CN116478108B - Sulfur-containing heterocyclic compound, optical material composition and application thereof - Google Patents
Sulfur-containing heterocyclic compound, optical material composition and application thereof Download PDFInfo
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- CN116478108B CN116478108B CN202310364329.5A CN202310364329A CN116478108B CN 116478108 B CN116478108 B CN 116478108B CN 202310364329 A CN202310364329 A CN 202310364329A CN 116478108 B CN116478108 B CN 116478108B
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- 239000000463 material Substances 0.000 title claims abstract description 59
- 230000003287 optical effect Effects 0.000 title claims abstract description 59
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 150000002391 heterocyclic compounds Chemical class 0.000 title claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 16
- 239000011593 sulfur Substances 0.000 title claims abstract description 16
- 239000000203 mixture Substances 0.000 title claims description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 239000002685 polymerization catalyst Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- -1 amino, mercapto Chemical class 0.000 abstract description 21
- 238000006116 polymerization reaction Methods 0.000 abstract description 18
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 7
- 239000011368 organic material Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 description 12
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- SHLSSLVZXJBVHE-UHFFFAOYSA-N 3-sulfanylpropan-1-ol Chemical compound OCCCS SHLSSLVZXJBVHE-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 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 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical group [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 3
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 description 2
- KSJBMDCFYZKAFH-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanyl)ethanethiol Chemical compound SCCSCCS KSJBMDCFYZKAFH-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 150000001298 alcohols Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- UQENZRRBEBJVEV-UHFFFAOYSA-N cyclopropylsulfanylcyclopropane Chemical compound C1CC1SC1CC1 UQENZRRBEBJVEV-UHFFFAOYSA-N 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 238000009849 vacuum degassing Methods 0.000 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 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ROHUXHMNZLHBSF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCC(CN=C=O)CC1 ROHUXHMNZLHBSF-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- FETFXNFGOYOOSP-UHFFFAOYSA-N 1-sulfanylpropan-2-ol Chemical compound CC(O)CS FETFXNFGOYOOSP-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 1
- YABKMAUHCMZQFO-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-5-butoxyphenol Chemical compound OC1=CC(OCCCC)=CC=C1N1N=C2C=CC=CC2=N1 YABKMAUHCMZQFO-UHFFFAOYSA-N 0.000 description 1
- QFNSAOSWJSCHID-UHFFFAOYSA-N 2-butylbenzenesulfonic acid Chemical compound CCCCC1=CC=CC=C1S(O)(=O)=O QFNSAOSWJSCHID-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- NEKBPETURGFTNC-UHFFFAOYSA-N 3-[(2,3-diisocyanato-6-methylphenyl)-phenylmethyl]-1,2-diisocyanato-4-methylbenzene Chemical compound CC1=CC=C(N=C=O)C(N=C=O)=C1C(C=1C(=C(N=C=O)C=CC=1C)N=C=O)C1=CC=CC=C1 NEKBPETURGFTNC-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 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 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- JSNABGZJVWSNOB-UHFFFAOYSA-N [3-(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=CC(CS)=C1 JSNABGZJVWSNOB-UHFFFAOYSA-N 0.000 description 1
- IYPNRTQAOXLCQW-UHFFFAOYSA-N [4-(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=C(CS)C=C1 IYPNRTQAOXLCQW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D277/18—Nitrogen atoms
-
- 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
Abstract
The application belongs to the field of novel organic materials, and relates to a sulfur-containing heterocyclic compound shown in a formula (1) and application thereof. The compound contains amino, mercapto and heterocycle, can introduce rigid groups such as C-N, C-S and a stable five-membered heterocycle structure into a polymer main chain, can participate in polymerization reaction, can effectively regulate and control the rate of the polymerization reaction, and ensures that high-temperature section polymerization is stable, thereby improving the Abbe number of an optical material, and can obtain an optical material with higher Abbe number and ultrahigh refractive index by adding the compound shown in the formula (1);
Description
Technical Field
The application belongs to the field of novel organic materials, and particularly relates to a sulfur-containing heterocyclic compound, an optical material composition and application thereof, which are suitable for optical materials such as plastic lenses, prisms, optical fibers, information storage substrates, filters and the like.
Background
The most important properties required of optical materials, especially ophthalmic lenses, are high refractive index, which allows for thinning of the lens, and high abbe number, which reduces chromatic aberration of the lens.
