CN116162050A - Polythiols and preparation method of high refractive index optical resin thereof - Google Patents
Polythiols and preparation method of high refractive index optical resin thereof Download PDFInfo
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- 229920005989 resin Polymers 0.000 title claims abstract description 46
- 239000011347 resin Substances 0.000 title claims abstract description 46
- 230000003287 optical effect Effects 0.000 title claims abstract description 36
- 229920006295 polythiol Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 150000002540 isothiocyanates Chemical class 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 230000002745 absorbent Effects 0.000 claims abstract description 4
- 239000002250 absorbent Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 125000006267 biphenyl group Chemical group 0.000 claims description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 claims description 2
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- -1 m-xylylene Chemical group 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- YFRLQYJXUZRYDN-UHFFFAOYSA-K trichloro(methyl)stannane Chemical compound C[Sn](Cl)(Cl)Cl YFRLQYJXUZRYDN-UHFFFAOYSA-K 0.000 claims description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001723 curing Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- XKEFYDZQGKAQCN-UHFFFAOYSA-N 1,3,5-trichlorobenzene Chemical compound ClC1=CC(Cl)=CC(Cl)=C1 XKEFYDZQGKAQCN-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KXCKKUIJCYNZAE-UHFFFAOYSA-N benzene-1,3,5-trithiol Chemical compound SC1=CC(S)=CC(S)=C1 KXCKKUIJCYNZAE-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 208000001491 myopia Diseases 0.000 description 1
- 230000004379 myopia Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001029 thermal curing 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
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/12—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by reactions not involving the formation of mercapto groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
- C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
- C07C321/28—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
Abstract
The invention belongs to the technical field of high-refractive-index optical resins, and particularly relates to a polythiol and a preparation method of the high-refractive-index optical resin. S1: mixing the isothiocyanates, the ultraviolet absorbent, the release agent, the antioxidant and the catalyst, and vacuum defoaming for 20-30min at 30 ℃ to obtain a material A; s2: adding polythiol into the material A obtained in the step S1, and carrying out vacuum defoaming for 30-45min at 15-20 ℃ to obtain a mixture B; s3: and (3) pouring the mixture B obtained in the step (S2) is completed, and the resin is solidified by adopting gradient temperature programming to obtain the optical resin lens with high refractive index.
Description
Technical Field
The invention belongs to the technical field of high-refractive-index optical resins, and particularly relates to a polythiol and a preparation method of the high-refractive-index optical resin.
Background
Currently, the refractive index of the mainstream lens in the market is about 1.50, and in recent years, with the increasing of the myopia degree of teenagers, the demand of resin lenses with higher degrees is increasing, the lower refractive index cannot meet the actual demand, and in order to prepare lenses with higher degrees, the refractive index can only be realized by increasing the thickness of the lenses, but the weight of the glasses is increased. With the continuous development of technology, polyurethane optical resin materials with higher refractive indexes are greatly developed, most of the resin materials are formed by thermal curing polymerization of isocyanate and polythiol, four types of polyurethane resin lenses with refractive indexes of 1.56, 1.60, 1.67 and 1.74 can be prepared, the refractive index of the optical resin is improved to a certain extent, but the requirement of higher lens degree is still difficult to meet, and the development of the optical resin with higher refractive index has become an important point of research in the field of optical lens resins.
Zhang Yunfang et al (synthesis of sulfur-containing high refractive index optical resin monomers, university of Zhongshan university journal of research (Nature sciences), 2006, 27 (4): 73-81) reported that optical lenses having refractive indices up to 1.80 were produced by using pentaerythritol and diphenyl sulfide-4, 4-diisothiocyanate, and U.S. Pat. No. 3, 0158352 reported that optical lenses having refractive indices of 1.80 were produced by using 1,3, 5-benzenetrithiol and 1,3, 5-triazine-2, 4, 6-triisocyanate. However, the lenses obtained from the raw materials have poor impact resistance due to over-strong rigidity, and the finished lenses are fragile and unsafe.
