CN105968409B - Thio epoxy base system optical material polymerism synthetic and thio epoxy base system optical material manufacturing method - Google Patents
Thio epoxy base system optical material polymerism synthetic and thio epoxy base system optical material manufacturing method Download PDFInfo
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- CN105968409B CN105968409B CN201610325788.2A CN201610325788A CN105968409B CN 105968409 B CN105968409 B CN 105968409B CN 201610325788 A CN201610325788 A CN 201610325788A CN 105968409 B CN105968409 B CN 105968409B
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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
-
- 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
-
- 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
-
- 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
-
- 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 thio epoxy base system optical material polymerism synthetics and thio epoxy base system optical material manufacturing method, the form and aspect instability problem that thio epoxy base system optical material occurs especially is solved, provides limpid, transparent high-quality thio epoxy base system optical material.The present invention provides a kind of thio epoxy base system polymerism synthetic comprising epithio is 1 weight % thio epoxy compounds below for chloroethene alcohol content.The present invention controls the epichlorohydrin content in the substance that sets out when synthesizing thio epoxy compounds or the epithio in thio epoxy compounds for chloroethene alcohol content, and the form and aspect instability problem that thio epoxy base system optical material occurs can be solved by easy way.The present invention can be with very high yield, the thio epoxy base system eyeglass of as clear as crystal high-quality easy to manufacture.Thio epoxy base system optical material of the invention can replace existing optical material, be widely used in multiple fields.
Description
The application is divisional application, and the international application no of original application is PCT/KR2013/000101, international filing date
It is on January 7th, 2013, for China national application No. is 201380004719.6, the date into China is on July 2nd, 2014, hair
Bright entitled " thio epoxy base system optical material polymerism synthetic and thio epoxy base system optical material manufacturing method ".
Technical field
The present invention relates to thio epoxy base system optical material polymerism synthetics and thio epoxy base system optical material system
Method is made, the form and aspect instability problem that thio epoxy base system optical material occurs especially is solved, limpid, transparent high-quality is provided
Thio epoxy base system optical material.
Background technique
The open one kind such as Korean Patent Laid bulletin No. 1993-0006918 and No. 1992-0005708 allows polysulfide alcohol compound
The sulphur urethane system eyeglass that object is reacted with polyisocyanate compounds.
Ebrean Registered Patent 10-0681218 discloses a kind of thio epoxy base system glass lens.Sulphur urethane eyeglass is bent
The problems such as light rate is high, and impact strength is outstanding, but there are lens surface difference of hardness, central concave, and Abbe when refractive index is got higher
Number sharply declines.Thio epoxy base system eyeglass refractive index is high, and there is high Abbe number, excellent performance, but problem to be that eyeglass holds
It is easily broken, not easy dyeing.
In order to solve sulphur urethane system's eyeglass and thio epoxy base system eyeglass there are the problem of, Ebrean Registered Patent 10-
No. 0417985, Japanese Patent Laid-Open Publication flat 11-292950 and Japanese Laid-Open Patent Publication 11-352302 etc. disclose two kinds of polymerization not
The side of the method for connatural resin, i.e. polymerised sulphur generation epoxy compounds and poly-thiol compound and polyisocyanate compounds
Method.
But the thio epoxy base system eyeglass containing thio epoxy group still has the unstable problem of form and aspect.KR published patent
No. 10-0681218 is found out in thio epoxy compounds manufacturing process that epoxy compounds are changed into thio epoxy compounds
During purity, i.e., in conversion process due to side reaction generate the thio epoxy compounds of impurity content be influence
The reason of eyeglass form and aspect, discloses a kind of polymerism synthesis for reducing and obtaining after the thio epoxy compounds content of this impurity
Object and the method for reducing the content.
Summary of the invention
The project of invention
It is an object of the present invention to find out the further determining property that is had an impact to the form and aspect of thio epoxy base system optical material because
Element solves the form and aspect instability problem of thio epoxy base system optical material by controlling this factor.In particular, the purpose of the present invention
It is, is more easier the form and aspect unstable factor of control by finding out, a kind of as clear as crystal high-quality sulphur easy to manufacture is provided
Method for epoxy base system optical material and the polymerism synthetic for manufacturing it.
Technical solution of the invention
Each inventor of the invention chances on epichlorohydrin (epichlorohydrin) continuation as the substance migration that sets out
Reaction system is remained in, being changed into epithio for chlorethanol (epithiochlorohydrin) is to thio epoxy base system optics material
The principal element that the form and aspect of material have an impact.That is, due to continuing to remain in reaction system as the epichlorohydrin for the substance migration that sets out
In, during being put into thiocarbamide (thiourea), carrying out epithio (episulfide), it is changed into epithio for chlorethanol,
The epithio generates conclusive influence to the form and aspect of optical material for chlorethanol.In addition, confirm through each inventor of the invention,
Even if not controlling the thio epoxy group chemical combination of impurity generated due to side reaction in thio epoxy compounds manufacturing process individually
The content of object, epithio as long as control is set out in epichlorohydrin and thio epoxy compounds in substance for chloroethene alcohol content,
It can solve the form and aspect problem of thio epoxy base system optical material.
The present invention provides a kind of thio epoxy base system polymerism synthetic, contains thio epoxy compounds, and feature exists
In: the epithio of the thio epoxy compounds is 1 weight % or less for chloroethene alcohol content.The polymerism synthetic can be with
Including polyisocyanate compounds and/or poly-thiol compound.
Preferably, the thio epoxy compounds can react epichlorohydrin with the method synthesis included the following steps
Content is 1 weight % sulfide compound below and thiocarbamide, carries out the step of epithio.
The present invention provides a kind of manufacturing method of thio epoxy base system optical material polymerism synthetic polymerization.
The present invention is provided the thio epoxy base system optical material obtained with the manufacturing method and is constituted with the optical material
Optical mirror slip.
" thio epoxy base system optical material " includes polymerised sulphur generation ring in the case where being not particularly limited in the present invention
Optical material obtained from optical material obtained from oxo-compound and the thio epoxy group of copolymerization and sulphur urethane.
Invention effect
The present invention controls the epichlorohydrin content or thio epoxy group in the substance that sets out when synthesizing thio epoxy compounds
Epithio in compound can solve the form and aspect that thio epoxy base system optical material occurs for chloroethene alcohol content by easy way
Instability problem.The present invention can be with very high yield, the thio epoxy base system eyeglass of as clear as crystal high-quality easy to manufacture.
Specific embodiment
Thio epoxy compounds contained by polymerism synthetic of the invention are the changes with more than one thio epoxy group
Close object.Epithio is that 1 weight % thio epoxy compounds below can be manufactured by a variety of methods for chloroethene alcohol content.It is best
It is that thio epoxy compounds are carried out by allowing epichlorohydrin content to react for 1 weight % sulfide compound below with thiocarbamide
The step of epithio, synthesizes.For example, addition epichlorohydrin and hydrogen sulfide gas, manufacture the chloro- 3- sulfydryl -2- propyl alcohol (1-chloro- of 1-
After 3-mercapto-2-propanol), addition reaction (addition reaction) is carried out with epichlorohydrin again, or first make
After making the chloro- 3- sulfydryl -2- propyl alcohol of 1-, addition reaction is carried out with epichlorohydrin again, or first manufactures the chloro- 3- sulfydryl -2- propyl alcohol of 1-
Afterwards, after carrying out itself disulphide (disulphide) change reaction, epoxy compounds are manufactured.During this, it is difficult completely
Epichlorohydrin is removed, but by sustained response, its remaining quantity is controlled in 1 weight % hereinafter, preferably 0.5 weight % is hereinafter, system
Make thio epoxy compounds.The thio epoxy compounds so manufactured can allow optical material to have and optimize form and aspect.