Currently, the high-folding products on the market are mainly 1.670 and 1.740, the abbe number thereof is usually between 32 and 33, and the products are mainly dependent on import, such as korea and japan, and the unit price of the products is expensive due to the import of the products, and the selection of consumers is affected due to the low abbe number and the severe dispersion of the products. The prior art reports many materials with high refractive index and high abbe number, the refractive index is above 1.68, and the abbe number is less than 36; or the Abbe number is more than 40, and the refractive index is only about 1.60, such as CN106574034B, CN111601835B, CN108689883B, CN107075065B, TWI431048B, CN104114608B, CN 101932630B.
In order to achieve a high refractive index and a high Abbe number, in recent years, many polyepisulfide compounds excellent in balance between refractive index and Abbe number have been reported, for example, JP-A9-71580, JP-A9-110979, and JP-A9-255781, and cases in which sulfur-containing heterocyclic compounds are used to increase Abbe number of an ophthalmic lens by 1.7 or more have been reported.
Disclosure of Invention
Aiming at the defects of the prior art, the application provides the sulfur-containing heterocyclic compound shown in the formula (1) and the optical material composition containing the compound, wherein the compound contains amino, sulfhydryl and heterocycle, and can introduce rigid groups such as C-N, C-S and a stable five-membered heterocycle structure into a polymer main chain, so that the polymer can participate in polymerization reaction, the polymerization reaction rate can be effectively regulated, and the high-temperature section polymerization is stable, thereby improving the Abbe number of the optical material, and the ultra-high refractive index optical material with higher Abbe number can be obtained by adding the compound shown in the formula (1).
The specific technical scheme of the application is as follows:
the present inventors have first provided a sulfur-containing heterocyclic compound represented by formula (1):
the preparation method of the sulfur-containing heterocyclic compound represented by the above formula (1) includes, but is not limited to, the following:
the compound shown in the formula (3) reacts with a vulcanizing agent under the condition of acid condition and the existence of a reaction solvent to prepare the compound:
wherein the vulcanizing agent is selected from one or two of thiourea and ammonium thiocyanate, preferably thiourea; the molar ratio of the vulcanizing agent to the formula (3) is 0.5-1.5, preferably 0.8-1.2; when the molar ratio is less than 0.5, the conversion of the raw material is low, whereas when the molar ratio is more than 1.5, the unreacted raw material remains too much to be preferable.
The acid used in the reaction process can be selected from inorganic acids or organic carboxylic acids or sulfonic acids; wherein the inorganic acid is selected from one or more of hydrochloric acid, boric acid and phosphoric acid; the organic carboxylic acid is selected from one or more of formic acid, acetic acid, peracetic acid, oxalic acid, salicylic acid, acetic anhydride and maleic anhydride; the sulfonic acid is selected from one or more of p-toluenesulfonic acid, methanesulfonic acid, butylbenzenesulfonic acid, dodecylbenzenesulfonic acid and trifluoromethanesulfonic acid;
among them, hydrochloric acid or formic acid or p-toluenesulfonic acid is preferably used, and hydrochloric acid is most preferred. The amount of the acid to be used is 0.1 to 1.5 in molar ratio to the formula (3), more preferably 0.5 to 1.0 in molar ratio; wherein the molar ratio is less than 0.5 or more than 1.5, the unreacted raw materials are not preferable because they remain too much.
The reaction solvent is selected from alcohols such as methanol or ethanol; ethers such as diethyl ether, tetrahydrofuran, and dioxane; halogenated hydrocarbons such as methylene chloride, chloroform, and chlorobenzene; or directly selecting water. Alcohols are preferred, and methanol is more preferred. The amount of the solvent is not particularly limited as long as the vulcanizing agent can be completely dissolved.
The reaction temperature is generally selected from 10 to 60℃and preferably from 25 to 45 ℃. The vulcanizing agent has poor solubility and slow reaction at the temperature lower than 10 ℃; above 60℃the polymer appears to affect the yield during the reaction.
The compound shown in the formula (1) has amino, sulfhydryl and heterocycle, can introduce rigid groups such as C-N, C-S and the like and a stable five-membered heterocycle structure into a polymer main chain, can participate in polymerization reaction, can effectively regulate and control the rate of the polymerization reaction, and ensures that high-temperature polymerization is stable, thereby improving Abbe number and mechanical property of the optical material.