Disclosure of Invention
The invention aims to provide a polythiol and a preparation method of an optical resin thereof, and aims to provide a high refractive index optical resin with refractive index exceeding 1.80 and a preparation method of the high refractive index optical resin.
The technical aim of the invention is realized by the following technical scheme: a polythiol which is one of the formulae (I) -formula (III):
the invention is further provided with: the polythiol is prepared by:
s1: 266.3-358g of thiourea and 181.9-198.4g of 1,2, 4-trichlorobenzene are added into 300-510g of carbon tetrachloride under the protection of nitrogen, the temperature is increased to 90-110 ℃, and the reaction is carried out for 3-4.5 hours, thus obtaining a first intermediate.
S2: under the protection of nitrogen, the temperature of the first intermediate is reduced to 25-45 ℃, 260-390g of ammonia water is dripped into the system, and the adding is completed within 30-45 min; after the dripping is finished, controlling the temperature at 50-65 ℃ for 3-5 hours, stopping the reaction, standing for layering, removing supernatant, washing lower liquid with 250-400g of deionized water for three times, removing water phase, decompressing oil phase at 65 ℃ to remove solvent, and obtaining a second intermediate.
S3: and (3) dropwise adding 350-480g of carbon tetrachloride into the second intermediate, dropwise adding 675-750g of disulfide (20 wt% carbon tetrachloride solution) at room temperature under the protection of nitrogen, continuously stirring for 5.5-7 hours after the dropwise adding is finished, and removing carbon tetrachloride from the product at 60 ℃ under negative pressure to obtain the polythiol.
The invention is further provided with: the high refractive index optical resin is prepared from the following raw materials in parts by mass:
the invention is further provided with: the isothiocyanate is selected from one of toluene diisoisothiocyanate, 4-diphenyl methane diisoisothiocyanate, diphenyl disulfide-4, 4-diisoisothiocyanate, m-xylylene diisoisothiocyanate and 1,3, 5-triazine-2, 4, 6-triisocyanate.
The invention is further provided with: the catalyst is selected from one or more of dibutyl tin dichloride, stannous octoate, methyl tin trichloride, trimethyl tin chloride and dibutyl tin dilaurate.
The invention is further provided with: the ultraviolet absorber is selected from one or more of UV-234, UV-9, UV-326 and UV-531.
The invention is further provided with: the release agent is one or more selected from DDP-10, DDP-8 and DDP-5.
The invention is further provided with: the antioxidant is selected from one of antioxidant 1010, antioxidant 164 and antioxidant 1076.
The invention is further provided with: a method for preparing a high refractive index optical resin, comprising the steps of:
s1: mixing the isothiocyanates, the ultraviolet absorbent, the release agent, the antioxidant and the catalyst, and vacuum defoaming for 20-30min at 30 ℃ to obtain a material A;
s2: adding polythiol into the material A obtained in the step S1, and carrying out vacuum defoaming for 30-45min at 15-20 ℃ to obtain a mixture B;
s3: and (3) pouring the mixture B obtained in the step (S3) is completed, curing the resin by adopting gradient temperature programming, so as to obtain the resin lens, wherein the temperature programming is that the initial temperature is 25-35 ℃, the temperature is kept for 1.5-3h, the temperature is increased to 50-65 ℃ through 6-8h, the temperature is increased to 85-90 ℃ through 2-4h, and the temperature is reduced to 95-105 ℃ through 0.5-1.5 h.
The beneficial effects of the invention are as follows: compared with the prior art of 1.80 high refractive index optical resin, the multi-thiol component structure of the ultra-high refractive index optical resin provided by the invention contains four thioether groups formed by sulfur, and the content of sulfur is improved, so that the refractive index of the optical resin is improved to more than 1.80 and 1.8260-1.8570, and the thioether group chain segment can freely rotate, and has an excellent flexible structure, so that the rigid structure formed by the benzene ring structure in the multi-thiol component and the isothiocyanate curing agent after curing is greatly relieved, the brittleness of the optical resin after curing is reduced, the impact resistance of the optical resin is improved, and the impact resistance is improved to 110g of pellets without breakage after impact.