The thio epoxy compounds 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 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) hexamethylene
Alkane) (bis (β-epithiopropylthio) cyclo hexane), 1,3 and 1,4- bis- (β-epithio is for propyl dithiocarbamate methyl) ring
Hexane) (bis (β-epithiopropylthiomethyl) cyclo hexane), two [4- (β-epithio is for propyl dithiocarbamate) hexamethylenes
Base] methane (bis [4- (β-epithiopropylthio) cyclo hexyl] methane), [4- (β-epithio generation third of 2,2- bis-
Base is thio) 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]
) etc. sulfide with 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) benzene
Base] sulphur (bis [4- (β-epithiopropylthio) phenyl] sulfin), 4,4- bis- (β-epithio is for propyl dithiocarbamate) hexichol
Base (4,4-bis (β-epithiopropylthio) biphenyl) etc. has the episulfide compound of aromatic series bone；2,5-
Two (β-epithio is for propyl dithiocarbamate methyl) -1,4- dithiane (2,5-bis (β-epithiopropylthiomethyl) -1,4-
Dithiane), (β-epithio is for propyl dithiocarbamate ethylenebis dithiocarbamate the methyl) -1,4- dithiane of 2,5- bis- (2,5-bis (β-epithiop
Ropylthioethylthiomethyl) -1,4-dithiane), 2,5- bis- (β-epithio is for propyl dithiocarbamate ethyl group) -1,4- two
Thiophene alkane (2,5-bis (β-epithiopropylthioethyl) -1,4-dithiane), (β-epithio is for propylthio by 2,3,5- tri-
For ethyl group) -1,4- dithiane (2,3,5-tri (β-epithiopropylthioethyl) -1,4-dithiane) etc. has
The episulfide compound of dithiane (dithiane) chain bone；2- (2- β-epithio is for propyl dithiocarbamate ethylenebis dithiocarbamate) -1,3- two
(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) is thio] -3- (β-epithio generation
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-ring sulfopropyl) sulfide (bis- (β-
Epithiopropyl) sulfide) etc. with aliphatic bone episulfide (episulfide) compound.In addition to this,
As thio epoxy compounds, the chlorine substitution product of the compound of band vulcanization (episulfide) base can also be used
The halogen families substitution product such as (substitution product), bromine substitution product, alkyl substitution product (alkyl
Substitution product), alkoxy substitution product (alkoxy substitution product), nitro replace produce
Object (nitro substitution product) or prepolymer (prepolymer) type denatured products with polymercaptan
(denaturant)。
Two-(2,3- ring sulfopropyl) sulfide (bis- (2,3- are preferably used as thio epoxy compounds
Epithiopropyl) sulfide), two-(2,3- ring sulfopropyl) disulphide (bis- (2,3-epithiopropyl)
Disulfide), 2,3- epidithio is for propylthio (2,3- epithio is for propylthio) sulfide, 2,3- epidithio for propylthio (2,3-
Epithio is for propylthio) disulphide, 1,3 and 1,4- bis- (β-epithio is for propyl dithiocarbamate) hexamethylene, 1,3 and the (β-epithio of 1,4- bis-
For propyl dithiocarbamate methyl) hexamethylene, 2,5- bis- (β-epithio is for propyl dithiocarbamate methyl) -1,4- dithiane, (β-epithio generation of 2,5- bis-
Propyl dithiocarbamate ethylenebis dithiocarbamate methyl) -1,4- dithiane, 2- (2- β-epithio is for propyl dithiocarbamate ethylenebis dithiocarbamate) (β-epithio of -1,3- two
One or more of for propyl dithiocarbamate) propane.
The polymerism synthetic can also include polyisocyanate compounds.The polyisocyanate compounds are without spy
It does not limit, at least compound of 1, band or more isocyanate group and/or different thiocyano- can be used.For example, using a kind with
Upper hexamethylene diisocyanate (hexa methylene diisocyanate), 2,2- dimethylpentane diisocyanate (2,
2-dimethyl pentane diisocyanate), 2,2,4- trimethylhexane diisocyanate (2,2,4-trimethyl
Hexane diisocyanate), butene diisocyanate (butene diisocyanate), 1,3- butadiene -1,4- two it is different
Cyanate (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 esters (bis (isocyanato ethyl)
Carbonate), the aliphatic isocyanates such as two (isocyanatoethyl) ether (bis (isocyanato ethyl) ether)
It closes object (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 hexylmethane diisocyanate), cyclohexane diisocyanate (cyclo hexane
Diisocyanate), methylcyclohexane diisocyanate (methyl cyclo hexane diisocyanate), dicyclohexyl
Dimethylmethane isocyanates (dicyclo hexyl dimethyl methane isocyanate), two ring of 2,2- dimethyl
The alicyclic isocyanic acids such as hexyl methane isocyanates (2,2-dimethyl dicyclo hexyl methane isocyanate)
Ester compounds (Cycloaliphatic isocyanate compounds)；Two (isocyanatoethyl) benzene (bis
(isocyanatoethyl) benzene), two (isocyanate group propyl) benzene (bis (isocyanato propyl) benzene),
Two (isocyanate group butyl) benzene (bis (isocyanato butyl) benzene), two (isocyanatometyl) naphthalene (bis
(isocyanato methyl) naphthalene), two (isocyanatometyl) diphenyl ether (bis (isocyanato
Methyl) diphenyl ether), phenylene vulcabond (phenylene diisocyanate), ethylphenylene two
Isocyanates (ethyl phenylene diisocyanate), isopropyl phenylene diisocyanate (isopropyl
Phenylene diisocyanate), dimethylphenylene diisocyanate (dimethyl phenylene
Diisocyanate), diethyl phenylene vulcabond (diethyl phenylene diisocyanate), diisopropyl
Phenylene vulcabond (diisopropyl phenylene diisocyanate), trimethylbenzene triisocyanate
(trimethyl benzene triisocyanate), benzene triisocyanate (benzene triisocyanate), biphenyl two
Isocyanates (biphenyl diisocyanate), toluidine diisocyanate (toluidine diisocyanate), 4,
4'- methyl diphenylene diisocyanate (4,4'-diphenyl methane diisocyanate), toluene di-isocyanate(TDI)
(tolylene diisocyanate), eylylene diisocyanate (xylylene diisocyanate (XDI)), 3,
3'- dimethyl diphenylmethane -4,4'- diisocyanate (3,3'-dimethyl diphenyl methane-4,4'-
Diisocyanate), bibenzyl -4,4'- diisocyanate (bibenzyl-4,4'-diisocyanate), two (isocyanate group benzene
Base) ethylene (bis (isocyanato phenyl) ethylene), 3,3'- dimethoxy-biphenyl -4,4'- diisocyanate (3,
3'-dimethoxy biphenyl-4,4'-diisocyanate), hexahydro phenylene diisocyanate (hexa hydrobenzene
Diisocyanate), hexahydro diphenyl methane -4,4'- diisocyanate (hexa hydro diphenyl methane-4,
The aromatic isocyanate compounds (aromatic isocyanate compounds) such as 4'-diisocyanate)；Two (isocyanides
Acidic group ethyl) sulfide (bis (isocyanato ethyl) sulphide), two (isocyanate group propyl) sulfide (bis
(isocyanato propyl) sulphide), two (isocyanatohexyl) sulfide (bis (isocyanato hexyl)
Sulphide), two (isocyanatometyl) sulphurs (bis (isocyanato methyl) sulfone), two (isocyanatometyls)
Disulphide (bis (isocyanato methyl) disulphide), two (isocyanate group propyl) disulphide (bis
(isocyanato propyl) disulphide), two (isocyanatometyl is thio) methane (bis (isocyanato methyl
Thio) methane), two (isocyanatoethyl is thio) methane (bis (isocyanato ethyl thio) methane), two
(isocyanatoethyl is thio) ethane (bis (isocyanato ethyl thio) ethane), two (isocyanatometyl is thio)
Ethane (bis (isocyanato methyl thio) ethane), 1,5- diisocyanate base -2- isocyanatometyl -3- are thio
The sulfur-bearings aliphatic isocyanates such as pentane (1,5-diisocyanato-2-isocyanato methyl-3-thia pentane)
Compound (sulfur aliphatic isocyanate compounds)；Diphenyl sulfide -2,4- diisocyanate
(diphenyl sulphide-2,4-diisocyanate), diphenyl sulfide -4,4'- diisocyanate (diphenyl
Sulphide-4,4'-diisocyanate), 3,3'- dimethoxy-4 ', 4'- diisocyanate base benzhydryl thio-ether (3,
3'-dimethoxy-4,4'-diisocyanato dibenzyl thio ether), two (4- isocyanatometyl benzene) vulcanization
