CN116693790A - Composition for optical material and optical material - Google Patents
Composition for optical material and optical material Download PDFInfo
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- CN116693790A CN116693790A CN202310765698.5A CN202310765698A CN116693790A CN 116693790 A CN116693790 A CN 116693790A CN 202310765698 A CN202310765698 A CN 202310765698A CN 116693790 A CN116693790 A CN 116693790A
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- Prior art keywords
- diisocyanate
- composition
- bis
- optical material
- optical materials
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- 230000003287 optical effect Effects 0.000 title claims abstract description 106
- 239000000463 material Substances 0.000 title claims abstract description 104
- 239000000203 mixture Substances 0.000 title claims abstract description 52
- -1 episulfide compound Chemical class 0.000 claims abstract description 55
- 239000002904 solvent Substances 0.000 claims abstract description 52
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 12
- 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 12
- KSJBMDCFYZKAFH-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanyl)ethanethiol Chemical compound SCCSCCS KSJBMDCFYZKAFH-UHFFFAOYSA-N 0.000 claims description 11
- 239000012948 isocyanate Substances 0.000 claims description 11
- 239000002685 polymerization catalyst Substances 0.000 claims description 6
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 6
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 claims description 3
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 claims description 3
- SHLSSLVZXJBVHE-UHFFFAOYSA-N 3-sulfanylpropan-1-ol Chemical compound OCCCS SHLSSLVZXJBVHE-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- AGJCSCSSMFRMFQ-UHFFFAOYSA-N 1,4-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=C(C(C)(C)N=C=O)C=C1 AGJCSCSSMFRMFQ-UHFFFAOYSA-N 0.000 claims description 2
- ROHUXHMNZLHBSF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCC(CN=C=O)CC1 ROHUXHMNZLHBSF-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
- 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
- RKXSRNCIRYMSRK-UHFFFAOYSA-N 1-isocyanato-4-propylbenzene Chemical compound CCCC1=CC=C(N=C=O)C=C1 RKXSRNCIRYMSRK-UHFFFAOYSA-N 0.000 claims description 2
- FETFXNFGOYOOSP-UHFFFAOYSA-N 1-sulfanylpropan-2-ol Chemical compound CC(O)CS FETFXNFGOYOOSP-UHFFFAOYSA-N 0.000 claims description 2
- YHPQGOBBXKLBEA-UHFFFAOYSA-N 2,6-bis(isocyanatomethyl)-1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalene Chemical compound C1C(CN=C=O)CCC2CC(CN=C=O)CCC21 YHPQGOBBXKLBEA-UHFFFAOYSA-N 0.000 claims description 2
- 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 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
- 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 claims description 2
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 claims description 2
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-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
- IYPNRTQAOXLCQW-UHFFFAOYSA-N [4-(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=C(CS)C=C1 IYPNRTQAOXLCQW-UHFFFAOYSA-N 0.000 claims description 2
- COYTVZAYDAIHDK-UHFFFAOYSA-N [5-(sulfanylmethyl)-1,4-dithian-2-yl]methanethiol Chemical compound SCC1CSC(CS)CS1 COYTVZAYDAIHDK-UHFFFAOYSA-N 0.000 claims description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003003 phosphines Chemical class 0.000 claims description 2
- VUTVSWPVTJZPFU-UHFFFAOYSA-N propylsulfanylmethanethiol Chemical compound CCCSCS VUTVSWPVTJZPFU-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
- 125000005442 diisocyanate group Chemical group 0.000 claims 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 claims 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims 1
- JZXFXRANXNJWOB-UHFFFAOYSA-N N(=C=O)C(N=C=O)C1=C(C=CC=C1)C(C1=CC=CC=C1)C1=C(C=CC=C1)C(N=C=O)N=C=O Chemical compound N(=C=O)C(N=C=O)C1=C(C=CC=C1)C(C1=CC=CC=C1)C1=C(C=CC=C1)C(N=C=O)N=C=O JZXFXRANXNJWOB-UHFFFAOYSA-N 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 26
- 229920005989 resin Polymers 0.000 abstract description 13
- 239000011347 resin Substances 0.000 abstract description 13
- 238000002834 transmittance Methods 0.000 abstract description 7
- 238000012805 post-processing Methods 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 17
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 8
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 8
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 8
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 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 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- LYKQCVSVGJKFGJ-UHFFFAOYSA-N 3,5-diisocyanato-3,5-dimethylcyclohexene Chemical compound O=C=NC1(C)CC=CC(C)(N=C=O)C1 LYKQCVSVGJKFGJ-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
- 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 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000003965 capillary gas chromatography Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000007774 longterm Effects 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
