CN105949096B - The post-processing approach of optical glasses sheet material, refined multi-thiol and multi-thiol crude product - Google Patents
The post-processing approach of optical glasses sheet material, refined multi-thiol and multi-thiol crude product Download PDFInfo
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- 239000012043 crude product Substances 0.000 title claims abstract description 51
- 239000000463 material Substances 0.000 title claims abstract description 38
- 238000012805 post-processing Methods 0.000 title claims abstract description 26
- 238000013459 approach Methods 0.000 title claims abstract description 25
- 239000005304 optical glass Substances 0.000 title claims abstract description 21
- 239000012535 impurity Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012074 organic phase Substances 0.000 claims abstract description 16
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 66
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 102000004377 Thiopurine S-methyltransferases Human genes 0.000 claims description 26
- 108090000958 Thiopurine S-methyltransferases Proteins 0.000 claims description 26
- 241000534944 Thia Species 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 8
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 239000003795 chemical substances by application 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
- 239000002585 base Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 claims 3
- 239000002904 solvent Substances 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 206010018612 Gonorrhoea Diseases 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 230000003679 aging effect Effects 0.000 abstract description 2
- 238000004383 yellowing Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 20
- 239000008346 aqueous phase Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 11
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- VLENVEGZSVNZDD-UHFFFAOYSA-N NC(=O)OCC.[S] Chemical class NC(=O)OCC.[S] VLENVEGZSVNZDD-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 235000015096 spirit Nutrition 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 3
- GHKCSRZBNZQHKW-UHFFFAOYSA-N 1-sulfanylethanol Chemical class CC(O)S GHKCSRZBNZQHKW-UHFFFAOYSA-N 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003750 conditioning effect Effects 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
- 238000009413 insulation Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010992 reflux Methods 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
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical class 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
- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical class CC(Cl)C(O)=O GAWAYYRQGQZKCR-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
- HDBQZGJWHMCXIL-UHFFFAOYSA-N 3,7-dihydropurine-2-thione Chemical compound SC1=NC=C2NC=NC2=N1 HDBQZGJWHMCXIL-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 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
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 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
- 230000009257 reactivity Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type 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
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- 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 the post-processing approach of a kind of optical glasses sheet material, refined multi-thiol and multi-thiol crude product.Technical scheme is that multi-thiol crude product is dissolved in the alkaline aqueous solution containing alkaline conditioner by (1), makes multi-thiol reaction generation mercaptan saline solution；(2) organic impurities of mercaptides can not be formed with alkali to remove in multi-thiol crude product with the above-mentioned mercaptan saline solution of organic solvent washing not soluble in water, and isolates the aqueous solution containing mercaptides；(3) acid regulator is added in the aqueous solution containing mercaptides into step (2) separates out multi-thiol, and organic phase is collected after standing liquid separation, then organic phase is washed with deionized and removes inorganic matter, obtains refined multi-thiol.The inventive method technique is simple, easy to operate, operating cost is low, good impurity removing effect, obtained optical lens yellowing-resistant ageing properties are excellent, and gonorrhoea almost being occurred without in lens manufacturing process, the problems such as yellow colour index is higher, Lens pass rate is improved significantly.
Description
Technical field
It is specifically a kind of optical glasses sheet material, refined more the present invention relates to a kind of ophthalmic len field of material preparation
The post-processing approach of first mercaptan and multi-thiol crude product.
Background technology
Traditional inorganic material has that density is big as optical glasses sheet material, not wear-resistant, low intensity, not shock resistance,
The shortcomings of frangible, substituted substantially by resin material now, resin material has the advantages of inorganic material is incomparable, already into
For optical glasses sheet material main flow.(CR-39, diallyl two are sweet for ADC for a few class optical resin spectacles lens materials main at present
Alcohol carbonic ester), acrylic (PMMA), PC (makrolon), 1.56 medium-index materials comprising Phthalates and poly-
(sulphur) urethane class etc., and poly- (sulphur) urethane material is due to refractive index is high, internal stress is small, intensity is high, easy to dye, processing etc.
Feature is gradually approved by users.From the perspective of refractive index is improved, poly- (sulphur) urethane class optical material uses mercaptan ratio
Alcohols is more particularly suitable, and reactivity is more easily controlled.