Object (bis (4-isocyanato methyl benzene) sulphide), the thio ethylene glycol -3,3- of 4,4- methoxybenzene
Diisocyanate (4,4-methoxy benzene thio ethylene glycol-3,3-diisocyanate), diphenyl
Disulphide -4,4'- diisocyanate (diphenyl disulphide-4,4'-diisocyanate), 2,2'- dimethyl two
Phenyl disulfide -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), two isocyanide of 3,3'- dimethyldiphenyldisulfide -6,6'-
Acid esters (3,3'-dimethyl diphenyl disulphide-6,6'-diisocyanate), 4,4'- dimethyl diphenyl two
Sulfide -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 aromatics isocyanate compound
(sulfur aromatic isocyanate compounds)；2,5- diisocyanate base thiophene (2,5-diisocyanato
Thiophene), 2,5- bis- (isocyanatometyl) thiophene (2,5-bis (isocyanato methyl) thiophene), 2,5-
Diisocyanate base thiophane (2,5-diisocyanato Tetra hydrothiophene), (the isocyanate group first of 2,5- bis-
Base) thiophane (2,5-bis (isocyanato methyl) Tetra hydrothiophene), (the isocyanate group first of 3,4- bis-
Base) thiophane (3,4-bis (isocyanato methyl) Tetra hydrothiophene), 2,5- diisocyanate base -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- diisocyanate base -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-1,3- dithiolane
Sulfur heterocyclic rings isocyanate compounds such as (4,5-bis (isocyanato methyl) -2-methyl-1,3-dithiolane)
(sulfur heterocyclic isocyanate compounds).The chlorine substitution product of these compounds can also be used
The halogen families substitution product such as (substitution product), bromine substitution product, alkyl substitution product (alkyl
Substitution product), alkoxy substitution product (alkoxy substitution product), nitro replace produce
Object (nitro substitution product) or prepolymer (prepolymer) type denatured products with multivalence alcohol or mercaptan
(denaturant), carbodiimides (carbodiimide) denatured products, urea (urea) denatured products, biuret
(biuret) denatured products or dimer (dimer) are changed or trimer (trimer) changes reaction product etc..As polyisocyanate
Ester compounds are preferably using selected from isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), hexamethylene
Diisocyanate (H12MDI), eylylene diisocyanate, 3,8- bis- (isocyanatomethyl) tricyclic [5,2,1,02,6] last of the ten Heavenly stems
Alkane (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-
Two (isocyanatomethyl) tricyclic [5,2,1,02,6] decane (4,8-bis (isocyanatemethyl) tri cyclo [5,2,1,
02,6] decane), 2,5- bis- (isocyanatomethyl) two ring [2,2,1] heptane (2,5-bis (isocyanatemethyl)
Bicyclo [2,2,1] heptane), 2,6- bis- (isocyanatomethyl) two ring [2,2,1] heptane (2,6-bis
(isocyanatemethyl) bicyclo [2,2,1] heptane) a kind or more.
The polymerism synthetic can also include poly-thiol compound.The poly-thiol compound is not particularly limited,
As long as the compound with 1 or more mercapto, that is, can be used alone or mix two or more use.For example, can be used two
(2- mercaptoethyl) sulfide (bis (2-mercapto ethyl) sulfide), 4- mercapto methyl -1,8- dimercapto -3,6- two
Thio octane (4-mercapto methyl-1,8-dimercapto-3,6-dithia octane), (the 2- sulfydryl second of 2,3- bis-
Base is thio) propane -1- mercaptan (2,3-bis (2-mercapto ethyl thio) propane-1-thiol), bis- (sulfydryl of 2,2-
Methyl) -1,3- propanedithiol (2,2-bis (mercapto methyl) -1,3-propane dithiol), four (sulfydryl first
Base) methane (Tetrakis (mercapto methyl) methane)；Two mercaptan of 2- (2- mercaptoethyl is thio) propane -1,3-
(2- (2-mercapto ethyl thio) propane-1,3-dithiol), 2- (2,3- bis- (2- mercaptoethyl is thio) propyl
It is thio) ethane thiol (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- dimercaptos third
Alcohol) disulphide (bis (2,3-dimercapto propanol) disulfide), 1,2- bis- (2- mercaptoethyl is thio) -3-
Thio propane (1,2-bis (2-mercapto ethyl thio) -3-mercapto propane), (2- (the 2- sulfydryl of 1,2- bis-
Ethylenebis dithiocarbamate) -3- mercaptopropyi is thio) ethane (1,2-bis (2- (2-mercapto ethyl thio) -3-mercapto
Propyl thio) ethane), two (2- (2- mercaptoethyl is thio) -3- mercaptopropyi) sulfide (bis (2- (2-mercapto
Ethyl thio) -3-mercapto propyl) sulfide), two (2- (2- mercaptoethyl is thio) -3- mercaptopropyi) two sulphur
Compound (bis (2- (2-mercapto ethyl thio) -3-mercapto propyl) disulfide), 2- (2- mercaptoethyl
It is thio) -3-2- sulfydryl -3- [3- sulfydryl -2- (2- mercaptoethyl is thio)-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--(the-the third acyloxymethyl of 3- sulfydryl)-butyl ester (2,2-
Bis- (3-mercapto-propionyl oxymethyl)-butyl ester), 2- (2- mercaptoethyl is thio) -3- (2- (2-
[3- sulfydryl -2- (2- mercaptoethyl is thio)-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), two (mercapto methyl) -3,6,9 (4R, 11S) -4,11-,
Four decane -1,14- of 12- tetrathio, two mercaptan ((4R, 11S) -4,11-bis (mercapto methyl) -3,6,9,12-Tetra
Thia Tetra decane-1,14-dithiol), two mercaptan of (S) -3- ((R-2,3- dimercapto propyl) is thio) propane -1,2-
((S) -3- ((R-2,3-dimercapto propyl) thio) propane-1,2-dithiol), (4R, 14R) -4,14- two
Thio two mercaptan of heptane -1,17- ((4R, the 14R) -4,14-bis (mercapto of (mercapto methyl) -3,6,9,12,15- five
Methyl) -3,6,9,12,15-Penta thia heptane-1,17-dithiol), (S) -3- ((R-3- sulfydryl -2- ((2-
Mercaptoethyl) thio) propyl) thio) propyl) thio) -2- ((2- mercaptoethyl) is thio) 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'- bis- thio two (two mercaptan of propane -1,2-) (3,3'-dithio bis
(propane-1,2-dithiol)), the thio heptadecane one of (7R, 11S) -7,11- two (mercapto methyl) -3,6,9,12,15- five
Hundred alkane -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 thio ten
Eight alkane -1,18-, two mercaptan ((7R, 12S) -7,12-bis (mercapto methyl) -3,6,9,10,13,16-hexa thia
Octadecane-1,18-dithiol), the thio hendecane (5,7- of 5,7- dimercapto methyl -1,11- dimercapto -3,6,9- three
Dimercapto methyl-1,11-dimercapto-3,6,9-trithia undecane), 4,7- dimercapto methyl-1,
Thio hendecane (the 4,7-dimercapto methyl-1,11-dimercapto-3,6,9- of 11- dimercapto -3,6,9- three
Trithia undecane), the thio hendecane (4,8- of 4,8- dimercapto methyl -1,11- dimercapto -3,6,9- three
Dimercapto methyl-1,11-dimercapto-3,6,9-trithia undecane), (the 3- sulfydryl third of pentaerythrite four
Acid esters) (Penta erythritol Tetrakis (3-mercapto propionate)), three methylol propane, three (3- sulfydryl
Propionic ester) (trimethylol propane tris (3-mercapto propionate)), (the 2- sulfydryl vinegar of pentaerythrite four
Hydrochlorate) (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 is thio) propane (1,1,3,3-Tetrakis (mercapto methyl thio) propane), 1,1,2,
2- tetra- (mercapto methyl is thio) ethane (1,1,2,2-Tetrakis (mercapto methyl thio) ethane), 4,6- bis-
(mercapto methyl is thio) -1,3- dithiane (4,6-bis (mercapto methyl thio) -1,3-dithiane) and 2- (2,
2- bis- (sulfydryl dimethyl thio) ethyl) -1,3- dithiane (2- (2,2-bis (mercapto dimethyl thio)
Ethyl) -1,3-dithiane) etc..Except, as long as the compound with 1 or more mercapto, it can using a kind of or
Person is mixed with two or more.Isocyanates or thio epoxy group chemical combination are added alternatively, it is also possible to use to poly-thiol compound
Object, vulcanization cyclopropane (Thietane) or the compound combined with unsaturation used with modifier, are obtained by prepolymerization
The polymerization denatured products arrived.As poly-thiol compound preferably to two (2- mercaptoethyl) sulfide or two (2- mercaptoethyls)
Sulfide mixes a kind or more other poly-thiol compounds and uses.
