CN117326997A - Polythiol compound, composition for optical material, and preparation method and application thereof - Google Patents
Polythiol compound, composition for optical material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN117326997A CN117326997A CN202311109239.8A CN202311109239A CN117326997A CN 117326997 A CN117326997 A CN 117326997A CN 202311109239 A CN202311109239 A CN 202311109239A CN 117326997 A CN117326997 A CN 117326997A
- Authority
- CN
- China
- Prior art keywords
- bis
- diisocyanate
- polythiol compound
- optical
- hydrochloric acid
- 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.)
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 91
- 229920006295 polythiol Polymers 0.000 title claims abstract description 89
- 230000003287 optical effect Effects 0.000 title claims abstract description 82
- 239000000463 material Substances 0.000 title claims abstract description 73
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 112
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 91
- 229910052742 iron Inorganic materials 0.000 claims description 47
- -1 polyol compound Chemical class 0.000 claims description 27
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 22
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 15
- 229920005862 polyol Polymers 0.000 claims description 14
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 150000002541 isothioureas Chemical class 0.000 claims description 9
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 8
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 239000005056 polyisocyanate Substances 0.000 claims description 5
- 229920001228 polyisocyanate Polymers 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- INBDPOJZYZJUDA-UHFFFAOYSA-N methanedithiol Chemical compound SCS INBDPOJZYZJUDA-UHFFFAOYSA-N 0.000 claims description 4
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- VLCCKNLIFIJYOQ-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] 2,2,3,3-tetrakis(sulfanyl)propanoate Chemical compound OCC(CO)(CO)COC(=O)C(S)(S)C(S)S VLCCKNLIFIJYOQ-UHFFFAOYSA-N 0.000 claims description 3
- COYTVZAYDAIHDK-UHFFFAOYSA-N [5-(sulfanylmethyl)-1,4-dithian-2-yl]methanethiol Chemical compound SCC1CSC(CS)CS1 COYTVZAYDAIHDK-UHFFFAOYSA-N 0.000 claims description 3
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 claims description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- JRNVQLOKVMWBFR-UHFFFAOYSA-N 1,2-benzenedithiol Chemical compound SC1=CC=CC=C1S JRNVQLOKVMWBFR-UHFFFAOYSA-N 0.000 claims description 2
- YRVDWKARENSLCA-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)adamantane Chemical compound C1C(C2)CC3CC1C(CN=C=O)C2(CN=C=O)C3 YRVDWKARENSLCA-UHFFFAOYSA-N 0.000 claims description 2
- YGKHJWTVMIMEPQ-UHFFFAOYSA-N 1,2-propanedithiol Chemical compound CC(S)CS YGKHJWTVMIMEPQ-UHFFFAOYSA-N 0.000 claims description 2
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 claims description 2
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 claims description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 claims description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- SRZXCOWFGPICGA-UHFFFAOYSA-N 1,6-Hexanedithiol Chemical compound SCCCCCCS SRZXCOWFGPICGA-UHFFFAOYSA-N 0.000 claims description 2
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 claims description 2
- BQFHAWXWURJCJM-UHFFFAOYSA-N 2,2-bis(isocyanatomethyl)thiolane Chemical compound O=C=NCC1(CN=C=O)CCCS1 BQFHAWXWURJCJM-UHFFFAOYSA-N 0.000 claims description 2
- MTZVWTOVHGKLOX-UHFFFAOYSA-N 2,2-bis(sulfanylmethyl)propane-1,3-dithiol Chemical compound SCC(CS)(CS)CS MTZVWTOVHGKLOX-UHFFFAOYSA-N 0.000 claims description 2
- IOMBOXJZZQRKSD-UHFFFAOYSA-N 2,6-bis(isocyanatomethyl)naphthalene Chemical compound C1=C(CN=C=O)C=CC2=CC(CN=C=O)=CC=C21 IOMBOXJZZQRKSD-UHFFFAOYSA-N 0.000 claims description 2
- CNDCQWGRLNGNNO-UHFFFAOYSA-N 2-(2-sulfanylethoxy)ethanethiol Chemical compound SCCOCCS CNDCQWGRLNGNNO-UHFFFAOYSA-N 0.000 claims description 2
- HCZMHWVFVZAHCR-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol Chemical compound SCCOCCOCCS HCZMHWVFVZAHCR-UHFFFAOYSA-N 0.000 claims description 2
- ZQLHFUHXRDOCBC-UHFFFAOYSA-N 2-[2-(3-sulfanylpropanoyloxy)ethoxy]ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOCCOC(=O)CCS ZQLHFUHXRDOCBC-UHFFFAOYSA-N 0.000 claims description 2
- GNDOBZLRZOCGAS-JTQLQIEISA-N 2-isocyanatoethyl (2s)-2,6-diisocyanatohexanoate Chemical compound O=C=NCCCC[C@H](N=C=O)C(=O)OCCN=C=O GNDOBZLRZOCGAS-JTQLQIEISA-N 0.000 claims description 2
- IPNDIMIIGZSERC-UHFFFAOYSA-N 4-(2-sulfanylacetyl)oxybutyl 2-sulfanylacetate Chemical compound SCC(=O)OCCCCOC(=O)CS IPNDIMIIGZSERC-UHFFFAOYSA-N 0.000 claims description 2
- JSOVZQSFWPMPKN-UHFFFAOYSA-N 4-(3-sulfanylpropanoyloxy)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCCCOC(=O)CCS JSOVZQSFWPMPKN-UHFFFAOYSA-N 0.000 claims description 2
- WREGWRFRXHKFGE-UHFFFAOYSA-N 4-(4-sulfanylphenoxy)benzenethiol Chemical compound C1=CC(S)=CC=C1OC1=CC=C(S)C=C1 WREGWRFRXHKFGE-UHFFFAOYSA-N 0.000 claims description 2
- GECFNYKBZPHYBN-UHFFFAOYSA-N 4-(4-sulfanylphenyl)sulfonylbenzenethiol Chemical compound C1=CC(S)=CC=C1S(=O)(=O)C1=CC=C(S)C=C1 GECFNYKBZPHYBN-UHFFFAOYSA-N 0.000 claims description 2
- RYXFMCKXOQMCSM-UHFFFAOYSA-N 4-[(4-sulfanylphenyl)methyl]benzenethiol Chemical compound C1=CC(S)=CC=C1CC1=CC=C(S)C=C1 RYXFMCKXOQMCSM-UHFFFAOYSA-N 0.000 claims description 2
- TVLGECZCQTWNOL-UHFFFAOYSA-N 4-propylbenzenethiol Chemical compound CCCC1=CC=C(S)C=C1 TVLGECZCQTWNOL-UHFFFAOYSA-N 0.000 claims description 2
- JLLMOYPIVVKFHY-UHFFFAOYSA-N Benzenethiol, 4,4'-thiobis- Chemical compound C1=CC(S)=CC=C1SC1=CC=C(S)C=C1 JLLMOYPIVVKFHY-UHFFFAOYSA-N 0.000 claims description 2
- WHQBUJCBZGKMIN-UHFFFAOYSA-N C=C.C=C.N=C=O.N=C=O Chemical compound C=C.C=C.N=C=O.N=C=O WHQBUJCBZGKMIN-UHFFFAOYSA-N 0.000 claims description 2
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- IDMCXJRWHDUNRT-UHFFFAOYSA-N [3-(sulfanylmethyl)cyclohexyl]methanethiol Chemical compound SCC1CCCC(CS)C1 IDMCXJRWHDUNRT-UHFFFAOYSA-N 0.000 claims description 2