It is the unacceptable problem of most of users that the aging conditions such as xanthochromia, which occur, for the eyeglass after long-time use, and is occurred
On the one hand xanthochromia is that the property of lens materials in itself determines, more main reasons is that impurity content is higher in lens materials, especially
It is that there are some impurity easily aoxidized to exist, and has greatly accelerated the process of eyeglass aging.
Poly- (sulphur) urethane material for optical mirror slip is typically aggregated, de- as raw material using multi-thiol and isocyanates
The processing of the processes such as gas, filtering, injection molding, solidification, the demoulding is made.Wherein, the preparation of multi-thiol is typically with polyalcohol or polynary
Halogenated compound is raw material, and thiocarbamide first obtains thiocarbamide salt under sour environment reaction, then is hydrolyzed and be prepared with alkali,
Accessory substance is more in obtained multi-thiol, can only be referred to as multi-thiol crude product, is used directly to further prepare optical lens
Material can have various problems, it is necessary to carry out further work-up, such as using rectification and purification or the method for pickling to polynary sulphur
Alcohol is post-processed, it is desirable to is gone the removal of impurity as far as possible, is improved the purity of multi-thiol.Due to the preparation of multi-thiol product
Raw material and intermediate are difficult that conversion is thorough in journey, and because the most boiling point of multi-thiol is very high, so as to be brought to rectification and purification
Very big difficulty, under high vacuum and high temperature rectifying obtain product, also tend to the problems such as product coloring easily occur.And use
The method of pickling, because impurity component is complicated in multi-thiol, the problem of there is also washes clean is difficult to.If deposited in multi-thiol
In more impurity, the performance of poly- (sulphur) urethane class optical material will certainly be influenceed, after a long time use easy aging yellowing, and
Often due to the influence of impurity in lens manufacturing process, it is higher gonorrhoea, yellow colour index probability bigger than normal occur, causes eyeglass
Qualification rate is low.
The content of the invention
The invention aims to solve above-mentioned technical problem, there is provided a kind of technique is simple, easy to operate, operating cost
Low, good impurity removing effect, for optical glasses sheet material multi-thiol crude product post-processing approach.
The present invention also provides a kind of refined multi-thiol obtained using above-mentioned post-processing approach.
It is that service life made from raw material is long, properties are excellent that the present invention, which also provides more than one and states refined multi-thiol,
Optical glasses sheet material.
The present invention is used for the post-processing approach of the multi-thiol crude product of optical glasses sheet material, comprises the following steps：
(1) multi-thiol crude product is dissolved in the alkaline aqueous solution containing alkaline conditioner, makes multi-thiol reaction generation
Mercaptan saline solution；
(2) can not be with to remove in multi-thiol crude product with the above-mentioned mercaptan saline solution of organic solvent washing not soluble in water
Alkali forms the organic impurities of mercaptides, and isolates the aqueous solution containing mercaptides；
(3) acid regulator is added in the aqueous solution containing mercaptides into step (2) separates out multi-thiol, stands and divides
Organic phase is collected after liquid, then organic phase is washed with deionized and removes inorganic matter, obtains refined multi-thiol.
In the step (3), after addition acid regulator separates out multi-thiol in the aqueous solution containing mercaptides, also may be used
To select to collect organic phase after extracting liquid separation with organic solvent again, then organic phase is washed with deionized and removes inorganic matter, go forward side by side
The concentration of one step obtains refined multi-thiol after removing organic solvent.
Alkaline conditioner in the step (1) preferably uses highly basic class conditioning agent, preferably sodium hydroxide, potassium hydroxide
Deng highly basic；The addition of alkaline conditioner in the step (1) is 1~1.5 times of mercapto equivalents value in multi-thiol crude product,
Still more preferably it is 1~1.3 times.
Organic solvent not soluble in water in the step (2) is toluene, tetrahydrofuran, ether etc., preferably toluene.
Acid regulator in the step (3) is hydrochloric acid, sulfuric acid or nitric acid etc., preferably hydrochloric acid.
The addition of acid regulator in the step (3) is 1~1.5 of mercapto equivalents value in multi-thiol crude product
Times, it is still more preferably 1~1.3 times.
