CN104066716B - The manufacture method of optical material poly-thiol compound and the optical material synthetic including this - Google Patents

Abstract

The present invention relates to form and aspect aspect present outstanding physical property high-quality optical material poly-thiol compound with include this optical material synthetic and the manufacture method of optical material.The present invention provides and allows the chloropropylene oxide that total content is 0.5 weight % of specific impurity and 2 mercaptoethanols carry out the optical material manufacture method reacted.The present invention can obtain the poly-thiol compound that coloring is inhibited, it is possible to utilizing this to obtain coloring and be inhibited, yellow chromaticity is low, and the poly-thiol compound of the urethane western optical material present invention that form and aspect are good can use as countless optical materials such as urethane systems.The good optical glass of form and aspect that the present invention obtains can substitute for existing being widely used in multiple fields, especially can be as eyeglass, polarized lenses, camera eyeglass etc..

Description

The manufacture method of optical material poly-thiol compound and the optical material including this are used Synthetic

Technical field

The present invention relates to the manufacture method of the poly-thiol compound for optical material and include this poly-thiol compound Optical material synthetic, particularly relates to a kind of high-quality optical material polysulfide in terms of form and aspect with preferable physical property and refines Compound and the optical material synthetic and the manufacture method of optical material that include this.

Background technology

With compared with the optical material that inorganic material is constituted, for the plastic optics material weight of the optical glasss such as glasses Gently, the most broken, can dye.At present various kinds of resin plastic material is used as optical material, wants the physical property of these materials is relevant Ask more and more higher.

Korean Patent No. 1993-0006918 and No. 1992-0005708 etc. disclose a kind of reaction poly-thiol compound and Polyisocyanate compounds and the sulfur urethane eyeglass that obtains.Poly-thiol compound and polyisocyanate compounds is used to manufacture Polysulfide urethane optical material is outstanding, by as optical frames in optical characteristics such as the transparency, Abbe number, light transmittance, hot strengths Sheet material is extensively applied.But, when the poly-thiol compound of polymerization is colored, it may occur that manufactured resin hue difference Problem.For the resin in order to obtain non-coloring, transparent, form and aspect are good, it is necessary to suppression is for the poly-thiol compound of polymerization as far as possible Coloring.

Korean Patent 10-2008-0090529 illustrates the hue difference that polyurethane (polyurethane) is resin and results from poly- Impurity two (the 2-hydroxyl ethane base) disulphide (bis (2-hydroxyl manufactured in raw material 2 mercapto ethanol of mercaptan Ethyl) disulfide), disclose one and allow two (2-hydroxyl ethane base) disulphide content be the 2-sulfydryl of 0.5 weight % The poly-thiol compound manufacture method that ethanol reacts with epihalohydrin (epihalohydrin) compound.

Summary of the invention

The problem of invention

Each inventor of the present invention have studied the coloring on poly-thiol compound and produces the many factors of impact.Result of study Show, although impurity two (the 2-hydroxyl ethane base) disulphide in 2 mercapto ethanol produces shadow to the coloring of poly-thiol compound Ring, even if but control this factor, the problem that coloring also can occur once in a while.By further study show that, poly-thiol compound Synthesize the content of specific impurities contained by stimulating food matter chloropropylene oxide (epichlorohydrin) compound and directly affect polymercaptan chemical combination The coloring of thing.

It is an object of the invention to provide a kind of by the specific impurities content in reconciliation statement chlorohydrination compound, manufacture coloring The manufacture method of few poly-thiol compound, including optical material synthetic and the optics of the poly-thiol compound obtained with this The manufacture method of material.

Embodiment

Each inventor of the present invention confirms, during synthesis poly-thiol compound, as the chloropropylene oxide chemical combination of the substance migration that sets out The coloring phenomenon of poly-thiol compound can be allowed when specific impurities total content is below certain limit contained by thing to minimize, and utilizing should Coloring can be suppressed during poly-thiol compound polymerization urethane system resin, the resin that yellow chromaticity is low, form and aspect are good can be obtained.

The invention provides:

A kind of optical material poly-thiol compound manufacture method, reacts with 2 mercapto ethanol including allowing chloropropylene oxide compound Stage, it is characterised in that:

Described chloropropylene oxide compound is contained by acrylic aldehyde (acrolein), allyl chloride (allylchloride), 1,2-bis- Chloropropane (1,2-dichloropropane), 2,3-dichloropropylene (2,3-dichloropropene), 2-methyl-2-amylalcohol (2-methyl-2-phentanol), 2-chlorine aryl alcohol (2-chloroaryl alcohol), cis-1,3-dichloropropylene (cis-1,3-dichloropropene), anti-form-1,3-dichloropropylene (trans-1,3-dichloropropene), 1,3-bis- Chloro isopropanol (1,3-dichloro iso propyl alcohol), 1,2,3-trichloropropane (1,2,3- And the content of impurities that constitutes of 2,3-dichlorohydrin (2,3-dichloropropanol) is 0.5 weight trichloropropane) Amount below %.

The present invention provides a kind of optical material synthetic containing the poly-thiol compound obtained by described manufacture method.

