toluene 2000g, approximately stir 10 minutes, carry out layering, with water, supernatant liquor organism being carried out to 2 times cleans, remove to greatest extent moisture, to there being which floor organic solution again to add methyl alcohol 400g, stir, add thiourea (thiourea) (1117.65g, 14.30mol) and Glacial acetic acid (70g) 8 times in temperature of reaction, temperature of reaction is heightened to 18, react 18 hours.Reaction end point is confirmed by HPLC, the material hour that sets out, and resultant does not further change and is as the criterion.After reaction finishes, stop stirring, with water clean 3 times by layer separates acquisition which floor has, remove organic solvent, obtaining epithio is two of 0.2 % by weight-(2 for chloroethanol content, 3-epithio is for propyl group) sulfide (EPS-1) (593g, 3.32mol, 68%).Recording refractive index (nD, 20 DEG C) is 1.614.
Synthesizing of [synthesis example 6] two (2,3 epithios are for propyl group) sulfide (EPS-2)
Adding the synthetic Epicholorohydrin content of synthesis example 4 to 10 liters of reaction vessels is two (the chloro-2-hydroxypropyl of 3-) sulfide (BCP-4) (1072.48g of 0.5 % by weight, 4.89mol), toluene (toluene) 1300g, methyl alcohol 800g, stir, temperature of reaction is transferred to 30.Arrive at 25 o'clock, drip NaOH (50%aq., 783.08g, 9.78mol), temperature of reaction when dropping is carried out 35～37, holding temperature, reacts.Dropping was carried out in 1 hour, under 37 conditions, place afterwards fermentation in approximately 30 minutes, after fermentation ends, add toluene 2000g, approximately stir 10 minutes, carry out layering, with water, supernatant liquor organism being carried out to 2 times cleans, remove to greatest extent moisture, to there being which floor organic solution again to add methyl alcohol 400g, stir, add thiourea (thiourea) (1117.65g, 14.30mol) and Glacial acetic acid (70g) 8 times in temperature of reaction, temperature of reaction is heightened to 18, react 18 hours.Reaction end point is confirmed by HPLC, the material hour that sets out, and resultant does not further change and is as the criterion.After reaction finishes, stop stirring, with water clean 3 times by layer separates acquisition which floor has, remove organic solvent, obtaining epithio is two of 0.41 % by weight-(2 for chloroethanol content, 3-epithio is for propyl group) sulfide (EPS-2) (593.01g, 3.32mol, 68%).Recording refractive index (nD, 20) is 1.614.
Synthesizing of [synthesis example 7] two (2,3 epithios are for propyl group) sulfide (EPS-3)
Adding the synthetic Epicholorohydrin content of synthesis example 3 to 10 liters of reaction vessels is two (the chloro-2-hydroxypropyl of 3-) sulfide (BCP-3) (1072.48g of 0.7 % by weight, 4.89mol), toluene (toluene) 1300g, methyl alcohol 800g, stir, temperature of reaction is transferred to 30.Arrive at 25 o'clock, drip NaOH (50%aq., 783.08g, 9.78mol), temperature of reaction when dropping is carried out 35～37, holding temperature, reacts.Dropping was carried out in 1 hour, under 37 conditions, place afterwards fermentation in approximately 30 minutes, after fermentation ends, add toluene 2000g, approximately stir 10 minutes, carry out layering, with water, supernatant liquor organism being carried out to 2 times cleans, remove to greatest extent moisture, to there being which floor organic solution again to add methyl alcohol 400g, stir, add thiourea (thiourea) (1117.65g, 14.30mol) and Glacial acetic acid (70g) 8 times in temperature of reaction, temperature of reaction is heightened to 18, react 18 hours.Reaction end point is confirmed by HPLC, the material hour that sets out, and resultant does not further change and is as the criterion.After reaction finishes, stop stirring, with water clean 3 times by layer separates acquisition which floor has, remove organic solvent, obtaining epithio is two of 0.57 % by weight-(2 for chloroethanol content, 3-epithio is for propyl group) sulfide (EPS-3) (587.23g, 3.29mol, 67%).Recording refractive index (nD, 20) is 1.614.