Polymerism synthetic of the invention may include internal mold release, and internal mold release includes preferably acid phosphoric acid ester
Compound.Acid phosphoesterase compound is by phosphorus pentoxide (P2O5) addition 2~3 moles alcoholic compound manufacture.Here,
By the alcohol type used, diversified forms phosphate compound can be obtained.Representative oriented aliphatic alcohol adds ethylene oxide
Or propylene oxide, or the type to the addition ethylene oxide such as nonyl phenol (nonylphenol) base or propylene oxide.The present invention
Polymerism synthetic as internal mold release use addition ethylene oxide or propylene oxide phosphate compound when, can obtain
The optical material good, of fine qualities to release property.As internal mold release, it is best to use from 4-PENPP [polyethylene glycol oxide nonyl
Alkylphenol ether phosphate (poly oxy ethylene nonyl phenol ether phosphate) (addition ethylene oxide 5
Mole 5 weight %, addition 4 moles of 80 weight %, 10 weight % of 3 moles of addition, 5 weight % of 1 mole of addition)], 8-
PENPP [polyoxyethylene nonyl phenol ether phosphate (3 weight % of 9 moles of ethylene oxide of addition, 80 weights of 8 moles of addition
Measure %, 5 weight % of 9 moles of addition, 6 weight % of 7 moles of addition, 6 weight % of 6 moles of addition)], 12-PENPP [polyoxy
Change ethylene nonyl phenol ether phosphate (3 weight % of 13 moles of ethylene oxide of addition, 80 weight % of 12 moles of addition, addition
11 moles of 8 weight %, 3 weight % of 9 moles of addition, 6 weight % of 4 moles of addition)], 16-PENPP [polyethylene glycol oxide nonyl
Alkylphenol ether phosphate (3 weight % of 17 moles of ethylene oxide of addition, 79 weight % of 16 moles of addition, 15 moles of addition
10 weight %, 4 weight % of 14 moles of addition, 4 weight % of 13 moles of addition)], 20-PENPP [polyoxyethylene nonyl benzene
Phenolic ether phosphate (5 weight % of 21 moles of ethylene oxide of addition, 76 weight % of 20 moles of addition, 7 weights of 19 moles of addition
Measure %, 6 weight % of 18 moles of addition, 4 weight % of 17 moles of addition)], 4-PPNPP [polypropylene oxide nonylphenyl ether phosphorus
Acid esters (poly oxy propylene nonyl phenol ether phosphate) (5 weights of 5 moles of propylene oxide of addition
Measure %, 80 weight % of 4 moles of addition, 10 weight % of 3 moles of addition, 5 weight % of 1 mole of addition)], 8-PPNPP is [poly-
Propylene oxide nonyl phenol ether phosphate (3 weight % of 9 moles of propylene oxide of addition, 80 weight % of 8 moles of addition, addition 9
Mole 5 weight %, addition 7 moles of 6 weight %, 6 weight % of 6 moles of addition)], 12-PPNPP [polypropylene oxide nonyl
Phenol ether phosphate (3 weight % of 13 moles of propylene oxide of addition, 80 weight % of 12 moles of addition, 8 weights of 11 moles of addition
Measure %, 3 weight % of 9 moles of addition, 6 weight % of 4 moles of addition)], 16-PPNPP [polypropylene oxide nonylphenyl ether phosphorus
(3 weight % of 17 moles of propylene oxide of addition, 79 weight % of 16 moles of addition, 10 weight % of 15 moles of addition add acid esters
Add 14 moles of 4 weight %, 4 weight % of 13 moles of addition)], 20-PPNPP [polypropylene oxide nonyl phenol ether phosphate
(5 weight % of 21 moles of propylene oxide of addition, 76 weight % of 20 moles of addition, 7 weight % of 19 moles of addition, addition 18
Mole 6 weight %, 17 moles of 4 weight % of addition)], Zelec UNTMMore than one phosphate compounds of middle selection.?
With the purpose of under, the halogen family substituent and various other substituents of this phosphate compound also can be used.
Polymerism synthetic of the invention is in order to improve the optics physical property of optical material, to adjust impact resistance, specific gravity
And for the purpose of monomer (monomer) viscosity etc., olefin(e) compound can be additionally added as modifier.It can be used as reactivity
Alkene (olefin) compound of modifier addition, than if any benzyl acrylate (benzylacrylate), benzyl first
Base acrylate (benzylmethacrylate), butoxy ethyl group acrylate (butoxy ethylacrylate), fourth
Oxygroup methylmethacrylic acid rouge (butoxy methyl methacrylate), cyclohexylacrylic rouge (cyclo hexyl
Acrylate), cyclohexyl methacrylate rouge (cyclo hexyl methacrylate), 2- hydroxyl ethane base acrylate
(2-hydroxyl ethylacrylate), 2- hydroxymethyl, methyl acrylate (2-hydroxyl methyl
Methacrylate), glycidyl acrylate (glycidyl acrylate), glycidyl methacrylate
(glycidyl methacrylate), phenoxy group ethyl group acrylate (phenoxy ethylacrylate), phenoxy group second
Alkyl methacrylate rouge (phenoxy ethylmethacrylate), phenyl methyl acrylate
(phenylmethacrylate), ethylene glycol diacrylate rouge (ethylene glycol diacrylate), ethylene second
Glycol dimethacrylate rouge (ethylene glycol dimethacrylate), diethyl allyl diglycol diacrylate rouge
(diethylene glycol diacrylate), divinyl ethyleneglycol dimethacrylate rouge (diethylene glycol
Dimethacrylate), trietbhlene glycol diacrylate rouge (triethylene glycol diacrylate), triethylene
Ethyleneglycol dimethacrylate rouge (triethylene glycol dimethacrylate), four ethylene glycol diacrylates
Rouge (tetra ethylene glycol diacrylate), four ethylene glycol dimethacrylate rouge (tetra
Ethylene glycol dimethacrylate), polyethylene glycol diacrylate rouge (polyethylene glycol
Diacrylate), polyethylene glycol dimethacrylate rouge (polyethylene glycol dimethacrylate), new
Amyl ethylene glycol diacrylate rouge (neopentyl glycol diacrylate), neopentyl ethyleneglycol dimethacrylate rouge
(neopentyl glycol dimethacrylate), ethylene glycol diepoxy propylacrylate rouge (ethylene
Glycol bisglycidyl acrylate), ethylene glycol diepoxy propyl methyl acid rouge (ethylene glycol
Bisglycidyl methacrylate), biphenol A diacrylate rouge (bisphenol A diacrylate), biphenol A bis-
Methacrylate (bisphenol A dimethacrylate), 2,2- bis- (4- allyl oxygen ethoxyl phenenyl) propane (2,2-
Bis (4-acryloxy ethoxy phenyl) propane), 2,2- bis- (4- methallyl 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) third
Alkane (2,2-bis (4-methacryloxydiethoxy phenyl) propane), biphenol F diacrylate rouge (bisphenol
F diacrylate), biphenol F dimethacrylate rouge (bisphenol F dimethacrylate), (the 4- allyl of 1,1- bis-
Oxygen ethoxyl phenenyl) methane (1,1-bis (4-acryloxy ethoxy phenyl) methane), (the 4- methallyl of 1,1- bis-
Oxygen ethoxyl phenenyl) methane (1,1-bis (4-methacryloxy ethoxy phenyl) methane), (the 4- allyl of 1,1- bis-
Oxygen diethoxy phenyl) methane (1,1-bis (4-acryloxy diethoxy phenyl) methane), (the 4- methyl of 1,1- bis-
Ethyoxyl diethoxy phenyl) methane (1,1-bis (4-methacryloxydiethoxy phenyl) methane), dihydroxy first
Three tristane diacrylate rouge of base (dimethylol tricyclo decane diacrylate), trimethylolpropane tris
Acrylate (trimethylol propane triacrylate), trimethylol propane trimethyl acrylate
(trimethylol propane trimethacrylate), glycerine diacrylate rouge (glycerol diacrylate),
Glycerine dimethacrylate rouge (glycerol dimethacrylate), five antierythrites, three acrylate (Penta
Erythritol triacrylate), five antierythrite tetrapropylene acid rouge (Penta erythritol tetra
Acrylate), five antierythrite tetramethyl acrylates (Penta erythritol tetra methacrylate), methyl
Thioacrylic acid rouge (methyl thio acrylate), methylthiomethyl acrylate (methyl thio
Methacrylate), phenyl acrylate (phenylthio acrylate), dibenzylsulfide are for methacrylate
Two mercaptan diacrylate rouge (xylylene dithiol of (benzylthio methacrylate), xyxylene
Diacrylate), two mercaptan dimethacrylate rouge of xyxylene (xylylene dithiol dimethacrylate), mercapto
Base ethyl group sulfide diacrylate rouge (mercapto ethylsulfide diacrylate), ethane thiol base sulfide two
(methyl) acrylates ((meth) such as methacrylate (mercapto ethylsulfide dimethacrylate)
Acrylate) compound and allyl glycidyl ethers (allyl glycidyl ether), diallyl phthalate
(diallyl phthalate), diallyl terephthalic acid's ester (diallyl terephthalate), diallyl isophthalic two
Acid esters (diallyl isophthalate), diallylcarbonate (diallyl carbonate), diethyl allyl diglycol diene
Allyls (allyl) compounds, styrene such as propyl carbonate (diethylene glycol bisallyl carbonate)
(styrene), chlorostyrene (chlorostyrene), methyl styrene (methyl styrene), bromostyrene
(bromostyrene), dibromo-benzene ethylene (dibromostyrene), divinylbenzene (divinyl benzene), 3,9-
The vinyl (vinyl) such as divinyl spiral shell two (m- diepoxide for example) (3,9-divinyl Spiro bi (m-dioxane)) are changed
Object is closed, but workable compound is not limited to the compound of above example.These alkene (olefin) compounds can be independent
Or mix two or more use.