The present invention provides and is polymerized the urethane system optical material manufacture method of described optical material synthetic and by being somebody's turn to do Urethane system optical material that method obtains and the optical glass being made up of this optical material.Described optical glass especially includes eye Mirror eyeglass.

Invention effect

As the spy in the chloropropylene oxide compound of the substance migration that sets out when the present invention synthesizes poly-thiol compound by regulating Determine impurity content, it is possible to obtain the poly-thiol compound of suppression coloring, use this poly-thiol compound can obtain coloring and obtain Suppression, the urethane system optical material that yellow chromaticity is low, form and aspect are good.

Detailed description of the invention

The poly-thiol compound of the present invention is manufactured by known manufacture method, and it includes allowing chloropropylene oxide compound and 2-mercapto The step of base ethanol synthesis.That is, allow chloropropylene oxide compound and 2 mercapto ethanol react, obtain the step of polyol compounds, allow institute State polyol compounds and thiourea (thiourea) and react, obtain the step of thiocarbamide salt (thiuronium), by described sulfur Urea salt is hydrolyzed (hydrolysis), obtains the step of poly-thiol compound, can manufacture required by these steps Poly-thiol compound.

Present invention manufacture method based on this poly-thiol compound, by regulating the chloropropylene oxide as the substance migration that sets out The content of the specific impurities in Compound Compound, it is thus achieved that the poly-thiol compound that coloring is inhibited.In chloropropylene oxide compound Specific impurities by acrylic aldehyde (acrolein), allyl chloride (acrolein), 1,2-dichloropropane, 2,3-dichloropropylene, 2- Methyl-2-amylalcohol, 2-chlorine aryl alcohol, cis-1,3-dichloropropylene, anti-form-1,3-dichloropropylene, 1,3-dichloroisopropanol, 1, 2,3-trichloropropanes and 2,3-dichlorohydrin is constituted, and the total content of these impurity is below 0.5 weight % of chloropropylene oxide compound Time, it is possible to obtain colour the poly-thiol compound that the form and aspect being inhibited are outstanding.