Synthesizing of [synthesis example 8] two (2,3 epithios are for propyl group) sulfide (EPS-4)
Adding the synthetic Epicholorohydrin content of synthesis example 1 to 10 liters of reaction vessels is two (the chloro-2-hydroxypropyl of 3-) sulfide (BCP-1) (1072.48g of 2.2 % by weight, 4.89mol), toluene (toluene) 1300g, methyl alcohol 800g, stir, temperature of reaction is transferred to 30.Arrive at 25 o'clock, drip NaOH (50%aq., 783.08g, 9.78mol), temperature of reaction when dropping is carried out 35～37, holding temperature, reacts.Dropping was carried out in 1 hour, placed afterwards fermentation in approximately 30 minutes, after fermentation ends under 37 conditions, add toluene 2000g, approximately stir 10 minutes, carry out layering, with water, supernatant liquor organism is carried out to 2 times and clean, remove to greatest extent moisture, to there being which floor organic solution again to add methyl alcohol 400g, stir, add thiourea (1117.65g, 14.30mol) and Glacial acetic acid (70g) 8 times in temperature of reaction, temperature of reaction is heightened to 18, react 18 hours.Reaction end point is confirmed by HPLC, the material hour that sets out, and resultant does not further change and is as the criterion.After reaction finishes, stop stirring, with water clean 3 times by layer separates acquisition which floor has, remove organic solvent, obtaining epithio is two of 1.89 % by weight-(2 for chloroethanol content, 3-epithio is for propyl group) sulfide (EPS-4) (584.95g, 3.28mol, 67%).Recording refractive index (nD, 20) is 1.614.
[embodiment 1]
Sulfo-epoxy compounds used epithio for chloroethanol content be the synthesis example 5 of 0.2 % by weight synthetic two (2, 3 epithios are for propyl group) sulfide (EPS-1) 89g, isocyanate compound has used isophorone diisocyanate 5g, mercaptan compound has used two (2-mercaptoethyl) sulfide 6g, internal mold release has used acid phosphoric acid ester 8-PENPP[polyoxyethylene nonylphenol ether phosphate (to add 3 % by weight of 9 moles, oxyethane, add 80 % by weight of 8 moles, add 5 % by weight of 9 moles, add 6 % by weight of 7 moles, add 6 % by weight of 6 moles)] 0.15g, four butyl phosphonium bromides (Tetrabutyl phosphonium Bromide) 0.2g, triphenylphosphine (Triphenylphosphine) 0.1g, organic dye HTAQ (20ppm) and PRD (10ppm), UV light absorber HOPBT1.5, mixed dissolution under 20 DEG C of conditions, obtain homogeneous solution.To this mixing solutions, under 400Pa condition, deaeration 1 hour.Filter with 1 μ m PTFE strainer afterwards, injected the mould being formed by glass and adhesive tape.Mould is rendered in polymerization baking box, from 25 DEG C～130 DEG C only, slowly heated up through 21 hours.After finishing, polymerization takes out mould from baking box.The release property of mould is good.Under 130 DEG C of conditions, the resin obtaining is carried out to 4 hours anneal.The resin characteristics obtaining is refractive index (nE) 1.697, and Abbe number is 35.Inject before mould, visual inspection the state after dissolving, after the demoulding, confirm that surface is bad, result is not abnormal, cannot see albefaction, YI value is 1.8, has obtained stay-in-grade resin.
[embodiment 2]
Be that the EPS-2 of synthesis example 6 of 0.41 % by weight, other compositions are identical with embodiment 1, manufactured resin composition for chloroethanol content except sulfo-epoxy compounds has used epithio, to this mixing solutions, under 400Pa condition, deaeration 1 hour.Filter with 1 μ m PTFE strainer afterwards, injected the mould being formed by glass and adhesive tape.Mould is rendered in polymerization baking box, from 25 DEG C～130 DEG C only, slowly heated up through 21 hours.After finishing, polymerization takes out mould from baking box.The release property of mould is good.Under 130 DEG C of conditions, the resin obtaining is carried out to 4 hours anneal.The resin characteristics obtaining is refractive index (nE) 1.697, and Abbe number is 35.Inject before mould, visual inspection the state after dissolving, after the demoulding, confirm that surface is bad, result is not abnormal, cannot see albefaction, YI value is 2.1, has obtained stay-in-grade resin.
