CN105949096A - Optical spectacle lens material, refined polythiol and post-treatment method of crude polythiol - Google Patents
Optical spectacle lens material, refined polythiol and post-treatment method of crude polythiol Download PDFInfo
- Publication number
- CN105949096A CN105949096A CN201610332556.XA CN201610332556A CN105949096A CN 105949096 A CN105949096 A CN 105949096A CN 201610332556 A CN201610332556 A CN 201610332556A CN 105949096 A CN105949096 A CN 105949096A
- Authority
- CN
- China
- Prior art keywords
- thiol
- post
- polythiol
- crude product
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title abstract description 20
- 230000003287 optical effect Effects 0.000 title abstract description 15
- 229920006295 polythiol Polymers 0.000 title abstract 9
- 239000012535 impurity Substances 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 68
- 239000012043 crude product Substances 0.000 claims description 39
- 239000000047 product Substances 0.000 claims description 29
- 238000012805 post-processing Methods 0.000 claims description 25
- 238000013459 approach Methods 0.000 claims description 24
- 239000005304 optical glass Substances 0.000 claims description 23
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 18
- 241000534944 Thia Species 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 208000035126 Facies Diseases 0.000 claims description 13
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 13
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- -1 hydrogen Sodium oxide Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 238000003672 processing method Methods 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 239000008367 deionised water Substances 0.000 abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 abstract description 8
- 230000032683 aging Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004383 yellowing Methods 0.000 abstract description 3
- 239000012670 alkaline solution Substances 0.000 abstract description 2
- 150000007944 thiolates Chemical class 0.000 abstract 5
- 239000012074 organic phase Substances 0.000 abstract 2
- 206010018612 Gonorrhoea Diseases 0.000 abstract 1
- 208000001786 gonorrhea Diseases 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 32
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 239000008346 aqueous phase Substances 0.000 description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 230000006837 decompression Effects 0.000 description 4
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 3
- 150000003673 urethanes Chemical class 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- HDBQZGJWHMCXIL-UHFFFAOYSA-N 3,7-dihydropurine-2-thione Chemical compound SC1=NC=C2NC=NC2=N1 HDBQZGJWHMCXIL-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 102000016397 Methyltransferase Human genes 0.000 description 1
- 108060004795 Methyltransferase Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/12—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms
- C07C321/14—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
- C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses optical spectacle lens material, refined polythiol and a post-treatment method of crude polythiol. A technical scheme refers to: (1), dissolving crude polythiol in alkaline solution containing an alkaline regulator so that the polythiol is reacted to produce thiolate solution; (2), washing the thiolate solution with a water-insoluble organic solvent to remove from the crude polythiol, organic impurities unable to form thiolates with bases, and separating an aqueous solution containing the thiolates; (3), adding an acid regulator into the thiolate-bearing solution of step (2) to dissolve out the polythiol, standing and separating, collecting an organic phase, and washing the organic phase with deionized water to remove inorganic matters to obtain the refined polythiol. The method of the invention has simple process, good operational convenience, low running cost and good impurity removal effect, a manufactured optical spectacle lens has excellent yellowing and aging resistances, a manufacture process of the lens is nearly free of gonorrhea, high yellow index and the like, and lens yield is evidently increased.
Description
Technical field
The present invention relates to a kind of lens field of material preparation, a kind of optical glasses
Sheet material, refined multi-thiol and the post-processing approach of multi-thiol crude product.
Background technology
Traditional inorganic material, as optical glasses sheet material, has density big, the most wear-resistant,
The shortcomings such as intensity is low, not shock resistance, frangible, are substituted by resin material the most substantially, resin
Material has the advantage that inorganic material is incomparable, becomes optical glasses sheet material main flow already.
A few class optical resin spectacles lens materials currently mainly are ADC (CR-39, diallyl diethylene glycol
Carbonic ester), acrylic (PMMA), PC (Merlon), comprise the 1.56 of Phthalates
Medium-index materials and poly-(sulfur) urethane class etc., and poly-(sulfur) urethane material is owing to having
Refractive index is high, internal stress is little, intensity is high, it is easy to dye, the feature such as processing is gradually by vast use
Family is approved.From the perspective of improving refractive index, poly-(sulfur) urethane class optical material uses sulfur
Alcohol is more more particularly suitable than alcohols, and reactivity is more easily controlled.
The aging conditions such as the eyeglass generation xanthochromia after long-time use are that most of user can not connect
The problem being subject to, on the one hand and it is the character decision of lens materials itself that xanthochromia occurs, mainly
Reason be that in lens materials, impurity content is higher, especially there is impurity of some easy oxidation
Exist, greatly accelerated the process that eyeglass is aging.