The multi-thiol crude product is 4- thiopurine methyltransferase -1,8- dimercapto -3,6- dithia octane crude products or the mercapto first of 4,8- bis-
The thia hendecanes of base -1,11- dimercaptos -3,6,9- three and the thias 11 of bis- thiopurine methyltransferase -1,11- dimercaptos -3,6,9- of 4,7- three
Alkane and the undecanoic crude mixture of the thias of bis- thiopurine methyltransferase -1,11- dimercaptos -3,6,9- of 5,7- three or 2- { 3- (2- sulfydryls-second
Sulfydryl) -2- [2- (2- sulfydryls-second sulfydryl)-second sulfydryl] third sulfydryl } one kind in ethyl mercaptan crude product.
The refined multi-thiol of the present invention is made by above-mentioned post-processing approach.
Optical glasses sheet material of the present invention, reacted and be made as primary raw material using the refined multi-thiol and isocyanates.
For problem present in background technology, inventor analyses in depth to the impurity in multi-thiol crude product, by
The process of thiocarbamide salinization reaction and basic hydrolysis is have passed through in the preparation of multi-thiol crude product, accessory substance and intermediate are more, because
Both contained insoluble in sour impurity or containing the impurity insoluble in alkali in this multi-thiol crude product, and traditional pickling is only capable of washing away
Partial impurities.Inventor further study show that, multi-thiol crude product is first reacted with alkaline solution, multi-thiol and alkali react
The mercaptides for being dissolved in water can be generated, and prevents those from forming mercaptides, organic impurities and mercaptides not soluble in water with alkali
Separate, then washed with organic solvent not soluble in water, the organic impurities are removed, the alkaline conditioner is excellent
Elect sodium hydroxide as, addition is preferably 1~1.3, to ensure the complete forming salt of multi-thiol crude product, and will not be because excessive too many
Cause meaningless waste.The preferred toluene of organic solvent not soluble in water；Now still suffered from the aqueous solution containing mercaptides inorganic
Thing impurity, and the target product of the present invention is refined multi-thiol, therefore Plus acidic conditioning agent is precipitated multi-thiol again, and
Impurity soluble in water will not then separate out, and realize the separation with multi-thiol, and solvent extraction point both can be used in the mercaptan of precipitation
From, also can directly and aqueous phase layering after separate.The acid regulator is preferably hydrochloric acid, and addition is preferably 1~1.3,
Excessive acid can excessively be caused, need more washing times, the very few mercaptides that can cause crude product can not be fully converted to product, influence
Yield.The preferred toluene of organic solvent.
Target product both be present in mercaptan crude product, there is also thio-alcohol and non-thio-alcohol organic impurities, thio-alcohol has
Machine thing impurity and target product mercaptan can be with alkaline conditioners together into salt in using aftertreatment technology of the present invention, it is impossible to this
Method removes, but same this kind of mercaptan impurities can also be formed together with isocyanate polymeric with target product multi-thiol it is poly-
(sulphur) urethane, the optical material of clear is formed, and with the property similar with the polyurethane optical material of target product formation
Matter, for example it is not easy aging easily etc., the property to optical material simultaneously has no significant effect.Rather than thio-alcohol impurity be then not easy and
Sodium hydroxide forming salt, it can be washed and removed by toluene, and such impurity exactly easily causes polyurethane optical material to occur in vain
Turbid, the problems such as yellow colour index is higher and ageing resistace is poor, so by aftertreatment technology of the present invention, it can solve well
Certainly because multi-thiol contains objectionable polyurethane optical material a series of problems that may be present brought.
Multi-thiol crude product of the present invention refers to the various multi-thiol crude products currently used for manufacturing optical glasses sheet material, such as
4- thiopurine methyltransferase -1,8- dimercapto -3,6- dithias octane, the thias 11 of bis- thiopurine methyltransferase -1,11- dimercaptos -3,6,9- of 4,8- three
Alkane and the thia hendecanes of bis- thiopurine methyltransferase -1,11- dimercaptos -3,6,9- of 4,7- three and thiopurine methyltransferase -1,11- dimercapto -3 of 5,7- bis-,
The undecanoic mixture of the thias of 6,9- tri-, 2- { 3- (2- sulfydryls-second sulfydryl) -2- [2- (2- sulfydryls-second sulfydryl)-second sulfydryl] third
Sulfydryl } ethyl mercaptan etc..The preparation of above-mentioned multi-thiol crude product can pass through the thiocarbamide salinization reaction described in background technology, alkali
Property hydrolysis technical process prepare, this is prior art, is not described further.Reacted using refined multi-thiol as raw material and isocyanates
The technical process for preparing 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, unfavorable in obtained refined multi-thiol
Impurity content is low, is resisted by refined multi-thiol produced by the present invention with the optical glasses sheet material that multicomponent isocyanate polymerize to obtain
Xanthochromia ageing properties are excellent, and almost occur without gonorrhoea in lens manufacturing process, the problems such as yellow colour index is higher, Lens pass
Rate is improved significantly.