The poly-thiol compound of the present invention is not particularly limited, it is possible to use containing more than 2 mercaptos in a molecule Compound.Such as, poly-thiol compound can be two (2-mercaptoethyl) sulfide (bis (2-mercapto ethyl) Sulfide), 4-mercapto methyl-1,8-dimercapto-3,6-dithiaoctane (4-mercapto methyl-1,8- Dimercapto-3,6-dithia octane), 2,3-bis-(2-mercaptoethyl sulfur generation) propane-1-mercaptan (2,3-bis (2- Mercapto ethyl thio) propane-1-thiol), 2,2-bis-(mercapto methyl)-1,3-propanedithiol (2,2-bis (mercapto methyl)-1,3-propane dithiol), four (mercapto methyl) methane (Tetrakis (mercapto methyl)methane)；2-(2-mercaptoethyl sulfur generation) propane-1,3-two mercaptan (2-(2-mercapto ethyl thio) Propane-1,3-dithiol), 2-(2,3-bis-(2-mercaptoethyl sulfur generation) propyl dithiocarbamate) ethane thiol (2-(2,3-bis (2- Mercapto ethyl thio) propyl thio) ethane thiol), two (2,3-dimercaptopropanol, BAL) sulfide (bis (2, 3-dimercapto propanol) sulfide), two (2,3-dimercaptopropanol, BAL) disulphide (bis (2,3-dimercapto Propanol) disulfide), 1,2-bis-(2-mercaptoethyl sulfur generation)-3-thio propane (1,2-bis (2-mercapto Ethyl thio)-3-mercapto propane), 1,2-bis-(2-(2-mercaptoethyl sulfur generation)-3-mercaptopropyi sulfur generation) ethane (1,2-bis (2-(2-mercapto ethyl thio)-3-mercapto propyl thio) ethane), two (2-(2-mercaptos Base ethylenebis dithiocarbamate)-3-mercaptopropyi) sulfide (bis (2-(2-mercapto ethyl thio)-3-mercapto Propyl) sulfide), two (2-(2-mercaptoethyl sulfur generation)-3-mercaptopropyi) disulphide (bis (2-(2-mercapto Ethyl thio)-3-mercapto propyl) disulfide), 2-(2-mercaptoethyl sulfur generation)-3-2-sulfydryl-3-[3-mercapto Base-2-(2-mercaptoethyl sulfur generation)-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 the-the third acyloxymethyl)-butyl ester (2,2-bis-(3-mercapto- Propionyl oxymethyl)-butyl ester), 2-(2-mercaptoethyl sulfur generation)-3-(2-(2-[3-sulfydryl-2-(2-mercapto Base ethylenebis dithiocarbamate)-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-two (mercapto methyl)-3,6,9,12-tetrathio four decane-1,14- Two 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) sulfur generation) propane-1,2-two mercaptan ((S)-3-((R-2,3- Dimercapto propyl) thio) propane-1,2-dithiol), (4R, 14R)-4,14-two (mercapto methyl)-3,6,9, 12,15-five sulfur is for heptane-1,17-two 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) sulfur generation) propyl group) sulfur Generation) propyl group) sulfur generation)-2-((2-mercaptoethyl) sulfur generation) 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-two mercaptan) (3,3'-dithio bis (propane-1,2- Dithiol)), (7R, 11S)-7,11-two (mercapto methyl)-3,6,9,12,15-five sulfur is for heptadecane-1,17-two mercaptan ((7R,11S)-7,11-bis(mercapto methyl)-3,6,9,12,15-Penta thia heptadecane-1,17- Dithiol), (7R, 12S)-7,12-two (mercapto methyl)-3,6,9,10,13,16-six sulfur is for octadecane-1,18-two 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 hendecane (5,7-dimercapto methyl- 1,11-dimercapto-3,6,9-trithia undecane), 4,7-dimercapto methyl-1,11-dimercapto-3,6,9-trithio For hendecane (4,7-dimercapto methyl-1,11-dimercapto-3,6,9-trithia undecane), 4,8-bis- Mercapto methyl-1,11-dimercapto-3,6,9-trithio hendecane (4,8-dimercapto methyl-1,11- Dimercapto-3,6,9-trithia undecane), tetramethylolmethane four (3-thiopropionate) (Penta erythritol Tetrakis (3-mercapto propionate)), three methylol propane three (3-thiopropionate) (trimethylol Propane tris (3-mercapto propionate)), tetramethylolmethane four (2-thioglycolate) (Pentaerythritol Tetrakis (2-mercapto acetate)), dipentaerythritol-ether-phenylpropyl alcohol stannum (3-thiopropionate) (bispenta Erythritol-ether-hexakis (3-mercapto propionate)), 1,1,3,3-tetra-(mercapto methyl sulfur generation) propane (1,1,3,3-Tetrakis (mercapto methyl thio) propane), 1,1,2,2-tetra-(mercapto methyl sulfur generation) ethane (1,1,2,2-Tetrakis (mercapto methyl thio) ethane), 4,6-bis-(mercapto methyl sulfur generation)-1,3-two thiophene Alkane (4,6-bis (mercapto methyl thio)-1,3-dithiane) and 2-(2,2-bis-(sulfydryl dimethyl thio) second Base)-1,3-dithiane (2-(2,2-bis (mercapto dimethyl thio) ethyl)-1,3-dithiane).Polymercaptan Compound preferably uses selected from 2-(2-mercaptoethyl sulfur generation) propane-1,3-two mercaptan, 2,3-bis-(2-mercaptoethyl sulfur generation) Propane-1-mercaptan, 2-(2,3-bis-(2-mercaptoethyl sulfur generation) propyl dithiocarbamate) ethane thiol, 1,2-bis-(2-mercaptoethyl sulfur Generation)-3-thio propane, 1,2-bis-(2-(2-mercaptoethyl sulfur generation)-3-mercaptopropyi sulfur generation) ethane, two (2-(2-mercaptoethyls Sulfur generation)-3-mercaptopropyi) sulfide, 2-(2-mercaptoethyl sulfur generation)-3-2-sulfydryl-3-[3-sulfydryl-2-(2-mercaptoethyl sulfur Generation)-propyl dithiocarbamate] propyl dithiocarbamate-propane-1-mercaptan, 2,2'-sulfur for bisethane mercaptan (thiodiethanethiol), 4, 14-bis-(mercapto methyl)-3,6,9,12,15-five sulfur is for heptadecyl-1,17-two mercaptan (-4,14-bis (mercapto Methyl)-3,6,9,12,15-Penta thia heptadecane-1,17-dithiol) 2-(2-mercaptoethyl sulfur generation)-3- [4-(1-{4-[3-sulfydryl-2-(2-mercaptoethyl sulfur generation)-propoxyl group]-phenyl }-1-Methylethyl)-phenoxy group]-propane-1- Mercaptan (2-(2-mercaptoethylthio)-3-[4-(1-{4-[3-mercapto-2-(2-mercaptoethylthio)- Propoxy]-phenyl}-1-methylethyl)-phenoxy]-propane-1-thiol), tetramethylolmethane four (3-sulfydryl third Acid esters) (Penta erythritolTetrakis (3-mercaptoPropionate)), tetramethylolmethane thioglycollate (Penta erythritolmercaptoacetate), trimethyl propane tri-thiol propionic ester (trimethyolpropanetrismercaptoPropionate), glycerol tri-thiol propionic ester (glyceroltrimercaptoPropionate), dipentaerythritol six mercaptopropionic acid ester (di penta ErythritolhexamercaptoPropionate) a certain kind in or two or more.Outside, the polymercaptan chemical combination of the present invention Thing can also include the compound being mixed with the unreacted reactant hydroxyl of a part of above-mentioned substance.

The optical material synthetic of the present invention includes the poly-thiol compound obtained by described manufacture method.The present invention Optical material synthetic can be the urethane system optics including described poly-thiol compound and polyisocyanate compounds Material synthetic." the optical material synthetic " of the present invention refers to the polymerizable of the optical materials such as hardenable one-tenth optical glass Synthetic.