[embodiment 3]
Be that the EPS-3 of synthesis example 7 of 0.57 % by weight, other compositions are identical with embodiment 1, manufactured resin composition for chloroethanol content except sulfo-epoxy compounds has used epithio, to this mixing solutions, under 400Pa condition, deaeration 1 hour.Filter with 1 μ m PTFE strainer afterwards, injected the mould being formed by glass and adhesive tape.Mould is rendered in polymerization baking box, from 25 DEG C～130 DEG C only, slowly heated up through 21 hours.After finishing, polymerization takes out mould from baking box.The release property of mould is good.Under 130 DEG C of conditions, the resin obtaining is carried out to 4 hours anneal.The resin characteristics obtaining is refractive index (nE) 1.697, and Abbe number is 35.Inject before mould, visual inspection the state after dissolving, after the demoulding, confirm that surface is bad, result is not abnormal, cannot see albefaction, YI value is 2.3, has obtained stay-in-grade resin.
[comparative example 1]
Sulfo-epoxy compounds used epithio for chloroethanol content be the synthesis example 8 of 1.89 % by weight synthetic two (2, 3 epithios are for propyl group) sulfide 89g, isocyanate compound has used isophorone diisocyanate 5g, mercaptan compound has used two (2-mercaptoethyl) sulfide 6g, internal mold release has used acid phosphoric acid ester 8-PENPP[polyoxyethylene nonylphenol ether phosphate (to add 3 % by weight of 9 moles, oxyethane, add 80 % by weight of 8 moles, add 5 % by weight of 9 moles, add 6 % by weight of 7 moles, add 6 % by weight of 6 moles)] 0.15g, four butyl phosphonium bromides (Tetrabutyl phosphonium Bromide) 0.2g, triphenylphosphine (Triphenylphosphine) 0.1g, organic dye HTAQ (20ppm) and PRD (10ppm), UV light absorber HOPBT1.5, mixed dissolution under 20 DEG C of conditions, obtain homogeneous solution.To this mixing solutions, under 400Pa condition, deaeration 1 hour.Filter with 1 μ m PTFE strainer afterwards, injected the mould being formed by glass and adhesive tape.Mould is rendered in polymerization baking box, from 25 DEG C～130 DEG C only, slowly heated up through 21 hours.After finishing, polymerization takes out mould from baking box.The release property of mould is very bad.Under 130 DEG C of conditions, the resin obtaining is carried out to 4 hours anneal.The resin characteristics obtaining is refractive index (nE) 1.697, and Abbe number is 35.Inject before mould, visual inspection the state after dissolving, after the demoulding, confirm that surface is bad, result is not abnormal, cannot see albefaction, YI value is 3.2.
The resin of described embodiment and comparative example synthesizes and result arranges as following table 1.
[table 1]
[abbreviation]
EPS: two (2,3-epithio is for propyl group) sulfide (bis (2,3-epithiopropyl) sulfide)
IPDI: isophorone diisocyanate (isophorondiisocyanate)
BMES: two-(2,3-epithio is for propyl group) sulfide (bis-(2,3-epithiopropyl) sulfide)
HOPBT:2-(2'-hydroxyl-5'-t-octyl phenyl)-2H-benzotriazole (2-(2'-hydroxy-5'-t-octylphenyl)-2H-benzotriazole)
HTQA:1-hydroxyl-4-(p-Tolylamine)-anthraquinone (1-hydroxy-4-(p-toluidine) anthraquinone
PRD: pyrene ketone dyes (perinone dye)
Industry is utilized feasibility
The present invention can easily solve the form and aspect instability problem that sulfo-epoxy base system optical material occurs, can manufacture as clear as crystal high-quality sulfo-epoxy base system eyeglass with very high yield.The as clear as crystal high quality sulfo-epoxy base system optical material of manufacture of the present invention can replace existing optical material, is widely used in various fields.Particularly, can be used for plastic eyeglass lens, the 3D polarized lenses that light polarizing film is manufactured is installed on glasses lens, and camera eyeglass etc., in addition can also be used in the multiple optical articles such as recording medium substrate or painted strainer and ultraviolet radiation absorption strainer such as bevelled mirror, fiber optics, CD.