After obtaining the above-mentioned episulfide compound, the inventors further provide a composition for optical materials, which contains a polymerizable compound mainly represented by the formula (1) and the formula (2), wherein the compound represented by the formula (1) accounts for 0.001 to 5% of the total weight of the composition for optical materials; still more preferably 0.1 to 3%; a compound represented by the formula (2):
in the formula (2), m represents 1 or 2.
When the compound of formula (1) is less than 0.001%, the effect may not be sufficiently obtained, and when the mechanical properties of the optical material are slightly poor and exceeds 5.0%, the Abbe number of the optical material may be slightly low. In the case of using the compound represented by the formula (2) as the polymerizable compound, the compound represented by the formula (2) in the composition for an optical material of the present application is preferably 55 to 95%, more preferably 65 to 90%, particularly preferably 70 to 88% based on the total weight of the composition for an optical material.
In addition to the polymerizable compound of the compound represented by the above formula (2), the composition for an optical material may further contain a thiol compound and an isocyanate compound:
in order to improve the heat resistance of the obtained optical material, the composition for optical material may contain a thiol compound as a polymerizable compound. The thiol compound is selected from one or more of 3-mercaptopropanol, 2-hydroxypropyl thiol, bis (2-mercaptoethyl) sulfide, 1, 3-bis (mercaptomethyl) benzene, 1, 4-bis (mercaptomethyl) benzene, 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiooctane, 4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithioundecane, pentaerythritol tetramercaptopropionate, and trimethylolpropane trimercapto propionate, preferably 3-mercaptopropanol, bis (2-mercaptoethyl) sulfide, and pentaerythritol tetramercapto propionate, and the thiol compound accounts for 2 to 25.0% by weight of the optical material composition, and more preferably 5.5 to 12.9% by weight.
In order to improve the strength of the obtained resin, the composition for an optical material of the present application may contain an isocyanate compound as a polymerizable compound. The isocyanate compound has at least 2 isocyanate groups. The isocyanate compound is selected from the group consisting of diethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 1, 4-bis (isocyanatomethyl) cyclohexane, o-tolidine diisocyanate, bis (diisocyanatotolyl) phenylmethane, 1, 4-phenylene diisocyanate, 4' -diisocyanatobiphenyl, dicyclohexylmethane-4, 4' -diisocyanate, 1' -methylenebis (4-isocyanatobenzene), p-xylylene diisocyanate, bis (isocyanatomethyl) norbornene, bis (isocyanatomethyl) adamantane, thiodipropyl diisocyanate, preferably isophorone diisocyanate, p-xylylene diisocyanate. The isocyanate compound is 3 to 20.0% by weight, more preferably 6 to 15.5% by weight of the optical material composition.
The inventors have also provided a polymerizable curable composition comprising the composition for an optical material in any one of the above combinations, and a polymerization catalyst in an amount of 0.0001 to 10% by weight based on the total weight of the composition for an optical material, wherein the polymerization catalyst may be one of imidazoles and phosphines, and further preferably the polymerization catalyst is tetrabutylphosphonium bromide, and the amount of the polymerization catalyst is 0.1 to 1%, and when the amount of the polymerization catalyst is more than 10%, rapid polymerization may occur, and when the amount of the polymerization catalyst is less than 0.0001%, the composition for an optical material may not be sufficiently cured and may have poor heat resistance.
In addition, the addition of an auxiliary agent to the above-mentioned polymerizable curable composition can further improve the practicality of the obtained optical material when the corresponding optical material is produced. That is, the polymerizable curable composition of the present application may further contain additives such as an ultraviolet absorber, a mold release agent, a blue agent, and a red agent; wherein the ultraviolet absorber is one or more selected from 5-chloro-2- (3, 5-di-tert-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole and 2- (2-hydroxy-4-butoxyphenyl) -2H-benzotriazole, and the addition amount is 0.001-1%, more preferably 0.01-0.5% of the composition for optical materials; the blue agent and the red agent are added according to the actual requirements of the optical materials, and the adding amount is not particularly required; the release agent is one or more selected from di-n-butyl phosphate, el310, polyoxyethylene nonylphenol phosphate and ZelecUNTM, and is added in an amount of 0.001-1% by mass, more preferably 0.01-0.5% by mass, of the composition for optical materials.
