CN116496463A - Optical resin material with high refractive index and high Abbe number and curing process thereof - Google Patents
Optical resin material with high refractive index and high Abbe number and curing process thereof Download PDFInfo
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- CN116496463A CN116496463A CN202310350974.1A CN202310350974A CN116496463A CN 116496463 A CN116496463 A CN 116496463A CN 202310350974 A CN202310350974 A CN 202310350974A CN 116496463 A CN116496463 A CN 116496463A
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- refractive index
- curing
- abbe number
- resin material
- optical resin
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- 239000000463 material Substances 0.000 title claims abstract description 81
- 239000011347 resin Substances 0.000 title claims abstract description 69
- 229920005989 resin Polymers 0.000 title claims abstract description 69
- 230000003287 optical effect Effects 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 39
- -1 episulfide compound Chemical class 0.000 claims description 32
- 229920006295 polythiol Polymers 0.000 claims description 20
- DASNDJBQHOUCAV-UHFFFAOYSA-N CCCCP(CCCC)(CCCC)CCCC.Br Chemical group CCCCP(CCCC)(CCCC)CCCC.Br DASNDJBQHOUCAV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 12
- 150000002513 isocyanates Chemical class 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 10
- 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 10
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- PAUHLEIGHAUFAK-UHFFFAOYSA-N 1-isocyanato-1-[(1-isocyanatocyclohexyl)methyl]cyclohexane Chemical compound C1CCCCC1(N=C=O)CC1(N=C=O)CCCCC1 PAUHLEIGHAUFAK-UHFFFAOYSA-N 0.000 claims description 5
- VRQFYSHDLYCPRC-UHFFFAOYSA-N (ethylsulfanyl)methanethiol Chemical compound CCSCS VRQFYSHDLYCPRC-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- MTZVWTOVHGKLOX-UHFFFAOYSA-N 2,2-bis(sulfanylmethyl)propane-1,3-dithiol Chemical compound SCC(CS)(CS)CS MTZVWTOVHGKLOX-UHFFFAOYSA-N 0.000 claims description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 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 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 239000002685 polymerization catalyst Substances 0.000 claims 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims 1
- YFNCATAIYKQPOO-UHFFFAOYSA-N thiophanate Chemical compound CCOC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OCC YFNCATAIYKQPOO-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 description 44
- 238000012423 maintenance Methods 0.000 description 29
- 238000001914 filtration Methods 0.000 description 22
- 238000001816 cooling Methods 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 18
- 239000011521 glass Substances 0.000 description 12
- 238000005266 casting Methods 0.000 description 11
- 239000012528 membrane Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 description 11
- 239000011148 porous material Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 238000009849 vacuum degassing Methods 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000004814 polyurethane Substances 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- VTLHIRNKQSFSJS-UHFFFAOYSA-N [3-(3-sulfanylbutanoyloxy)-2,2-bis(3-sulfanylbutanoyloxymethyl)propyl] 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCC(COC(=O)CC(C)S)(COC(=O)CC(C)S)COC(=O)CC(C)S VTLHIRNKQSFSJS-UHFFFAOYSA-N 0.000 description 5
- DWRNEZSALFWUFE-UHFFFAOYSA-N butan-2-ylsulfanylcyclopropane Chemical compound CCC(C)SC1CC1 DWRNEZSALFWUFE-UHFFFAOYSA-N 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- ZERULLAPCVRMCO-UHFFFAOYSA-N sulfure de di n-propyle Natural products CCCSCCC ZERULLAPCVRMCO-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000012653 anionic ring-opening polymerization Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003573 thiols Chemical class 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
- C08G18/40—High-molecular-weight compounds
- C08G18/52—Polythioethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- 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
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
The invention belongs to the technical field of optical resin, and particularly relates to an optical resin material with high refractive index and high Abbe number and a curing process thereof.
Description
Technical Field
The invention belongs to the technical field of optical resin, and particularly relates to an optical resin material with high refractive index and high Abbe number and a curing process thereof.
Technical Field
Compared with glass materials, the optical resin material has the advantages of low specific gravity, high impact toughness, difficult breakage, comfortable wearing, convenient processing, rich product series, easy dyeing and the like, and is increasingly widely applied to the optical lens market.