Embodiment
Multi-thiol embodiment 1
The preparation of multi-thiol crude product：Into 500 milliliters of three-necked flasks equipped with agitator, thermometer and reflux condenser
53.2g mercaptoethanols are added, and are cooled to 10~15 DEG C, are slowly added dropwise to the sodium hydroxide solutions of 54.5g 25%, 20 minutes left sides
The right side is added dropwise；Then 31.5g epoxychloropropane is slowly added dropwise to thereto, and outer temperature maintains 5~10 DEG C, 3.5 hours or so
It is added dropwise；After being added dropwise, start to warm up, after being warming up to 70 DEG C, be incubated 1 hour at this temperature.Stop stirring and cold
But to after room temperature, a small amount of white solid is separated out, after adding 40g water to dissolve the white solid, starts that 36% dense salt of 175.1g is added dropwise
Acid, drip within 20~30 minutes, then put into 85.4g thiocarbamides, and start to warm up.After being warming up to 108 DEG C of backflows, protect at this temperature
Temperature reaction 3 hours.Stop stirring and be cooled to 50 DEG C or so, the ammoniacal liquor of 148.4g 25%, 30 minutes left sides are added dropwise into reaction solution
The right side is added dropwise；Insulation reaction 1 hour at 50 DEG C.Stop stirring and heating, after temperature is down to room temperature, product and aqueous phase point
Layer, the gas producing formation that lower floor is separated using separatory funnel produce 4- thiopurine methyltransferase -1,8- dimercapto -3,6- dithia octane crude products.
The post-processing approach of crude product：After above-mentioned crude product is added into the dissolving of 196.3g 25% (ww%) sodium hydroxide solution, add
Enter 400ml toluene (A) to be washed, collect the aqueous phase of lower floor, then add 124.2g 36% (ww%) hydrochloric acid in aqueous phase to make production
Product separate out, and add 400ml toluene (B) and carry out extraction liquid separation, collect organic phase.Successively using the ammonia spirits of 100ml 0.5% and
The deionized water of 100ml × 3 washing toluene phase, and the micro-moisture of toluene and residual is removed by being evaporated under reduced pressure, obtain colourless
Prescribed liquid is refined 4- thiopurine methyltransferase -1,8- dimercapto -3,6- dithia octane crude product mercaptan.
Multi-thiol embodiment 2
31.5g epoxy chloropropionates are added into 500 milliliters of three-necked flasks equipped with agitator, thermometer and reflux condenser
Alkane, outer temperature maintain 25~30 DEG C, and the mixed solution of 26.6g mercaptoethanols and 0.5g triethylamines is added dropwise into epoxychloropropane
In, it is added dropwise within 2 hours or so；After being added dropwise, start to warm up, after being warming up to 60 DEG C, be incubated 1 hour at this temperature.
Then at 60 DEG C, 42.6g Na are slowly added dropwise to2S·9H2O is dissolved in the solution of 50ml deionized waters, is added dropwise within 2 hours or so
Finish, then insulation reaction 1 hour at 60 DEG C.After reactant mixture is down into room temperature, add the hydrochloric acid of 147.7g 36% and
72.3g thiocarbamides, then heat to 106 DEG C of back flow reactions 6 hours.Reactant mixture is down to room temperature, is slowly added dropwise to
118.9g25% ammoniacal liquor, it is added dropwise within 20 minutes, then heats to 50 DEG C and react 1 hour.Stop stirring and heating, treat that temperature drops
To room temperature, product and aqueous phase layering, the gas producing formation that lower floor is separated using separatory funnel produce the thiopurine methyltransferases -1,11- bis- of 4,8- bis-
The thia hendecanes of sulfydryl -3,6,9- three and the thia hendecanes of bis- thiopurine methyltransferase -1,11- dimercaptos -3,6,9- of 4,7- three and 5,7- bis-
The undecanoic mixtures of thia of thiopurine methyltransferase -1,11- dimercaptos -3,6,9- three.