Optical material of the invention is obtained by injection molding polymerization.It is sealed that is, polymer composition is injected by sealing element or adhesive tape
Mold between, carry out polymerization reaction.Here, according to the requirement physical property of glass lens, vacuum deaerator can be carried out as needed or is added
The filtration treatments such as pressure, decompression.Polymerizing condition is by the type and dosage of polymerism synthetic, catalyst, and the shape presentation of mold is very
Big difference, therefore do not limit, but at a temperature of about -50~150 DEG C, it was carried out through 1~50 hour.Sometimes according to situation, 10
It maintains or is gradually warmed up under~150 DEG C of temperature ranges, being carried out within 1~48 hour hardening is advisable.
By hardening obtained thio epoxy compounds and isocyanate compound and mercaptan compound copolymer, according to
It needs that the processing such as anneal can be carried out.Treatment temperature is usually 50~150 DEG C, and preferably 90~140 DEG C.
In addition to this, polymerism synthetic of the invention presses well known forming method, may include various additives, such as
Chain extender (chain extender), crosslinking agent (cross linking agent), polymerization initiator (polymerization
Initiator), internal mold release, light stabilizer, heat stabilizer, antioxidant, ultraviolet absorbing agent, coloring agent, organic
The various additives such as pigment, inorganic pigment, filler, adhesiveness reinforcing agent.Polymerization initiator (catalyst) is important to having hardened
Effect.The type of catalyst is usually using epoxy curing agent, but strong amine can allow isocyanates vigorous reaction, and when use should be more
Filling meaning.The present invention mainly uses Barbiturates, phosphonium salt (phosphonium salt) class, hydrogen phosphide (phosphine) class of amine
And three-level amine with electron-withdrawing group (electron withdrawing group), lewis acid (Lewis acid) class, from
By base initiator (radical initiators) etc., the type and usage amount of catalyst can be different.
Copolymer resin of the invention, mold when by replacement injection molding polymerization, can obtain the formed body of various shapes,
It can be used as the various optical materials such as eyeglass, camera eyeglass, light emitting diode (LED) to use.In particular, resin of the invention is clear
Clear transparent, being suitable as correcting lens, sunglasses eyeglass, fashion eyeglass, color-changing lens, camera eyeglass, Optical devices eyeglass etc. makes
With.
The optical mirror slip obtained through the invention can form coating on two sides as needed.There is priming paint as coating
(primer) layer, sclerocortex, anti-reflection layer, anti-fog layer, anti-contamination layer, waterproof layer.These coatings can be formed separately, or
Multilayer forms multiple coatings.When coating is implemented on two sides, two sides is respectively formed different coating or identical coating.
Embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution carry out clear, complete description, it is clear that described embodiments are some of the embodiments of the present invention, rather than
Whole embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work premise
Under every other embodiment obtained, shall fall within the protection scope of the present invention.
Test and evaluation method
Form and aspect: the implementation that the YI value of the resin detected with colour difference meter is 0.01 weight % for chloroethene alcohol content relative to epithio
Example 1, present ± 1 or more gap when be recorded as " X ", deficiency ± 1 when be recorded as " O ".
Refractive index and Abbe number: IT the and DR-M4 model Abbe dioptrometer of Atago company has been used, has been detected at 20 DEG C.
[synthesis example 1] two (the chloro- 2- hydroxypropyl of 3-) sulfide (bis (3-chloro-2-hydroxylpropyl)
Sulfide) the synthesis of (BCP-1)
To 10 liters of reactor additions epichlorohydrin (epichlorohydrin) (5563g, 60.12mol) and methanol (2500g)
Afterwards, reaction temperature is adjusted to 6 DEG C, when reaction temperature reach 6 DEG C when addition caustic soda (caustic soda) (50%aq,
5g).NaSH.xH is added into another 10 liters of reactors2O (70%NaSH, 3660g, 45.75mol), methanol (1000g) and water
(500g) is slowly added dropwise hydrochloric acid, the hydrogen sulfide of generation is added to epichlorohydrin solution, is obtained after stirring thawing completely
Two (the chloro- 2- hydroxypropyl of 3-) sulfide.The end point of reaction is to confirm end product, epichlorohydrin and the chloro- 2- hydroxyl of 3- by GC
Base-propyl -1- mercaptan compound completely disappears, the time point that two (the chloro- 2- hydroxypropyl of 3-) sulfide generate.In order to remove excess
3- chlorine-2-hydroxyl-propyl -1- mercaptan, by GC calculate relative integral than content, be added to epichlorohydrin.It is analyzed, is closed by GC
Two (the chloro- 2- hydroxypropyl of 3-) sulfide (BCP-1) (6388.73g, the 58.31mol for being 2.2% at epichlorohydrin content
97%).
The synthesis of [synthesis example 2] two (the chloro- 2- hydroxypropyl of 3-) sulfide (BCP-2)
To 10 liters of reactor additions epichlorohydrin (epichlorohydrin) (5563g, 60.12mol) and methanol (2500g)
Afterwards, reaction temperature is adjusted to 6 DEG C, when reaction temperature reach 6 DEG C when addition caustic soda (caustic soda) (50%aq,
5g).NaSH.xH is added into another 10 liters of reactors2O (70%NaSH, 3660g, 45.75mol), methanol (1000g) and water
(500g) is slowly added dropwise hydrochloric acid, the hydrogen sulfide of generation is added to epichlorohydrin solution, is obtained after stirring thawing completely
Two (the chloro- 2- hydroxypropyl of 3-) sulfide.It is added to two (the chloro- 2- hydroxypropyl of the 3-) sulfide that epichlorohydrin content is 2.2 weight %
Hydrogen sulfide gas is analyzed by GC, has synthesized two (the chloro- 2- hydroxypropyl of 3-) sulfide that epichlorohydrin content is 0.2 weight %
(BCP-2) (6456.11g, 58.92mol, 98%).