Detailed Description
The technical solutions in the embodiments will be clearly and completely described below. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
EXAMPLE 1 preparation of polythiol formula (I)
In the first step, 266.3g of thiourea and 181.9g of 1,2, 4-trichlorobenzene are added into 300g of carbon tetrachloride under the protection of nitrogen, the temperature is increased to 90 ℃, and the reaction is carried out for 3 hours, thus obtaining a first intermediate.
Step two, under the protection of nitrogen, the temperature of the first intermediate is reduced to 25 ℃, 260g of ammonia water is added dropwise into the system, and the addition is completed within 30 min; after the completion of the dropwise addition, the temperature was controlled at 50℃and the reaction was allowed to proceed for 3 hours, the reaction was terminated, the layer was allowed to stand still, the supernatant was removed, the lower layer liquid was washed three times with 250g of deionized water, the aqueous phase was removed, and the oil phase was subjected to removal of the solvent under reduced pressure at 65℃to obtain a second intermediate.
And step three, adding 350g of carbon tetrachloride into the second intermediate, dropwise adding 675g of disulfide (20 wt% carbon tetrachloride solution) at room temperature under the protection of nitrogen, continuously stirring for 5.5 hours after the dropwise adding is finished, and removing carbon tetrachloride from the product at 60 ℃ under negative pressure to obtain the product of the polythiol formula (I).
EXAMPLE 2 preparation of polythiol formula (II)
In the first step, 358g of thiourea and 198.4g of 1,3, 5-trichlorobenzene are added into 510g of carbon tetrachloride under the protection of nitrogen, the temperature is raised to 110 ℃, and the reaction is carried out for 4.5 hours, thus obtaining a first intermediate.
Step two, under the protection of nitrogen, the temperature of the first intermediate is reduced to 45 ℃, 390g of ammonia water is dripped into the system, and the addition is completed within 45 min; after the completion of the dropwise addition, the temperature was controlled at 65℃and the reaction was allowed to proceed for 5 hours, the reaction was terminated, the layer was allowed to stand still, the supernatant was removed, the lower layer liquid was washed three times with 400g of deionized water, the aqueous phase was removed, and the oil phase was subjected to removal of the solvent under reduced pressure at 65℃to obtain a second intermediate.
Adding 480g of carbon tetrachloride into the second intermediate, dropwise adding 750g of disulfide (20 wt% of carbon tetrachloride solution) at room temperature under the protection of nitrogen, continuously stirring for 7 hours after the dropwise adding is finished, and removing carbon tetrachloride from the product at 60 ℃ under negative pressure to obtain the product of the polythiol formula (II).
EXAMPLE 3 preparation of polythiol formula (III)
In the first step, under the protection of nitrogen, adding 320.4 thiourea and 185.3g of 1,2, 3-trichlorobenzene into 450g of carbon tetrachloride, raising the temperature to 100 ℃, and reacting for 4 hours to obtain a first intermediate.
Step two, under the protection of nitrogen, the temperature of the first intermediate is reduced to 30 ℃, 310g of ammonia water is added dropwise into the system, and the addition is completed within 35 min; after the completion of the dropwise addition, the temperature was controlled at 60℃and the reaction was allowed to proceed for 4 hours, the reaction was terminated, the layer was allowed to stand still, the supernatant was removed, then the lower layer liquid was washed three times with 310g of deionized water, the aqueous phase was removed, and the oil phase was subjected to removal of the solvent under reduced pressure at 65℃to obtain a second intermediate.
And step three, adding 420g of carbon tetrachloride into the second intermediate, dropwise adding 715g of disulfide (20 wt% carbon tetrachloride solution) at room temperature under the protection of nitrogen, continuously stirring for 6 hours after the dropwise adding is finished, and removing carbon tetrachloride from the product at 60 ℃ under negative pressure to obtain the product of the polythiol formula (III).
Comparative example 1 preparation of polythiol
Prepared as in example 1, without carrying out the procedure of step three, the second intermediate obtained is the polythiol of comparative example 1.