Poly-(sulfur) urethane material for optical glass is typically with multi-thiol and Carbimide.
The processes such as ester is that raw material is aggregated, deaerate, filter, injection molding, solidification, the demoulding process and prepare.
Wherein, the preparation of multi-thiol is typically with polyhydric alcohol or polynary halogenated compound as raw material, and
Thiourea first obtains thiocarbamide salt under sour environment reacts, then is hydrolyzed with alkali and prepares,
In the multi-thiol obtained, by-product is more, can only be referred to as multi-thiol crude product, be used directly to into
One step prepares optical glasses sheet material can exist various problem, needs to carry out further work-up,
As used the method for rectification and purification or pickling that multi-thiol is carried out post processing, it is desirable to as far as possible
Go the removal of impurity, improve the purity of multi-thiol.Due in the preparation process of multi-thiol goods
Raw material and intermediate are difficult to convert thoroughly, and owing to the most boiling point of multi-thiol is the highest, thus give
Rectification and purification brings the biggest difficulty, even if under fine vacuum and high temperature, rectification obtains product, also
Tend to that the problems such as product coloring occur.And the method using pickling, due in multi-thiol
Impurity component is complicated, there is also the problem being difficult to washes clean.If multi-thiol existing more
Impurity, will certainly affect the performance of poly-(sulfur) urethane class optical material, after a long time use
Easily aging yellowing, and often due to the impact of impurity in lens manufacturing process, occur white
Turbid, yellow colour index probability bigger than normal is higher, causes Lens pass rate low.
Summary of the invention
The invention aims to solve above-mentioned technical problem, it is provided that a kind of technique is simple, behaviour
Make easy, operating cost is low, good impurity removing effect, multi-thiol for optical glasses sheet material
The post-processing approach of crude product.
The present invention also provides for a kind of refined multi-thiol using above-mentioned post-processing approach to obtain.
The present invention also provides for more than one and states refined multi-thiol is the service life that raw material prepares
Optical glasses sheet material long, that properties is excellent.
The present invention is used for the post-processing approach of the multi-thiol crude product of optical glasses sheet material, including
Following steps:
(1) multi-thiol crude product is dissolved in the alkaline aqueous solution containing alkaline conditioner, makes
Multi-thiol reaction generates mercaptides aqueous solution；
(2) polynary to remove with water-fast organic solvent washing above-mentioned mercaptides aqueous solution
Mercaptan crude product with the organic impurities of alkali formation mercaptides, and can not be isolated containing mercaptides
Aqueous solution；
(3) make many containing addition acid regulator in the aqueous solution of mercaptides in step (2)
Unit's mercaptan separates out, and collects organic facies, then be washed with deionized organic facies removing after standing separatory
Inorganic matter, obtains refined multi-thiol.
In described step (3), the aqueous solution containing mercaptides adds acid regulator and makes many
After unit's mercaptan separates out, it is also possible to select to collect organic facies after organic solvent extraction separatory again, then
It is washed with deionized organic facies and removes inorganic matter, and concentrate further and remove after organic solvent
To refined multi-thiol.
Alkaline conditioner in described step (1) is preferably used highly basic class regulator, is preferably
The highly basic such as sodium hydroxide, potassium hydroxide；The interpolation of the alkaline conditioner in described step (1)
Measure as in multi-thiol crude product 1～1.5 times of mercapto equivalents value, the most preferably 1～1.3
Times.
Water-fast organic solvent in described step (2) is toluene, oxolane, ether
Deng, preferably toluene.
Acid regulator in described step (3) is hydrochloric acid, sulphuric acid or nitric acid etc., is preferably
Hydrochloric acid.
The addition of the acid regulator in described step (3) is sulfydryl in multi-thiol crude product
1～1.5 times of equivalent value, the most preferably 1～1.3 times.
Described multi-thiol crude product is that 4-thiopurine methyltransferase-1,8-dimercapto-3,6-dithia octane is thick
Product or 4,8-bis-thiopurine methyltransferase-1,11-dimercapto-3,6,9-three thia hendecane and 4,7-bis-mercapto
Methyl isophthalic acid, 11-dimercapto-3,6,9-three thia hendecane and 5,7-bis-thiopurine methyltransferase-1,11-two mercapto
The undecanoic crude mixture of base-3,6,9-three thia or 2-{3-(2-sulfydryl-second sulfydryl)
-2-[2-(2-sulfydryl-second sulfydryl)-second sulfydryl] the third sulfydryl } one in ethyl mercaptan crude product.