- JSNABGZJVWSNOB-UHFFFAOYSA-N [3-(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=CC(CS)=C1 JSNABGZJVWSNOB-UHFFFAOYSA-N 0.000 claims description 2
- HRPVDGZEKVNVQW-UHFFFAOYSA-N [4-(sulfanylmethyl)cyclohexyl]methanethiol Chemical compound SCC1CCC(CS)CC1 HRPVDGZEKVNVQW-UHFFFAOYSA-N 0.000 claims description 2
- IYPNRTQAOXLCQW-UHFFFAOYSA-N [4-(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=C(CS)C=C1 IYPNRTQAOXLCQW-UHFFFAOYSA-N 0.000 claims description 2
- MSILJOYZYPRFDK-UHFFFAOYSA-N [4-[4-(sulfanylmethyl)phenoxy]phenyl]methanethiol Chemical compound C1=CC(CS)=CC=C1OC1=CC=C(CS)C=C1 MSILJOYZYPRFDK-UHFFFAOYSA-N 0.000 claims description 2
- WMOSGVRFIUEZSX-UHFFFAOYSA-N [4-[4-(sulfanylmethyl)phenyl]sulfanylphenyl]methanethiol Chemical compound C1=CC(CS)=CC=C1SC1=CC=C(CS)C=C1 WMOSGVRFIUEZSX-UHFFFAOYSA-N 0.000 claims description 2
- UZDQMYFEXFNUFJ-UHFFFAOYSA-N [4-[[4-(sulfanylmethyl)phenyl]methyl]phenyl]methanethiol Chemical compound C1=CC(CS)=CC=C1CC1=CC=C(CS)C=C1 UZDQMYFEXFNUFJ-UHFFFAOYSA-N 0.000 claims description 2
- DHHJQXAJIIVBES-UHFFFAOYSA-N [5-(sulfanylmethyl)thiophen-2-yl]methanethiol Chemical compound SCC1=CC=C(CS)S1 DHHJQXAJIIVBES-UHFFFAOYSA-N 0.000 claims description 2
- ZWOASCVFHSYHOB-UHFFFAOYSA-N benzene-1,3-dithiol Chemical compound SC1=CC=CC(S)=C1 ZWOASCVFHSYHOB-UHFFFAOYSA-N 0.000 claims description 2
- WYLQRHZSKIDFEP-UHFFFAOYSA-N benzene-1,4-dithiol Chemical compound SC1=CC=C(S)C=C1 WYLQRHZSKIDFEP-UHFFFAOYSA-N 0.000 claims description 2
- SMTOKHQOVJRXLK-UHFFFAOYSA-N butane-1,4-dithiol Chemical compound SCCCCS SMTOKHQOVJRXLK-UHFFFAOYSA-N 0.000 claims description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 claims description 2
- YKRCKUBKOIVILO-UHFFFAOYSA-N cyclohexane-1,2-dithiol Chemical compound SC1CCCCC1S YKRCKUBKOIVILO-UHFFFAOYSA-N 0.000 claims description 2
- UMSNERSLSHPBNT-UHFFFAOYSA-N cyclohexane-1,3-dithiol Chemical compound SC1CCCC(S)C1 UMSNERSLSHPBNT-UHFFFAOYSA-N 0.000 claims description 2
- QQKBIYRSRXCROF-UHFFFAOYSA-N cyclohexane-1,4-dithiol Chemical compound SC1CCC(S)CC1 QQKBIYRSRXCROF-UHFFFAOYSA-N 0.000 claims description 2
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 claims description 2
- WNIMPVMSRDFHTD-UHFFFAOYSA-N methanetrithiol Chemical compound SC(S)S WNIMPVMSRDFHTD-UHFFFAOYSA-N 0.000 claims description 2
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 claims description 2
- TWXMZYPORGXIFB-UHFFFAOYSA-N thiophene-3,4-dithiol Chemical compound SC1=CSC=C1S TWXMZYPORGXIFB-UHFFFAOYSA-N 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N 1-propanol Substances CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 1
- MXTOXODEXBYZFX-UHFFFAOYSA-N 2-[2-(2-sulfanylethylsulfanyl)ethylsulfanyl]ethanethiol Chemical compound SCCSCCSCCS MXTOXODEXBYZFX-UHFFFAOYSA-N 0.000 claims 1
- LPUUPYOHXHWKAR-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol 3,3,3-tris(sulfanyl)propanoic acid Chemical compound SC(CC(=O)O)(S)S.C(O)C(CC)(CO)CO LPUUPYOHXHWKAR-UHFFFAOYSA-N 0.000 claims 1
- SERCPQYXEUPQHB-UHFFFAOYSA-N 5,6-diisocyanato-5-methylcyclohexa-1,3-diene Chemical compound O=C=NC1(C)C=CC=CC1N=C=O SERCPQYXEUPQHB-UHFFFAOYSA-N 0.000 claims 1
- JCELWOGDGMAGGN-UHFFFAOYSA-N N=C=O.N=C=O.C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 JCELWOGDGMAGGN-UHFFFAOYSA-N 0.000 claims 1
- WCPXJPRLMDLMDU-UHFFFAOYSA-N SCCSCC1SCC(SC1)CSCCS.SCC1SCC(SC1)CS Chemical compound SCCSCC1SCC(SC1)CSCCS.SCC1SCC(SC1)CS WCPXJPRLMDLMDU-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 2
- 235000011167 hydrochloric acid Nutrition 0.000 description 52
- 239000011347 resin Substances 0.000 description 49
- 229920005989 resin Polymers 0.000 description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
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- 238000012797 qualification Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000009776 industrial production Methods 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 229920000388 Polyphosphate Polymers 0.000 description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000001205 polyphosphate Substances 0.000 description 4
- 235000011176 polyphosphates Nutrition 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 3
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- 239000012298 atmosphere Substances 0.000 description 3
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- WNPSAOYKQQUALV-UHFFFAOYSA-N 1,3-bis(sulfanyl)propan-2-ol Chemical compound SCC(O)CS WNPSAOYKQQUALV-UHFFFAOYSA-N 0.000 description 1
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- BDLJDZLEOKUVHM-UHFFFAOYSA-N 2,5-bis(isocyanatomethyl)thiophene Chemical compound O=C=NCC1=CC=C(CN=C=O)S1 BDLJDZLEOKUVHM-UHFFFAOYSA-N 0.000 description 1
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-UHFFFAOYSA-N 0.000 description 1
- KSJBMDCFYZKAFH-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanyl)ethanethiol Chemical compound SCCSCCS KSJBMDCFYZKAFH-UHFFFAOYSA-N 0.000 description 1
- NQLQMVQEQFIDQB-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanyl)propane-1,3-dithiol Chemical compound SCCSC(CS)CS NQLQMVQEQFIDQB-UHFFFAOYSA-N 0.000 description 1
- HAQZWTGSNCDKTK-UHFFFAOYSA-N 2-(3-sulfanylpropanoyloxy)ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOC(=O)CCS HAQZWTGSNCDKTK-UHFFFAOYSA-N 0.000 description 1
- VGEOIVXAFNNZKM-UHFFFAOYSA-N 2-(sulfanylmethyl)butane-1,4-dithiol Chemical compound SCCC(CS)CS VGEOIVXAFNNZKM-UHFFFAOYSA-N 0.000 description 1
- FOBHCEPKFIUKPH-UHFFFAOYSA-N 2-(sulfanylmethyl)propane-1,3-dithiol Chemical compound SCC(CS)CS FOBHCEPKFIUKPH-UHFFFAOYSA-N 0.000 description 1
- LOSJLAVLYJUGJO-UHFFFAOYSA-N 2-[1,3-bis(sulfanyl)propan-2-ylsulfanyl]propane-1,3-dithiol Chemical compound SCC(CS)SC(CS)CS LOSJLAVLYJUGJO-UHFFFAOYSA-N 0.000 description 1
- ISGHUYCZFWLBRU-UHFFFAOYSA-N 2-[2-(2-sulfanylacetyl)oxyethoxy]ethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOCCOC(=O)CS ISGHUYCZFWLBRU-UHFFFAOYSA-N 0.000 description 1
