CN113444247A - High-refractive-index super-tough optical resin material and preparation method thereof - Google Patents
High-refractive-index super-tough optical resin material and preparation method thereof Download PDFInfo
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- CN113444247A CN113444247A CN202110713256.7A CN202110713256A CN113444247A CN 113444247 A CN113444247 A CN 113444247A CN 202110713256 A CN202110713256 A CN 202110713256A CN 113444247 A CN113444247 A CN 113444247A
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- 239000011347 resin Substances 0.000 title claims abstract description 62
- 229920005989 resin Polymers 0.000 title claims abstract description 62
- 230000003287 optical effect Effects 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 18
- JFLJVRLBIZHFSU-UHFFFAOYSA-N 1,4-dithiane-2,5-dithiol Chemical compound SC1CSC(S)CS1 JFLJVRLBIZHFSU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920006295 polythiol Polymers 0.000 claims abstract description 13
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 10
- 239000010452 phosphate Substances 0.000 claims abstract description 10
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 9
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 9
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 6
- -1 UV-O Chemical compound 0.000 claims description 23
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 15
- 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 15
- MLGITEWCALEOOJ-UHFFFAOYSA-N 2-(thiiran-2-ylmethylsulfanylmethyl)thiirane Chemical compound C1SC1CSCC1CS1 MLGITEWCALEOOJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002250 absorbent Substances 0.000 claims description 11
- 230000002745 absorbent Effects 0.000 claims description 11
- 239000000038 blue colorant Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical group [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 9
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 claims description 7
- 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 7
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 9
- CXWGKAYMVASWDQ-UHFFFAOYSA-N 1,2-dithiane Chemical group C1CCSSC1 CXWGKAYMVASWDQ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 6
- 239000012986 chain transfer agent Substances 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 13
- 239000001062 red colorant Substances 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000007688 edging Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 230000000630 rising effect Effects 0.000 description 7
- 238000009849 vacuum degassing Methods 0.000 description 7
- KSJBMDCFYZKAFH-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanyl)ethanethiol Chemical compound SCCSCCS KSJBMDCFYZKAFH-UHFFFAOYSA-N 0.000 description 3
- 125000005068 thioepoxy group Chemical group S(O*)* 0.000 description 3
- 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 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000003116 impacting effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 1
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/06—Polythioethers from cyclic thioethers
- C08G75/08—Polythioethers from cyclic thioethers from thiiranes
-
- 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
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a high-refractive-index super-tough optical resin material and a preparation method thereof, wherein the optical resin material comprises the following components in parts by weight: 60-95 parts of bis (2, 3-thiocyclopropyl) sulfide, 5-30 parts of polythiol, 2-15 parts of polyisocyanate, 0.01-1 part of initiator, 0.05-1 part of ultraviolet absorber and 0.05-1 part of phosphate release agent; the polythiol is selected from 1, 4-dithiane-2, 5-dithiol and/or 1, 4-dithiane-2, 5-di (methyl mercaptan). According to the invention, mercaptan containing a dithiane structure is introduced into an optical resin system as a chain transfer agent, so that the mechanical property of the optical resin system can be improved, and the glass transition temperature is further improved; the mercaptan with the dithiane structure can not only not increase dispersion, but also improve Abbe number.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a high-refractive-index super-tough optical resin material and a preparation method thereof.
Background
Under the same photometric lens, the high-refractive-index resin can greatly reduce the thickness of the lens and meet the wearing comfort of people, so that the 1.70 high-refractive-index lens is developed.
It is well known that the higher the refractive index, the more chromatic dispersion, and the less sharp the image will be. How to use a thioepoxy-based optical material in the patent "a high refractive index, high abbe number resin lens" and "thioepoxy-based optical manufacturing method and polymer composition thereof" can solve the problem of the high refractive index and high abbe number without increasing the dispersion, i.e., the high refractive index and the high abbe number. But has poorer mechanical property compared with the 1.60 polyurethane optical lens. Korean registered patent No. 10-0681218 discloses a thioepoxy resin lens having a high refractive index, a high abbe number, and excellent properties, but has problems in that the lens is easily broken and has poor mechanical properties.
Disclosure of Invention
In view of the above, the present invention aims to provide a high refractive index super-tough optical resin material and a preparation method thereof, wherein the optical resin material has excellent mechanical properties.