The present invention refines multi-thiol and is prepared by above-mentioned post-processing approach.
Optical glasses sheet material of the present invention, is main with described refined multi-thiol and isocyanates
Raw material reaction prepares.
For problem present in background technology, inventor is to the impurity in multi-thiol crude product
Analyse in depth, owing to the preparation of multi-thiol crude product have passed through thiourea salinization reaction and alkali
Property hydrolysis process, by-product and intermediate are many, have therefore both contained insoluble in multi-thiol crude product
Impurity in acid also contains the impurity insoluble in alkali, and traditional pickling to be only capable of washing away part miscellaneous
Matter.Inventor further study show that, is first reacted with alkaline solution by multi-thiol crude product, many
Unit's mercaptan and alkali reaction can generate the mercaptides being dissolved in water, and make those can not form mercaptan with alkali
Salt, water-fast organic impurities are separated with mercaptides, then with water-fast organic
Solvent washs, and is removed by described organic impurities, and described alkaline conditioner is preferably hydrogen-oxygen
Changing sodium, addition is preferably 1～1.3, to ensure that multi-thiol crude product forms salt completely, and not
Meaningless waste can be caused too much because of excess.The preferred toluene of water-fast organic solvent；Now
Aqueous solution containing mercaptides still suffers from inorganic contaminants, and the target product of the present invention is essence
Multi-thiol processed, the most Plus acidic regulator makes multi-thiol be precipitated, and soluble in water
Impurity then will not separate out, it is achieved that separates with multi-thiol, and the mercaptan of precipitation both can use molten
Agent extract and separate, it is possible to directly and separate after aqueous phase layering.Described acid regulator is preferred
For hydrochloric acid, addition is preferably 1～1.3, too much can cause excessive acid, needs more washing times,
Cross that I haven't seen you for ages causes the mercaptides of crude product can not be fully converted to product, affect yield.Described organic
The preferred toluene of solvent.
In mercaptan crude product, both there is target product, there is also thio-alcohol and non-thio-alcohol Organic substance
Impurity, thio-alcohol organic impurities and target product mercaptan are in using aftertreatment technology of the present invention
Salt can be together become, it is impossible to remove with this method, but same this kind of mercaptan is miscellaneous with alkaline conditioner
Matter can also form poly-(sulfur) urethane with isocyanate polymeric together with target product multi-thiol,
Form the optical material of clear, and there is the polyurethane optical material formed with target product
Similar character, is such as not easy the most aging etc., the character of optical material be there is no obvious shadow
Ring.Rather than thio-alcohol impurity is then not easy to form salt with sodium hydroxide, can be removed by toluene washing
Go, and this type of impurity the most easily causes polyurethane optical material to occur, and nebulousurine, yellow colour index are inclined
The problems such as high and ageing resistace is poor, so by the aftertreatment technology that the present invention relates to, can be very
Good solution may be deposited owing to multi-thiol contains the objectionable polyurethane optical material brought
Series of problems.
Multi-thiol crude product of the present invention refers to be currently used for manufacturing the various of optical glasses sheet material
Multi-thiol crude product, such as 4-thiopurine methyltransferase-1,8-dimercapto-3,6-dithia octane, 4,8-bis-
Thiopurine methyltransferase-1,11-dimercapto-3,6,9-three thia hendecane and 4,7-bis-thiopurine methyltransferase-1,11-two
Sulfydryl-3,6,9-three thia hendecane and 5,7-bis-thiopurine methyltransferase-1,11-dimercapto-3,6,9-three
The undecanoic mixture of thia, 2-{3-(2-sulfydryl-second sulfydryl)-2-[2-(2-sulfydryl-second
Sulfydryl)-second sulfydryl] the third sulfydryl } ethyl mercaptan etc..The preparation of above-mentioned multi-thiol crude product all can be led to
Cross the thiourea salinization reaction described in background technology, prepared by the technical process of basic hydrolysis, this
For prior art, it is not described further.Preparation is reacted for raw material and isocyanates with refined multi-thiol
The technical process of optical glasses sheet material is also prior art, is not described further.
The inventive method is simple, production cost is low, energy consumption is low, good impurity removing effect, the essence obtained
In multi-thiol processed, unfavorable impurity content is low, the present invention the refined multi-thiol prepared is with polynary
The optical glasses sheet material yellowing-resistant ageing properties that isocyanate polymeric obtains is excellent, and at eyeglass
Occurring the problems such as nebulousurine, yellow colour index be higher in manufacture process hardly, Lens pass rate obtains
Significantly improve.