- WVWWFRBCDIXMGT-UHFFFAOYSA-N 2-[[5-(2-sulfanylethylsulfanylmethyl)-1,4-dithian-2-yl]methylsulfanyl]ethanethiol Chemical compound SCCSCC1CSC(CSCCS)CS1 WVWWFRBCDIXMGT-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- WMTLVUCMBWBYSO-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1OC1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1OC1=CC=CC=C1 WMTLVUCMBWBYSO-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- VYQRBKCKQCRYEE-UHFFFAOYSA-N ctk1a7239 Chemical compound C12=CC=CC=C2N2CC=CC3=NC=CC1=C32 VYQRBKCKQCRYEE-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008029 eradication Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000008177 pharmaceutical agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002578 polythiourethane polymer Polymers 0.000 description 1
- UWHMFGKZAYHMDJ-UHFFFAOYSA-N propane-1,2,3-trithiol Chemical compound SCC(S)CS UWHMFGKZAYHMDJ-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Classifications
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C335/30—Isothioureas
- C07C335/32—Isothioureas having sulfur atoms of isothiourea groups bound to acyclic carbon atoms
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of manufacturing optical materials such as plastic lenses, prisms, filters and the like, and particularly relates to a polythiol compound, a composition for optical materials, a preparation method and application thereof.
Description
Technical Field
The invention belongs to the technical field of manufacturing optical materials such as plastic lenses, prisms, filters and the like, and particularly relates to a polythiol compound, a composition for the optical materials, a preparation method and application thereof.
Background
Compared with inorganic glass, optical resins have the advantages of light weight, high toughness, dyeability, and the like, and have been rapidly popularized in the field of optical elements in optical instruments and optical systems in recent years. Optical resins used in the field of optical resin lenses such as spectacles and lenses are required to have higher performance, and high transparency, low yellowness, high refractive index, high abbe number, high strength, and the like are required. The high refractive index can thin the lens, and the high abbe number reduces chromatic aberration of the lens.
Polythiourethane type optical resin materials, which are important developments in recent years, have excellent properties such as high transparency, low yellowness, high refractive index, high abbe number, and high strength. The resin material is mainly prepared from polythiol compounds and isocyanate serving as raw materials.
However, since the polythiol compound has a high color purity and poor color stability, the raw material requirements for producing an optical resin lens excellent in performance cannot be satisfied, and the optical resin material produced from the polythiol compound and the polyisocyanate has a problem that the optical resin material is yellowish in primary color, where primary color means the color of the optical resin material produced without adding a pigment. Poor stability of the color fastness of the polythiol compound may result in a lower product yield of the polythiol compound and the optical resin material, thereby seriously affecting the industrial production efficiency and industrial production benefit of the polythiol compound and the optical resin material.
The preparation of the low-chroma and stable-chroma polythiol compound not only can meet the requirements of industries such as fine chemical engineering and the like, but also can improve the quality of downstream products, further improve the quality and commercial value of the optical resin lens, and is easier to prepare the optical resin lens with excellent performance, so that the preparation of the low-chroma and stable-chroma polythiol compound is very important from the aspects of industrial production efficiency and economy.
Disclosure of Invention
Aiming at the technical problems existing in the prior art, the invention provides a polythiol compound, a composition for optical materials, a preparation method and application thereof, and hydrochloric acid with limited specific iron content is used for reducing the chromaticity of the industrially produced polythiol compound, improving the qualification rate of the polythiol compound and further improving the qualification rate of optical material products.
The inventors have made intensive studies to solve the above-mentioned problems, and have found that a polythiol compound having a low chromaticity and a high chromaticity stability can be obtained by producing a polythiol compound from hydrochloric acid having an iron content of a specific amount or less as a raw material in a process for producing a polythiol compound, and that an optical resin material having a stable color using the polythiol compound can be obtained by affecting the chromaticity of the polythiol compound used and the chromaticity of the polythiol compound. Hydrochloric acid and thiourea are added into a polyol compound formed by reacting mercaptoethanol, epichlorohydrin and alkali solution under certain conditions for reaction in the production process of the polythiol compound, thiocyanate impurities containing thiocyanate radicals in the thiourea are subjected to complexation reaction with iron ions, so that the chromaticity of the polythiol compound is influenced, the thiocyanate impurities in the thiourea are complex in technical requirements for removing the thiocyanate impurities and incomplete in eradication, the iron content of the polyol compound is not easy to control, the technical process for reducing the iron content is complex and difficult, the amount of the iron element in hydrochloric acid is easy to control, and the method for reducing the iron content in the hydrochloric acid is various, simple in process and simple and convenient to operate. Therefore, the inventor controls the iron ion content in the hydrochloric acid to inhibit the generation of the complexing reaction, so that the prepared polythiol compound has low and stable chromaticity, and the quality of the optical material product is further ensured.