The post-processing approach of crude product：After above-mentioned crude product is added into the dissolving of 196.2g 25% (ww%) sodium hydroxide solution, add
Enter 400ml toluene (A) to be washed, collect the aqueous phase of lower floor, then add 124.1g 36% (ww%) hydrochloric acid in aqueous phase to make production
Product separate out, and add 400ml toluene (B) and carry out extraction liquid separation, collect organic phase.Successively using the ammonia spirits of 100ml 0.5% and
The deionized water of 100ml × 3 washing toluene phase, and the micro-moisture of toluene and residual is removed by being evaporated under reduced pressure, obtain colourless
Prescribed liquid is the thia hendecane of bis- thiopurine methyltransferase -1,11- dimercaptos -3,6,9- of 4,8- three and thiopurine methyltransferase -1 of 4,7- bis- refined,
The thia hendecanes of 11- dimercaptos -3,6,9- three and thiopurine methyltransferase -1,11- dimercaptos three thias of -3,6,9- of 5,7- bis- are undecanoic mixed
Compound.
Multi-thiol embodiment 3
25% sodium hydroxide solution (99.5g) is added dropwise into 2- thiopurine methyltransferase -1,5- dimercapto -4- thias pentanes (41.5g),
Drip off within 0.5 hour or so, temperature is no more than 45 DEG C.Then stirring reaction after 1 hour, is added dropwise to ethylene chlorhydrin at 45 DEG C
(50.0g), drip off within about 2 hours, because this process can continue heat release, react and carried out in ice-water bath.Then it is anti-in 45 DEG C of stirrings
After answering 3 hours, temperature is down to 30 DEG C.Thiocarbamide (56.8g) and 36% concentration hydrochloric acid are added into polyhydric alcohol solutions obtained above
(81.0g).Back flow reaction 5 hours, are cooled to room temperature at 110 DEG C.At 30 DEG C, 25% ammoniacal liquor (104.6g) is added, then
It is warming up to 60 DEG C to react 1 hour, is down to room temperature.Product and aqueous phase layering, the gas producing formation that lower floor is separated using separatory funnel are produced
2- { 3- (2- sulfydryls-second sulfydryl) -2- [2- (2- sulfydryls-second sulfydryl)-second sulfydryl] the third sulfydryl } ethyl mercaptan crude product.
The post-processing approach of crude product：Added after above-mentioned crude product is added into the dissolving of 99.8g 25% (ww%) sodium hydroxide solution
250ml toluene (A) is washed, and collects the aqueous phase of lower floor, then addition 63.2g 36% (ww%) hydrochloric acid makes product in aqueous phase
Separate out, add 250ml toluene (B) and carry out extraction liquid separation, collect organic phase.Again successively using the ammonia spirits of 100ml 0.5% and
The deionized water of 100ml × 3 washing toluene phase, and the micro-moisture of toluene and residual is removed by being evaporated under reduced pressure, obtain refined
2- { 3- (2- sulfydryls-second sulfydryl) -2- [2- (2- sulfydryls-second sulfydryl)-second sulfydryl] the third sulfydryl } ethyl mercaptan.
Multi-thiol embodiment 4
Except by the amount of alkaline conditioner 25% (ww%) sodium hydroxide in the post-processing approach of multi-thiol embodiment 1
163.5g is changed to, the amount of acid regulator 36% (ww%) hydrochloric acid is changed to 104.3g, and other conditions are constant, obtain refined 4- mercaptos
Methyl isophthalic acid, 8- dimercapto -3,6- dithia octanethiols.
Multi-thiol embodiment 5
Except the amount of 25% (ww%) sodium hydroxide in the post-processing approach of multi-thiol embodiment 1 is changed to
180.6g, it is constant that the amount of 36% (ww%) hydrochloric acid is changed to 114.7g other conditions, obtain refined 4- thiopurine methyltransferases -1,8- dimercapto -
3,6- dithia octanethiols.