Polyisocyanate compounds contained by the optical material synthetic of the present invention is not particularly limited, it is possible to use at least With more than 1 Carbimide. and/or the compound of different thiocyano-.Such as, more than a kind 2 is used, 2-dimethyl pentane two isocyanide Acid esters (2,2-dimethyl pentane diisocyanate), hexamethylene diisocyanate (hexa methylene Diisocyanate), 2,2,4-trimethylhexane diisocyanate (2,2,4-trimethyl hexane Diisocyanate), butene diisocyanate (butene diisocyanate), 1,3-butadiene-1,4-diisocyanate (1,3-butadiene-1,4-diisocyanate), 2,4,4-trimethyl hexamethylene diisocyanate (2,4,4- Trimethyl hexa methylene diisocyanate), 1,6,11-hendecane triisocyanate (1,6,11- Undecane triisocyanate), 1,3,6-hexa-methylene triisocyanate (1,3,6-hexa methylene Triisocyanate), 1,8-diisocyanate-4-isocyanatometyl octane (1,8-diisocyanate-4- Isocyanato methyl octane), two (isocyanatoethyl) carbonic ester (bis (isocyanato ethyl) Carbonate), the aliphatic isocyanates such as two (isocyanatoethyl) ether (bis (isocyanato ethyl) ether) Compound (aliphatic isocyanate compounds)；Isophorone diisocyanate (isophorone Diisocyanate), 1,2-bis-(isocyanatometyl) hexamethylene (1,2-bis (isocyanato methyl) cyclo Hexane), 1,3-bis-(isocyanatometyl) hexamethylene (1,3-bis (isocyanato methyl) cyclo hexane), 1, 4-bis-(isocyanatometyl) hexamethylene (1,4-bis (isocyanato methyl) cyclo hexane), dicyclohexyl methyl hydride Diisocyanate (dicyclo hexyl methane diisocyanate), cyclohexane diisocyanate (cyclo hexane Diisocyanate), methylcyclohexane diisocyanate (methyl cyclo hexane diisocyanate), dicyclohexyl Dimethylmethane isocyanates (dicyclo hexyl dimethyl methane isocyanate), 2,2-dimethyl bicyclo- The alicyclic Carbimide .s such as hexyl methane isocyanates (2,2-dimethyl dicyclo hexyl methane isocyanate) Ester compounds (Cycloaliphatic isocyanate compounds)；Eylylene diisocyanate (xylylene Diisocyanate (XDI)), two (isocyanatoethyl) benzene (bis (isocyanatoethyl) benzene), two (Carbimide .s Base propyl group) benzene (bis (isocyanato propyl) benzene), two (isocyanate group butyl) benzene (bis (isocyanato Butyl) benzene), two (isocyanatometyl) naphthalene (bis (isocyanato methyl) naphthalene), two (isocyanides Acidic group methyl) diphenyl ether (bis (isocyanato methyl) diphenyl ether), phenylene vulcabond (phenylene diisocyanate), ethylphenylene diisocyanate (ethyl phenylene diisocyanate), Isopropyl phenylene diisocyanate (isopropyl phenylene diisocyanate), dimethylphenylene two Carbimide. Ester (dimethyl phenylene diisocyanate), diethyl phenylene vulcabond (diethyl phenylene Diisocyanate), diisopropyl phenylene vulcabond (diisopropyl phenylene diisocyanate), three Methylbenzene triisocyanate (trimethyl benzene triisocyanate), benzene triisocyanate (benzene Triisocyanate), biphenyl diisocyanate (biphenyl diisocyanate), toluidine diisocyanate (toluidine diisocyanate), 4,4-methyl diphenylene diisocyanate (4,4-diphenyl methane Diisocyanate), 3,3-dimethyl diphenylmethane-4,4-diisocyanate (3,3-dimethyl diphenyl Methane-4,4-diisocyanate), bibenzyl-4,4-diisocyanate (bibenzyl-4,4-diisocyanate), two (isocyanatophenyl) ethylene (bis (isocyanato phenyl) ethylene), 3,3-dimethoxy-biphenyl-4,4-two are different Cyanate (3,3-dimethoxy biphenyl-4,4-diisocyanate), hexahydrobenzene diisocyanate (hexa Hydrobenzene diisocyanate), hexahydro diphenyl methane-4,4-diisocyanate (hexa hydro diphenyl Aromatic isocyanate compound (the aromatic isocyanate such as methane-4,4-diisocyanate) compounds)；Two (isocyanatoethyl) sulfide (bis (isocyanato ethyl) sulphide), two (isocyanate groups Propyl group) sulfide (bis (isocyanato propyl) sulphide), two (isocyanatohexyl) sulfide (bis (isocyanato hexyl) sulphide), two (isocyanatometyl) sulphur (bis (isocyanato methyl) Sulfone), two (isocyanatometyl) disulphide (bis (isocyanato methyl) disulphide), two (Carbimide .s Base propyl group) disulphide (bis (isocyanato propyl) disulphide), two (isocyanatometyl sulfur generation) methane (bis (isocyanato methyl thio) methane), two (isocyanatoethyl sulfur generation) methane (bis (isocyanato Ethyl thio) methane), two (isocyanatoethyl sulfur generation) ethane (bis (isocyanato ethyl thio) Ethane), two (isocyanatometyl sulfur generation) ethane (bis (isocyanato methyl thio) ethane), 1,5-bis-are different Cyanic acid base-2-isocyanatometyl-3-sulfur is for pentane (1,5-diisocyanato-2-isocyanato methyl-3-thia The sulfur-bearing aliphatic isocyanates compound (sulfur aliphatic isocyanate compounds) such as pentane)；Two Phenyl sulfide-2,4-diisocyanate (diphenyl sulphide-2,4-diisocyanate), diphenyl sulfide-4, 4-diisocyanate (diphenyl sulphide-4,4-diisocyanate), 3,3-dimethoxy-4 ', 4-bis-isocyanate group Benzhydryl thio-ether (3,3-dimethoxy-4,4-diisocyanato dibenzyl thio ether), two (4-is different Cyanic acid ylmethyl benzene) sulfide (bis (4-isocyanato methyl benzene) sulphide), 4,4-methoxybenzene sulfur For ethylene glycol-3,3-diisocyanate (4,4-methoxy benzene thio ethylene glycol-3,3- Diisocyanate), diphenyl disulfide-4,4-diisocyanate (diphenyl disulphide-4,4- Diisocyanate), 2,2-dimethyldiphenyldisulfide-5,5-diisocyanate (2,2-dimethyl diphenyl Disulphide-5,5-diisocyanate), 3,3-dimethyldiphenyldisulfide-5,5-diisocyanate (3,3- Dimethyl diphenyl disulphide-5,5-diisocyanate), 3,3-dimethyldiphenyldisulfide-6,6- Diisocyanate (3,3-dimethyl diphenyl disulphide-6,6-diisocyanate), 4,4-dimethyl hexichol Based bisulfide-5,5-diisocyanate (4,4-dimethyl diphenyl disulphide-5,5-diisocyanate), 3,3-dimethoxydiphenyl disulphide-4,4-diisocyanate (3,3-dimethoxy diphenyl disulphide- 4,4-diisocyanate), 4,4-dimethoxydiphenyl disulphide-3,3-diisocyanate (4,4-dimethoxy Diphenyl disulphide-3,3-diisocyanate) etc. sulfur-containing aromatic isocyanate compound (sulfur aromatic isocyanate compounds)；2,5-bis-isocyanate group thiophene (2,5-diisocyanato Thiophene), 2,5-bis-(isocyanatometyl) thiophene (2,5-bis (isocyanato methyl) thiophene), 2,5- Two isocyanate group Tetramethylene sulfides (2,5-diisocyanato Tetra hydrothiophene), 2,5-bis-(isocyanate group first Base) Tetramethylene sulfide (2,5-bis (isocyanato methyl) Tetra hydrothiophene), 3,4-bis-(isocyanate group first Base) Tetramethylene sulfide (3,4-bis (isocyanato methyl) Tetra hydrothiophene), 2,5-bis-isocyanate group-1, 4-dithiane (2,5-diisocyanato-1,4-dithiane), 2,5-bis-(isocyanatometyl)-1,4-dithiane (2,5- Bis (isocyanato methyl)-1,4-dithiane), 4,5-bis-isocyanate group-1,3-dithiolane (4,5- Diisocyanato-1,3-dithiolane), 4,5-bis-(isocyanatometyl)-1,3-dithiolane (4,5-bis (isocyanato methyl)-1,3-dithiolane), 4,5-bis-(isocyanatometyl)-2-methyl isophthalic acid, 3-dithiolane Sulfur heterocyclic ring isocyanate compounds such as (4,5-bis (isocyanato methyl)-2-methyl-1,3-dithiolane) (sulfur heterocyclic isocyanate compounds).Outside, as long as have more than at least 1 Carbimide. And/or different thiocyanic acid based compound, it is possible to use one kind or two or more, it is also possible to use the chlorine of these isocyanate compounds Halogen family substitution product, the alkyl substitution product (alkyl such as substitution product (substitution product), bromine substitution product Substitution product), alkoxyl substitution product (alkoxy substitution product), nitro replace produce Thing (nitro substitution product) or prepolymer (prepolymer) the type denatured products with multivalence alcohol or mercaptan (denaturant), carbodiimides (carbodiimide) denatured products, carbamide (urea) denatured products, biuret (biuret) denatured products or dimer (dimer) are changed or trimer (trimer) changes reaction product etc..