The application also provides an optical material which is obtained by curing the polymerization curing composition, and the specific steps are as follows:
a) Uniformly mixing the polymerization curing composition and the auxiliary agent to obtain a mixed reactant; the mixing temperature is 0-15 ℃ and the mixing time is 30-60 min;
b) Injecting the mixed reactant obtained in the step a) into a mold through a filter membrane, performing primary curing, demolding, and performing secondary curing to obtain the optical material with high refractive index and high Abbe number;
wherein, in step b), the temperature-raising procedure of the first curing: the initial temperature is 15-25 ℃, the temperature is kept for 2.0-3.5 h, then the temperature is raised to 45-60 ℃ for 2.0-4.0 h to 75-90 ℃ for 10-15 h, and finally the temperature is lowered to 60-75 ℃ for 1.5-2.5 h; the temperature of the second curing in the step b) is 80-110 ℃ and the time is 2-4 h.
The optical material obtained above can be used in the preparation of optical lenses.
In summary, compared with the prior art, the sulfur-containing heterocyclic compound shown in the formula (1) and the optical material composition containing the compound, which are obtained by the application, contain amino, mercapto and heterocycle, and can introduce rigid groups such as C-N, C-S and a stable five-membered heterocycle structure into a polymer main chain, so that the polymer can participate in polymerization reaction, and can effectively regulate and control the polymerization reaction rate, so that the high-temperature polymerization is stable, the Abbe number of the optical material is improved, and the optical material with higher Abbe number can be obtained by adding the compound shown in the formula (1).
Drawings
FIG. 1 is a secondary mass spectrum of the sulfur-containing heterocyclic compound of formula (1) in example 1;
FIG. 2 is a schematic view of a sulfur-containing heterocyclic compound of the formula (1) in example 1 1 H NMR spectrum;
FIG. 3 is a schematic view of a sulfur-containing heterocyclic compound of the formula (1) in example 1 13 C NMR spectrum.
Detailed Description
The above-described aspects of the present application will be described in further detail by way of the following embodiments, but it should not be construed that the scope of the above-described subject matter of the present application is limited to the following examples. All techniques based on the above description of the present application are within the scope of the present application, and the raw materials used in the following examples are all commercially available products, except for the specific descriptions.
A compound represented by the following formula (2):
in the formula (2), m represents 1 or 2.
Example 1
126.5g (1 mol) of the compound shown in the formula (3) is weighed, 83.6g (1.1 mol) of thiourea, 200g of methanol and 17.2g (0.1 mol) of concentrated hydrochloric acid are added, the reaction temperature is 35 ℃, the reflux reaction is carried out, the residual amount of thiourea is detected by liquid chromatography until the residual amount is not changed any more, and the reaction is stopped.
The reacted material was subjected to cooling crystallization, filtration, and drying of precipitated solid to obtain white crystals, which were then purified and refined further by silica gel column chromatography to obtain 31g (yield 21%) of the sulfur-containing heterocyclic compound represented by the above formula (1).
Carrying out secondary mass spectrometry qualitative analysis and nuclear magnetic characterization on the obtained compound, wherein the diagrams are shown in fig. 1, 2 and 3, and the secondary mass spectrometry method comprises the following steps: ESI (electrospray ion source), frag (capillary outlet voltage) =125v, cid (collision energy) =5.0v.
Mass spectrometry (ESI): M+H + 149, as shown in FIG. 1, wherein the molecular ions, fragment ions and corresponding m/z are as shown in the following table:
1 H-NMR(400MHz)：
δ＝2.66ppm(m，2H，hydrogen atom bonded to carbon atom at 4 position), δ=3.64 ppm (m, 1H, hydrogen atom bonded to carbon atom at 3 position), δ=3.87 ppm (m, 2H, hydrogen atom bonded to carbon atom at 2 position), δ=4.71 ppm (D 2 A hydrogen atom in O);
13 C-NMR：
δ=181.6 ppm (carbon atom at position 1), δ=47.2 ppm (carbon atom at position 2), δ=71.8 ppm (carbon atom at position 3), δ=27.1 ppm (carbon atom at position 4);
examples 2 to 4
The compound represented by the formula (1) was added to the compound represented by the formula (2), namely, dicyclopropyl sulfide (m=1) at 20 ℃ to obtain a composition for an optical material, wherein the addition amount of the compound represented by the formula (1) is shown in table 1, 80g of the compound represented by the formula (2) (m=1), 7.5g of p-xylyl diisocyanate, 12.0g of 3-mercaptopropanol, 0.2g of tetrabutylphosphonium bromide, and 0.1g of a release agent.