The synthesis of [synthesis example 3] two (the chloro- 2- hydroxypropyl of 3-) sulfide (BCP-3)
To 10 liters of reactor additions epichlorohydrin (epichlorohydrin) (5563g, 60.12mol) and methanol (2500g)
Afterwards, reaction temperature is adjusted to 6 DEG C, when reaction temperature reach 6 DEG C when addition caustic soda (caustic soda) (50%aq,
5g).NaSH.xH is added into another 10 liters of reactors2O (70%NaSH, 3660g, 45.75mol), methanol (1000g) and water
(500g) is slowly added dropwise hydrochloric acid, the hydrogen sulfide of generation is added to epichlorohydrin solution, is obtained after stirring thawing completely
Two (the chloro- 2- hydroxypropyl of 3-) sulfide.The end point of reaction is to confirm such as there is 3- chlorine-2-hydroxyl-propyl -1- sulphur by GC
Alcohol then calculates relative integral ratio by GC, adds epichlorohydrin, has synthesized two (the chloro- 2- of 3- that epichlorohydrin content is 0.7 weight %
Hydroxypropyl) sulfide (BCP-3) (6455g, 58.91mol, 98%).
The synthesis of [synthesis example 4] two (the chloro- 2- hydroxypropyl of 3-) sulfide (BCP-4)
To 10 liters of reactor additions epichlorohydrin (epichlorohydrin) (5563g, 60.12mol) and methanol (2500g)
Afterwards, reaction temperature is adjusted to 6 DEG C, when reaction temperature reach 6 DEG C when addition caustic soda (caustic soda) (50%aq,
5g).NaSH.xH is added into another 10 liters of reactors2O (70%NaSH, 3660g, 45.75mol), methanol (1000g) and water
(500g) is slowly added dropwise hydrochloric acid, the hydrogen sulfide of generation is added to epichlorohydrin solution, is obtained after stirring thawing completely
Two (the chloro- 2- hydroxypropyl of 3-) sulfide.It is added to two (the chloro- 2- hydroxypropyl of the 3-) sulfide that epichlorohydrin content is 2.2 weight %
Hydrogen sulfide gas has synthesized two (the chloro- 2- hydroxypropyl of 3-) sulfide (BCP-4) that epichlorohydrin content is 0.5 weight %
(6521.11g, 59.51mol, 99%).
The synthesis of [synthesis example 5] two (2,3 ring sulfopropyl) sulfide (EPS-1)
Two (the chloro- 2- hydroxypropyls of 3- that the epichlorohydrin content synthesized to 10 liters of reaction vessel addition synthesis examples 2 is 0.2 weight %
Base) sulfide (BCP-2) (1072.48g, 4.89mol), toluene (toluene) 1300g, methanol 800g, it is stirred, anti-
Temperature is answered to be transferred to 30 DEG C.It when reaching 25 DEG C, is added dropwise NaOH (50%aq., 783.08g, 9.78mol), reaction temperature when dropwise addition
Maintain temperature at 35 DEG C~37 DEG C, reacted.It is added dropwise and carries out within 1 hour, placed about under the conditions of 37 DEG C later
It ferments within 30 minutes, after fermentation, adds toluene 2000g, about stir 10 minutes, be layered, with water to supernatant organic matter
2 cleanings are carried out, moisture removal is removed to greatest extent, adds methanol 400g again to organic layer organic solution, is stirred, reacting
Thiourea (thiourea) (1117.65g, 14.30mol) and acetic anhydride (70g) are added at 8 DEG C of temperature, reaction temperature tune
Height reacts 18 hours to 18 DEG C.It reacts end point to confirm by HPLC, the substance that sets out disappears, and product is not further change in
Subject to.After reaction, stop stirring, wash with water 3 organic layers obtained by layer separation, remove organic solvent, obtain
Epithio for chloroethene alcohol content be 0.2 weight % two-(2,3- ring sulfopropyl) sulfide (EPS-1) (593g, 3.32mol,
68%).Measuring refractive index (nD, 20 DEG C) is 1.614.
The synthesis of [synthesis example 6] two (2,3 ring sulfopropyl) sulfide (EPS-2)
Two (the chloro- 2- hydroxypropyls of 3- that the epichlorohydrin content synthesized to 10 liters of reaction vessel addition synthesis examples 4 is 0.5 weight %
Base) sulfide (BCP-4) (1072.48g, 4.89mol), toluene (toluene) 1300g, methanol 800g, it is stirred, anti-
Temperature is answered to be transferred to 30 DEG C.It when reaching 25 DEG C, is added dropwise NaOH (50%aq., 783.08g, 9.78mol), reaction temperature when dropwise addition
Maintain temperature at 35 DEG C~37 DEG C, reacted.It is added dropwise and carries out within 1 hour, placed about under the conditions of 37 DEG C later
It ferments within 30 minutes, after fermentation, adds toluene 2000g, about stir 10 minutes, be layered, with water to supernatant organic matter
2 cleanings are carried out, moisture removal is removed to greatest extent, adds methanol 400g again to organic layer organic solution, is stirred, reacting
Thiourea (thiourea) (1117.65g, 14.30mol) and acetic anhydride (70g) are added at 8 DEG C of temperature, reaction temperature tune
Height reacts 18 hours to 18 DEG C.It reacts end point to confirm by HPLC, the substance that sets out disappears, and product is not further change in
Subject to.After reaction, stop stirring, wash with water 3 organic layers obtained by layer separation, remove organic solvent, obtain
Epithio for chloroethene alcohol content be 0.41 weight % two-(2,3- ring sulfopropyl) sulfide (EPS-2) (593.01g,
3.32mol, 68%).Measuring refractive index (nD, 20) is 1.614.
The synthesis of [synthesis example 7] two (2,3 ring sulfopropyl) sulfide (EPS-3)
Two (the chloro- 2- hydroxypropyls of 3- that the epichlorohydrin content synthesized to 10 liters of reaction vessel addition synthesis examples 3 is 0.7 weight %
Base) sulfide (BCP-3) (1072.48g, 4.89mol), toluene (toluene) 1300g, methanol 800g, it is stirred, anti-
Temperature is answered to be transferred to 30 DEG C.It when reaching 25 DEG C, is added dropwise NaOH (50%aq., 783.08g, 9.78mol), reaction temperature when dropwise addition
Maintain temperature at 35 DEG C~37 DEG C, reacted.It is added dropwise and carries out within 1 hour, placed about under the conditions of 37 DEG C later
It ferments within 30 minutes, after fermentation, adds toluene 2000g, about stir 10 minutes, be layered, with water to supernatant organic matter
2 cleanings are carried out, moisture removal is removed to greatest extent, adds methanol 400g again to organic layer organic solution, is stirred, reacting
Thiourea (thiourea) (1117.65g, 14.30mol) and acetic anhydride (70g) are added at 8 DEG C of temperature, reaction temperature tune
Height reacts 18 hours to 18 DEG C.It reacts end point to confirm by HPLC, the substance that sets out disappears, and product is not further change in
Subject to.After reaction, stop stirring, wash with water 3 organic layers obtained by layer separation, remove organic solvent, obtain
Epithio for chloroethene alcohol content be 0.57 weight % two-(2,3- ring sulfopropyl) sulfide (EPS-3) (587.23g,
3.29mol, 67%).Measuring refractive index (nD, 20) is 1.614.