Multi-thiol embodiment 6
Except the amount of (ww%) sodium hydroxide 25% in the post-processing approach of multi-thiol embodiment 1 is changed into 212.3g,
The amount of 36% (ww%) hydrochloric acid is changed to 135.4g, and other conditions are constant, obtains refined 4- thiopurine methyltransferase -1,8- dimercaptos -3,6-
Dithia octanethiol.
Multi-thiol embodiment 7
Except the amount of (ww%) sodium hydroxide 25% in the post-processing approach of Polyol Example 1 is changed into 244.8g,
The amount of 36% (ww%) hydrochloric acid is changed to 155.1g, and other conditions are constant, obtains refined 4- thiopurine methyltransferase -1,8- dimercaptos -3,6-
Dithia octanethiol.
Multi-thiol embodiment 8
Except the post-processing approach of multi-thiol embodiment 1 to be changed to operate as follows, remaining condition is constant：
Stop stirring and heating, after temperature is down to room temperature, product and aqueous phase layering, lower floor is separated using separatory funnel
Gas producing formation, addition 400ml toluene (A) is washed after adding the dissolving of 196.1g 25% (ww%) sodium hydroxide solution, under collection
The aqueous phase of layer, then adding 124.3g 36% (ww%) hydrochloric acid in aqueous phase separates out product, is collected after product and aqueous phase layering
Organic phase.Successively using the deionized water cleaning product of the ammonia spirits of 40ml 0.5% and 40ml × 3, then removed by being evaporated under reduced pressure
Micro moisture is removed, obtains the liquid of water white transparency, obtains refined 4- thiopurine methyltransferase -1,8- dimercapto -3,6- dithia octanes
Mercaptan.
Multi-thiol comparative example 1
Except the post-processing approach of multi-thiol embodiment 1 to be changed to operate as follows, other conditions are constant.
Stop stirring and heating, after temperature is down to room temperature, adds 400ml toluene and carry out extracting the first that liquid separation separates upper strata
Benzene phase, then successively using the deionized water washing toluene phase of the hydrochloric acid solutions of 100ml 36% and 200ml × 3, and it is evaporated under reduced pressure removing
Toluene and micro-moisture, obtain colourless transparent liquid, as comparative example 4- thiopurine methyltransferases -1,8- dimercapto -3,6- dithia octane
Mercaptan.
Multi-thiol comparative example 2
Except the post-processing approach of multi-thiol embodiment 1 to be changed to operate as follows, other conditions are constant.
Stop stirring and heating, after temperature is down to room temperature, standing is layered product and aqueous phase, is separated using separatory funnel
The gas producing formation organic phase of lower floor, then obtained successively using the deionized water washing organic phase of the hydrochloric acid solutions of 50ml 36% and 50ml × 3
To colourless transparent liquid, as comparative example 4- thiopurine methyltransferases -1,8- dimercapto -3,6- dithia octanethiol.
Resin optical lens preparation example：
At 15 DEG C, 31.38g m-xylylene diisocyanates and 28.97g multi-thiols are added into single port bottle,
0.01g catalyst, 0.05g internal mold releases, 0.1g ultra-violet absorbers, half an hour is stirred, while with below 300Pa's
Vacuum is de-gassed processing.Implantation glass mould and adhesive tape is utilized after above-mentioned composition is filtered using 3 microns of filter cores
Sealed.The mould for filling full composition is placed in baking oven, was to slowly warm up to 120 DEG C from 15 DEG C in 22 hours, and
120 DEG C are continued to cool after solidifying 15 minutes, are placed in after eyeglass is deviate from from mould in baking oven and secondary solidification is carried out at 120 DEG C
2 hours, obtain optical resin lens.
The multi-thiol being prepared in multi-thiol embodiment 1-8 and multi-thiol comparative example 1,2 is respectively adopted
The method of stating is prepared resin optical lens 1-8 and compares resin optical lens 1,2, and the resin optical lens to obtaining are carried out
Test, experimental method is as follows, and test result is shown in Table 1.
Experimental method
Yellow colour index：Take the spectrophotometers of model Lambda 35 test that Perkin Elmer companies produce.
Ageing resistance：Including heat resistance and sunproof overall target.