Stirring the obtained composition at 20 ℃ for 50min to obtain a prepolymer liquid, vacuum degassing for 30min, filtering and injecting the prepolymer liquid into a glass mold through a polytetrafluoroethylene filter membrane with the pore diameter of 3 mu m, and then placing the mold into a programmed temperature curing furnace for primary curing to obtain a primary cured resin lens; the temperature rise program of the primary curing is as follows: the initial temperature is 20 ℃, the heat is preserved for 2 hours, the temperature is raised to 45 ℃ for 3.5 hours, the temperature is raised to 55 ℃ for 3 hours, the temperature is raised to 100 ℃ for 6 hours, the heat is preserved for 4 hours, and the temperature is reduced to 70 ℃ for 2 hours. And (3) performing secondary curing on the obtained resin lens subjected to primary curing for 4 hours at 120 ℃ to obtain the optical resin material lens.
Examples 5 to 7
The amount of the compound represented by the formula (1) added to the compound represented by the formula (2), i.e., the dicyclopropyl sulfide (m=2), in the composition for optical materials at 20 ℃ is shown in table 1. 80g of a compound (m=2) represented by the formula (2), 6.5g of isophorone diisocyanate, 10.7g of pentaerythritol tetrasulfopropionate, 0.2g of tetrabutylphosphonium bromide and 0.1g of a release agent.
Stirring the obtained composition at 20 ℃ for 50min to obtain a prepolymer liquid, vacuum degassing for 30min, filtering and injecting the prepolymer liquid into a glass mold through a polytetrafluoroethylene filter membrane with the pore diameter of 3 mu m, and then placing the mold into a programmed temperature curing furnace for primary curing to obtain a primary cured resin lens; the temperature rise program of the primary curing is as follows: the initial temperature is 20 ℃, the heat is preserved for 2 hours, the temperature is raised to 45 ℃ for 3.5 hours, the temperature is raised to 55 ℃ for 3 hours, the temperature is raised to 100 ℃ for 6 hours, the heat is preserved for 4 hours, and the temperature is reduced to 70 ℃ for 2 hours. And (3) performing secondary curing on the obtained resin lens subjected to primary curing for 4 hours at 120 ℃ to obtain the optical resin material lens.
Comparative examples 1 to 2
The same operation conditions as in the examples were not added with the compound represented by the formula (1), refractive index (Ne): detecting by adopting a multi-wavelength Abbe refractometer (DR-M4); abbe number (Vd): detecting by adopting a multi-wavelength Abbe refractometer (DR-M4); the results of the respective performance tests are shown in the following table (in the following table, the addition amount of the compound represented by the formula (1) is a percentage of the total weight of the compound represented by the formula (1) and the polymerizable compound mainly comprising the compound represented by the formula (2), the thiol compound and the isocyanate compound, which is described herein).
TABLE 1 Performance test results Table of different optical resin materials
From the results of the table, the Abbe number of the optical resin material lens is obviously improved after the compound shown in the formula (1) is added, the environment where a molecular chain is located is changed by adding the compound shown in the formula (1) for copolymerization, and the main chain is introduced with rigid groups such as C-N, C-S and the like and a stable five-membered heterocyclic structure, so that the optical resin material can participate in polymerization reaction, can effectively regulate and control the polymerization reaction rate, ensures that high-temperature polymerization is stable, and further improves the Abbe number of the optical material.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A sulfur-containing heterocyclic compound is characterized in that the chemical formula is shown in a formula (1):
（1）。
2. a composition for optical materials, which comprises the sulfur-containing heterocyclic compound according to claim 1 and a polymerizable compound; the polymerizable compound is a compound represented by the following formula (2):
(2) In the formula (2), m represents 1 or 2.
3. The composition for optical material according to claim 2, wherein the sulfur-containing heterocyclic compound is contained in an amount of 0.001 to 5.0%.
4. The composition for optical materials according to claim 3, wherein the polymerizable compound is contained in an amount of 95.0 to 99.999%.
5. The composition for optical materials according to claim 2, wherein the compound represented by the formula (2) in the composition for optical materials is 55.0 to 95.0% by weight based on the total weight of the composition.
6. A method for producing an optical material, comprising adding the polymerization catalyst in an amount of 0.0001 to 10% based on the total weight of the optical material composition to the optical material composition according to any one of claims 3 to 5, and polymerizing and curing the mixture to produce the optical material.
7. An optical material characterized by: a method for producing an optical material according to claim 6.
8. An optical lens, characterized by: an optical material according to claim 7.
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