The synthesis of [synthesis example 8] two (2,3 ring sulfopropyl) sulfide (EPS-4)
Two (the chloro- 2- hydroxypropyls of 3- that the epichlorohydrin content synthesized to 10 liters of reaction vessel addition synthesis examples 1 is 2.2 weight %
Base) sulfide (BCP-1) (1072.48g, 4.89mol), toluene (toluene) 1300g, methanol 800g, it is stirred, anti-
Temperature is answered to be transferred to 30 DEG C.It when reaching 25 DEG C, is added dropwise NaOH (50%aq., 783.08g, 9.78mol), reaction temperature when dropwise addition
Maintain temperature at 35 DEG C~37 DEG C, reacted.It is added dropwise and carries out within 1 hour, placed about under the conditions of 37 DEG C later
It ferments within 30 minutes, after fermentation, adds toluene 2000g, about stir 10 minutes, be layered, with water to supernatant organic matter
2 cleanings are carried out, moisture removal is removed to greatest extent, adds methanol 400g again to organic layer organic solution, is stirred, reacting
Thiourea (1117.65g, 14.30mol) and acetic anhydride (70g) are added at 8 DEG C of temperature, and reaction temperature is turned up to 18 DEG C, instead
It answers 18 hours.It reacts end point to confirm by HPLC, the substance that sets out disappearance, subject to product is not further change in.Reaction knot
Shu Hou stops stirring, washs with water 3 organic layers obtained by layer separation, removes organic solvent, obtains epithio for chlorethanol
Content is two-(2,3- ring sulfopropyl) sulfide (EPS-4) (584.95g, 3.28mol, 67%) of 1.89 weight %.It measures
Refractive index (nD, 20) is 1.614.
[embodiment 1]
Thio epoxy compounds used epithio for chloroethene alcohol content be 0.2 weight % synthesis example 5 synthesize two (2,
3 ring sulfopropyls) sulfide (EPS-1) 89g, isocyanate compound has used isophorone diisocyanate 5g, Thiolation
It closes object and has used two (2- mercaptoethyl) sulfide 6g, internal mold release has used acid phosphoric acid ester 8-PENPP [polyethylene glycol oxide
Nonyl phenol ether phosphate (3 weight % of 9 moles of ethylene oxide of addition, 80 weight % of 8 moles of addition, the 5 of 9 moles of addition
Weight %, 6 weight % of 7 moles of addition, 6 weight % of 6 moles of addition)] 0.15g, Si butyl phosphonium bromide (Tetrabutyl
Phosphonium Bromide) 0.2g, triphenylphosphine (Triphenylphosphine) 0.1g, organic dyestuff HTAQ (20ppm)
And PRD (10ppm), ultraviolet absorbing agent HOPBT 1.5, mixed dissolution, has obtained homogeneous solution at 20 °C.It is mixed to this
Close solution, under the conditions of 400Pa, deaeration 1 hour.It is filtered, is filled with by glass and glue with 1 μm of PTFE filter later
With in the mold constituted.Mold is launched into polymerization oven, only from 25 DEG C~130 DEG C, was slowly heated up through 21 hours.Polymerization knot
Shu Houcong oven takes out mold.The release property of mold is good.Under the conditions of 130 DEG C, the resin of acquisition anneal within 4 hours
Processing.The resin characteristics of acquisition are refractive index (nE) 1.697, Abbe number 35.Before injecting mold, visually observe dissolved
State confirms that surface is bad after demoulding, as a result without abnormal, invisible albefaction, YI value is 1.8, obtains the stable tree of quality
Rouge.
[embodiment 2]
In addition to thio epoxy compounds have used epithio for the EPS- for the synthesis example 6 that chloroethene alcohol content is 0.41 weight %
Except 2, other compositions are same as Example 1, manufactured resin composition, to the mixed solution, under the conditions of 400Pa, and deaeration 1
Hour.It is filtered, is filled in the mold being made of glass and adhesive tape with 1 μm of PTFE filter later.Mold dispensing is arrived
It polymerize in oven, only from 25 DEG C~130 DEG C, slowly heated up through 21 hours.Mold is taken out from oven after polymerization.Mold takes off
Mould is good.Under the conditions of 130 DEG C, the resin of acquisition make annealing treatment within 4 hours.The resin characteristics of acquisition are refractive index
(nE) 1.697, Abbe number 35.Before injecting mold, dissolved state has been visually observed, has confirmed that surface is bad after demoulding, knot
For fruit without abnormal, invisible albefaction, YI value is 2.1, obtains the stable resin of quality.
[embodiment 3]
In addition to thio epoxy compounds have used epithio for the EPS- for the synthesis example 7 that chloroethene alcohol content is 0.57 weight %
Except 3, other compositions are same as Example 1, manufactured resin composition, to the mixed solution, under the conditions of 400Pa, and deaeration 1
Hour.It is filtered, is filled in the mold being made of glass and adhesive tape with 1 μm of PTFE filter later.Mold dispensing is arrived
It polymerize in oven, only from 25 DEG C~130 DEG C, slowly heated up through 21 hours.Mold is taken out from oven after polymerization.Mold takes off
Mould is good.Under the conditions of 130 DEG C, the resin of acquisition make annealing treatment within 4 hours.The resin characteristics of acquisition are refractive index
(nE) 1.697, Abbe number 35.Before injecting mold, dissolved state has been visually observed, has confirmed that surface is bad after demoulding, knot
For fruit without abnormal, invisible albefaction, YI value is 2.3, obtains the stable resin of quality.
[comparative example 1]
Thio epoxy compounds have used two that epithio is synthesized for the synthesis example 8 that chloroethene alcohol content is 1.89 weight %
(2,3 ring sulfopropyl) sulfide 89g, isocyanate compound have used isophorone diisocyanate 5g, mercaptan compound
Two (2- mercaptoethyl) sulfide 6g are used, internal mold release has used acid phosphoric acid ester 8-PENPP [polyoxyethylene nonyl
Phenol ether phosphate (3 weight % of 9 moles of ethylene oxide of addition, 80 weight % of 8 moles of addition, 5 weights of 9 moles of addition
Measure %, 6 weight % of 7 moles of addition, 6 weight % of 6 moles of addition)] 0.15g, Si butyl phosphonium bromide (Tetrabutyl
Phosphonium Bromide) 0.2g, triphenylphosphine (Triphenylphosphine) 0.1g, organic dyestuff HTAQ (20ppm)
And PRD (10ppm), ultraviolet absorbing agent HOPBT 1.5, mixed dissolution, has obtained homogeneous solution at 20 °C.It is mixed to this
Close solution, under the conditions of 400Pa, deaeration 1 hour.It is filtered, is filled with by glass and glue with 1 μm of PTFE filter later
With in the mold constituted.Mold is launched into polymerization oven, only from 25 DEG C~130 DEG C, was slowly heated up through 21 hours.Polymerization knot
Shu Houcong oven takes out mold.The release property of mold is very bad.Under the conditions of 130 DEG C, the resin of acquisition has been carried out 4 hours
Annealing.The resin characteristics of acquisition are refractive index (nE) 1.697, Abbe number 35.Before injecting mold, dissolution has been visually observed
State afterwards confirms that surface is bad after demoulding, as a result without abnormal, invisible albefaction, YI value is 3.2.
The resins synthesis and result of the Examples and Comparative Examples arrange such as the following table 1.
[table 1]
[abbreviation]
EPS: two (2,3- ring sulfopropyl) sulfide (bis (2,3-epithiopropyl) sulfide)
IPDI: isophorone diisocyanate (isophorondiisocyanate)
BMES: two-(2,3- ring sulfopropyl) 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- toluidines)-anthraquinone (1-hydroxy-4- (p-toluidine) anthraquinone
PRD: pyrene ketone dyes (perinone dye)
Industry utilization feasibility
The present invention can easily solve the form and aspect instability problem that thio epoxy base system optical material occurs, can be with very high
Yield manufacture the thio epoxy base system eyeglass of as clear as crystal high-quality.The thio ring of as clear as crystal high quality produced by the present invention
Oxygroup system optical material can replace existing optical material, be widely used in various fields.Specifically, it can be used for Plastic eyeglasses mirror
Piece, in addition to this 3D polarized lenses of installation light polarizing film manufacture, camera eyeglass etc. can also be used in trigone on eyeglass
A variety of optical articles such as the recording mediums such as mirror, fiber optics, CD substrate or coloring filter and ultraviolet absorption filter.
Claims (8)
1. a kind of thio epoxy base system optical material manufacturing method, which comprises
Two (the chloro- 2- hydroxypropyl of 3-) sulfide are obtained using epichlorohydrin as the substance that sets out, from above-mentioned two (the chloro- 2- hydroxypropyl of 3-) sulphur
In compound manufacture epichlorohydrin content be 0.5 weight % epoxy compounds below, then make above-mentioned epoxy compounds with
Thiocarbamide reaction, to obtain containing 1 weight % epithio below for the step of two (2,3- ring sulfopropyl) sulfide of chlorethanol
Suddenly；
The step of injection molding polymerization is carried out to the polymerism synthetic of two (the 2,3- ring sulfopropyl) sulfide obtained containing above-mentioned steps
Suddenly.