Detailed description of the invention
Multi-thiol embodiment 1
The preparation of multi-thiol crude product: to 500 milliliters equipped with agitator, thermometer and returned cold
The there-necked flask of condenser adds 53.2g mercaptoethanol, and is cooled to 10～15 DEG C, slowly drip
Add 54.5g 25% sodium hydroxide solution, within about 20 minutes, drip complete；The slowest
Slowly being added dropwise to 31.5g epoxychloropropane, outer temperature maintains 5～10 DEG C, within about 3.5 hours, drips
Add complete；After dropping, start to warm up, after being warming up to 70 DEG C, protect at this temperature
Temperature 1 hour.After stopping stirring and being cooled to room temperature, separate out a small amount of white solid, add 40g water
After dissolving this white solid, start to drip 175.1g 36% concentrated hydrochloric acid, within 20～30 minutes, drip,
Put into 85.4g thiourea again, and start to warm up.After being warming up to 108 DEG C of backflows, at this temperature
Insulation reaction 3 hours.Stop stirring and be cooled to about 50 DEG C, being added dropwise in reactant liquor
148.4g 25% ammonia, drips complete in about 30 minutes；Insulation reaction 1 hour at 50 DEG C.
Stop stirring and heating, after temperature is down to room temperature, product and aqueous phase layering, utilize separatory to leak
Bucket separates the gas producing formation of lower floor, and i.e. to obtain 4-thiopurine methyltransferase-1,8-dimercapto-3,6-dithia octane thick
Product.
The post-processing approach of crude product: above-mentioned crude product is added 196.3g 25% (ww%) sodium hydroxide
After solution dissolves, add 400ml toluene (A) and wash, the aqueous phase of collection lower floor, then
Adding 124.2g 36% (ww%) hydrochloric acid in aqueous phase makes product separate out, and adds 400ml toluene (B)
Carry out extracting separatory, collect organic facies.Successively use 100ml 0.5% ammonia spirit and
100ml × 3 deionized water wash toluene phase, and toluene and residual are distilled off by decompression
Micro-moisture, obtains colourless transparent liquid and is refined 4-thiopurine methyltransferase-1,8-dimercapto-3,6-
Dithia octane crude product mercaptan.
Multi-thiol embodiment 2
Add to equipped with in 500 milliliters of there-necked flasks of agitator, thermometer and reflux condenser
31.5g epoxychloropropane, outer temperature maintains 25～30 DEG C, by 26.6g mercaptoethanol and 0.5g
The mixed solution of triethylamine is added dropwise in epoxychloropropane, within about 2 hours, drips complete；Dropping
After, start to warm up, after being warming up to 60 DEG C, insulation 1 hour at this temperature.So
After at 60 DEG C, be slowly added dropwise to 42.6g Na2S·9H2O is dissolved in 50ml deionized water
Solution, drips complete in about 2 hours, then insulation reaction 1 hour at 60 DEG C.Will reaction
After mixture is down to room temperature, adds 147.7g 36% hydrochloric acid and 72.3g thiourea, then heat up
To 106 DEG C of back flow reaction 6 hours.Reactant mixture is down to room temperature, is slowly added dropwise to 118.9g
25% ammonia, dropping in 20 minutes is complete, then heats to 50 DEG C and reacts 1 hour.Stop stirring
And heating, after temperature is down to room temperature, product and aqueous phase layering, utilize separatory funnel to separate down
Layer gas producing formation i.e. obtain 4,8-bis-thiopurine methyltransferase-1,11-dimercapto-3,6,9-three thia hendecane and
4,7-bis-thiopurine methyltransferase-1,11-dimercapto-3,6,9-three thia hendecane and 5,7-bis-thiopurine methyltransferase
-1,11-dimercapto-3,6,9-three undecanoic the mixture of thia.
The post-processing approach of crude product: above-mentioned crude product is added 196.2g 25% (ww%) sodium hydroxide
After solution dissolves, add 400ml toluene (A) and wash, the aqueous phase of collection lower floor, then
Adding 124.1g 36% (ww%) hydrochloric acid in aqueous phase makes product separate out, and adds 400ml toluene (B)
Carry out extracting separatory, collect organic facies.Successively use 100ml 0.5% ammonia spirit and
100ml × 3 deionized water wash toluene phase, and toluene and residual are distilled off by decompression
Micro-moisture, obtains colourless transparent liquid and is refined 4,8-bis-thiopurine methyltransferase-1,11-bis-mercapto
Base-3,6,9-three thia hendecane and 4,7-bis-thiopurine methyltransferase-1,11-dimercapto-3,6,9-trithio
Miscellaneous hendecane and the 5,7-bis-thiopurine methyltransferase-1,11-dimercapto-3,6,9-three undecanoic mixing of thia
Thing.