The invention provides a method for preparing a polythiol composition, which can inhibit the formation of the complexation reaction by controlling the iron content of hydrochloric acid, thereby stabilizing and reducing the chromaticity of industrially produced polythiol compounds, stabilizing the primary colors of optical resin materials, and finally improving the industrial production efficiency and the industrial production benefit of the polythiol compounds and the optical resin materials. The technical scheme of the invention is as follows:
a polythiol compound is prepared from a polyalcohol compound, hydrochloric acid and thiourea to prepare isothiourea salt, and the isothiourea salt is hydrolyzed to obtain the polythiol compound, wherein the structural formula of the polyalcohol compound is shown as a formula (1):
the hydrochloric acid has an iron content of 20ppm or less and an iron content of 20ppm or less, and thus the polythiol compound produced using the hydrochloric acid has a low color. When an optical resin material is produced using such a polythiol compound, an optical resin material having stable primary color is obtained.
Preferably, it is 10ppm or less. The iron content of the hydrochloric acid can be measured by an atomic absorption spectrometer.
Preferably, the mass fraction of the hydrochloric acid is 20% -38%.
Preferably, the polyol compound is prepared by reacting mercaptoethanol, epichlorohydrin and alkali solution under certain conditions, and the structural formula of the polyol compound is shown as formula (2):
preferably, a polythiol compound is prepared by the following steps:
step A:
2-mercaptoethanol, epichlorohydrin and alkali solution react under certain conditions to synthesize a polyol compound, and after the 2-mercaptoethanol and the alkali solution are mixed, the epichlorohydrin is added dropwise for reaction; the reaction may be carried out at a temperature in the range of 10 to 50 ℃, preferably 15 to 50 ℃, more preferably 30 to 45 ℃; the reaction may be carried out for 0.5 to 3 hours, preferably 1 to 2 hours, more preferably 1.5 hours. The reaction time includes an epichlorohydrin dropping time, and the temperature of the reaction solution at the time of dropping needs to be adjusted to the above reaction temperature.
The amount of 2-mercaptoethanol to be used is preferably 1.5 to 2.5 moles, more preferably 1.8 to 2.2 moles, and still more preferably 1.9 to 2.1 moles, based on 1 mole of epichlorohydrin; the alkali solution may be sodium hydroxide solution, and in the case of a monobasic alkali, the amount of sodium hydroxide solution to be used is 0.5 to 2.0 moles, preferably 0.8 to 1.7 moles, more preferably 0.9 to 1.1 moles, relative to 1 mole of epihalohydrin.
And (B) working procedure:
adding hydrochloric acid and thiourea into the polyol compound obtained in the step A for reaction to obtain isothiourea salt; the amount of hydrochloric acid to be used is preferably 3.0 to 18.0 moles, more preferably 3.0 to 10.0 moles, and still more preferably 3.0 to 6.0 moles, based on 1 mole of the polyol compound; the amount of thiourea to be used is preferably 2.6 to 9.0 moles, more preferably 2.8 to 7.0 moles, and still more preferably 2.8 to 3.2 moles, based on 1 mole of the polyol compound; the reaction temperature is 30 to 120 ℃, preferably 70 to 120 ℃, more preferably 110 ℃; hydrochloric acid is used in a specific amount or less, that is, hydrochloric acid having an iron content of 20ppm or less is used, and the mass fraction concentration of hydrochloric acid is 37%.
And (C) working procedure:
adding an alkaline solution to the reaction solution containing the isothiourea salt obtained in the step B, and hydrolyzing the isothiourea salt to obtain a polythiol compound; while maintaining the temperature of the reaction solution containing isothiouronium salt at 15 to 60 ℃, preferably 20 to 55 ℃, more preferably 25 to 35 ℃, an alkaline solution is added to the reaction solution for 80 minutes or less, preferably 70 minutes or less, more preferably 20 to 60 minutes.
The alkaline solution may be added with ammonia (NH) in such an amount that the amount of ammonia is 1 mol based on the amount of hydrogen chloride used 3 ) In the amount of 1.0 to 12.0 moles, preferably 1 to 3 moles, more preferably 1.1 to 2 moles or less. After addition of the aqueous ammonia, the reaction temperature is 45 to 70 ℃, preferably 50 to 60 ℃, more preferably 55 ℃, and the reaction time is 2 to 6 hours, preferably 2 to 4 hours.
And step D:
the polythiol compound obtained in step C is purified by washing and drying. Specifically, the washing is performed a plurality of times, preferably 1 to 3 times, more preferably 2 times. The drying mode is preferably vacuum dehydration, and the drying temperature is preferably 60-80 ℃, more preferably 70 ℃.
The above steps may be performed in the atmosphere or in an atmosphere other than the atmosphere, for example, in a nitrogen atmosphere.
The composition for optical material comprises, by weight, 20-60 parts of the polythiol compound, 0-40 parts of other polythiol compounds, and 30-60 parts of polyisocyanate.
Preferably, the method comprises the steps of, other polythiol compounds are 4, 7-dimercaptomethyl-1, 11-dimercaptomethyl-3, 6, 9-trithioundecane, 4, 8-dimercaptomethyl-1, 11-dimercaptoethyl-3, 6, 9-trithioundecane, 5, 7-dimercaptomethyl-1, 11-dimercaptoethyl-3, 6, 9-trithioundecane, methanedithiol, methanetrithiol, bis (2-mercaptoethyl) ether, tetrakis (mercaptomethyl) methane, 1, 2-dimercaptopropane, 1, 3-dimercaptopropane, 1, 4-dimercaptobutane, 1, 6-dimercaptohexane, 2-dimercaptopropane, 1, 2-bis (2-mercaptoethoxy) ethane, 1, 2-bis (2-mercaptoethylthio) ethane 2, 3-dimercapto-1-propanol, 1, 2-dimercaptoethane, 1, 3-dimercapto-2-propanol, 2-mercaptomethyl-1, 3-dimercaptopropane, 2-mercaptomethyl-1, 4-dimercaptobutane, 1,2, 3-trimercapto-propane, 2- (2-mercaptoethylthio) -1, 3-dimercaptopropane, 2, 4-dimercaptomethyl-1, 5-dimercapto-3-thiapentane, bis (2-mercaptoethyl) sulfide, ethylene glycol bis (3-mercaptopropionate), diethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (2-mercaptoacetate), 1, 4-butanediol bis (2-mercaptoacetate), trimethylolpropane trimercapto propionate, pentaerythritol tetramercapto acetate, diethylene glycol bis (3-mercaptopropionate), pentaerythritol tetramercapto propionate, 1, 2-dimercaptocyclohexane, 1-tris (mercaptomethyl) propane, 1, 4-butanediol bis (3-mercaptopropionate), 1, 3-dimercaptocyclohexane, trimethylolpropane trimercaptate, 1, 4-dimercaptocyclohexane, 1, 3-bis (mercaptomethyl) cyclohexane, 1, 4-bis (mercaptomethyl) cyclohexane, bis (4-mercaptophenyl) sulfone, 2, 5-dimercaptomethyl-1, 4-dithiane, 2, 5-bis (2-mercaptoethylthiomethyl) -1, 4-dithiane 2, 5-dimercaptomethyl-1-thiane, 2, 5-dimercaptoethyl-1-thiane, 2, 5-dimercaptomethyl thiophene, bis (4-mercaptophenyl) sulfide, 1, 2-dimercaptobenzene, 1, 3-dimercaptobenzene, 1, 4-dimercaptobenzene, 1, 3-bis (mercaptomethyl) benzene, 2, 5-dimercaptomethyl-1, 4-dithiane, 1, 4-bis (mercaptomethyl) benzene, 2 '-dimercaptobenzene, bis (4-mercaptophenyl) methane, 2-bis (4-mercaptophenyl) propane, 4' -dimercaptobenzene, bis (4-mercaptophenyl) ether, bis (4-mercaptomethylphenyl) methane, one or more of 1, 3-tetra (mercapto methylthio) propane 2, 2-bis (4-mercapto methylphenyl) propane, bis (4-mercapto methylphenyl) ether, bis (4-mercapto methylphenyl) sulfide, 2, 5-dimercapto-1, 3, 4-thiadiazole, and 3, 4-thiophene dithiol.