2. thio epoxy base system optical material manufacturing method according to claim 1, it is characterised in that:
The polymerism synthetic further includes polyisocyanate compounds.
3. thio epoxy base system optical material manufacturing method according to claim 2, it is characterised in that:
The polymerism synthetic further includes poly-thiol compound.
4. thio epoxy base system optical material manufacturing method according to claim 2 or 3, it is characterised in that:
The polyisocyanate compounds are 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) tricyclic [5,2,1,02,6] decane, 4,8- bis- (isocyanatomethyl)
Tricyclic [5,2,1,02,6] decane, 2,5- bis- (isocyanatomethyl) two ring [2,2,1] heptane, two ring of 2,6- bis- (isocyanatomethyl)
[2,2,1] a kind or more substance of heptane.
5. thio epoxy base system optical material manufacturing method according to any one of claims 1 to 3, feature exist
In:
The polymerism synthetic further includes the olefin(e) compound used as reaction resin modifying agent.
6. thio epoxy base system optical material manufacturing method according to any one of claims 1 to 3, feature exist
In:
The polymerism synthetic further includes a kind selected from the following or more the phosphate compound used as internal mold release:
By the 5 moles of ethylene oxide adducts of 5 weight %, the 4 moles of ethylene oxide adducts of 80 weight %, 3 moles of 10 weight %
The polyoxyethylene nonyl phenol ether phosphate of the 1 moles of ethylene oxide adduct of ethylene oxide adduct and 5 weight % composition；
By the 9 moles of ethylene oxide adducts of 3 weight %, the 8 moles of ethylene oxide adducts of 80 weight %, 5 weight % 9 moles of rings
The 6 moles of ethylene oxide adducts composition of oxidative ethane adduct, the 7 moles of ethylene oxide adducts of 6 weight % and 6 weight %
Polyoxyethylene nonyl phenol ether phosphate；By the 13 moles of ethylene oxide adducts of 3 weight %, 12 moles of rings of 80 weight %
Oxidative ethane adduct, the 11 moles of ethylene oxide adducts of 8 weight %, 3 weight % 9 moles of ethylene oxide adducts and 6 weights
Measure the polyoxyethylene nonyl phenol ether phosphate of the 4 moles of ethylene oxide adducts composition of %；By 17 moles of rings of 3 weight %
Oxidative ethane adduct, the 16 moles of ethylene oxide adducts of 79 weight %, the 15 moles of ethylene oxide adducts of 10 weight %, 4
The polyethylene glycol oxide nonyl of the 13 moles of ethylene oxide adducts composition of the 14 moles of ethylene oxide adducts and 4 weight % of weight %
Alkylphenol ether phosphate；By the 21 moles of ethylene oxide adducts of 5 weight %, the 20 moles of ethylene oxide adductions of 76 weight %
Object, the 19 moles of ethylene oxide adducts of 7 weight %, the 18 moles of ethylene oxide adducts of 6 weight % and 4 weight % 17 rub
The polyoxyethylene nonyl phenol ether phosphate of your ethylene oxide adduct composition；By the 5 mol propylenoxy adductions of 5 weight %
Object, the 4 mol propylenoxy adducts of 80 weight %, the 3 mol propylenoxy adducts of 10 weight % and 5 weight % 1 rub
The polypropylene oxide nonyl phenol ether phosphate of your propylene oxide adduct composition；By the 9 mol propylenoxy adductions of 3 weight %
Object, the 8 mol propylenoxy adducts of 80 weight %, the 9 mol propylenoxy adducts of 5 weight %, 7 moles of 6 weight %
The polypropylene oxide nonyl phenol ether phosphate of the 6 mol propylenoxy adducts of propylene oxide adduct and 6 weight % composition；
It 11 is rubbed by the 13 mol propylenoxy adducts of 3 weight %, the 12 mol propylenoxy adducts of 80 weight %, 8 weight %
That propylene oxide adduct, the 9 mol propylenoxy adducts of 3 weight % and the 4 mol propylenoxy adduct groups of 6 weight %
At polypropylene oxide nonyl phenol ether phosphate；It 16 is rubbed by the 17 mol propylenoxy adducts of 3 weight %, 79 weight %
Your propylene oxide adduct, the 15 mol propylenoxy adducts of 10 weight %, 4 weight % 14 mol propylenoxy adducts
The polypropylene oxide nonyl phenol ether phosphate formed with the 13 mol propylenoxy adducts of 4 weight %；By the 21 of 5 weight %
Mol propylenoxy adduct, the 20 mol propylenoxy adducts of 76 weight %, 7 weight % 19 mol propylenoxy adductions
The polyoxygenated third of the 17 mol propylenoxy adducts composition of object, the 18 mol propylenoxy adducts of 6 weight % and 4 weight %
Alkene nonyl phenol ether phosphate；Zelec UNTM。
7. a kind of thio epoxy base system optical material, it is characterised in that:
It is obtained with the manufacturing method of claim 1.
8. a kind of thio epoxy base system optical mirror slip, it is characterised in that:
It is constituted with the optical material of claim 7.
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| KR20120002127 | 2012-01-06 | ||
| KR10-2012-0002127 | 2012-01-06 | ||
| CN201380004719.6A CN104039860A (en) | 2012-01-06 | 2013-01-07 | Polymeric composition for thioepoxy-based optical material and method of manufacturing thioepoxy-based optical material |
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| CN105669640B (en) * | 2016-03-29 | 2018-04-03 | 黄河三角洲京博化工研究院有限公司 | A kind of clean method for preparing of episulfide compounds |
| CN106397370B (en) * | 2016-08-30 | 2018-08-17 | 黄河三角洲京博化工研究院有限公司 | A method of producing high-quality epoxide |
| 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 |
| 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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|---|---|---|---|---|
| EP0942072A2 (en) * | 1998-03-12 | 1999-09-15 | Lucent Technologies Inc. | Method for fabricating fluorinated diamond-like carbon layers |
| JP2001163878A (en) * | 1999-12-10 | 2001-06-19 | Mitsui Chemicals Inc | Thioepoxy-based compound |
| CN1462290A (en) * | 2001-04-06 | 2003-12-17 | 三菱瓦斯化学株式会社 | Polymerization regulators, and compositions for resin |
| CN101400648A (en) * | 2006-04-20 | 2009-04-01 | 三井化学株式会社 | Method for producing polythiol compound for optical material and polymerizable composition containing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3405934B2 (en) * | 1999-03-10 | 2003-05-12 | 三井化学株式会社 | New optical resin |
| JP3797820B2 (en) * | 1999-06-24 | 2006-07-19 | 三井化学株式会社 | Novel polyepithioethyl compounds |
| AU2003221343A1 (en) * | 2002-03-12 | 2003-09-22 | Mitsui Chemicals, Inc. | Thioepoxy based polymerizable composition and method for production thereof |
| JP2005220162A (en) * | 2004-02-03 | 2005-08-18 | Seiko Epson Corp | Polymerizable composition, resin for optical material, and plastic lens |
-
2013
- 2013-01-07 CN CN201610325788.2A patent/CN105968409B/en not_active Expired - Fee Related
- 2013-01-07 KR KR20130001720A patent/KR101487709B1/en active IP Right Review Request
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0942072A2 (en) * | 1998-03-12 | 1999-09-15 | Lucent Technologies Inc. | Method for fabricating fluorinated diamond-like carbon layers |
| JP2001163878A (en) * | 1999-12-10 | 2001-06-19 | Mitsui Chemicals Inc | Thioepoxy-based compound |
| CN1462290A (en) * | 2001-04-06 | 2003-12-17 | 三菱瓦斯化学株式会社 | Polymerization regulators, and compositions for resin |
| CN101400648A (en) * | 2006-04-20 | 2009-04-01 | 三井化学株式会社 | Method for producing polythiol compound for optical material and polymerizable composition containing same |
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| CN105968409A (en) | 2016-09-28 |
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| WO2013103277A1 (en) | 2013-07-11 |
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