Multi-thiol embodiment 3
Dropping 25% hydroxide in 2-thiopurine methyltransferase-1,5-dimercapto-4-thia pentane (41.5g)
Sodium solution (99.5g), drips off for about 0.5 hour, and temperature is less than 45 DEG C.Then at 45 DEG C
After lower stirring reaction 1 hour, it is added dropwise to ethylene chlorhydrin (50.0g), within about 2 hours, drips off,
Owing to this process can continue heat release, reaction is carried out in ice-water bath.Then anti-45 DEG C of stirrings
After answering 3 hours, temperature is down to 30 DEG C.Thiourea is added in polyhydric alcohol solutions obtained above
(56.8g) He 36% concentration hydrochloric acid (81.0g).At 110 DEG C, back flow reaction 5 hours, cold
But to room temperature.At 30 DEG C, add 25% ammonia (104.6g), then heat to 60 DEG C instead
Answer 1 hour, be down to room temperature.Product and aqueous phase layering, utilize separatory funnel to separate the product of lower floor
Product layer i.e. obtains 2-{3-(2-sulfydryl-second sulfydryl)-2-[2-(2-sulfydryl-second sulfydryl)-second mercapto
Base] the third sulfydryl } ethyl mercaptan crude product.
The post-processing approach of crude product: above-mentioned crude product is added 99.8g 25% (ww%) sodium hydroxide
Solution adds 250ml toluene (A) after dissolving and washs, and collects the aqueous phase of lower floor, then at water
Adding 63.2g 36% (ww%) hydrochloric acid in mutually makes product separate out, and adds 250ml toluene (B) and carries out
Extraction separatory, collects organic facies.Use 100ml 0.5% ammonia spirit and 100ml × 3 the most successively
Deionized water wash toluene phase, and the micro-moisture of toluene and residual is distilled off by decompression,
Obtain 2-{3-(2-sulfydryl-second sulfydryl)-2-[2-(2-sulfydryl-second sulfydryl)-second refined
Sulfydryl] the third sulfydryl } ethyl mercaptan.
Multi-thiol embodiment 4
Except by the alkaline conditioner 25% (ww%) in the post-processing approach of multi-thiol embodiment 1
The amount of sodium hydroxide changes 163.5g into, and the amount of acid regulator 36% (ww%) hydrochloric acid changes into
104.3g, other conditions are constant, obtain 4-thiopurine methyltransferase-1 refined, 8-dimercapto-3,6-bis-
Thia octanethiol.
Multi-thiol embodiment 5
Except by 25% (ww%) sodium hydroxide in the post-processing approach of multi-thiol embodiment 1
Amount change 180.6g into, it is constant that the amount of 36% (ww%) hydrochloric acid changes other conditions of 114.7g into,
To refined 4-thiopurine methyltransferase-1,8-dimercapto-3,6-dithia octanethiol.
Multi-thiol embodiment 6
Except by 25% (ww%) sodium hydroxide in the post-processing approach of multi-thiol embodiment 1
Amount changes 212.3g into, and the amount of 36% (ww%) hydrochloric acid changes 135.4g into, and other conditions are constant,
To refined 4-thiopurine methyltransferase-1,8-dimercapto-3,6-dithia octanethiol.
Multi-thiol embodiment 7
Except by the amount of 25% (ww%) sodium hydroxide in the post-processing approach of Polyol Example 1
Changing 244.8g into, the amount of 36% (ww%) hydrochloric acid changes 155.1g into, and other conditions are constant, obtain
Refined 4-thiopurine methyltransferase-1,8-dimercapto-3,6-dithia octanethiol.
Multi-thiol embodiment 8
Except changing into operating as follows by the post-processing approach of multi-thiol embodiment 1, remaining condition
Constant:
Stop stirring and heating, after temperature is down to room temperature, product and aqueous phase layering, utilization point
Liquid funnel separates the gas producing formation of lower floor, adds 196.1g 25% (ww%) sodium hydroxide solution and dissolves
Rear addition 400ml toluene (A) is washed, and collects the aqueous phase of lower floor, then adds in aqueous phase
124.3g 36% (ww%) hydrochloric acid makes product separate out, and collects organic facies after product and aqueous phase are layered.