The invention provides a high-refractive-index super-tough optical resin material which comprises the following components in parts by weight:
60-95 parts of bis (2, 3-thiocyclopropyl) sulfide, 5-30 parts of polythiol, 2-15 parts of polyisocyanate, 0.01-1 part of initiator, 0.05-1 part of ultraviolet absorber and 0.05-1 part of phosphate release agent;
the polythiol is selected from 1, 4-dithiane-2, 5-dithiol (DSDT) and/or 1, 4-dithiane-2, 5-bis (methanethiol).
In the present invention, the 1, 4-dithiane-2, 5-dithiol has CAS number of 645404-26-8 and molecular formula of C4H8S4The molecular weight is 184g/mol, and the structural formula is as follows:
in the present invention, the 1, 4-dithiane-2, 5-bis (methanethiol) has a CAS number of 136122-15-1 and a molecular formula of C6H12S4Molecular weight of 212g/mol, structural formula
The refractive index of the polythiol is as high as 1.6530, the sulfur content is high, the dispersion is not increased, and the Abbe number is improved.
In the present invention, the polyisocyanate is selected from one or more of norbornane diisocyanate, 4-dicyclohexylmethane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
In the present invention, the phosphate ester release agent is selected from one or more of di-n-butyl phosphate, El310, polyoxyethylene lauryl ether phosphate, polyoxyethylene nonylphenol phosphate and zelecun (tm).
In the invention, the ink also comprises a blue toner and a red toner;
the concentration of the blue colorant is 3-3.5 ppm;
the concentration of the red toner is 1-2 ppm.
In a specific embodiment of the present invention, the optical resin material includes 5 parts of 1, 4-dithiane-2, 5-dithiol, 7.00 parts of norbornane diisocyanate, 0.1 part of ultraviolet absorber UV-324, 0.2 part of release agent ((98% norbornane diisocyanate and 2% dibutyl phosphate), 0.07 part of tetrabutylphosphonium bromide, 3.0ppm of blue colorant, 1.5ppm of red colorant, and 88 parts of bis (2, 3-cyclopropylthio) sulfide.
Or comprises 22.0 parts of 1, 4-dithiane-2, 5-dithiol, 8.0 parts of 4, 4-dicyclohexylmethane diisocyanate, 0.1 part of ultraviolet absorbent UV-329, 0.3 part of release agent (99% of 4, 4-dicyclohexylmethane diisocyanate and 1% of polyoxyethylene lauryl ether phosphate), 0.15 part of tetrabutyl phosphonium bromide, 3.0ppm of blue colorant, 1.5ppm of red colorant and 70 parts of bis (2, 3-epithiopropyl) sulfide.
Or comprises 12.0 parts of 1, 4-dithiane-2, 5-dimethylmercaptan, 3.0 parts of isophorone diisocyanate, 0.1 part of ultraviolet absorber UV-324, 0.15 part of a mold release agent (93% of isophorone diisocyanate and 7% of Zelec UNTM), 0.10 part of triphenylphosphine and 85 parts of bis (2, 3-thiocyclopropyl) sulfide;
or comprises 15.0 parts of 1, 4-dithiane-2, 5-dimethylmercaptan, 5.0 parts of hexamethylene diisocyanate, 0.1 part of ultraviolet absorbent UV-324, 0.3 part of release agent (94% hexamethylene diisocyanate and 6% nonylphenol polyoxyethylene ether phosphate), 0.8 part of tetrabutylphosphonium bromide, 3.0ppm of blue colorant, 1.5ppm of red colorant and 80 parts of bis (2, 3-epithiopropyl) sulfide;
or comprises 2.0 parts of 1, 4-dithiane-2, 5-dithiol, 5.0 parts of isophorone diisocyanate, 0.1 part of ultraviolet absorber UV-329, 0.25 part of release agent (99% isophorone diisocyanate and 1% dibutyl phosphate), 0.1 part of tetrabutyl phosphonium bromide, 3.0ppm of blue colorant, 1.5ppm of red colorant and 93 parts of bis (2, 3-cyclithiopropyl) sulfide.