Under the same photometric lens, the high refractive index resin can greatly reduce the thickness of the lens and meet the comfort level of wearing by people. The abbe number, also known as the dispersion coefficient, of a lens is an important parameter for measuring the dispersion phenomenon generated by a resin lens, and the higher the abbe number of the resin lens, the lower the dispersion, and the clearer the lens.
In the optical resin technology, the technology is still in reference to the foreign technology and is produced according to experience, so that the quality of the product is far from foreign. Particularly, the research on the episulfide compound in China is less, the episulfide compound is started late, and the production raw material is monopoly of foreign enterprises; the technology for producing optical resins of episulfide compounds is thus far lower than foreign levels.
Generally, the higher the refractive index of the resin material, the more chromatic dispersion and the lower the definition of the image. There has been a great interest in reducing the dispersion while pursuing a high refractive index, i.e., a resin lens having a high refractive index and a high abbe number. At present, in CN105254907B, by accurately determining the curing temperature rising gradient of polyurethane optical resin, the method can greatly improve the curing efficiency and the resin performance in the primary and secondary curing stages for polyurethane optical resins with different refractive index series and same series and different formulas, so that the mechanical property, the thermal property and other properties of the finally obtained resin are optimal. The technology has better use effect on a polyurethane material system which is polymerized step by step, but is not applicable to an anionic ring-opening polymerized polythioether material system with insignificant heat release, and does not play a role in Abbe number promotion in the technology. CN114605639a, by designing the composition, achieves an optimized improvement in storage stability, polymerization rate during the reaction, and heat resistance of the optical material, while controlling the rate of temperature rise in the curing procedure of its embodiment, but does not play a role in improving abbe number.
Disclosure of Invention
Aiming at the defects in the production technology, the invention aims to provide an optical resin material with high refractive index and high Abbe number and a curing process thereof.
The technical scheme of the invention is as follows:
an optical resin material with high refractive index and high Abbe number is prepared from episulfide compound, polythiol and isocyanate, wherein the chlorine content of polythiol is less than or equal to 500ppm, and the chlorine content of isocyanate is less than or equal to 1000ppm.
Preferably, the polythiol has a chlorine content of 400ppm or less and the isocyanate has a chlorine content of 300ppm or less.
Preferably, the episulfide compound is 70-80 parts, polythiol is 8-20 parts, and isocyanate is 5-15 parts by weight.
Preferably, the episulfide compound is one or more of bis (β -episulfide propyl) sulfide, bis (β -episulfide propyl) disulfide, bis (β -episulfide propyl) trisulfide, bis (β -episulfide propyl sulfide) methane, 1, 2-bis (β -episulfide propyl sulfide) ethane, 1, 3-bis (β -episulfide propyl sulfide) propane, 1, 4-bis (β -episulfide propyl sulfide) butane, bis (β -episulfide propyl sulfide).
Preferably, the polythiol is one or more of thiobis Gan Liuchun, 2, 3-dithio (2-mercapto) -1-propanethiol, 1,5,9, 13-tetramercapto-3, 7, 11-tritridecane, 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiooctane, tetrakis (mercaptomethyl) methane, pentaerythritol tetrakis (3-mercaptopropionic) ester, pentaerythritol tris (3-mercaptopropionic) ester, 1, 2-tetrakis (mercaptomethylthiothio) ethane, dipentaerythritol hexa (3-mercaptopropionic) ester, pentaerythritol tetrakis (3-mercaptobutyric acid) ester.
Preferably, the isocyanate is one or more of 4, 4-dicyclohexylmethane diisocyanate, norbornane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, methylene dicyclohexyl diisocyanate, hydrogenated xylylene diisocyanate.
The curing process of the optical resin material with high refractive index and high Abbe number comprises primary curing and secondary curing, wherein the curing temperature rise interval of the primary curing is within the range of 20-80 ℃, and the total duration is 11.5-15 h.
Preferably, the curing temperature rise interval comprises 20 ℃ to 55 ℃ and 55 ℃ to 80 ℃, wherein the average temperature rise rate is 5 ℃ to 20 ℃ per hour at 55 ℃ to 80 ℃.
Further preferably, the primary curing comprises in particular five stages, in particular:
the first stage: maintaining at 20deg.C for 2 hr;
and a second stage: raising the temperature to 55 ℃ at 2.50 ℃/h;
and a third stage: raising the temperature to 80 ℃ at a speed of 5-20 ℃/h;
fourth stage: maintaining at 80deg.C for 4 hr;
fifth stage: the temperature was reduced to 60℃at 20℃per hour.