Use 40ml 0.5% ammonia spirit and 40ml × 3 deionized water wash product successively, then lead to
Cross decompression and the moisture of trace is distilled off, obtain water white liquid, obtain the 4-refined
Thiopurine methyltransferase-1,8-dimercapto-3,6-dithia octanethiol.
Multi-thiol comparative example 1
Except changing into operating as follows by the post-processing approach of multi-thiol embodiment 1, other conditions
Constant.
Stop stirring and heating, after temperature is down to room temperature, adds 400ml toluene and extract
Separatory separates the toluene phase on upper strata, then uses 100ml 36% hydrochloric acid solution and 200ml × 3 successively
Deionized water wash toluene phase, and reduce pressure toluene and micro-moisture are distilled off, obtain colourless
Transparency liquid, is comparative example 4-thiopurine methyltransferase-1,8-dimercapto-3,6-dithia octanethiol.
Multi-thiol comparative example 2
Except changing into operating as follows by the post-processing approach of multi-thiol embodiment 1, other conditions
Constant.
Stop stirring and heating, after temperature is down to room temperature, stands and make product and aqueous phase layering,
Utilize separatory funnel to separate the gas producing formation organic facies of lower floor, then use 50ml 36% hydrochloric acid successively
Solution and 50ml × 3 deionized water wash organic facies, obtain colourless transparent liquid, be ratio
Relatively example 4-thiopurine methyltransferase-1,8-dimercapto-3,6-dithia octanethiol.
Resin optical lens preparation example:
At 15 DEG C, in single port bottle add 31.38g m-xylylene diisocyanate and
28.97g multi-thiol, 0.01g catalyst, 0.05g internal mold release, 0.1g ultraviolet is inhaled
Receiving agent, stirring mixes half an hour, is de-gassed process with the vacuum of below 300Pa simultaneously.
Implantation glass mould utilize adhesive tape after above-mentioned composition utilizes 3 microns of filter elements filter
Seal.The mould filling full compositions is placed in baking oven, from 15 DEG C in 22 hours
It is to slowly warm up to 120 DEG C, and lowers the temperature, by eyeglass from mould after 120 DEG C of continuation solidify 15 minutes
In tool, abjection is placed in baking oven and carries out secondary solidification 2 hours at 120 DEG C, obtains optics tree
Fat eyeglass.
It is many by multi-thiol embodiment 1-8 and multi-thiol comparative example 1,2 prepare
Unit's mercaptan is respectively adopted said method and prepares resin optical lens 1-8 and compare resin light
Learning eyeglass 1,2, and test the resin optical lens obtained, experimental technique is as follows,
Test result is shown in Table 1.
Experimental technique
Yellow colour index: the model taking Perkin Elmer company to produce is Lambda 35 light splitting
Photometer is tested.
Ageing resistance: include thermostability and sunproof aggregative indicator.
Thermostability is tested: be placed in baking oven by resin optical lens, heats at a temperature of 120 DEG C
12 hours, changes delta YI of testing lens yellow colour index.
Light resistance is tested, and carries out following experiment respectively: 1) utilize mercury vapor lamp to divide on eyeglass
Not Zhao She 6 days and 12 days, exposure rate is 35000lx, the change of testing lens yellow colour index
Change Δ YI；2) eyeglass is irradiated 3 days in QUV testing machine, testing lens yellow colour index
Changes delta YI, experiment condition is: light source uses UVB-340, exposure rate 0.76W/m2, black
Plate temperature 60 DEG C.
Monomer prepares Lens pass rate: nebulousurine or yellow colour index occur not by 100 eyeglasses of preparation
Qualified sheet number judges qualification rate, occurs that more than 5 defective are i.e. judged as that monomer is defective.
Table 1 embodiment 1～8 and the optical glass test result of comparative example 1～2 preparation
Claims (10)
1. it is used for a post-processing approach for the multi-thiol crude product of optical glasses sheet material, its
It is characterised by, comprises the following steps:
(1) multi-thiol crude product is dissolved in the alkaline aqueous solution containing alkaline conditioner, makes
Multi-thiol reaction generates mercaptides aqueous solution；
(2) polynary to remove with water-fast organic solvent washing above-mentioned mercaptides aqueous solution
Mercaptan crude product with the organic impurities of alkali formation mercaptides, and can not be isolated containing mercaptides
Aqueous solution；
(3) make many containing addition acid regulator in the aqueous solution of mercaptides in step (2)
Unit's mercaptan separates out, and collects organic facies, then be washed with deionized organic facies removing after standing separatory
Inorganic matter, obtains refined multi-thiol.