Preferably, the polyisocyanate is one or more of tetramethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, 4' -diisocyanate dicyclohexylmethane, isophorone diisocyanate, norbornane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethylm-xylylene diisocyanate, dithiodipropyl diisocyanate, dithiodiethyl diisocyanate, 2, 5-diisocyanatomethyl thiophene, 2, 5-diisocyanatomethyl-1, 4-dithiane, 2, 5-diisocyanate-1, 4-dithiane, thiodihexyl diisocyanate, thiodipropyl diisocyanate, bis (isocyanatomethyl) adamantane, bis (isocyanatomethyl) tetrahydrothiophene, 2, 6-bis (isocyanatomethyl) naphthalene, 1, 5-naphthalene diisocyanate, diethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine triisocyanate, toluene diisocyanate, o-tolidine diisocyanate, diphenylmethane diisocyanate, diphenyl ether diisocyanate, triphenylmethane.
A method for preparing an optical material, comprising the steps of: adding a catalyst in an amount of 0.001 to 0.2% by mass based on the total mass of the optical material composition into the optical material composition, and polymerizing and curing the mixture.
Preferably, the catalyst is one of dibutyl tin dilaurate, dibutyl tin dichloride, dibutyl tin oxide and stannous octoate.
Industrial hydrochloric acid has a high iron content due to the production process, transportation and storage processes, and the iron content of the hydrochloric acid can be reduced by a known warm roasting method, an evaporation method, an ion exchange method, a membrane treatment method (including an electrodialysis method, a nanofiltration method, an electrolysis method and the like) and a chemical conversion method.
A preparation method of an optical material comprises the following steps: adding a catalyst in an amount of 0.001 to 0.2% by mass based on the total mass of the optical material composition into the optical material composition, and polymerizing and curing the mixture.
Preferably, the catalyst is added in an amount of 0.005 to 0.2%, more preferably 0.01 to 0.1%, still more preferably 0.01 to 0.05%. An amount of catalyst added less than 0.005% may cause incomplete polymerization, resulting in poor mechanical formation of the optical material. When the catalyst addition amount is more than 0.2%, the polymerization rate may sometimes become too high, resulting in an increase in the color tone of the optical material.
Preferably, the catalyst is one of dibutyl tin dilaurate, dibutyl tin dichloride, dibutyl tin oxide and stannous octoate. Further preferred is one of dibutyltin dilaurate and dibutyltin dichloride. In addition to the catalyst, a release agent, an ultraviolet absorber, a toner, a release agent, and the like may be added as needed in the preparation method of the optical material, thereby further improving the usability of the optical material.
The optical material prepared by the preparation method of the optical material is applied to the field of optical elements in preparation of optical instruments or optical systems.
The invention provides a polythiol compound, a composition for an optical material and a preparation method thereof, wherein the chromaticity of the polythiol compound produced industrially can be stabilized by the polythiol compound with specific iron content, the qualification rate of the polythiol compound is improved, and finally the primary color of the optical material prepared by the polythiol compound is regulated and controlled, so that the qualification rate of an optical material product is improved.
Detailed Description
The technical solutions in the present embodiment will be described in detail below, but the described embodiments are only some embodiments of the present invention and not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
In the following examples and comparative examples: 1 iron content in hydrochloric acid
The measurement was performed using an atomic absorption spectrometer of Agilent 240FS AA.
2. Chromaticity of polythiol compound
The measurement chromaticity of the polythiol compound obtained in the example of the present invention was measured by a high-precision multifunctional spectrocolorimeter (HunterLab UltraScan PRO).
3. The primary color characterization method comprises the following steps:
two pieces of plate glass with the diameter of 80mm and an adhesive tape are clamped by a semi-automatic die clamping machine to prepare a die with the thickness of 2mm, and the optical material composition added with the catalyst and the parting agent is injected into the die for programmed heating and curing. And cooling after curing is finished, demoulding to obtain the optical material, and detecting the b value of the material by adopting a colorimeter, wherein the higher the b value is, the more yellow the color of the material is, and the smaller the b value is, the lighter the color of the material is.
4. Curing and heating program: maintaining at 30deg.C for 180min, heating to 45deg.C for 120min, heating to 50deg.C for 90min, heating to 60deg.C for 120min, heating to 120deg.C for 240min, maintaining at 120deg.C for 240min, and cooling to 80deg.C for 120 min.
The present invention will be described in further detail with reference to examples, but the present invention is not limited thereto.
In this example, the sources of the pharmaceutical agents are not particularly limited, the raw materials are all commercial products, the following hydrochloric acid can be obtained by purchasing, and if the purchased products cannot meet the requirements, the following method can be used to reduce the iron content in the hydrochloric acid.
A method of reducing the iron content of hydrochloric acid:
the ion exchange resin for reducing the iron content of industrial hydrochloric acid is ASD-003 of Shaanxi Ministry of new material technology, and ASD-003 is a macroporous weak alkaline anion exchange resin which mainly uses polystyrene skeleton, and is widely applied to removing metal iron ions from high-concentration hydrochloric acid.