The invention provides a preparation method of a high-refractive-index super-tough optical resin material, which comprises the following steps:
uniformly mixing polyisocyanate, polythiol, an initiator, an ultraviolet absorbent and a phosphate ester release agent, and then mixing the mixture with bis (2, 3-epithiopropyl) thioether to obtain a mixture;
and injecting the mixture into a mold through a filter membrane, carrying out primary curing, demolding, and then carrying out secondary curing to obtain the high-refractive-index super-tough optical resin material.
In the invention, the temperature for mixing with the bis (2, 3-epithiopropyl) sulfide is 0-15 ℃ and the time is 30-60 min.
In the present invention, the temperature raising procedure of the first curing: the initial temperature is 15-25 ℃, the heat is preserved for 2.0-3.5 hours, the temperature is raised to 45-60 ℃ after 10-15 hours, the temperature is raised to 75-90 ℃ after 2-4 hours, and finally the temperature is lowered to 60-75 ℃ after 1.5-2.5 hours;
the temperature of the second curing is 80-110 ℃, and the time is 2-4 h.
The invention provides a high-refractive-index super-tough optical resin material which comprises the following components in parts by weight: 60-95 parts of bis (2, 3-thiocyclopropyl) sulfide, 5-30 parts of polythiol, 2-15 parts of polyisocyanate, 0.01-1 part of initiator, 0.05-1 part of ultraviolet absorber and 0.05-1 part of phosphate release agent; the polythiol is selected from 1, 4-dithiane-2, 5-dithiol and/or 1, 4-dithiane-2, 5-di (methyl mercaptan). According to the invention, mercaptan containing a dithiane structure is introduced into an optical resin system as a chain transfer agent, so that the mechanical property of the optical resin system can be improved, and the glass transition temperature is further improved; the mercaptan with the dithiane structure can not only not increase dispersion, but also improve Abbe number. The experimental results show that: the refractive index of the optical resin material is 1.7093-1.7218, and the Abbe number is 37-38.7; the glass transition temperature is 91-97 ℃; the 16g small ball is not broken by free body impacting the center of the fine product for 60-102 times at the height of 1.27 m.
Detailed Description
In order to further illustrate the present invention, the following examples are provided to describe the high refractive index super tough optical resin material and the preparation method thereof in detail, but they should not be construed as limiting the scope of the present invention.
In the following examples, BEPS: bis (2, 3-thiocyclopropyl) sulfide; DMDS 2,2' -thiodiethanethiol; BES 2, 3-bis (2-mercaptoethylthio) -3-propyl-1-thiol; PETMP pentaerythritol tetrakis (3-mercaptopropionate); DSDT is 1, 4-dithiane-2, 5-dithiol; BMMD is 1, 4-dithiane-2, 5-dimethylmercaptan; IPDI is isophorone diisocyanate; NBDI is norbornane diisocyanate; HMDI 4, 4-dicyclohexylmethane diisocyanate; HDI is hexamethylene diisocyanate.
TABLE 1 raw materials used in examples and comparative examples
Example 1
The preparation method of the optical resin comprises the following steps:
(1) adding 1, 4-dithiane-2, 5-dithiol 5.0g, norbornane diisocyanate 7.0g, ultraviolet absorbent UV-324 0.1g, release agent 0.2g (98% norbornane diisocyanate and 2% dibutyl phosphate), tetrabutyl phosphonium bromide 0.07g, blue colorant 3.0ppm and red colorant 1.5ppm in sequence at 20 ℃, stirring and dissolving completely, adding bis (2, 3-thiocyclopropyl) sulfide 88g, and stirring for 50min at 20 ℃ to obtain prepolymer feed liquid;
(2) vacuum degassing the prepolymerization feed liquid obtained in the step (1) for 30min, filtering the prepolymerization feed liquid by a polytetrafluoroethylene filter membrane with the aperture of 3 mu m, injecting the filtrate into a glass mold, and placing the mold into a temperature-programmed curing furnace for primary curing to obtain a resin lens subjected to primary curing; the temperature rising procedure of the primary curing is as follows: the initial temperature is 20 ℃, the heat preservation is carried out for 2.5h, the temperature is raised to 40 ℃ for 3h, the temperature is raised to 50 ℃ for 3h, the temperature is raised to 60 ℃ for 2h, the temperature is raised to 100 ℃ for 4h after 4h, and the temperature is finally lowered to 70 ℃ for 2 h;
(3) taking out the resin lens subjected to primary curing obtained in the step (2) by using a release device, and detecting the yield; cleaning and edging, and detecting the yield; and finally, carrying out secondary curing for 4h at 120 ℃ to obtain the optical resin material lens.