Comparative example 2 preparation of polythiol
Prepared as in example 2, without carrying out the procedure of step three, the second intermediate obtained is the polythiol of comparative example 2.
Preparation of resin lenses
According to the raw material ratios provided in table 1, optical lenses were prepared according to the preparation methods of optical resin lenses, the obtained lenses were respectively labeled as JP01-JP05, and the lenses corresponding to comparative example 1 and comparative example 2 were respectively DB01 and DB02, the preparation methods thereof being prepared according to JP01 and JP02, respectively. The preparation method of the lens comprises the following steps:
mixing the isothiocyanates, the ultraviolet absorbent, the release agent, the antioxidant and the catalyst, and vacuum defoaming for 20-30min at 30 ℃ to obtain a material A; adding polybasic mercaptan into the material flow A, and carrying out vacuum defoaming for 30-45min at 15-20 ℃ to obtain a mixture B; and (3) pouring the mixture B, curing the resin by adopting gradient temperature programming to obtain a resin lens, wherein the temperature programming is that the initial temperature is 25-35 ℃, the temperature is kept for 1.5-3h, the temperature is increased to 50-65 ℃ for 6-8h, the temperature is increased to 85-90 ℃ for 2-4h, and the temperature is reduced to 95-105 ℃ for 0.5-1.5 h.
TABLE 1 optical resin raw materials
The testing method comprises the following steps:
1. refractive index: the ND value is measured by a multi-wavelength Abbe refractometer, and the model of the Abbe refractometer is WYA-2S digital Abbe refractometer of Shanghai electric analysis instruments Co., ltd;
2. impact resistance: measuring the bearable steel ball mass of the lens by adopting a falling ball impact tester, and measuring the steel ball mass of 16g, 32g, 50g, 64g, 90g, 110g and 500g with the height of 1.27 m according to an FDA standard measurement method;
3. transmittance: the light transmittance is measured by an optical light transmittance tester, and the manufacturer and model are LS108A of Shenzhen Baichuan electronics Inc.
Table 2, optical lens performance test results
| JP01 | JP02 | JP03 | JP04 | JP05 | DB01 | DB02 | |
| Refractive index | 1.8321 | 1.8570 | 1.8260 | 1.8275 | 1.8317 | 1.8012 | 1.7985 |
| Transmittance/% | 91.8 | 89.6 | 91.7 | 90.5 | 91.5 | 89.5 | 87.8 |
| Impact resistance/g | 110 | 110 | 500 | 110 | 110 | 32 | 16 |
The resin lenses DB01, DB02 obtained in comparative examples 1 and 2 have lower refractive index and larger brittleness than the resin lenses JP01, JP02 obtained in examples 1 and 2 of the present invention, because the sulfur content in the comparative examples is lower than that in the examples of the present invention, and thus the refractive index is lower than that in the examples of the present invention, and there is no soft segment in the resin structure, and thus the resin obtained is large in brittleness. The impact resistance obtained by the invention is more excellent, because the polythiol contains 4 flexible sulfur bond structures in the middle, the brittleness of the resin after curing is reduced, and the toughness and the impact resistance are improved.
Claims (9)
1. A polythiol characterized by: the polythiol is one of the formulas (I) - (III):
2. a polythiol as claimed in claim 1, wherein: the polythiol is prepared by:
s1: 266.3-358g of thiourea and 181.9-198.4g of 1,2, 4-trichlorobenzene are added into 300-510g of carbon tetrachloride under the protection of nitrogen, the temperature is increased to 90-110 ℃, and the reaction is carried out for 3-4.5 hours, thus obtaining a first intermediate.
S2: under the protection of nitrogen, the temperature of the first intermediate is reduced to 25-45 ℃, 260-390g of ammonia water is dripped into the system, and the adding is completed within 30-45 min; after the dripping is finished, controlling the temperature at 50-65 ℃ for 3-5 hours, stopping the reaction, standing for layering, removing supernatant, washing lower liquid with 250-400g of deionized water for three times, removing water phase, decompressing oil phase at 65 ℃ to remove solvent, and obtaining a second intermediate.