The method comprises the following specific steps:
(1) Pretreatment of resin: taking a plurality of ion exchange resins, washing the ion exchange resins by using distilled water, pumping the ion exchange resins, taking a plurality of pumped resins, adding a 4% sodium hydroxide solution with the concentration of 2 times of the resin volume, soaking the resin for overnight, washing and replacing the resin by using distilled water until the pH value of the effluent is 7-9, finishing washing, pumping the resin, adding a 4% hydrochloric acid with the concentration of 2 times of the resin volume, soaking the resin for overnight, washing and replacing the resin by using distilled water until the pH value of the effluent is 5-7, finishing washing, and pumping the resin for later use.
(2) Resin column filling: mixing a plurality of pretreated ion exchange resins with deionized water in a beaker, pouring the mixed resin aqueous solution into a measuring cylinder to enable the resins to fully settle (a knocking method can be adopted), filling and removing the resin volume to be leveled with corresponding scales (required resin volume) to finish the measurement of the resins, closing an outlet valve at the lower end of an ion exchange column, fully introducing the resins in the measuring cylinder into the ion exchange column by using a washing bottle (filled with deionized water), opening the outlet valve of the ion exchange column (paying attention to the opening of the valve to enable the outlet water to become streamline, enabling the resins to settle and compact in the column, and then closing the outlet valve of the ion exchange column for standby; note that: the liquid level is kept 1-2cm higher than the resin bed layer, and the dry column is avoided.
(3) The outlet of the ion exchange column is received by a receiving barrel, the top of the receiving barrel is connected with a tail gas absorbing bottle, and a group of absorbent cotton is plugged into the top of the ion exchange column;
(4) Injecting hydrochloric acid to be treated into an outlet of an ion exchange column by using a peristaltic pump, controlling the flow of the hydrochloric acid to be 1-50 BV/h (BV: resin volume, 1 BV=1 resin volume) by controlling the peristaltic pump, ensuring that the liquid level of the hydrochloric acid in the resin column is 1-2cm higher than a resin interface in the exchange process, and periodically sampling and analyzing the content of iron in the hydrochloric acid, wherein when the content of iron exceeds a standard, the exchange is stopped to perform resin regeneration operation;
(5) Resin regeneration: the resin is washed by deionized water in a countercurrent mode, the flow rate is controlled to be 3BV per hour, the iron content in effluent liquid is required to be continuously checked during washing, the washing is finished until no iron exists, and the exchange process can be carried out again after the resin regeneration operation is finished.
The iron ion content of the hydrochloric acid is 100ppm, and the hydrochloric acid flow rates of 1BV/h, 3BV/h, 5BV/h, 8BV/h, 12BV/h, 20BV/h and 33BV/h are controlled by controlling a peristaltic metering pump, and the iron content of different hydrochloric acids collected under the hydrochloric acid flow rates is detected to be 0.5ppm, 1ppm, 5ppm, 10ppm, 20ppm, 25ppm and 30ppm respectively.
Example 1
A polythiol compound:
68.0g of a 32% strength aqueous sodium hydroxide solution and 46.3g of epichlorohydrin were sequentially added to 82.0g of 2-mercaptoethanol and reacted at a temperature ranging from 30 to 45℃for 1.5 hours to obtain a reaction mixture of the polyol compound represented by the formula (2); then 200g of hydrochloric acid with the iron content of 0.5ppm and the mass fraction of 37 percent and 125g of thiourea with the purity of 99.20 percent are added, and reflux is carried out for 3 hours at the temperature of 110 ℃ to obtain isothiouronium salt; cooling to below 30 ℃, adding 250g of ammonia water with the concentration of 18% (mass percent) into the isothiourea salt obtained in the previous step, reacting for 3 hours at 55 ℃, standing for layering, separating a lower organic phase to obtain a polythiol compound crude product shown in the formula (1), washing the polythiol compound crude product with water for 2 times, and carrying out vacuum dehydration at 70 ℃ to obtain the polythiol compound shown in the formula (1). The chromaticity of the polythiol compound was measured by a high-precision multi-functional spectrocolorimeter (HunterLab UltraScan PRO), and the evaluation results are shown in table 1.
The preparation method of the optical material comprises the following steps:
52.0 parts by mass of xylylene diisocyanate, 0.01 parts by mass of catalyst (dibutyl tin dichloride) and 0.08 parts by mass of release agent (polyphosphate) are added into a flask, and stirred and dissolved at 15 ℃; adding 48.0 parts by mass of the polythiol compound obtained in the above, uniformly stirring, degassing by using a vacuum pump, controlling the pressure below 350Pa and the degassing time to be 0.8 hour to prepare a mixed solution, pouring the solution into a mold with the diameter of 80mm and the center thickness of 2.0mm, placing into an oven for programmed heating and solidification, taking out the mold after the temperature of the oven is reduced to 80 ℃, opening the mold to obtain an optical material, naturally cooling the material for 1 hour at the room temperature of 25 ℃, detecting the b value by using a colorimeter, and evaluating the result shown in table 1.
Example 2
The difference with respect to example 1 is that: the iron content of the hydrochloric acid was 1ppm, and the remainder was the same as in example 1.
Example 3
The difference with respect to example 1 is that: the iron content of the hydrochloric acid was 5ppm, and the remainder was the same as in example 1.
Example 4
The difference with respect to example 1 is that: the iron content of the hydrochloric acid was 10ppm, and the remainder was the same as in example 1.
Example 5
The difference with respect to example 1 is that: the iron content of the hydrochloric acid was 20ppm, and the remainder was the same as in example 1.
Comparative example 1
The difference with respect to example 1 is that: the iron content of the hydrochloric acid was 25ppm, and the remainder was the same as in example 1.
Comparative example 2
The difference with respect to example 1 is that: the iron content of the hydrochloric acid was 30ppm, and the remainder was the same as in example 1.
Table 1 the polythiol compounds of examples 1 to 5 and comparative examples 1 to 2 and the evaluation results of the optical materials.
Example 6
A polythiol compound:
68.0g of a 32% strength aqueous sodium hydroxide solution and 46.3g of epichlorohydrin were sequentially added to 82.0g of 2-mercaptoethanol and reacted at a temperature ranging from 30 to 45℃for 1.5 hours to obtain a reaction mixture of the polyol compound represented by the formula (2); then 200g of hydrochloric acid with the iron content of 0.5ppm and the mass fraction of 37 percent and 125g of thiourea with the purity of 99.20 percent are added, and reflux is carried out for 3 hours at the temperature of 110 ℃ to obtain isothiouronium salt; cooling to below 30 ℃, adding 250g of 18% ammonia water into the isothiourea salt obtained in the previous step, reacting for 3 hours at 55 ℃, standing for layering, separating a lower organic phase to obtain a polythiol compound crude product shown in a formula (1), washing the polythiol compound crude product for 2 times, and carrying out vacuum dehydration at 70 ℃ to obtain the polythiol compound shown in the formula (1); the chromaticity of the polythiol compound was measured by a high-precision multi-functional spectrocolorimeter (HunterLab UltraScan PRO), and the evaluation results are shown in table 2.