Example 2
The preparation method of the optical resin comprises the following steps:
(1) at 20 ℃, adding 22.0g of 1, 4-dithiane-2, 5-dithiol, 8.0g of 4, 4-dicyclohexyl methane diisocyanate, 0.1g of ultraviolet absorbent UV-329, 0.3g of release agent (99% of 4, 4-dicyclohexyl methane diisocyanate and 1% of polyoxyethylene lauryl ether phosphate), 0.15g of tetrabutyl phosphonium bromide, 3.0ppm of blue colorant and 1.5ppm of red colorant in sequence, stirring and dissolving completely, adding 70g of bis (2, 3-epithiopropyl) sulfide, and stirring for 50min at 20 ℃ to obtain prepolymerization feed liquid;
(2) vacuum degassing the prepolymerization feed liquid obtained in the step (1) for 30min, filtering the prepolymerization feed liquid by a polytetrafluoroethylene filter membrane with the aperture of 3 mu m, injecting the filtrate into a glass mold, and placing the mold into a temperature-programmed curing furnace for primary curing to obtain a resin lens subjected to primary curing; the temperature rising procedure of the primary curing is as follows: the initial temperature is 25 ℃, the temperature is kept for 2.5h, the temperature is raised to 50 ℃ for 10h, the temperature is raised to 85 ℃ for 3.5h, the temperature is kept for 2.5h, and finally the temperature is lowered to 70 ℃ for 1.5 h;
(3) taking out the resin lens subjected to primary curing obtained in the step (2) by using a release device, and detecting the yield; cleaning and edging, and detecting the yield; and finally, carrying out secondary curing for 2h at 120 ℃ to obtain the optical resin material lens.
Example 3
The preparation method of the optical resin comprises the following steps:
(1) at 20 ℃, adding 1.0 g, 4-dithiane-2, 5-dimethylmercaptan, 3.0g isophorone diisocyanate, 0.1g ultraviolet absorbent UV-324, 0.15g release agent (93% isophorone diisocyanate and 7% Zelec UNTM), 0.10g triphenylphosphine, 85g bis (2, 3-thiocyclopropyl) sulfide, and stirring for 50min at 20 ℃ to obtain prepolymerization feed liquid;
(2) vacuum degassing the prepolymerization feed liquid obtained in the step (1) for 30min, filtering the prepolymerization feed liquid by a polytetrafluoroethylene filter membrane with the aperture of 3 mu m, injecting the filtrate into a glass mold, and placing the mold into a temperature-programmed curing furnace for primary curing to obtain a resin lens subjected to primary curing; the temperature rising procedure of the primary curing is as follows: the initial temperature is 25 ℃, the temperature is kept for 2.5h, the temperature is raised to 50 ℃ for 8h, the temperature is raised to 85 ℃ for 3.5h, the temperature is kept for 2.5h, and finally the temperature is lowered to 70 ℃ for 1 h;
(3) taking out the resin lens subjected to primary curing obtained in the step (2) by using a release device, and detecting the yield; cleaning and edging, and detecting the yield; and finally, carrying out secondary curing for 2h at 110 ℃ to obtain the optical resin material lens.
Example 4
The preparation method of the optical resin comprises the following steps:
(1) adding 1, 4-dithiane-2, 5-dimethylmercaptan 15.0g, hexamethylene diisocyanate 5.0g, ultraviolet absorbent UV-324 0.1g, demolding agent 0.3g (94% hexamethylene diisocyanate and 6% polyoxyethylene nonylphenol phosphate), tetrabutyl phosphonium bromide 0.8g, blue colorant 3.0ppm and red colorant 1.5ppm in sequence at 20 ℃, stirring and dissolving completely, adding bis (2, 3-epithiopropyl) sulfide 80g, and stirring at 20 ℃ for 50min to obtain prepolymer solution;
(2) vacuum degassing the prepolymerization feed liquid obtained in the step (1) for 30min, filtering the prepolymerization feed liquid by a polytetrafluoroethylene filter membrane with the aperture of 3 mu m, injecting the filtrate into a glass mold, and placing the mold into a temperature-programmed curing furnace for primary curing to obtain a resin lens subjected to primary curing; the temperature rising procedure of the primary curing is as follows: the initial temperature is 20 ℃, the temperature is kept for 2.5h, the temperature is raised to 55 ℃ for 12h, the temperature is raised to 80 ℃ for 3.5h, the temperature is kept for 3h, and finally the temperature is lowered to 70 ℃ for 1 h;
(3) taking out the resin lens subjected to primary curing obtained in the step (2) by using a release device, and detecting the yield; cleaning and edging, and detecting the yield; and finally, carrying out secondary curing for 2h at 110 ℃ to obtain the optical resin material lens.