- 239000005304 optical glass Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004383 yellowing Methods 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
- C08G18/3874—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing heterocyclic rings having at least one sulfur atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of optical resin, and particularly relates to a composition for an optical material and the optical material, wherein the composition for the optical material comprises an episulfide compound, and the solvent content is below 1500ppm; the composition can improve the heat resistance of the optical material when producing the optical material with high refractive index, ensure the feasibility of post-processing and the safety of the use process of the lens, ensure the haze of the produced optical material to be lower and ensure the light transmittance of the lens.
Description
Technical Field
The invention belongs to the field of novel organic materials and optical materials, and in particular relates to a composition for an optical material and the optical material, which are suitable for optical materials such as plastic lenses, prisms, optical fibers, information storage substrates, filters and the like.
Background
Currently, the refractive index of mainstream glasses in the market is about 1.6, so that to manufacture a high-power lens, it is necessary to increase the thickness of the glasses, which increases the weight of the glasses. Compared with optical glass, the resin optical material has the advantages of high refractive index, light weight, impact resistance, easy processing and forming and the like, and can be better applied to products such as spectacle lenses and the like. However, the latter process and use of the ophthalmic lens require both high resistance to heat distortion and high heat resistance.
Currently, commercially available resin lenses are a representative solution for improving heat resistance to add special isocyanates having high cost, highly rigid structure and high refractive index. From the viewpoint of cost, the use of 1, 4-cyclohexane diisocyanate, m-xylylene diisocyanate, isophorone diisocyanate, 1, 6-diisocyanatohexane, diisocyanato polyethylene glycol, dicyclohexylmethane 4, 4-diisocyanate and other isocyanates with low cost, excellent yellowing resistance and higher refractive index is the mainstream of developing low-cost polyurethane resin lenses at present, but the problem of low heat resistance temperature of the polyurethane resin lenses is unavoidable, and the problem greatly aggravates the quality hidden trouble of the low-cost polyurethane resin lenses in the later processing and long-term use. In addition, the haze of the resin lenses on the market is about 1%, and the haze of the resin lenses on the market is below 0.5 if the resin lenses are required to have high light transmittance, but the resin lenses on the market cannot meet the requirement of higher light transmittance of the resin lenses.
Disclosure of Invention
Aiming at a plurality of defects existing in the prior art, the invention provides the composition for the optical material and the optical material, and the solvent content in the episulfide compound is controlled below 1500ppm, so that the heat resistance of the optical material can be improved when the optical material with high refractive index is produced, the feasibility of post processing and the safety of the using process of the lens are ensured, the haze of the produced optical material is lower, and the light transmittance of the lens is ensured.
The inventors have conducted intensive studies on the problem of heat resistance and the problem of haze of an optical material having a high refractive index, and have found that the solvent content in an episulfide compound has a decisive influence on the heat resistance and the haze of the optical material. When the solvent content in the episulfide compound is too high, the crosslinking degree of the episulfide compound in the curing process is reduced, so that the heat resistance of the product is poor, and the probability of deformation is higher; however, a certain amount of solvent is needed, because a certain amount of solvent exists, the compatibility of the UV powder and the main resin can be improved, and the problem that the haze value of the lens is increased and the lens is in a hazy state due to separation and precipitation in the process of heating and curing the resin is avoided; when the solvent residue exceeds a certain value, the UV powder has low compatibility in the composition, and light scattering is easily generated in the inside or on the surface of the lens during the lens production process, thereby causing a cloudy state. Through researches, only when the solvent content of the episulfide compound is less than 1500ppm, the heat resistance of the optical material is effectively improved, the haze of the optical material is lower, and the requirements of high-heat-resistance and high-light-transmittance high-refractive-index resin lenses on the market are met.