2. it is used for the multi-thiol crude product of optical glasses sheet material as claimed in claim 1
Post-processing approach, it is characterised in that in described step (3), containing the aqueous solution of mercaptides
Middle addition acid regulator makes multi-thiol separate out, then has with collecting after organic solvent extraction separatory
Machine phase, then it is washed with deionized organic facies removing inorganic matter, and it is organic to concentrate removal further
Refined multi-thiol is obtained after solvent.
3. the multi-thiol for optical glasses sheet material as claimed in claim 1 or 2 is thick
The post-processing approach of product, it is characterised in that the alkaline conditioner in described step (1) is hydrogen
Sodium oxide or potassium hydroxide.
4. the multi-thiol for optical glasses sheet material as claimed in claim 1 or 2 is thick
The post-processing approach of product, it is characterised in that adding of the alkaline conditioner in described step (1)
Dosage is 1～1.5 times of mercapto equivalents value in multi-thiol crude product.
5. the multi-thiol for optical glasses sheet material as claimed in claim 1 or 2 is thick
The post-processing approach of product, it is characterised in that water-fast organic in described step (2)
Solvent is toluene, oxolane or ether.
6. the multi-thiol for optical glasses sheet material as claimed in claim 1 or 2 is thick
The post-processing approach of product, it is characterised in that the acid regulator in described step (3) is salt
Acid, sulphuric acid or nitric acid.
7. the multi-thiol for optical glasses sheet material as claimed in claim 1 or 2 is thick
The post-processing approach of product, it is characterised in that adding of the acid regulator in described step (3)
Dosage is 1～1.5 times of mercapto equivalents value in multi-thiol crude product.
8. the multi-thiol for optical glasses sheet material as claimed in claim 1 or 2 is thick
The post-processing approach of product, it is characterised in that described multi-thiol crude product is 4-thiopurine methyltransferase-1,8-
Dimercapto-3,6-dithia octane crude product, 4,8-bis-thiopurine methyltransferase-1,11-dimercapto-3,6,9-
Three thia hendecanes and 4,7-bis-thiopurine methyltransferase-1,11-dimercapto-3,6,9-three thia hendecane and
The 5,7-bis-thiopurine methyltransferase-1,11-dimercapto-3,6,9-three undecanoic crude mixture of thia or
2-{3-(2-sulfydryl-second sulfydryl)-2-[2-(2-sulfydryl-second sulfydryl)-second sulfydryl] the third sulfydryl }
One in ethyl mercaptan crude product.
9. a refined multi-thiol, it is characterised in that after any one of claim 1-8
Processing method prepares.
10. an optical glasses sheet material, it is characterised in that with refined described in claim 9
Multi-thiol and isocyanates are that primary raw material reaction prepares.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610332556.XA CN105949096B (en) | 2016-05-19 | 2016-05-19 | The post-processing approach of optical glasses sheet material, refined multi-thiol and multi-thiol crude product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610332556.XA CN105949096B (en) | 2016-05-19 | 2016-05-19 | The post-processing approach of optical glasses sheet material, refined multi-thiol and multi-thiol crude product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105949096A true CN105949096A (en) | 2016-09-21 |
| CN105949096B CN105949096B (en) | 2018-03-02 |
Family
ID=56912771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610332556.XA Expired - Fee Related CN105949096B (en) | 2016-05-19 | 2016-05-19 | The post-processing approach of optical glasses sheet material, refined multi-thiol and multi-thiol crude product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105949096B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107235876A (en) * | 2017-06-30 | 2017-10-10 | 山东益丰生化环保股份有限公司 | A kind of post-processing approach of many sulfhydryl compound crude products |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1279231A (en) * | 1999-06-30 | 2001-01-10 | 中国石油化工集团公司 | Process for refining coarse phenol containing sulfur |
| CN1894203A (en) * | 2003-10-17 | 2007-01-10 | 霍尼韦尔国际公司 | O-substituted hydroxylamine and salts thereof |
| CN104321308A (en) * | 2012-05-23 | 2015-01-28 | 可奥熙搜路司有限公司 | Novel method for preparing polythiol compound and polymeric composition for optical material comprising same |
| CN104311505A (en) * | 2014-09-30 | 2015-01-28 | 天津一化化工有限公司 | Purification method of 2-mercaptobenzothiazole serving as rubber vulcanization accelerator M |
| CN104321307A (en) * | 2012-08-14 | 2015-01-28 | 三井化学株式会社 | Production method for polythiol compound, polymerizable composition for optical material and use therefor |