In the polyurethane material system, the aim of high refractive index and Abbe number can not be met at the same time, if Abbe number is more than 35, the refractive index of the polyurethane material is generally less than 1.63, if the refractive index is more than 1.65, the Abbe number is generally lower than 32, and the technology of the polythioether material system is not universal because of the difference between the anionic ring-opening polymerization polythioether material system with insignificant heat release and the polyurethane material system. The inventors have developed studies on a polythioether resin material in order to obtain a resin material having a high refractive index and an Abbe number, specifically as follows: in the polythioether resin material, halogen exists in a form of an end capping group, the existence of the halogen directly influences the crosslinking degree of the material, the lower the crosslinking degree is, the worse the temperature resistance of the material is, the halogen is easy to reduce the weather resistance of the material and easy to yellow; meanwhile, with the improvement of the curing temperature, particularly under the condition of rapid heat release caused by the rapid reaction of the curing rate, the problems of reduced crosslinking degree, reduced temperature resistance and poor weather resistance caused by halogen exist, so that the material is easier to oxidize and break bonds, short-wavelength spectrum absorption is generated, the refractive index nF value is increased, and the Abbe number is reduced. In the same material, the variation fluctuation of Abbe number is mainly influenced by a polymerization process, and aiming at the polythioether resin material, the curing program is usually controlled by adopting temperature programming, mainly because the provided environment temperature is matched with the reaction rate, if the provided temperature is higher than the temperature required by curing, the reaction rate is passively accelerated, rapid heat release and even explosion polymerization are generated, the material is poorly polymerized, and meanwhile, short-wavelength spectrum absorption is generated due to the oxidation of a local overheat molecular chain, the nF value is increased, and the Abbe value is reduced; if the temperature rising rate is too slow, the polymerization reaction proceeds smoothly, but the production efficiency is seriously affected. Meanwhile, according to classical electromagnetic theory, the dispersion of an optical material can be expressed as:
R 1 in 2 in As molecular dispersion, see R 1 in 2 in The polarization ratio of meson at 1 and 2 wavelengths is proportional to the difference of the polarization ratio and the relative molecular mass M, and the polarization ratio is inversely proportional to the density, so that the proper temperature rising rate is selected in the polymer synthesis process, the increase of the M/rho value of the product is ensured, and the corresponding polymer dispersion is relatively reduced, namely the Abbe number is increased. Therefore, the inventors have searched for a polythioether resin material, and have found that an optical resin material having a high refractive index and an Abbe number can be obtained by using an episulfide compound, a polythiol and an isocyanate as raw materials, controlling the chlorine content of the thiol to be 500ppm or less and the chlorine content of the isocyanate to be 1000ppm or less, and matching a specific temperature-increasing program.
The optical resin material with high refractive index and high Abbe number and the curing process thereof provided by the invention can be used for preparing the optical resin with lower dispersion and better definition by utilizing the specific raw materials and the specific curing process.
Detailed Description
The technical solutions in the present embodiment will be described in detail below, but the described embodiments are only some embodiments of the present invention and not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
Example 1
An optical resin material with high refractive index and high Abbe number:
(1) Preparation of a prepolymerization liquid: accurately weighing 10g (chloride ion content 230 ppm) of isophorone diisocyanate, 75g of 1, 4-bis (beta-cyclopropylthio) butane, 15g (150 ppm) of pentaerythritol tetra (3-mercaptobutyrate) and 0.10g of tetrabutylphosphine bromide, mixing and dissolving to obtain a prepolymer liquid;
(2) Casting a sample: vacuum degassing the prepolymerized material liquid obtained in the step (1) for 30min, and filtering and injecting the prepolymerized material liquid into a glass die through a polytetrafluoroethylene filtering membrane with the pore diameter of 3 mu m;
(3) Primary curing: then the mould is put into a temperature programming curing furnace for primary curing, and the specific temperature control procedure is as follows:
| program segment | Temperature (. Degree. C.) | Time (h) | Status of | Rate of temperature control |
| 1 | 20 | 2h | Maintenance of | / |
| 2 | 55 | 10h | Heating up | 2.50℃/h |
| 3 | 80 | 1.5h | Heating up | 16.67℃/h |
| 4 | 80 | 4h | Maintenance of | / |
| 5 | 60 | 1h | Cooling down | 20℃/h |
(4) Secondary curing: taking out the resin lens obtained in the step (3) after primary curing by a mold releaser, and performing secondary curing, wherein the secondary curing temperature control procedure is as follows:
| program segment | Temperature (. Degree. C.) | Time (h) | Status of | Rate of temperature control |
| 1 | 100 | 2h | Maintenance of | / |
| 2 | 60 | 1h | Cooling down | 40℃/h |
Example 2
An optical resin material with high refractive index and high Abbe number:
(1) Preparation of a prepolymerization liquid: accurately weighing 10g (chloride ion content 230 ppm) of isophorone diisocyanate, 75g of 1, 4-bis (beta-cyclopropylthio) butane, 15g (150 ppm) of pentaerythritol tetra (3-mercaptobutyrate) and 0.10g of tetrabutylphosphine bromide, mixing and dissolving to obtain a prepolymer liquid;
(2) Casting a sample: vacuum degassing the prepolymerized material liquid obtained in the step (1) for 30min, and filtering and injecting the prepolymerized material liquid into a glass die through a polytetrafluoroethylene filtering membrane with the pore diameter of 3 mu m;
(3) Primary curing: then the mould is put into a temperature programming curing furnace for primary curing, and the specific temperature control procedure is as follows:
| program segment | Temperature (. Degree. C.) | Time (h) | Status of | Rate of temperature control |
| 1 | 20 | 2h | Maintenance of | / |
| 2 | 55 | 10h | Heating up | 2.50℃/h |
| 3 | 80 | 2h | Heating up | 12.5℃/h |
| 4 | 80 | 4h | Maintenance of | / |
| 5 | 60 | 1h | Cooling down | 20℃/h |
(4) Secondary curing: taking out the resin lens obtained in the step (3) after primary curing by a mold releaser, and performing secondary curing, wherein the secondary curing temperature control procedure is as follows:
| program segment | Temperature (. Degree. C.) | Time (h) | Status of | Rate of temperature control |
| 1 | 100 | 2h | Maintenance of | / |
| 2 | 60 | 1h | Cooling down | 40℃/h |
Example 3
An optical resin material with high refractive index and high Abbe number:
(1) Preparation of a prepolymerization liquid: accurately weighing 10g (chloride ion content 230 ppm) of isophorone diisocyanate, 75g of 1, 4-bis (beta-cyclopropylthio) butane, 15g (150 ppm) of pentaerythritol tetra (3-mercaptobutyrate) and 0.10g of tetrabutylphosphine bromide, mixing and dissolving to obtain a prepolymer liquid;
(2) Casting a sample: vacuum degassing the prepolymerized material liquid obtained in the step (1) for 30min, and filtering and injecting the prepolymerized material liquid into a glass die through a polytetrafluoroethylene filtering membrane with the pore diameter of 3 mu m;
(3) Primary curing: then the mould is put into a temperature programming curing furnace for primary curing, and the specific temperature control procedure is as follows:
| program segment | Temperature (. Degree. C.) | Time (h) | Status of | Rate of temperature control |
| 1 | 20 | 2h | Maintenance of | / |
| 2 | 55 | 10h | Heating up | 2.50℃/h |
| 3 | 80 | 3h | Heating up | 8.33℃/h |
| 4 | 80 | 4h | Maintenance of | / |
| 5 | 60 | 1h | Cooling down | 20℃/h |
(4) Secondary curing: taking out the resin lens obtained in the step (3) after primary curing by a mold releaser, and performing secondary curing, wherein the secondary curing temperature control procedure is as follows:
| program segment | Temperature (. Degree. C.) | Time (h) | Status of | Rate of temperature control |
| 1 | 100 | 2h | Maintenance of | / |
| 2 | 60 | 1h | Cooling down | 40℃/h |
Example 4
An optical resin material with high refractive index and high Abbe number:
(1) Preparation of a prepolymerization liquid: accurately weighing 8g of methylene dicyclohexyl diisocyanate (with the chloride ion content of 300 ppm), 77g of bis (beta-cyclopropylsulfanyl) sulfide, 15g of pentaerythritol tri (3-mercaptopropionic acid) ester (with the chloride ion content of 400 ppm) and 0.10g of tetrabutylphosphine bromide, mixing and dissolving to obtain a prepolymer liquid;
(2) Casting a sample: vacuum degassing the prepolymerized material liquid obtained in the step (1) for 30min, and filtering and injecting the prepolymerized material liquid into a glass die through a polytetrafluoroethylene filtering membrane with the pore diameter of 3 mu m;
(3) Primary curing: then the mould is put into a temperature programming curing furnace for primary curing, and the specific temperature control procedure is as follows:
| program segment | Temperature (. Degree. C.) | Time (h) | Status of | Rate of temperature control |
| 1 | 20 | 2h | Maintenance of | / |
| 2 | 55 | 10h | Heating up | 2.50℃/h |
| 3 | 80 | 2.5h | Heating up | 10℃/h |
| 4 | 80 | 4h | Maintenance of | / |
| 5 | 60 | 1h | Cooling down | 20℃/h |
(4) Secondary curing: taking out the resin lens obtained in the step (3) after primary curing by a mold releaser, and performing secondary curing, wherein the secondary curing temperature control procedure is as follows:
| program segment | Temperature (. Degree. C.) | Time (h) | Status of | Rate of temperature control |
| 1 | 100 | 2h | Maintenance of | / |
| 2 | 60 | 1h | Cooling down | 40℃/h |
Example 5
An optical resin material with high refractive index and high Abbe number:
(1) Preparation of a prepolymerization liquid: accurately weighing 8g of methylene dicyclohexyl diisocyanate (with the chloride ion content of 300 ppm), 77g of bis (beta-cyclopropylsulfanyl) sulfide, 15g of pentaerythritol tri (3-mercaptopropionic acid) ester (with the chloride ion content of 400 ppm) and 0.10g of tetrabutylphosphine bromide, mixing and dissolving to obtain a prepolymer liquid;
(2) Casting a sample: vacuum degassing the prepolymerized material liquid obtained in the step (1) for 30min, and filtering and injecting the prepolymerized material liquid into a glass die through a polytetrafluoroethylene filtering membrane with the pore diameter of 3 mu m;
(3) Primary curing: then the mould is put into a temperature programming curing furnace for primary curing, and the specific temperature control procedure is as follows:
| program segment | Temperature (. Degree. C.) | Time (h) | Status of | Rate of temperature control |
| 1 | 20 | 2h | Maintenance of | / |
| 2 | 55 | 10h | Heating up | 2.50℃/h |
| 3 | 80 | 4h | Heating up | 6.25℃/h |
| 4 | 80 | 4h | Maintenance of | / |
| 5 | 60 | 1h | Cooling down | 20℃/h |
(4) Secondary curing: taking out the resin lens obtained in the step (3) after primary curing by a mold releaser, and performing secondary curing, wherein the secondary curing temperature control procedure is as follows:
| program segment | Temperature (. Degree. C.) | Time (h) | Status of | Rate of temperature control |
| 1 | 100 | 2h | Maintenance of | / |
| 2 | 60 | 1h | Cooling down | 40℃/h |
Example 6
An optical resin material with high refractive index and high Abbe number:
(1) Preparation of a prepolymerization liquid: accurately weighing 8g of methylene dicyclohexyl diisocyanate (with the chloride ion content of 300 ppm), 77g of bis (beta-cyclopropylsulfanyl) sulfide, 15g of pentaerythritol tri (3-mercaptopropionic acid) ester (with the chloride ion content of 400 ppm) and 0.10g of tetrabutylphosphine bromide, mixing and dissolving to obtain a prepolymer liquid;
(2) Casting a sample: vacuum degassing the prepolymerized material liquid obtained in the step (1) for 30min, and filtering and injecting the prepolymerized material liquid into a glass die through a polytetrafluoroethylene filtering membrane with the pore diameter of 3 mu m;