Under the guidance of the conception, the technical scheme of the invention is as follows:
a composition for optical materials comprising an episulfide compound having the structural formula:
wherein m is 1 or 2, and the solvent content is less than 1500ppm.
Preferably, the solvent content of the episulfide compound is 500 to 1500ppm.
Preferably, the episulfide compound accounts for 60 to 95% of the total weight of the composition for optical materials. It is further preferred that the episulfide compound accounts for 70 to 90% of the total weight of the composition for an optical material.
Preferably, the optical material composition further comprises a thiol compound and an isocyanate compound. Further preferably, the thiol compound is 1 to 20% by weight, more preferably 3 to 10% by weight, of the total weight of the composition for optical materials, and the isocyanate compound is 1 to 20% by weight, more preferably 3 to 10% by weight, of the total weight of the composition for optical materials.
Further preferred thiol compounds are selected from 2-mercaptoethanol, 3-mercaptopropanol, 2-hydroxypropyl-thiol, n-hexanethiol, n-octanethiol, bis (2-mercaptoethyl) sulfide, 2, 5-dimercaptomethyl-1, 4-dithiane, 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, 4, 7-dimercaptomethyl-1, 11-dimercaptoethyl-3, 6, 9-trithioundecane, 5, 7-dimercaptomethyl-1, 11-dimercaptoethyl-3, 6, 9-trithioundecane, 1, 3-tetrakis (mercaptomethyl thio) propane, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrathioglycol ester, trimethylolpropane trimetha propionate, trimethylolpropane or trimethylol propionate. More preferred thiol compounds are selected from one or more of 2-mercaptoethanol, 3-mercaptopropanol, 2-hydroxypropyl mercaptan, bis (2-mercaptoethyl) sulfide, and 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiooctane.
Further preferably, the isocyanate compound has at least 2 isocyanate groups, the isocyanate compound is selected from one or more of diethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, 1, 4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 2, 6-bis (isocyanatomethyl) decalin, tolylene diisocyanate, o-tolylene diisocyanate, diphenylmethane diisocyanate, diphenyl ether diisocyanate, 2 '-bis (4-isocyanatophenyl) propane, triphenylmethane triisocyanate, bis (diisocyanatotolyl) phenylmethane, 1, 3-m-xylylene diisocyanate, 1, 4-p-xylylene diisocyanate, 4' -diisocyanatobiphenyl, dicyclohexylmethane-4, 4 '-diisocyanate, 1' -methylenebis (4-isocyanatobenzene), m-xylylene diisocyanate, p-xylylene diisocyanate, m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate, bis (isocyanatomethyl) norbornene, bis (isocyanatomethyl) diisocyanato, thioethyl diisocyanate, thiodiamantane, and thio-diisocyanate. More preferred isocyanate compounds are one of isophorone diisocyanate, m-xylyl diisocyanate, and 1, 3-bis (isocyanatomethyl) cyclohexane.
Preferably, the optical material composition further comprises a polymerization catalyst of imidazoles or phosphines, the polymerization catalyst accounting for 0.01 to 1% of the total weight of the optical material composition. The amount of the polymerization catalyst added varies depending on the components, mixing ratio and curing method of the composition, and the polymerization catalyst accounts for 0.03% to 0.5% of the total weight of the composition for optical materials.