Example 5
The preparation method of the optical resin comprises the following steps:
(1) sequentially adding 1, 4-dithiane-2, 5-dithiol, 5.0g isophorone diisocyanate, 0.1g ultraviolet absorbent UV-329, 0.25g release agent (99% isophorone diisocyanate and 1% dibutyl phosphate), 0.1g tetrabutyl phosphonium bromide, 3.0ppm blue colorant and 1.5ppm red colorant at 20 ℃, stirring and dissolving completely, adding 93g bis (2, 3-epithiopropyl) thioether, and stirring for 50min at 20 ℃ to obtain prepolymerization feed liquid;
(2) vacuum degassing the prepolymerization feed liquid obtained in the step (1) for 30min, filtering the prepolymerization feed liquid by a polytetrafluoroethylene filter membrane with the aperture of 3 mu m, injecting the filtrate into a glass mold, and placing the mold into a temperature-programmed curing furnace for primary curing to obtain a resin lens subjected to primary curing; the temperature rising procedure of the primary curing is as follows: the initial temperature is 25 ℃, the temperature is kept for 3h, the temperature is raised to 50 ℃ for 10h, the temperature is raised to 85 ℃ for 3h, the temperature is kept for 2.5h, and finally the temperature is lowered to 70 ℃ for 1.5 h;
(3) taking out the resin lens subjected to primary curing obtained in the step (2) by using a release device, and detecting the yield; cleaning and edging, and detecting the yield; and finally, carrying out secondary curing for 2h at 110 ℃ to obtain the optical resin material lens.
Comparative example 1
The preparation method of the optical resin comprises the following steps:
(1) adding 6.5g of 2,2' -thiodiethanethiol, 5.0g of isophorone diisocyanate, 0.1g of ultraviolet absorber UV-324, 0.2g of release agent (98% of isophorone diisocyanate and 2% of dibutyl phosphate), 0.07g of tetrabutyl phosphonium bromide, 3.0ppm of blue colorant and 1.5ppm of red colorant in sequence at 20 ℃, stirring and dissolving completely, adding 88.5g of bis (2, 3-cyclosulfanyl) sulfide, and stirring for 50min at 20 ℃ to obtain prepolymer feed liquid;
(2) vacuum degassing the prepolymerization feed liquid obtained in the step (1) for 30min, filtering the prepolymerization feed liquid by a polytetrafluoroethylene filter membrane with the aperture of 3 mu m, injecting the filtrate into a glass mold, and placing the mold into a temperature-programmed curing furnace for primary curing to obtain a resin lens subjected to primary curing; the temperature rising procedure of the primary curing is as follows: the initial temperature is 20 ℃, the heat preservation is carried out for 2.5h, the temperature is raised to 40 ℃ for 3h, the temperature is raised to 50 ℃ for 3h, the temperature is raised to 60 ℃ for 2h, the temperature is raised to 100 ℃ for 4h after 4h, and the temperature is finally lowered to 70 ℃ for 2 h;
(3) taking out the resin lens subjected to primary curing obtained in the step (2) by using a release device, and detecting the yield; cleaning and edging, and detecting the yield; and finally, carrying out secondary curing for 4h at 120 ℃ to obtain the optical resin material lens.