Preferably use selected from isophorone diisocyanate (IPDI), hexa-methylene two as polyisocyanate compounds Isocyanates (HDI), cyclohexane diisocyanate (H12MDI), eylylene diisocyanate (XDI), 3,8-bis-(isocyanide 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-(isocyanatomethyl) three ring [5,2,1,02,6] decane (3,9-bis (isocyanatemethyl) tri Cyclo [5,2,1,02,6] decane), 4,8-bis-(isocyanatomethyl) three ring [5,2,1,02,6] decane (4,8-bis (isocyanatemethyl) tri cyclo [5,2,1,02,6] decane), 2,5-bis-(isocyanatomethyl) bicyclo-[2,2,1] Heptane (2,5-bis (isocyanatemethyl) bicyclo [2,2,1] heptane), 2,6-bis-(isocyanatomethyl) bicyclo- [2,2,1] more than a kind in heptane (2,6-bis (isocyanatemethyl) bicyclo [2,2,1] heptane).

In addition, the optical material synthetic of the present invention can also include as required catalyst, internal mold release, The arbitrarily composition such as UV absorbent, dyestuff, stabilizer, (bluing) agent of giving a protective coating to metal objects.Furthermore it is also possible to include can be with urethane tree The epoxy resin compound of fat synthetic copolymerization, thio epoxy compound, compound containing vinyl or unsaturated group, or Metallic compound etc..

The optical material of the present invention is by polymerization described optical material synthetic, i.e. poly-thiol compound and polyisocyanate Ester compounds, and the synthetic manufacture containing any composition being added as needed on.The urethane system optical material that the present invention manufactures, Especially urethane system eyeglass is manufactured by injection molding polymerization.Specifically, dissolve various additives to polyisocyanate compounds and urge After agent, add mercaptan compound, vacuum deaerator while cooling down.Afterwards, after appropriate time, inject with adhesive tape solid In fixed glass mold, through 24～48 hours, it is slowly warmed up high temperature from low temperature, hardens.

The urethane system optical material that the present invention manufactures, high refractive index, low dispersion, thermostability, durability are outstanding, weight Gently, impact resistance is outstanding, and especially form and aspect are good, as clear as crystal.Therefore, the urethane system resin of the present invention be suitable for eyeglass or The optical materials such as prism, are particularly suitable for the eyeglass such as eyeglass, camera eyeglass.

The optical glass of the present invention, can carry out surface finish, antistatic process, die process, areflexia as required Physics, the chemical treatments such as process, dyeing process, variable color process, in order to be compound in and prevent reflection, high rigidity, wear-resistant, corrosion resistant The requirement of the aspects such as erosion, antistatic, fashion.

[embodiment]

Embodiments of the invention are intended merely to illustrate the present invention and propose, and the claim of the present invention is not only restricted to These embodiments.

Evaluation methodology

Analyze compound by the following method.The poly-thiol compound and the form and aspect of resin that obtain are commented with YI and APHA value Valency, YI and APHA value is with following Evaluation on the experiment method.

The content of chloropropylene oxide and the analysis of impurity: divided by gas chromatographic analysis (chromatography), gas chromatograph Analysis-quality analysis (GC-MS) and NMR analyze, and have carried out content and species analysis.

The form and aspect (YI or dYI) of polymercaptan: in the present invention, YI (yellow colour index, Yellow Index) value is passed through The colour analysis device being provided with IRS-2200 light collecting device on SHIMADZU company Model UV-2450 detects.A length of Two identical silica gel grid (Silica Cell) of 1cm put into distilled water, determines datum mark (base line), polymercaptan is put Enter equipped with in the silica gel grid of distilled water, have detected form and aspect YI value.In form and aspect evaluation, YI value means yellow colour index, is available color The value of color difference meter detection, the least form and aspect of YI value are the best.

The form and aspect (YI or dYI) of polymercaptan urethane system glass lens: by SHIMADZU company Model UV-2450 On the colour analysis device of IRS-2200 light collecting device be installed detect.Detection method is, using air as datum mark, mirror Sheet is fixing on the securing means, have detected form and aspect YI value.In form and aspect evaluation, YI value means yellow colour index, is available color aberration The value of meter detection, the least form and aspect of YI value are the best.

The APHA of polymercaptan: in the present invention, APHA is that the ColorQuest XE by Hunterlab company detects. Quartzy grid test portion being put into a length of 1cm of transmission detects, according to modulate with dissolving platinum and cobalt reagent in advance The program that concentration of standard solution datumization is built-in, by with sample liquid relatively have detected APHA value.The value of detection is the least, and form and aspect are more Good.

The APHA of polymercaptan urethane system glass lens: examined by the ColorQuest XE of Hunterlab company Survey.It is directly placed into glass lens to detect.According in advance to dissolve platinum and the concentration of standard solution datumization of cobalt reagent modulation Built-in program, by with sample liquid relatively have detected APHA value.The value of detection is the least, and form and aspect are the best.

[embodiment 1]