The preparation method of the optical material comprises the following steps:
49.8 parts by mass of hydrogenated xylylene diisocyanate, 0.10 parts by mass of catalyst (dibutyl tin dichloride) and 0.10 parts by mass of release agent (polyphosphate) are added into a flask, and stirred and dissolved at 15 ℃; adding and mixing 30.2 parts by mass of the obtained polythiol compound and 20.0 parts by mass of pentaerythritol tetrasulfuryl propionate, and uniformly stirring; degassing by a vacuum pump under the pressure of 350Pa and the degassing time of 0.8 hour to prepare a mixed solution, pouring the solution into a mold with the diameter of 80mm and the center thickness of 2.0mm, placing the mold into an oven for programmed heating and solidification, cooling the temperature of the oven to 80 ℃, taking out the mold, opening the mold, naturally cooling the material for 1 hour at the room temperature of 25 ℃, and detecting the value b by using a colorimeter. The evaluation results are shown in Table 2.
Example 7
The difference with respect to example 6 is that: the iron content of the hydrochloric acid was 1ppm, and the remainder was the same as in example 6.
Example 8
The difference with respect to example 6 is that: the iron content of the hydrochloric acid was 5ppm, and the remainder was the same as in example 6.
Example 9
The difference with respect to example 6 is that: the iron content of the hydrochloric acid was 10ppm, and the remainder was the same as in example 6.
Example 10
The difference with respect to example 6 is that: the iron content of the hydrochloric acid was 20ppm, and the remainder was the same as in example 6.
Comparative example 3
The difference with respect to example 6 is that: the iron content of the hydrochloric acid was 25ppm, and the remainder was the same as in example 6.
Comparative example 4
The difference with respect to example 6 is that: the iron content of the hydrochloric acid was 30ppm, and the remainder was the same as in example 6.
Table 2 shows the evaluation results of polythiol compounds and optical materials of examples 6 to 10 and comparative examples 3 to 4:
example 11
A polythiol compound:
68.0g of a 32% strength aqueous sodium hydroxide solution and 46.3g of epichlorohydrin were sequentially added to 82.0g of 2-mercaptoethanol and reacted at a temperature ranging from 30 to 45℃for 1.5 hours to obtain a reaction mixture of the polyol compound represented by the formula (2); then 200g of hydrochloric acid with the iron content of 10ppm and the mass fraction of 36 percent and 125g of thiourea with the purity of 99.20 percent are added, and reflux is carried out for 3 hours at the temperature of 110 ℃ to obtain isothiouronium salt; cooling to below 30 ℃, adding 250g of 18 wt% ammonia water into the isothiourea salt obtained in the previous step, reacting for 3 hours at 55 ℃, standing for layering, separating a lower organic phase to obtain a polythiol compound crude product shown in a formula (1), washing the polythiol compound crude product with water for 2 times, and vacuum dehydrating at 70 ℃ to obtain the polythiol compound shown in the formula (1). The chroma of the polythiol compound was measured to be 7.6 by a high-precision multifunctional spectrocolorimeter (HunterLab UltraScan PRO).
The preparation method of the optical material comprises the following steps:
22.8 parts by mass of hexamethylene diisocyanate, 10.0 parts by mass of isophorone diisocyanate, 16.0 parts by mass of hydrogenated xylylene diisocyanate, 0.15 parts by mass of catalyst (dibutyltin dichloride) and 0.10 parts by mass of release agent (polyphosphate) were added to the flask, and the mixture was stirred and dissolved at 15 ℃. Adding and mixing 33.0 parts by mass of the obtained polythiol compound and 18.2 parts by mass of pentaerythritol tetramercaptopropionate, uniformly stirring, degassing by a vacuum pump, controlling the pressure below 350Pa, preparing a mixed solution after the degassing time is 0.8 hour, pouring the solution into a mold with the diameter of 80mm and the center thickness of 2.0mm, placing into an oven for programmed heating and solidification, cooling the temperature of the oven to 80 ℃, taking out the mold, opening the mold, naturally cooling the material for 1 hour at the room temperature of 25 ℃, and detecting the b value of 0.32 by a colorimeter.
Example 12
A polythiol compound:
68.0g of a 32% strength aqueous sodium hydroxide solution and 46.3g of epichlorohydrin were successively added to 82.0g of 2-mercaptoethanol and reacted at a temperature in the range of 25℃for 1.5 hours to obtain a reaction mixture having a polyol compound. Then, 200g of hydrochloric acid having an iron content of 10ppm and a mass fraction of 36% and 125g of thiourea having a purity of 99.20% were added, and refluxed at 110℃for 3 hours to obtain an isothiouronium salt. Cooling to 25 ℃, adding 250g of 18 wt% ammonia water into the obtained reaction mixture, reacting for 3 hours at 55 ℃, standing for layering, separating the lower organic phase to obtain a polythiol compound crude product shown in the formula (1), washing the polythiol compound crude product with water for 2 times, and vacuum dehydrating at 70 ℃ to obtain the polythiol compound shown in the formula (1). The chroma of the polythiol compound was measured to be 7.6 by a high-precision multifunctional spectrocolorimeter (HunterLab UltraScan PRO).
The preparation method of the optical material comprises the following steps:
49.6 parts by mass of norbornane diisocyanate, 0.03 parts by mass of catalyst (dibutyl tin dichloride) and 0.75 parts by mass of release agent (polyphosphate) were added to the flask, and the mixture was stirred and dissolved at 10 to 20 ℃. 25.5 parts by mass of the polythiol compound obtained above, 23.9 parts by mass of pentaerythritol tetrasulfopropionate were added and mixed, followed by stirring. Degassing by a vacuum pump under the pressure of 350Pa and the degassing time of 0.8 hour to prepare a mixed solution, pouring the solution into a mold with the diameter of 80mm and the center thickness of 2.0mm, placing the mold into an oven for programmed heating and solidification, cooling the temperature of the oven to 80 ℃, taking out the mold, opening the mold, naturally cooling the material for 1 hour at the room temperature of 25 ℃, and detecting the b value of 0.35 by using a colorimeter.
As is clear from the results of the above examples and comparative examples, the polythiol compound obtained using hydrochloric acid having an iron content of 20ppm or less has a low color and a stable color, and the b value of the optical material produced using the polythiol compound is low and stable. In contrast, the polythiol compounds obtained in comparative examples 1 to 4 using hydrochloric acid having an iron content exceeding 20ppm exhibited high chromaticity, and the b-value of the obtained optical resin materials was also high. The optical materials obtained in examples and comparative examples were colorless and transparent, but when all the optical resin materials were observed and compared, the optical resin materials of comparative examples were observed to be yellowish as compared with the optical resin materials of examples.