(3) Primary curing: then the mould is put into a temperature programming curing furnace for primary curing, and the specific temperature control procedure is as follows:
| program segment | Temperature (. Degree. C.) | Time (h) | Status of | Rate of temperature control |
| 1 | 20 | 2h | Maintenance of | / |
| 2 | 55 | 10h | Heating up | 2.50℃/h |
| 3 | 80 | 5h | Heating up | 5℃/h |
| 4 | 80 | 4h | Maintenance of | / |
| 5 | 60 | 1h | Cooling down | 20℃/h |
(4) Secondary curing: taking out the resin lens obtained in the step (3) after primary curing by a mold releaser, and performing secondary curing, wherein the secondary curing temperature control procedure is as follows:
| program segment | Temperature (. Degree. C.) | Time (h) | Status of | Rate of temperature control |
| 1 | 100 | 2h | Maintenance of | / |
| 2 | 60 | 1h | Cooling down | 40℃/h |
Comparative example 1
An optical resin material with high refractive index and high Abbe number:
(1) Preparation of a prepolymerization liquid: accurately weighing 10g (chloride ion content 230 ppm) of isophorone diisocyanate, 75g of 1, 4-bis (beta-cyclopropylthio) butane, 15g (chloride ion content 150 ppm) of pentaerythritol tetra (3-mercaptobutyrate) and 0.10g of tetrabutylphosphine bromide, mixing and dissolving to obtain a prepolymer liquid;
(2) Casting a sample: vacuum degassing the prepolymerized material liquid obtained in the step (1) for 30min, and filtering and injecting the prepolymerized material liquid into a glass die through a polytetrafluoroethylene filtering membrane with the pore diameter of 3 mu m;
(3) Primary curing: then the mould is put into a temperature programming curing furnace for primary curing, and the specific temperature control procedure is as follows:
(4) Secondary curing: taking out the resin lens obtained in the step (3) after primary curing by a mold releaser, and performing secondary curing, wherein the secondary curing temperature control procedure is as follows:
| program segment | Temperature (. Degree. C.) | Time (h) | Status of | Rate of temperature control |
| 1 | 100 | 2h | Maintenance of | / |
| 2 | 60 | 1h | Cooling down | 40℃/h |
Comparative example 2
An optical resin material with high refractive index and high Abbe number:
(1) Preparation of a prepolymerization liquid: accurately weighing 10g (chloride ion content 230 ppm) of isophorone diisocyanate, 75g of 1, 4-bis (beta-cyclopropylthio) butane, 15g (chloride ion content 150 ppm) of pentaerythritol tetra (3-mercaptobutyrate) and 0.10g of tetrabutylphosphine bromide, mixing and dissolving to obtain a prepolymer liquid;
(2) Casting a sample: vacuum degassing the prepolymerized material liquid obtained in the step (1) for 30min, and filtering and injecting the prepolymerized material liquid into a glass die through a polytetrafluoroethylene filtering membrane with the pore diameter of 3 mu m;
(3) Primary curing: then the mould is put into a temperature programming curing furnace for primary curing, and the specific temperature control procedure is as follows:
| program segment | Temperature (. Degree. C.) | Time (h) | Status of | Rate of temperature control |
| 1 | 20 | 2h | Maintenance of | / |
| 2 | 55 | 10h | Heating up | 2.50℃/h |
| 3 | 90 | 5h | Heating up | 7℃/h |
| 4 | 90 | 4h | Maintenance of | / |
| 5 | 60 | 1h | Cooling down | 30℃/h |
(4) Secondary curing: taking out the resin lens obtained in the step (3) after primary curing by a mold releaser, and performing secondary curing, wherein the secondary curing temperature control procedure is as follows:
| program segment | Temperature (. Degree. C.) | Time (h) | Status of | Rate of temperature control |
| 1 | 100 | 2h | Maintenance of | / |
| 2 | 60 | 1h | Cooling down | 40℃/h |
Comparative example 3
An optical resin material with high refractive index and high Abbe number:
(1) Preparation of a prepolymerization liquid: accurately weighing 8g (chloride ion content 200 ppm) of 1, 2-tetra (mercapto methylthio) ethane, 77g of bis (beta-cyclopropylthioethyl) sulfide, 15g (chloride ion content 230 ppm) of isophorone diisocyanate and 0.10g of tetrabutyl phosphine bromide, mixing and dissolving to obtain a prepolymer liquid;
(2) Casting a sample: vacuum degassing the prepolymerized material liquid obtained in the step (1) for 30min, and filtering and injecting the prepolymerized material liquid into a glass die through a polytetrafluoroethylene filtering membrane with the pore diameter of 3 mu m;