Comparative example 2
The preparation method of the optical resin comprises the following steps:
(1) sequentially adding 2,2' -thiodiethanethiol 890.0 g, 4-dicyclohexylmethane diisocyanate 2g, ultraviolet absorbent UV-329 0.1g, release agent (99% isophorone diisocyanate and 1% polyoxyethylene lauryl ether phosphate) 0.3g, tetrabutyl phosphonium bromide 0.15g, blue pigment 3.0ppm and red pigment 1.5ppm at 20 ℃, stirring and dissolving completely, adding bis (2, 3-epithiopropyl) sulfide 90g, and stirring at 20 ℃ for 50min to obtain prepolymerization feed liquid;
(2) vacuum degassing the prepolymerization feed liquid obtained in the step (1) for 30min, filtering the prepolymerization feed liquid by a polytetrafluoroethylene filter membrane with the aperture of 3 mu m, injecting the filtrate into a glass mold, and placing the mold into a temperature-programmed curing furnace for primary curing to obtain a resin lens subjected to primary curing; the temperature rising procedure of the primary curing is as follows: the initial temperature is 25 ℃, the temperature is kept for 2.5h, the temperature is raised to 50 ℃ for 10h, the temperature is raised to 85 ℃ for 3.5h, the temperature is kept for 2.5h, and finally the temperature is lowered to 70 ℃ for 1.5 h;
(3) taking out the resin lens subjected to primary curing obtained in the step (2) by using a release device, and detecting the yield; cleaning and edging, and detecting the yield; and finally, carrying out secondary curing for 2h at 120 ℃ to obtain the optical resin material lens.
Refractive index (Ne): detecting by using a multi-wavelength Abbe refractometer (DR-M4);
abbe number (Vd): detecting by using a multi-wavelength Abbe refractometer (DR-M4);
glass transition temperature (Tg): detecting by using a DSC-3 differential scanning calorimeter at the temperature rise rate of 10K/min;
impact resistance: the refractive index, Abbe number, glass transition temperature and impact resistance of the optical resin material lenses provided by the embodiments 1-5 and the comparative examples 1-2 are respectively detected; wherein the refractive index (Ne) and Abbe number are detected by a multi-wavelength Abbe refractometer (DR-M4); glass transition temperature (T)g) Detecting by using a DSC-3 differential scanning calorimeter at the temperature rise rate of 10K/min; performing the American FDA standard, and keeping the impact of free falling body on the center of the lens at the height of 1.27 meters for 16g of small balls without breaking, and accumulating the times; the results of the various property measurements are shown in table 2:
table 2 results of performance test of resin lenses prepared in examples and comparative examples
| Refractive index | Abbe number | Glass transition temperature | Mechanical properties | |
| Example 1 | 1.7093 | 38.7 | 94℃ | 86 |
| Example 2 | 1.7102 | 37.0 | 91℃ | 95 |
| Example 3 | 1.7218 | 37.5 | 98℃ | 60 |
| Example 4 | 1.7168 | 38.2 | 96℃ | 102 |
| Example 5 | 1.7172 | 38 | 97℃ | 68 |
| Comparative example 1 | 1.6980 | 36.2 | 94℃ | 2 |
| Comparative example 2 | 1.7010 | 35.4 | 90℃ | 3 |
From the above embodiments, the present invention provides a high refractive index super-tough optical resin material, which comprises the following components in parts by weight: 60-95 parts of bis (2, 3-thiocyclopropyl) sulfide, 5-30 parts of polythiol, 2-15 parts of polyisocyanate, 0.01-1 part of initiator, 0.05-1 part of ultraviolet absorber and 0.05-1 part of phosphate release agent; the polythiol is selected from 1, 4-dithiane-2, 5-dithiol and/or 1, 4-dithiane-2, 5-di (methyl mercaptan). According to the invention, mercaptan containing a dithiane structure is introduced into an optical resin system as a chain transfer agent, so that the mechanical property of the optical resin system can be improved, and the glass transition temperature is further improved; the mercaptan with the dithiane structure can not only not increase dispersion, but also improve Abbe number. The experimental results show that: the refractive index of the optical resin material is 1.7093-1.7218, and the Abbe number is 37-38.7; the glass transition temperature is 91-97 ℃; the 16g small ball is not broken by free body impacting the center of the fine product for 60-102 times at the height of 1.27 m.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A high-refractive-index super-tough optical resin material comprises the following components in parts by weight:
60-95 parts of bis (2, 3-thiocyclopropyl) sulfide, 5-30 parts of polythiol, 2-15 parts of polyisocyanate, 0.01-1 part of initiator, 0.05-1 part of ultraviolet absorber and 0.05-1 part of phosphate release agent;
the polythiol is selected from 1, 4-dithiane-2, 5-dithiol and/or 1, 4-dithiane-2, 5-di (methyl mercaptan).