Claims (15)
1. a sulfo-epoxy base system polymerizability synthetics, it,, containing sulfo-epoxy compounds, is characterized in that: the epithio of described sulfo-epoxy compounds is below 1 % by weight for chloroethanol content.
2. sulfo-epoxy base system polymerizability synthetics according to claim 1, is characterized in that:
Also comprise polyisocyanate compounds.
3. sulfo-epoxy base system polymerizability synthetics according to claim 1, is characterized in that:
Also comprise poly-thiol compound.
4. sulfo-epoxy base system polymerizability synthetics according to claim 2, is characterized in that:
Also comprise poly-thiol compound.
5. according to a certain described sulfo-epoxy base system polymerizability synthetics in claim 1 to 4, it is characterized in that:
Described sulfo-epoxy compounds is to be selected from two-(2, 3-epithio is for propyl group) sulfide, two-(2, 3-epithio is for propyl group) disulphide, 1, 3 and 1, 4-bis-(β-epithio is for propyl dithiocarbamate) hexanaphthene, 1, 3 and 1, 4-bis-(β-epithio is for propyl dithiocarbamate methyl) hexanaphthene, 2, 5-bis-(β-epithio is for propyl dithiocarbamate methyl)-1, 4-dithiane, 2, 5-bis-(β-epithio is for propyl dithiocarbamate ethylenebis dithiocarbamate methyl)-1, 4-dithiane, 2-(2-β-epithio is for propyl dithiocarbamate ethylenebis dithiocarbamate)-1, more than a kind material in 3-bis-(β-epithio is for propyl dithiocarbamate) propane.
6. according to the sulfo-epoxy base system polymerizability synthetics described in claim 2 or 4, it is characterized in that:
Described polyisocyanate compounds is to be selected from isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), cyclohexyl diisocyanate (H12MDI), eylylene diisocyanate (XDI), 3, 8-bis-(isocyanic acid methyl) three rings [5, 2, 1, 02, 6] decane, 3, 9-bis-(isocyanic acid methyl) three rings [5, 2, 1, 02, 6] decane, 4, 8-bis-(isocyanic acid methyl) three rings [5, 2, 1, 02, 6] decane, 2, 5-bis-(isocyanic acid methyl) two rings [2, 2, 1] heptane, 2, 6-bis-(isocyanic acid methyl) two rings [2, 2, 1] more than 1 of heptane kind material.
7. according to a certain described sulfo-epoxy base system polymerizability synthetics in claim 1 to 4, it is characterized in that:
Also comprise olefin(e) compound as reaction resin properties-correcting agent.
8. according to a certain described sulfo-epoxy base system polymerizability synthetics in claim 1 to 4, it is characterized in that:
As internal mold release, also comprise that being selected from 4-PENPP[polyoxyethylene nonylphenol ether phosphate (adds 5 % by weight of 5 moles, oxyethane, add 80 % by weight of 4 moles, add 10 % by weight of 3 moles, add 5 % by weight of 1 mole)], 8-PENPP[polyoxyethylene nonylphenol ether phosphate (adds 3 % by weight of 9 moles, oxyethane, add 80 % by weight of 8 moles, add 5 % by weight of 9 moles, add 6 % by weight of 7 moles, add 6 % by weight of 6 moles)], 12-PENPP[polyoxyethylene nonylphenol ether phosphate (adds 3 % by weight of 13 moles, oxyethane, add 80 % by weight of 12 moles, add 8 % by weight of 11 moles, add 3 % by weight of 9 moles, add 6 % by weight of 4 moles)], 16-PENPP[polyoxyethylene nonylphenol ether phosphate (adds 3 % by weight of 17 moles, oxyethane, add 79 % by weight of 16 moles, add 10 % by weight of 15 moles, add 4 % by weight of 14 moles, add 4 % by weight of 13 moles)], 20-PENPP[polyoxyethylene nonylphenol ether phosphate (adds 5 % by weight of 21 moles, oxyethane, add 76 % by weight of 20 moles, add 7 % by weight of 19 moles, add 6 % by weight of 18 moles, add 4 % by weight of 17 moles)], 4-PPNPP[polyoxytrimethylene nonylphenol ether phosphate (poly oxy propylene nonyl phenol ether phosphate) (adds 5 % by weight of 5 moles of propylene oxide, add 80 % by weight of 4 moles, add 10 % by weight of 3 moles, add 5 % by weight of 1 mole)], 8-PPNPP[polyoxytrimethylene nonylphenol ether phosphate (adds 3 % by weight of 9 moles of propylene oxide, add 80 % by weight of 8 moles, add 5 % by weight of 9 moles, add 6 % by weight of 7 moles, add 6 % by weight of 6 moles)], 12-PPNPP[polyoxytrimethylene nonylphenol ether phosphate (adds 3 % by weight of 13 moles of propylene oxide, add 80 % by weight of 12 moles, add 8 % by weight of 11 moles, add 3 % by weight of 9 moles, add 6 % by weight of 4 moles)], 16-PPNPP[polyoxytrimethylene nonylphenol ether phosphate (adds 3 % by weight of 17 moles of propylene oxide, add 79 % by weight of 16 moles, add 10 % by weight of 15 moles, add 4 % by weight of 14 moles, add 4 % by weight of 13 moles)], 20-PPNPP[polyoxytrimethylene nonylphenol ether phosphate (adds 5 % by weight of 21 moles of propylene oxide, add 76 % by weight of 20 moles, add 7 % by weight of 19 moles, add 6 % by weight of 18 moles, add 4 % by weight of 17 moles)], Zelec UN
tMmore than a kind phosphate compound.
9. a sulfo-epoxy base system optical material manufacture method, is characterized in that:
A certain polymerizability synthetics in injection molding polymerization claim 1 to 4.
10. sulfo-epoxy base system optical material manufacture method according to claim 9, is characterized in that:
Described sulfo-epoxy compounds is synthetic by the method that comprises the steps, and reaction table chloropharin content is sulfide compound and thiocarbamide below 1 % by weight, the step of carrying out epithio.
11. sulfo-epoxy base system optical material manufacture method according to claim 9, is characterized in that:
Described sulfo-epoxy compounds is to be selected from two-(2, 3-epithio is for propyl group) sulfide (bis-(2, 3-epithiopropyl) sulfide), two-(2, 3-epithio is for propyl group) disulphide (bis-(2, 3-epithiopropyl) disulfide), 1, 3 and 1, 4-bis-(β-epithio is for propyl dithiocarbamate) hexanaphthene, 1, 3 and 1, 4-bis-(β-epithio is for propyl dithiocarbamate methyl) hexanaphthene, 2, 5-bis-(β-epithio is for propyl dithiocarbamate methyl)-1, 4-dithiane, 2, 5-bis-(β-epithio is for propyl dithiocarbamate ethylenebis dithiocarbamate methyl)-1, 4-dithiane, 2-(2-β-epithio is for propyl dithiocarbamate ethylenebis dithiocarbamate)-1, more than a kind material in 3-bis-(β-epithio is for propyl dithiocarbamate) propane.
12. sulfo-epoxy base system optical material manufacture method according to claim 9, is characterized in that:
Described polymerizability synthetics, also comprises the olefin(e) compound using as reaction resin properties-correcting agent.