(3) Primary curing: then the mould is put into a temperature programming curing furnace for primary curing, and the specific temperature control procedure is as follows:
(4) Secondary curing: taking out the resin lens obtained in the step (3) after primary curing by a mold releaser, and performing secondary curing, wherein the secondary curing temperature control procedure is as follows:
| program segment | Temperature (. Degree. C.) | Time (h) | Status of | Rate of temperature control |
| 1 | 100 | 2h | Maintenance of | / |
| 2 | 60 | 1h | Cooling down | 40℃/h |
Comparative example 4
An optical resin material with high refractive index and high Abbe number:
(1) Preparation of a prepolymerization liquid: accurately weighing 8g (chloride ion content is 450 ppm) of 1, 2-tetra (mercapto methyl thio) ethane, 77g of bis (beta-cyclopropyl thio-ethyl) sulfide, 15g (chloride ion content is 350 ppm) of isophorone diisocyanate and 0.10g of tetrabutyl phosphine bromide, mixing and dissolving to obtain a prepolymer liquid;
(2) Casting a sample: vacuum degassing the prepolymerized material liquid obtained in the step (1) for 30min, and filtering and injecting the prepolymerized material liquid into a glass die through a polytetrafluoroethylene filtering membrane with the pore diameter of 3 mu m;
(3) Primary curing: then the mould is put into a temperature programming curing furnace for primary curing, and the specific temperature control procedure is as follows:
| program segment | Temperature (. Degree. C.) | Time (h) | Status of | Rate of temperature control |
| 1 | 20 | 2h | Maintenance of | / |
| 2 | 55 | 10h | Heating up | 2.50℃/h |
| 3 | 80 | 16h | Heating up | 1.56℃/h |
| 4 | 80 | 4h | Maintenance of | / |
| 5 | 60 | 1h | Cooling down | 30℃/h |
(4) Secondary curing: taking out the resin lens obtained in the step (3) after primary curing by a mold releaser, and performing secondary curing, wherein the secondary curing temperature control procedure is as follows:
| program segment | Temperature (. Degree. C.) | Time (h) | Status of | Rate of temperature control |
| 1 | 100 | 2h | Maintenance of | / |
| 2 | 60 | 1h | Cooling down | 40℃/h |
Comparative example 5
An optical resin material with high refractive index and high Abbe number:
(1) Preparation of a prepolymerization liquid: accurately weighing 8g (chloride ion content 600 ppm) of 1, 2-tetra (mercapto methylthio) ethane, 77g of bis (beta-cyclopropylthioethyl) sulfide, 15g (chloride ion content 1200 ppm) of isophorone diisocyanate and 0.10g of tetrabutyl phosphine bromide, mixing and dissolving to obtain a prepolymer liquid;
(2) Casting a sample: vacuum degassing the prepolymerized material liquid obtained in the step (1) for 30min, and filtering and injecting the prepolymerized material liquid into a glass die through a polytetrafluoroethylene filtering membrane with the pore diameter of 3 mu m;
(3) Primary curing: then the mould is put into a temperature programming curing furnace for primary curing, and the specific temperature control procedure is as follows:
| program segment | Temperature (. Degree. C.) | Time (h) | Status of | Rate of temperature control |
| 1 | 20 | 2h | Maintenance of | / |
| 2 | 55 | 10h | Heating up | 2.50℃/h |
| 3 | 80 | 10h | Heating up | 2.50℃/h |
| 4 | 80 | 4h | Maintenance of | / |
| 5 | 60 | 1h | Cooling down | 30℃/h |
(4) Secondary curing: taking out the resin lens obtained in the step (3) after primary curing by a mold releaser, and performing secondary curing, wherein the secondary curing temperature control procedure is as follows:
| program segment | Temperature (. Degree. C.) | Time (h) | Status of | Rate of temperature control |
| 1 | 100 | 2h | Maintenance of | / |
| 2 | 60 | 1h | Cooling down | 40℃/h |
Physical properties of the optical resin materials prepared in examples and comparative examples were tested in accordance with the following methods.
Refractive index (ne): the sample was prepared as described above, and data at a wavelength of 546.1nm (mercury green e line) was measured at 20℃using an Abbe refractometer Multi-wave length Abbe Refractometer DR-M4 (ATTGO Co., ltd.).