The synthesis of 1,2-bis-[(2-mercaptoethyl) sulfur generation]-3-thio propane

To being provided with agitator, change of current cooling water-separator, nitrogen purification (Purge) pipe and 10 liter of 5 district of thermometer In reaction flask, put into 2 mercapto ethanol 676g (8.65mol), the water 340g of purity more than 99.9%.Under the conditions of 30 DEG C, warp After within 30 minutes, instilling the sodium hydrate aqueous solution 691.2g (1.08mol) of 25 weight %, at the same temperature, instilled through 3 hours Chloropropylene oxide 399.6g (4.32mol) places 1 hour afterwards.The purity of the chloropropylene oxide used is more than 99.9%, and it is contained by propylene Aldehyde (acrolein), allyl chloride (acrolein), 1,2-dichloropropane, 2,3-dichloropropylene, 2-methyl-2-amylalcohol, 2-chlorine Aryl alcohol, cis-1,3-dichloropropylene, anti-form-1,3-dichloropropylene, 1,3-dichloroisopropanol, 1,2,3-trichloropropane and 2, Impurity (hereinafter referred to as " the specific impurities ") total content that 3-dichlorohydrin is constituted is less than 0.1%.Next 35 weight % are put into Hydrochloric acid 1800g (17.28mol), thiourea 987.6g (12.97mol), place 3 hours, it is thus achieved that thiourea under 110 DEG C of flooding disaster Salt.After being cooled to 20 DEG C, add 1880g toluene (toluene), 25 weight % ammonia spirit 1324.4g (19.47mol), enter Row hydrolysis, it is thus achieved that with 1,2-bis-[(2-mercaptoethyl) sulfur generation]-3-thio propane is the polymercaptan toluene solution of main constituent.Right Described toluene solution carries out pickling and washing, heats, reduces pressure, and eliminates toluene and micro-moisture.It is filtrated to get afterwards With 1,2-bis-[(2-mercaptoethyl) sulfur the generation]-3-thio propane polymercaptan 1074.8g as main constituent.The polymercaptan obtained APHA is 7, YI value: 0.75.

The manufacture of glass lens

Take m-eylylene diisocyanate 52g, as hardening catalyst dibutyl tin dichloride (dibutyl Tin dichloride) 0.015g, Stepan company Jie Leike UN (trade name, acid phosphoric acid ester) 0.10g, Ba Yiousuo skin 583 (trade name, UV absorbent) 0.05g, mixed dissolution under the conditions of 20 DEG C.Put into mixing previously obtained with 1,2- Two [(2-mercaptoethyl) sulfur generation]-3-thio propane is the polymercaptan 48g of main constituent, it is thus achieved that uniformly mixed liquor.At 600Pa bar Under part, this uniform mixed liquor is carried out deaeration in 1 hour.Afterwards, after being filtered by 1 μm PTFE filter, inject by glass In the model that mould and adhesive tape are constituted.Described model is put in baking box, from 10 DEG C of 120 DEG C slowly heated up, is polymerized 20 hours. After polymerization terminates, take out model from baking box, obtained resin by the demoulding.The resin obtained is carried out 3 under the conditions of 120 DEG C little Time annealing.APHA and the YI value of gained resin is respectively 10 and 0.9.Result is as shown in table 1.

[embodiment 2]

In addition to specific impurities total content contained by the chloropropylene oxide that used is 0.05 weight %, other and embodiment 1 phase With, and having manufactured with 1 in the same manner as in Example 1,2-bis-[(2-mercaptoethyl) sulfur generation]-3-thio propane is main constituent Polymercaptan.Being able to 1,2-bis-[(2-mercaptoethyl) sulfur generation]-3-thio propane is the polymercaptan of main constituent, its APHA is 8, YI value is 0.81.Utilize this polymercaptan, manufacture glass lens in the same manner as in Example 1, evaluate.Evaluation result is such as Shown in table 1.

[embodiment 3]

In addition to specific impurities total content contained by the chloropropylene oxide that used is 0.01 weight %, other and embodiment 1 phase With, and having manufactured with 1 in the same manner as in Example 1,2-bis-[(2-mercaptoethyl) sulfur generation]-3-thio propane is main constituent Polymercaptan.Being able to 1,2-bis-[(2-mercaptoethyl) sulfur generation]-3-thio propane is the polymercaptan of main constituent, and its APHA is 11, YI value is 0.92.Utilize this polymercaptan, manufacture glass lens in the same manner as in Example 1, evaluate.Evaluate knot Fruit is as shown in table 1.

[embodiment 4]

In addition to specific impurities total content contained by the chloropropylene oxide that used is 0.23 weight %, other and embodiment 1 phase With, and having manufactured with 1 in the same manner as in Example 1,2-bis-[(2-mercaptoethyl) sulfur generation]-3-thio propane is main constituent Polymercaptan.Being able to 1,2-bis-[(2-mercaptoethyl) sulfur generation]-3-thio propane is the polymercaptan of main constituent, and its APHA is 13, YI value is 1.12.Utilize this polymercaptan, manufacture glass lens in the same manner as in Example 1, evaluate.Evaluate knot Fruit is as shown in table 1.

[embodiment 5]

In addition to specific impurities total content contained by the chloropropylene oxide that used is 0.4 weight %, other and embodiment 1 phase With, and having manufactured with 1 in the same manner as in Example 1,2-bis-[(2-mercaptoethyl) sulfur generation]-3-thio propane is main constituent Polymercaptan.Being able to 1,2-bis-[(2-mercaptoethyl) sulfur generation]-3-thio propane is the polymercaptan of main constituent, and its APHA is 16, YI value is 1.23.Utilize this polymercaptan, manufacture glass lens in the same manner as in Example 1, evaluate.Evaluate knot Fruit is as shown in table 1.