S3: and (3) dropwise adding 350-480g of carbon tetrachloride into the second intermediate, dropwise adding 675-750g of disulfide (20 wt% carbon tetrachloride solution) at room temperature under the protection of nitrogen, continuously stirring for 5.5-7 hours after the dropwise adding is finished, and removing carbon tetrachloride from the product at 60 ℃ under negative pressure to obtain the polythiol.
3. A high refractive index optical resin according to claim 1, characterized in that: the composite material comprises the following raw materials in parts by mass:
4. a high refractive index optical resin according to claim 3, wherein: the isothiocyanate is selected from one of toluene diisoisothiocyanate, 4-diphenyl methane diisoisothiocyanate, diphenyl disulfide-4, 4-diisoisothiocyanate, m-xylylene diisoisothiocyanate and 1,3, 5-triazine-2, 4, 6-triisocyanate.
5. A high refractive index optical resin according to claim 3, wherein: the catalyst is selected from one or more of dibutyl tin dichloride, stannous octoate, methyl tin trichloride, trimethyl tin chloride and dibutyl tin dilaurate.
6. A high refractive index optical resin according to claim 3, wherein: the ultraviolet absorber is selected from one or more of UV-234, UV-9, UV-326 and UV-531.
7. A high refractive index optical resin according to claim 3, wherein: the release agent is one or more selected from DDP-10, DDP-8 and DDP-5.
8. A high refractive index optical resin according to claim 3, wherein: the antioxidant is selected from one of antioxidant 1010, antioxidant 164 and antioxidant 1076.
9. A method for producing a high refractive index optical resin according to claim 3, wherein: the method comprises the following steps:
s1: mixing the isothiocyanates, the ultraviolet absorbent, the release agent, the antioxidant and the catalyst, and vacuum defoaming for 20-30min at 30 ℃ to obtain a material A;
s2: adding polythiol into the material A obtained in the step S1, and carrying out vacuum defoaming for 30-45min at 15-20 ℃ to obtain a mixture B;
s3: and (3) pouring the mixture B obtained in the step (S2) is completed, curing the resin by adopting gradient temperature programming, so as to obtain the resin lens, wherein the temperature programming is that the initial temperature is 25-35 ℃, the temperature is kept for 1.5-3h, the temperature is increased to 50-65 ℃ through 6-8h, the temperature is increased to 85-90 ℃ through 2-4h, and the temperature is reduced to 95-105 ℃ through 0.5-1.5 h.
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| CN1039429A (en) * | 1988-07-14 | 1990-02-07 | 三井东圧化学株式会社 | Resin with high refractive index contains the lens of this resin and prepares the method for these lens |
| JPH06134773A (en) * | 1992-10-27 | 1994-05-17 | Mitsui Toatsu Chem Inc | Method of molding sulfur-containing urethane resin and molding of transparent sulfur-containing urethane resin |
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| CN101684085A (en) * | 2009-08-28 | 2010-03-31 | 上海伟星光学有限公司 | Method for preparing tetra-sulfenyl polyhydric mercaptan and method for preparing polyurethane-based resin lens by using tetra-sulfenyl polyhydric mercaptan |
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2023
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| CN1039429A (en) * | 1988-07-14 | 1990-02-07 | 三井东圧化学株式会社 | Resin with high refractive index contains the lens of this resin and prepares the method for these lens |
| JPH06134773A (en) * | 1992-10-27 | 1994-05-17 | Mitsui Toatsu Chem Inc | Method of molding sulfur-containing urethane resin and molding of transparent sulfur-containing urethane resin |
| CN1111619A (en) * | 1994-01-26 | 1995-11-15 | 三井东压化学株式会社 | Polythiol, process for producing same, sulfur-containing urethane-base resin prepared from the polythiol, proces for producing the resin, and lens |
| CN101684085A (en) * | 2009-08-28 | 2010-03-31 | 上海伟星光学有限公司 | Method for preparing tetra-sulfenyl polyhydric mercaptan and method for preparing polyurethane-based resin lens by using tetra-sulfenyl polyhydric mercaptan |
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