2. The high refractive index super tough optical resin material according to claim 1, wherein the polyisocyanate is one or more selected from the group consisting of norbornane diisocyanate, 4-dicyclohexylmethane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
3. The high refractive index super tough optical resin material according to claim 1, wherein the initiator is selected from tetrabutylphosphonium bromide and/or triphenylphosphine;
the ultraviolet absorbent is one or more selected from UV-P, UV-O, UV-9, UV-531, UV-324, UV-326, UV-329, UV-541 and UV-1157.
4. The high refractive index super tough optical resin material according to claim 1, wherein the phosphate ester release agent is selected from one or more of di-n-butyl phosphate, El310, polyoxyethylene lauryl phosphate, polyoxyethylene nonylphenol phosphate, and zelecun.
5. The high refractive index super tough optical resin material according to claim 1, further comprising a blue agent and a red agent;
the concentration of the blue colorant is 3-3.5 ppm;
the concentration of the red toner is 1-2 ppm.
6. A method for preparing the high refractive index super tough optical resin material according to any one of claims 1 to 5, comprising the following steps:
uniformly mixing polyisocyanate, polythiol, an initiator, an ultraviolet absorbent and a phosphate ester release agent, and then mixing the mixture with bis (2, 3-epithiopropyl) thioether to obtain a mixture;
and injecting the mixture into a mold through a filter membrane, carrying out primary curing, demolding, and then carrying out secondary curing to obtain the high-refractive-index super-tough optical resin material.
7. The method according to claim 6, wherein the temperature of the mixture of bis (2, 3-epithiopropyl) sulfide and bis (2, 3-epithiopropyl) sulfide is 0 to 15 ℃ and the time is 30 to 60 minutes.
8. The production method according to claim 6, wherein the temperature rise procedure of the first curing is: the initial temperature is 15-25 ℃, the heat is preserved for 2.0-3.5 hours, the temperature is raised to 45-60 ℃ after 10-15 hours, the temperature is raised to 75-90 ℃ after 2-4 hours, and finally the temperature is lowered to 60-75 ℃ after 1.5-2.5 hours;
the temperature of the second curing is 80-110 ℃, and the time is 2-4 h.
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| CN116120554A (en) * | 2022-12-12 | 2023-05-16 | 益丰新材料股份有限公司 | Composition for optical lens material with high refractive index and low thermal expansion coefficient |
| CN116120508A (en) * | 2022-12-12 | 2023-05-16 | 益丰新材料股份有限公司 | Transparent resin material composition for high transmission ratio in spectrum and transparent resin material |
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| CN1313513A (en) * | 2000-03-15 | 2001-09-19 | 保谷株式会社 | Plastic spectacle lens |
| CN1601306A (en) * | 2003-09-22 | 2005-03-30 | 保谷株式会社 | Process of producing plastic lens and plastic lens |
| CN110483734A (en) * | 2019-08-27 | 2019-11-22 | 黄河三角洲京博化工研究院有限公司 | A kind of high softening temperature, high impact toughness and polyurethane optical resin material of yellowing-resistant and preparation method thereof |
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| CN1313513A (en) * | 2000-03-15 | 2001-09-19 | 保谷株式会社 | Plastic spectacle lens |
| CN1601306A (en) * | 2003-09-22 | 2005-03-30 | 保谷株式会社 | Process of producing plastic lens and plastic lens |
| CN110483734A (en) * | 2019-08-27 | 2019-11-22 | 黄河三角洲京博化工研究院有限公司 | A kind of high softening temperature, high impact toughness and polyurethane optical resin material of yellowing-resistant and preparation method thereof |
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| CN116120554A (en) * | 2022-12-12 | 2023-05-16 | 益丰新材料股份有限公司 | Composition for optical lens material with high refractive index and low thermal expansion coefficient |
| CN116120508A (en) * | 2022-12-12 | 2023-05-16 | 益丰新材料股份有限公司 | Transparent resin material composition for high transmission ratio in spectrum and transparent resin material |
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