Preferably, in the production of the corresponding optical material, the addition of an auxiliary agent to the above-mentioned polymerization curable composition can further improve the practicality of the obtained optical material. The optical material composition may further contain additives such as ultraviolet absorbers, mold release agents, blue agents, and red agents; wherein the ultraviolet absorbent is selected from one or more of UV-P, UV-9, UV-531, UV-324, UV-326, UV-329 and UV-1157, and the addition amount is 0.001% -1%, and more preferably 0.01% -0.5%; the blue agent and the red agent are added according to the actual requirements of the optical materials; the release agent is one or more selected from di-n-butyl phosphate, el310, polyoxyethylene nonylphenol phosphate and ZelecUNTM, and the addition amount is 0.001-1%, and more preferably 0.01-0.5%.
An optical material is obtained by curing the optical material composition, and comprises the following specific steps:
a) Uniformly mixing the composition for the optical material to obtain a mixed reactant;
b) And c), injecting the reaction mixture obtained in the step a) into a mold through a filter membrane, performing primary curing, and performing secondary curing after demolding to obtain the optical resin material.
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 by the technical scheme of the invention can be used for optical lenses, and the refractive index of the prepared optical material is above 1.7056, the softening temperature is above 92 ℃ and the haze is below 0.55.
In summary, the composition for optical materials and the optical material provided by the invention can improve the heat resistance of the optical material and reduce the haze of the optical material when the optical material with high refractive index is obtained, improve the heat stability of the optical material and improve the light transmittance at the same time, and the material with excellent performance can be suitable for optical materials such as plastic lenses, prisms, optical fibers, information storage substrates, filters and the like, and has higher popularization value and commercial value.
Drawings
FIG. 1 is a gas chromatogram of bis (. Beta. -cyclopropylsulfanyl) sulfide of example 1.
Detailed Description
The above-described aspects of the present invention 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 invention is limited to the following examples. All the techniques realized based on the above-mentioned matters of the present invention are within the scope of the present invention, and unless otherwise specified, the raw materials used in the following examples and comparative examples are all commercially available products, and episulfide compounds obtained by commercial purchase or preparation by other documents can be used as they are if the solvent-limited content of the episulfide compound defined by the present invention can be reached; if the solvent content in the episulfide compound is higher than the solvent limit residue of the episulfide compound defined by the invention, the episulfide compound can be treated by adopting the existing solvent removal method in the prior art to reach the specific solvent content, and then the episulfide compound is used, for example, a centrifugal molecular distiller is used for removing the solvent, so that the solvent content of the episulfide compound is reduced to a specific value; if the solvent content in the episulfide compound is lower than the content defined by the solvent of the episulfide compound defined in the present invention, the solvent existing in the episulfide compound or the solvent common in the episulfide compound may be added to the episulfide compound so that a specific solvent content is reached, and then used.
The present invention will be further described in detail below.
1. Determination of solvent content
The solvent content of the episulfide compound was determined by using a gilent 6890N gas chromatograph, agilent g 1888 headspace sampler using headspace sampling-capillary gas chromatography.
2. Solvent removal method
The solvent residue of the desired episulfide compound was obtained by controlling the heating temperature to 20-40 ℃ and the vacuum degree to 10pa-1000pa using a centrifugal molecular still. The method comprises the following steps:
bis (. Beta. -cyclopropyl) sulfide having a solvent content of 2500ppm: heating at 30deg.C under vacuum of 500pa until 1500ppm of solvent remains; bis (. Beta. -cyclopropyl) sulfide having a solvent content of 2500ppm: the heating temperature was 35℃and the vacuum was 100pa until 500ppm of solvent remained. During the actual operation, the appropriate heating temperature and vacuum level are chosen according to the desired final solvent content.
3. Measurement of Heat resistance
Glass transition temperature (Tg) the glass transition temperature of the optical material is measured by a Differential Scanning Calorimeter (DSC);
4. haze measurement
HunterLab UltraScan PRO spectrocolorimeter, the haze value is respectively equal to or greater than 1% of the quality of the optical material, and the haze value is poor; the quality of the product is good, and the haze value is more than or equal to 0.5% and less than 1%; the haze value is less than 0.5, and the quality is excellent.