The invention provides a polythiol compound, a composition for an optical material and a preparation method thereof, wherein the chromaticity of the polythiol compound produced industrially can be stabilized by the polythiol compound with specific iron content, the qualification rate of the polythiol compound is improved, and finally the primary color of the optical material prepared by the polythiol compound is regulated and controlled, so that the qualification rate of an optical material product is improved. According to the technical scheme of the invention, the polythiol compound for colorless transparent optical materials with low and stable chromaticity and the optical materials with low and stable primary colors can be manufactured. The invention is very beneficial to the application in the field of preparing optical elements in optical instruments or optical systems.
The above description of a preparation method of a polythiol compound with high color stability, provided by the present invention, has been provided in detail, and specific examples are provided herein to illustrate the principles and embodiments of the present invention, and the above examples are provided to facilitate understanding of the methods of the present invention and their core ideas, and to enable any person skilled in the art to practice the present invention, including making and using any devices or systems, and performing any incorporated methods. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (10)
1. A polythiol compound is prepared from an isothiourea salt by a polyalcohol compound, hydrochloric acid and thiourea, and is hydrolyzed to obtain the polythiol compound, and is characterized in that the polythiol compound has a structural formula shown in a formula (1):
the iron content of the hydrochloric acid is below 20 ppm.
2. A polythiol compound according to claim 1, wherein the iron content of the hydrochloric acid is 10ppm or less.
3. A polythiol compound according to claim 1, wherein the mass fraction of the hydrochloric acid is 20% to 38%.
4. The polythiol compound of claim 1, wherein the polyol compound is prepared by reacting mercaptoethanol, epichlorohydrin and an alkali solution under certain conditions, and the structural formula of the polyol compound is shown in formula (2):
5. a composition for optical materials comprising 20 to 60 parts by weight of the polythiol compound of claim 1, 0 to 40 parts by weight of another polythiol compound, and 30 to 60 parts by weight of a polyisocyanate.
6. The composition for optical materials according to claim 5, wherein the other polythiol compound is 4, 7-dimercaptomethyl-1, 11-dimercaptomethyl-3, 6, 9-trithioundecane, 4, 8-dimercaptomethyl-1, 11-dimercaptoethyl-3, 6, 9-trithioundecane, 5, 7-dimercaptomethyl-1, 11-dimercaptoethane, methane dithiol, methane trithiol, bis (2-mercaptoethyl) ether, tetra (mercaptomethyl) methane, 1, 2-dimercaptopropane, 1, 3-dimercaptopropane, 1, 4-dimercaptobutane, 1, 6-dimercaptohexane, 2-dimercaptopropane, 1, 2-bis (2-mercaptoethoxy) ethane, 1, 2-bis (2-mercaptoethylthio) ethane, 2, 3-dimercaptoethan-1-propanol, 1, 2-dimercaptoethan, 2-3, 3-dimercaptoethane, 2-dimercaptoethane, 1, 2-dimercaptoethan, 2-3, 2-dimercaptoethan, 2-4-dimercaptoethan, 2-dio, 2-dimercaptoethane, 2-4-dimercaptoethanate), diethylene glycol, 2-dimercaptoethanoate, 2-4-dimercaptoethanoate, diethylene glycol, 2-4-dimercaptoethanoate, 4-dimercaptoethanoate, 1, 4-butanediol bis (2-mercaptoacetate), trimethylolpropane trimercapto-propionate, pentaerythritol tetramercaptoacetate, diethylene glycol bis (3-mercaptopropionate), pentaerythritol tetramercapto-propionate, 1, 2-dimercaptocyclohexane, 1-tris (mercaptomethyl) propane, 1, 4-butanediol bis (3-mercaptopropionate), 1, 3-dimercaptocyclohexane, trimethylolpropane trimercaptate, 1, 4-dimercaptocyclohexane, 1, 3-bis (mercaptomethyl) cyclohexane, 1, 4-bis (mercaptomethyl) cyclohexane, bis (4-mercaptophenyl) sulfone, 2, 5-dimercaptomethyl-1, 4-dithiane 2, 5-bis (2-mercaptoethylthiomethyl) -1, 4-dithiane, 2, 5-dimercaptomethyl-1-thiane, 2, 5-dimercaptoethyl-1-thiane, 2, 5-dimercaptomethyl thiophene, bis (4-mercaptophenyl) sulfide, 1, 2-dimercaptobenzene, 1, 3-dimercaptobenzene, 1, 4-dimercaptobenzene, 1, 3-bis (mercaptomethyl) benzene, 2, 5-dimercaptomethyl-1, 4-dithiane, 1, 4-bis (mercaptomethyl) benzene, 2 '-dimercaptobenzene, bis (4-mercaptophenyl) methane, 2-bis (4-mercaptophenyl) propane, 4' -dimercaptobenzene, bis (4-mercaptophenyl) ether, bis (4-mercaptomethylphenyl) methane, one or more of 1, 3-tetra (mercapto methylthio) propane 2, 2-bis (4-mercapto methylphenyl) propane, bis (4-mercapto methylphenyl) ether, bis (4-mercapto methylphenyl) sulfide, 2, 5-dimercapto-1, 3, 4-thiadiazole, and 3, 4-thiophene dithiol.
7. The composition for optical materials according to claim 5, wherein the polyisocyanate is one of tetramethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, 4' -diisocyanate dicyclohexylmethane, isophorone diisocyanate, norbornane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethylm-xylylene diisocyanate, dithiodipropylene diisocyanate, dithiodiethyl diisocyanate, 2, 5-diisocyanatothio methylthiophene, 2, 5-diisocyanatothyl-1, 4-dithiane, 2, 5-diisocyanatothio-1, 4-dithiane, thiodihexyl diisocyanate, thiodipropyl diisocyanate, bis (isocyanatomethyl) adamantane, bis (isocyanatomethyl) tetrahydrothiophene, 2, 6-bis (isocyanatomethyl) naphthalene, 1, 5-naphthalene diisocyanate, diethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine triisocyanate, toluene diisocyanate, o-tolylene diisocyanate, diphenyl ether, triphenylmethane diisocyanate, or triphenylether.
8. A method for preparing an optical material, comprising the steps of: adding a catalyst in an amount of 0.001 to 0.2% by mass based on the total mass of the composition for optical material to the composition for optical material according to any one of claims 5 to 7, and polymerizing and curing the mixture.
9. The method for preparing an optical material according to claim 8, wherein the catalyst is one of dibutyltin dilaurate, dibutyltin dichloride, dibutyltin oxide, and stannous octoate.
10. Use of an optical material according to any one of claims 8-9 in the field of optical elements in the preparation of optical instruments or optical systems.
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