[comparative example 1]

In addition to specific impurities total content contained by the chloropropylene oxide that used is 0.8 weight %, other and embodiment 1 phase With, and having manufactured with 1 in the same manner as in Example 1,2-bis-[(2-mercaptoethyl) sulfur generation]-3-thio propane is main constituent Polymercaptan.Being able to 1,2-bis-[(2-mercaptoethyl) sulfur generation]-3-thio propane is the polymercaptan of main constituent, and its APHA is 26, YI value is 1.87.Utilize this polymercaptan, manufacture glass lens in the same manner as in Example 1, evaluate.Evaluate knot Fruit is as shown in table 1.

[comparative example 2]

In addition to specific impurities total content contained by the chloropropylene oxide that used is 1.3 weight %, other and embodiment 1 phase With, and having manufactured with 1 in the same manner as in Example 1,2-bis-[(2-mercaptoethyl) sulfur generation]-3-thio propane is main constituent Polymercaptan.Being able to 1,2-bis-[(2-mercaptoethyl) sulfur generation]-3-thio propane is the polymercaptan of main constituent, and its APHA is 30, YI value is 2.36.Utilize this polymercaptan, manufacture glass lens in the same manner as in Example 1, evaluate.Evaluate knot Fruit is as shown in table 1.

[comparative example 3]

In addition to specific impurities total content contained by the chloropropylene oxide that used is 1.8 weight %, other and embodiment 1 phase With, and having manufactured with 1 in the same manner as in Example 1,2-bis-[(2-mercaptoethyl) sulfur generation]-3-thio propane is main constituent Polymercaptan.Being able to 1,2-bis-[(2-mercaptoethyl) sulfur generation]-3-thio propane is the polymercaptan of main constituent, and its APHA is 38, YI value is 2.53.Utilize this polymercaptan, manufacture glass lens in the same manner as in Example 1, evaluate.Evaluate knot Fruit is as shown in table 1.

[table 1]

* it is by acrylic aldehyde (acrolein), allyl chloride (acrolein), 1,2-dichloropropane, 2,3-dichloropropylene, 2- Methyl-2-amylalcohol, 2-chlorine aryl alcohol, cis-1,3-dichloropropylene, anti-form-1,3-dichloropropylene, 1,3-dichloroisopropanol, 1, The content of impurities that 2,3-trichloropropane and 2,3-dichlorohydrin are constituted

To embodiment and comparative example gained resin compares it can be seen that the resin of comparative example more presents Huang than embodiment Color.

By example performed as described above and comparative example result, even if using, as raw material, the 2 mercapto ethanol that purity is the highest, As long as the specific impurities content in chloropropylene oxide exceedes more than a certain amount of, just it is proportional to total content, allows the polysulfide finally obtained refine The form and aspect of compound are deteriorated, and accompany therewith, and the form and aspect of resin are also deteriorated.Particularly, the specific impurities total content in chloropropylene oxide exceeds During 0.5 weight %, the form and aspect of polymercaptan and resin significantly deteriorate.Thus, the total content of specific impurities contained by chloropropylene oxide is 0.5 weight During amount below %, it is possible to obtain the poly-thiol compound of the good form and aspect that coloring is inhibited and polyurethane series resin.

Industry utilizes feasibility

The present invention can obtain the optical material poly-thiol compound that coloring is inhibited, and then can use this polymercaptan Compound obtains the optical material that coloring is inhibited, yellow chromaticity reduces, form and aspect are good.The poly-thiol compound of the present invention can be used for The manufacture of the multiple optical materials such as urethane system, the optical glass that the form and aspect that obtained by the present invention are good can substitute for existing optics Eyeglass, is widely used in various field, especially to use as eyeglass, polarized lenses, camera eyeglass etc..

Claims (3)

1. a manufacture method for optical material poly-thiol compound, reacts with 2 mercapto ethanol including allowing chloropropylene oxide compound Stage, it is characterised in that:

Described chloropropylene oxide compound is contained by acrylic aldehyde, allyl chloride, 1,2-dichloropropane, 2,3-dichloropropylene, 2-methyl-2- Amylalcohol, 2-chlorine aryl alcohol, cis-1,3-dichloropropylene, anti-form-1,3-dichloropropylene, 1,3-dichloroisopropanol, 1,2,3-trichlorine The content of impurities that propane and 2,3-dichlorohydrin are constituted is below 0.5 weight %.

2. a manufacture method for urethane system optical material, comprising:

Method according to claim 1 prepares poly-thiol compound；

Preparation comprises the optical material synthetic of described poly-thiol compound and polyisocyanate compounds；With

Described optical material synthetic is carried out injection molding polymerization.

Method the most according to claim 2, it is characterised in that:

Described polyisocyanate compounds is selected from isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), cyclohexane diisocyanate (H12MDI), eylylene diisocyanate (XDI), 3,8-bis-(isocyanatomethyl) three Ring [5,2,1,02,6] decane, 3,9-bis-(isocyanatomethyl) three ring [5,2,1,02,6] decane, 4,8-bis-(isocyanatomethyl) Three rings [5,2,1,02,6] decane, 2,5-bis-(isocyanatomethyl) bicyclo-[2,2,1] heptane, 2,6-bis-(isocyanatomethyl) bicyclo- [2,2,1] more than a kind in heptane.