Wherein m is 1 or 2, and m is 1, and m is 2, the episulfide compound is bis (. Beta. -cyclopropyl) disulfide.
An optical material is obtained by curing an optical material composition, and comprises the following specific steps:
a) Uniformly mixing the composition for the optical material to obtain a mixed reactant;
b) And b) injecting the reaction mixture obtained in the step a) into a mold through a filter membrane, performing primary curing, and removing b) injecting the reaction mixture obtained in the step a) into the mold through the filter membrane, performing primary curing, demolding, and performing secondary curing to obtain the optical resin material.
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.
Example 1
The preparation method of the optical material comprises the following steps:
the optical material composition comprises the following components: 90 parts by mass of bis (beta-cyclopropyl) sulfide (the solvent content is 1500 ppm), 6.2 parts by mass of bis (2-mercaptoethyl) sulfide, 3.1 parts by mass of isophorone diisocyanate, 0.5 part by mass of catalyst tetrabutylphosphonium bromide, 0.1 part by mass of release agent-di-n-butyl phosphate and 0.1 part by mass of UV326 ultraviolet absorber;
the preparation method comprises the following specific steps: the optical material composition was subjected to normal temperature degassing, filtered through a 0.5 μm ptfe filter after the degassing was completed, poured into a mold, and program curing was started, and the temperature-raising program for the first curing was started: the initial temperature is 25 ℃, the temperature is kept for 3.5 hours, then the temperature is raised to 60 ℃ for 3.0 hours, the temperature is raised to 85 ℃ for 3.0 hours, and the temperature is lowered to 60 ℃ for 2.5 hours; the second curing in step b) is carried out at a temperature of 110 ℃ for 4 hours, thereby obtaining an optical lens material
Example 2
The preparation method of the optical material comprises the following steps:
the optical material composition comprises the following components: 90 parts by mass of bis (beta-cyclopropyl) sulfide (solvent content is 1300 ppm), 6.2 parts by mass of bis (2-mercaptoethyl) sulfide, 3.1 parts by mass of isophorone diisocyanate, 0.5 part by mass of catalyst tetrabutylphosphonium bromide, 0.1 part by mass of release agent-di-n-butyl phosphate and 0.1 part by mass of UV326 ultraviolet absorber;
the specific preparation procedure is the same as in example 1.
Example 3
The preparation method of the optical material comprises the following steps:
the optical material composition comprises the following components: 90 parts by mass of bis (beta-cyclopropyl) sulfide (the solvent content is 1100 ppm), 6.2 parts by mass of bis (2-mercaptoethyl) sulfide, 3.1 parts by mass of isophorone diisocyanate, 0.5 part by mass of catalyst tetrabutylphosphonium bromide, 0.1 part by mass of release agent-di-n-butyl phosphate and 0.1 part by mass of UV326 ultraviolet absorber;
the specific preparation procedure is the same as in example 1.
Example 4
The preparation method of the optical material comprises the following steps:
the optical material composition comprises the following components: 90 parts by mass of bis (beta-cyclopropyl) sulfide (the solvent content is 900 ppm), 6.2 parts by mass of bis (2-mercaptoethyl) sulfide, 3.1 parts by mass of isophorone diisocyanate, 0.5 part by mass of catalyst tetrabutylphosphonium bromide, 0.1 part by mass of release agent-di-n-butyl phosphate and 0.1 part by mass of UV326 ultraviolet absorber;
the specific preparation procedure is the same as in example 1.