13. sulfo-epoxy base system optical material manufacture method according to claim 9, is characterized in that:
Described polymerizability synthetics, also comprise that the 4-PENPP[polyoxyethylene nonylphenol ether phosphate (poly oxy ethylene nonyl phenol ether phosphate) that is selected from using as internal mold release (adds 5 % by weight of 5 moles, oxyethane, add 80 % by weight of 4 moles, add 10 % by weight of 3 moles, add 5 % by weight of 1 mole)], 8-PENPP[polyoxyethylene nonylphenol ether phosphate (adds 3 % by weight of 9 moles, oxyethane, add 80 % by weight of 8 moles, add 5 % by weight of 9 moles, add 6 % by weight of 7 moles, add 6 % by weight of 6 moles)], 12-PENPP[polyoxyethylene nonylphenol ether phosphate (adds 3 % by weight of 13 moles, oxyethane, add 80 % by weight of 12 moles, add 8 % by weight of 11 moles, add 3 % by weight of 9 moles, add 6 % by weight of 4 moles)], 16-PENPP[polyoxyethylene nonylphenol ether phosphate (adds 3 % by weight of 17 moles, oxyethane, add 79 % by weight of 16 moles, add 10 % by weight of 15 moles, add 4 % by weight of 14 moles, add 4 % by weight of 13 moles)], 20-PENPP[polyoxyethylene nonylphenol ether phosphate (adds 5 % by weight of 21 moles, oxyethane, add 76 % by weight of 20 moles, add 7 % by weight of 19 moles, add 6 % by weight of 18 moles, add 4 % by weight of 17 moles)], 4-PPNPP[polyoxytrimethylene nonylphenol ether phosphate (poly oxy propylene nonyl phenol ether phosphate) (adds 5 % by weight of 5 moles of propylene oxide, add 80 % by weight of 4 moles, add 10 % by weight of 3 moles, add 5 % by weight of 1 mole)], 8-PPNPP[polyoxytrimethylene nonylphenol ether phosphate (adds 3 % by weight of 9 moles of propylene oxide, add 80 % by weight of 8 moles, add 5 % by weight of 9 moles, add 6 % by weight of 7 moles, add 6 % by weight of 6 moles)], 12-PPNPP[polyoxytrimethylene nonylphenol ether phosphate (adds 3 % by weight of 13 moles of propylene oxide, add 80 % by weight of 12 moles, add 8 % by weight of 11 moles, add 3 % by weight of 9 moles, add 6 % by weight of 4 moles)], 16-PPNPP[polyoxytrimethylene nonylphenol ether phosphate (adds 3 % by weight of 17 moles of propylene oxide, add 79 % by weight of 16 moles, add 10 % by weight of 15 moles, add 4 % by weight of 14 moles, add 4 % by weight of 13 moles)], 20-PPNPP[polyoxytrimethylene nonylphenol ether phosphate (adds 5 % by weight of 21 moles of propylene oxide, add 76 % by weight of 20 moles, add 7 % by weight of 19 moles, add 6 % by weight of 18 moles, add 4 % by weight of 17 moles)], Zelec UN
tMmore than a kind phosphate compound.
14. 1 kinds of sulfo-epoxy base system optical materials, is characterized in that:
Manufacture method with claim 9 obtains.
15. 1 kinds of sulfo-epoxy base system optical mirror slips, is characterized in that:
Optical material with claim 14 forms.
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| CN105669640A (en) * | 2016-03-29 | 2016-06-15 | 黄河三角洲京博化工研究院有限公司 | Clean preparation method of episulfides |
| CN106397370A (en) * | 2016-08-30 | 2017-02-15 | 黄河三角洲京博化工研究院有限公司 | Method for producing high-quality epoxy compound |
| CN107548409A (en) * | 2015-05-04 | 2018-01-05 | 可奥熙搜路司有限公司 | The preparation method of thio epoxy base system optical material and thio epoxy base system polymerizable composition for optical material |
| CN110156748A (en) * | 2019-06-18 | 2019-08-23 | 江苏可奥熙光学材料科技有限公司 | A kind of preparation method of high refractive index lens monomer |
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| WO2023076233A1 (en) * | 2021-10-25 | 2023-05-04 | Meta Platforms Technologies, Llc | Systems and methods of making polymeric optical layers for optical layering applications |
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- 2013-01-07 CN CN201380004719.6A patent/CN104039860A/en active Pending
- 2013-01-07 WO PCT/KR2013/000101 patent/WO2013103277A1/en active Application Filing
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| CN107548409A (en) * | 2015-05-04 | 2018-01-05 | 可奥熙搜路司有限公司 | The preparation method of thio epoxy base system optical material and thio epoxy base system polymerizable composition for optical material |
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| CN105968409A (en) | 2016-09-28 |
| CN105968409B (en) | 2019-07-30 |
| KR20130081257A (en) | 2013-07-16 |
| WO2013103277A1 (en) | 2013-07-11 |
| KR101487709B1 (en) | 2015-01-29 |
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Application publication date: 20140910 |