Heat resistance is tested：Resin optical lens are placed in baking oven, heated 12 hours at a temperature of 120 DEG C, testing lens
The changes delta YI of yellow colour index.
Light resistance is tested, and carries out following test respectively：1) eyeglass is irradiated into 6 days and 12 days respectively using mercury vapor lamp,
Exposure intensity is 35000lx, the changes delta YI of testing lens yellow colour index；2) eyeglass is irradiated 3 days in QUV testing machines, surveyed
The changes delta YI of trial lens yellow colour index, experiment condition are：Light source uses UVB-340, exposure intensity 0.76W/m2, blackboard temperature
60℃。
Monomer prepares Lens pass rate：There is the underproof number judgement of gonorrhoea or yellow colour index by 100 eyeglasses are prepared
Qualification rate, occur more than 5 it is unqualified be judged as that monomer is unqualified.
Optical mirror slip test result prepared by the embodiment 1~8 of table 1 and comparative example 1~2
Claims (8)
1. the post-processing approach of a kind of multi-thiol crude product for optical glasses sheet material, it is characterised in that including following step
Suddenly：
(1) multi-thiol crude product is dissolved in the alkaline aqueous solution containing alkaline conditioner, makes multi-thiol reaction generation mercaptan
Saline solution；
(2) can not be with alkali shape in multi-thiol crude product to remove with the above-mentioned mercaptan saline solution of organic solvent washing not soluble in water
Into the organic impurities of mercaptides, and isolate the aqueous solution containing mercaptides；
(3) acid regulator is added in the aqueous solution containing mercaptides into step (2) separates out multi-thiol, after standing liquid separation
Organic phase is collected, then organic phase is washed with deionized and removes inorganic matter, obtains refined multi-thiol.
2. being used for the post-processing approach of the multi-thiol crude product of optical glasses sheet material as claimed in claim 1, its feature exists
In, adding acid regulator in the step (3), in the aqueous solution containing mercaptides separates out multi-thiol, then with organic molten
Organic phase is collected after agent extraction liquid separation, then organic phase is washed with deionized and removes inorganic matter, and further concentration removal is organic
Refined multi-thiol is obtained after solvent.
3. it is used for the post-processing approach of the multi-thiol crude product of optical glasses sheet material, its feature as claimed in claim 1 or 2
It is, the alkaline conditioner in the step (1) is sodium hydroxide or potassium hydroxide.
4. it is used for the post-processing approach of the multi-thiol crude product of optical glasses sheet material, its feature as claimed in claim 1 or 2
It is, the addition of the alkaline conditioner in the step (1) is 1~1.5 times of mercapto equivalents value in multi-thiol crude product.
5. it is used for the post-processing approach of the multi-thiol crude product of optical glasses sheet material, its feature as claimed in claim 1 or 2
It is, the organic solvent not soluble in water in the step (2) is toluene or ether.
6. it is used for the post-processing approach of the multi-thiol crude product of optical glasses sheet material, its feature as claimed in claim 1 or 2
It is, the acid regulator in the step (3) is hydrochloric acid, sulfuric acid or nitric acid.
7. it is used for the post-processing approach of the multi-thiol crude product of optical glasses sheet material, its feature as claimed in claim 1 or 2
It is, the addition of the acid regulator in the step (3) is 1~1.5 times of mercapto equivalents value in multi-thiol crude product.
8. it is used for the post-processing approach of the multi-thiol crude product of optical glasses sheet material, its feature as claimed in claim 1 or 2
Be, the multi-thiol crude product be 4- thiopurine methyltransferase -1,8- dimercapto -3,6- dithia octane crude products or the thiopurine methyltransferase of 4,8- bis- -
The thia hendecanes of 1,11- dimercaptos -3,6,9- three and the thia hendecanes of bis- thiopurine methyltransferase -1,11- dimercaptos -3,6,9- of 4,7- three and
The undecanoic crude mixture of the thias of bis- thiopurine methyltransferase -1,11- dimercaptos -3,6,9- of 5,7- three or 2- { 3- (2- sulfydryls-second mercapto
Base) -2- [2- (2- sulfydryls-second sulfydryl)-second sulfydryl] third sulfydryl } one kind in ethyl mercaptan crude product.
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