Abbe number (vd): the sample was prepared in the above manner, and the refractive indices (nd, nF, nC) at a wavelength of 589.3nm (d-line in sodium spectrum), a wavelength of 480.0nm (F-line in hydrogen spectrum), and a wavelength of 656.3nm (C-line in hydrogen spectrum) were measured at 20℃using an Abbe refractometer Multi-wave length Abbe Refractometer DR-M4 (ATTGO Co., ltd.) to obtain Abbe numbers (vd) as follows:
the various physical properties tested on the optical resins obtained in examples 1-6 and comparative examples 1-5 are specifically shown in Table 1:
table 1: test performance of examples 1-6 and comparative examples 1-4
As is evident from the data in Table 1, the refractive index and Abbe number of the optical resin materials in examples 1 to 6 are higher than those of comparative examples 1 to 5, and it is effectively demonstrated that the selection of the raw materials of the specific chlorine content polythioether resin material of the present invention in combination with the specific curing process gives a resin material having a high refractive index (. Gtoreq.1.66) and a high Abbe number (. Gtoreq.38), and by the present invention, an optical resin having a lower dispersion and a better definition can be produced. The price of the common polythioether resin material (the refractive index is about 1.63, the Abbe number is less than 38) is 10-15 ten thousand yuan, the price of the resin material with high refractive index (more than or equal to 1.66) and high Abbe number (more than or equal to 38) is more than 30 ten thousand yuan, and the invention adopts specific raw materials to be matched with a specific curing process, thereby obtaining remarkable progress and having significance and value of industrial production and application.
Claims (10)
1. An optical resin material with high refractive index and high Abbe number is characterized in that the raw materials comprise an episulfide compound, polythiol and isocyanate, wherein the chlorine content of the polythiol is less than or equal to 500ppm, and the chlorine content of the isocyanate is less than or equal to 1000ppm.
2. An optical resin material of high refractive index and high abbe number according to claim 1, wherein the chlorine content of the polythiol is 400ppm or less and the chlorine content of the isocyanate is 300ppm or less.
3. The high refractive index and high abbe number optical resin material according to claim 1 or 2, wherein the episulfide compound is 70-80 parts, the polythiol is 8-20 parts, and the isocyanate is 5-15 parts by weight.
4. The high refractive index and high abbe number optical resin material according to claim 1, wherein the cyclic sulfur compound is one or more of bis (β -cyclic thiopropyl) sulfide, bis (β -cyclic thiopropyl) disulfide, bis (β -cyclic thiopropyl) trisulfide, bis (β -cyclic thiopropyl) thiophanate, 1, 2-bis (β -cyclic thiopropyl) ethane, 1, 3-bis (β -cyclic thiopropyl) propane, 1, 4-bis (β -cyclic thiopropyl) thiopropane, and bis (β -cyclic thiopropyl) thiopthyl) sulfide.
5. The high refractive index and high abbe number optical resin material according to claim 1, wherein the polythiol is one or more of thiobis Gan Liuchun, 2, 3-dithio (2-mercapto) -1-propanethiol, 1,5,9, 13-tetramercapto-3, 7, 11-tritridecane, 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiooctane, tetra (mercaptomethyl) methane, pentaerythritol tetra (3-mercaptopropionic acid) ester, pentaerythritol tri (3-mercaptopropionic acid) ester, 1, 2-tetra (mercaptomethylthio) ethane, dipentaerythritol hexa (3-mercaptopropionic acid) ester, pentaerythritol tetra (3-mercaptobutyric acid) ester.
6. The high refractive index and high abbe number optical resin material according to claim 1, wherein the isocyanate is one or more of 4, 4-dicyclohexylmethane diisocyanate, norbornane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, methylenedicyclohexyl diisocyanate, and hydrogenated xylylene diisocyanate.
7. The high refractive index and high abbe number optical resin material according to claim 1, further comprising a polymerization catalyst, wherein the polymerization catalyst is tetrabutylphosphine bromide.
8. The process for curing an optical resin material with high refractive index and high abbe number according to any one of claims 1 to 7, comprising primary curing and secondary curing, wherein the curing temperature rise interval of the primary curing is within the range of 20 ℃ to 80 ℃ and the total duration is 11.5h to 15h.
9. The process for curing an optical resin material having a high refractive index and a high abbe number according to claim 8, wherein the curing temperature rise interval comprises 20 ℃ to 55 ℃ and 55 ℃ to 80 ℃, wherein the average temperature rise rate is 5 ℃ to 20 ℃/h in the temperature rise interval of 55 ℃ to 80 ℃.
10. The process for curing an optical resin material with high refractive index and high abbe number according to claim 9, wherein the primary curing comprises five stages, in particular:
the first stage: maintaining at 20deg.C for 2 hr;
and a second stage: raising the temperature to 55 ℃ at 2.50 ℃/h;
and a third stage: raising the temperature to 80 ℃ at a speed of 5-20 ℃/h;
fourth stage: maintaining at 80deg.C for 4 hr;
fifth stage: the temperature was reduced to 60℃at 20℃per hour.
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