-
2016
- 2016-05-19 CN CN201610332556.XA patent/CN105949096B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1279231A (en) * | 1999-06-30 | 2001-01-10 | 中国石油化工集团公司 | Process for refining coarse phenol containing sulfur |
| CN1894203A (en) * | 2003-10-17 | 2007-01-10 | 霍尼韦尔国际公司 | O-substituted hydroxylamine and salts thereof |
| CN104321308A (en) * | 2012-05-23 | 2015-01-28 | 可奥熙搜路司有限公司 | Novel method for preparing polythiol compound and polymeric composition for optical material comprising same |
| CN104321307A (en) * | 2012-08-14 | 2015-01-28 | 三井化学株式会社 | Production method for polythiol compound, polymerizable composition for optical material and use therefor |
| CN104321306A (en) * | 2012-08-14 | 2015-01-28 | 三井化学株式会社 | Production method for polythiol compound, polymerizable composition for optical material and use therefor |
| CN104311505A (en) * | 2014-09-30 | 2015-01-28 | 天津一化化工有限公司 | Purification method of 2-mercaptobenzothiazole serving as rubber vulcanization accelerator M |
Non-Patent Citations (1)
| Title |
|---|
| DONG GYU JANG 等: "Synthesis of Novel Polythiol for Plastic Optical Lens and its Ophthalmic Lens", 《BULL.KOREAN CHEM.SOC.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107235876A (en) * | 2017-06-30 | 2017-10-10 | 山东益丰生化环保股份有限公司 | A kind of post-processing approach of many sulfhydryl compound crude products |
| CN107235876B (en) * | 2017-06-30 | 2019-01-18 | 山东益丰生化环保股份有限公司 | A kind of post-processing approach of more sulfhydryl compound crude products |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105949096B (en) | 2018-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105777596B (en) | High refraction sulfur-bearing optical resin monomer of a kind of polyurethane-type and preparation method thereof | |
| CN106279289B (en) | A kind of sulfur-containing epoxy resin monomer, optical resin material and preparation method thereof | |
| JP2014234429A (en) | Polymerizable composition for optical material, and method for producing the same | |
| CN110776491B (en) | Multi-branched thioether-type ring sulfur compound and preparation method and application thereof | |
| CN110183369A (en) | A method of the separating-purifying N-Methyl pyrrolidone from useless paint stripper | |
| CN105949096A (en) | Optical spectacle lens material, refined polythiol and post-treatment method of crude polythiol | |
| JP2014234430A (en) | Polymerizable composition for optical material, and method for producing the same | |
| CN107235876B (en) | A kind of post-processing approach of more sulfhydryl compound crude products | |
| CN107200846B (en) | Sulfur-containing optical resin material with high transmittance and high refractive index and preparation method thereof | |
| EP2540714A1 (en) | Manufacturing method for episulphide compound | |
| CN110156748A (en) | A kind of preparation method of high refractive index lens monomer | |
| JP3628054B2 (en) | Polythiol derivative and lens using the same | |
| US20240034829A1 (en) | Polythiol composition, optical composition, and optical product | |
| CN107200847A (en) | High index of refraction, high rigidity sulfur-bearing optical resin material and preparation method thereof | |
| CN107188836B (en) | Tri- thiopurine methyltransferase benzene compound of 1,3,5- and preparation method thereof | |
| CN116457385A (en) | Polythiol composition, optical composition and optical product | |
| CN107721892A (en) | A kind of thio multi-thiol, preparation method and the application in transparent polyurethane material | |
| CN102491951B (en) | Production process of triallyl cyanurate | |
| CN107188882A (en) | 1,3,5 3 epithiopropyl thiopurine methyltransferase benzene compounds and preparation method thereof | |
| EP4212566A1 (en) | Polythiol composition and optical composition comprising same | |
| CN109053507B (en) | Polythiol compound for optical resin material and preparation method thereof | |
| CN112480095B (en) | Preparation method of bis (2, 3-thiocyclopropyl) sulfide | |
| US20240002336A1 (en) | Polythiol composition, optical composition, and optical product | |
| CN109627386B (en) | Resin monomer composition | |
| KR102036246B1 (en) | Preparation method of high-quality polythiol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 430057 Hubei city of Wuhan Province Economic and Technological Development Zone East Jinghe Road No. 1 Applicant after: HUBEI DINGLONG Co.,Ltd. Address before: 430057 Hubei city of Wuhan Province Economic and Technological Development Zone East Jinghe Road No. 1 Applicant before: Hubei Dinglong Chemical Co.,Ltd. |
|
| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180302 |