Example 5
The preparation method of the optical material comprises the following steps:
the optical material composition comprises the following components: 90 parts by mass of bis (beta-cyclopropyl) disulfide (the solvent content is 700 ppm), 6.2 parts by mass of bis (2-mercaptoethyl) sulfide, 3.1 parts by mass of isophorone diisocyanate, 0.5 part by mass of catalyst tetrabutylphosphonium bromide, 0.1 part by mass of release agent-di-n-butyl phosphate and 0.1 part by mass of UV326 ultraviolet absorber;
the specific preparation procedure is the same as in example 1.
Example 6
The preparation method of the optical material comprises the following steps:
the optical material composition comprises the following components: 90 parts by mass of bis (beta-cyclopropyl) disulfide (the solvent content is 500 ppm), 6.2 parts by mass of bis (2-mercaptoethyl) sulfide, 3.1 parts by mass of isophorone diisocyanate, 0.5 part by mass of catalyst tetrabutylphosphonium bromide, 0.1 part by mass of release agent-di-n-butyl phosphate and 0.1 part by mass of UV326 ultraviolet absorber;
the specific preparation procedure is the same as in example 1.
Example 7
The preparation method of the optical material comprises the following steps:
the optical material composition comprises the following components: 90 parts by mass of bis (beta-cyclopropyl) disulfide (the solvent content is 300 ppm), 6.2 parts by mass of bis (2-mercaptoethyl) sulfide, 3.1 parts by mass of isophorone diisocyanate, 0.5 part by mass of catalyst tetrabutylphosphonium bromide, 0.1 part by mass of release agent-di-n-butyl phosphate and 0.1 part by mass of UV326 ultraviolet absorber;
the specific preparation procedure is the same as in example 1.
Example 8
The preparation method of the optical material comprises the following steps:
the optical material composition comprises the following components: 90 parts by mass of bis (beta-cyclopropyl) disulfide (the solvent content is 100 ppm), 6.2 parts by mass of bis (2-mercaptoethyl) sulfide, 3.1 parts by mass of isophorone diisocyanate, 0.5 part by mass of catalyst tetrabutylphosphonium bromide, 0.1 part by mass of release agent-di-n-butyl phosphate and 0.1 part by mass of UV326 ultraviolet absorber;
the specific preparation procedure is the same as in example 1.
Comparative example 1
The procedure of example 1 was followed except that bis (. Beta. -cyclopropyl) sulfide was used, the solvent content of which was 1700 ppm.
Comparative example 2
The procedure of example 1 was followed except that bis (. Beta. -cyclopropylsulfanyl) sulfide having a solvent content of 1900ppm was used.
Comparative example 3
The procedure of example 5 was followed except that bis (. Beta. -cyclopropylsulfanyl) disulfide was used in a solvent content of 2100 ppm.
Comparative example 4
The procedure of example 5 is followed, except that bis (. Beta. -cyclopropylsulfanyl) disulfide having a solvent content of 2300ppm is used.
Comparative example 5
The procedure of example 7 was followed except that bis (. Beta. -cyclopropylsulfanyl) sulfide having a solvent content of 2500ppm was used.
Comparative example 6
The procedure of example 7 was repeated except that bis (. Beta. -cyclopropylsulfanyl) sulfide having a solvent content of 2700ppm was used.
Comparative example 7
The procedure of example 7 was repeated except that bis (. Beta. -cyclopropylsulfanyl) sulfide having a solvent content of 2900ppm was used.
Comparative example 8
The procedure of example 7 was followed except that bis (. Beta. -cyclopropyl) sulfide was used in an amount of 3100ppm as the solvent.
The final product properties for each example and comparative example are shown in Table 1 below:
as can be seen from the results of the above table, when the solvent content in the episulfide compound in examples 1-8 is 1500ppm or less, the optical lens material obtained by curing has higher Tg and lower haze, and the products prepared in examples 1-6 have higher comprehensive properties than those in examples 7-8, and it is proved that the episulfide compound controls the solvent content to 500-1500ppm, so that the optical lens material has excellent properties of higher Tg and lower haze; the solvent content of the cyclic sulfur compound in comparative examples 1 to 8 was more than 1500ppm, tg of the cured optical lens material was relatively low, haze was relatively high, and as the solvent content was increased, the softening temperature was continuously decreased and the haze was gradually increased. The optical material obtained by the technical scheme of the invention can be used for optical lenses, and the prepared optical material has refractive index of above 1.7056, softening temperature of above 92 ℃ and haze of below 0.55, and has high popularization value.
In summary, the composition for optical material and the optical material provided by the invention can improve the heat resistance of the optical material and reduce the haze of the optical material when obtaining the optical material with high refractive index, and improve the heat stability of the optical material and the light transmittance.
The embodiments described above are presented to enable a person skilled in the art to make and use the invention. 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 invention. Thus, the present invention 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 (10)
1. A composition for optical materials comprising an episulfide compound having the structural formula:
wherein m is 1 or 2, characterized in that: the solvent content is below 1500ppm.
2. A composition for optical materials according to claim 1, characterized in that: the solvent content of the episulfide compound is 500-1500ppm.
3. A composition for optical materials according to claim 1, characterized in that: the episulfide compound accounts for 60-95% of the total weight of the composition for optical materials.
4. A composition for optical materials according to claim 3, characterized in that: the episulfide compound accounts for 70-90% of the total weight of the composition for optical materials.
5. A composition for optical materials according to claim 1, characterized in that: the optical material composition further includes a thiol compound and an isocyanate compound.
6. A composition for optical materials according to claim 1, characterized in that: the mercaptan compound accounts for 1-20% of the total weight of the composition for optical materials, and the isocyanate compound accounts for 1-20% of the total weight of the composition for optical materials.
7. A composition for optical materials according to claim 1, characterized in that: the mercaptan compound is selected from any proportion of 2-mercaptoethanol, 3-mercaptopropanol, 2-hydroxypropyl mercaptan, n-hexanethiol, n-octanethiol, bis (2-mercaptoethyl) thioether, 2, 5-dimercaptomethyl-1, 4-dithiane, 1, 3-bis (mercaptomethyl) benzene, 1, 4-bis (mercaptomethyl) benzene, 4-mercaptomethyl-1, 8-dimercaptoethyl-3, 6-dithiooctane, 4, 8-dimercaptomethyl-1, 11-dimercaptoethyl-3, 6, 9-trithioundecane, 4, 7-dimercaptomethyl-1, 11-dimercaptoethyl-3, 6, 9-trithioundecane, 5, 7-dimercaptomethyl-1, 11-dimercaptoethyl-3, 6, 9-trithioundecane, 1, 3-tetrakis (mercaptomethylthio) propane, pentaerythritol tetrakis (3-mercaptopropionate), tetrathioethylene glycol ester, trimethylol propane or trimethylol propane.
8. A composition for optical materials according to claim 1, characterized in that: the isocyanate compound contains at least 2 isocyanate groups, and the isocyanate compound is selected from diethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, 1, 4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 2, 6-bis (isocyanatomethyl) decalin, tolylene diisocyanate, o-tolidine diisocyanate, diphenylmethane diisocyanate, diphenyl ether diisocyanate, 2 '-bis (4-isocyanatophenyl) propane, triphenylmethane triisocyanate, bis (diisocyanatomethylphenyl) phenylmethane, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, 4' -diisocyanatobiphenyl, dicyclohexylmethane-4, 4 '-diisocyanate, 1' -methylenebis (4-isocyanatobenzene), m-xylylene diisocyanate, m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate, bis (methyl) xylylene diisocyanate, adamantyl diisocyanate, thioxylylene diisocyanate, thiobis (hexamethylene diisocyanate, or thio) diisocyanate.
9. A composition for optical materials according to claim 1, characterized in that: the optical material composition further comprises a polymerization catalyst of imidazoles or phosphines, wherein the polymerization catalyst accounts for 0.01-1% of the total weight of the optical material composition.
10. An optical material characterized by: curing with an optical material composition according to any one of claims 1 to 9.
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