CN114181374B - Preparation method of thianthrene structure bromine element high-refractive index optical resin - Google Patents

Preparation method of thianthrene structure bromine element high-refractive index optical resin Download PDF

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CN114181374B
CN114181374B CN202111508619.XA CN202111508619A CN114181374B CN 114181374 B CN114181374 B CN 114181374B CN 202111508619 A CN202111508619 A CN 202111508619A CN 114181374 B CN114181374 B CN 114181374B
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thianthrene
refractive index
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epoxy resin
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CN114181374A (en
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姚伯龙
倪亚洲
王宇通
陈欢
程广鸿
张晋瑞
王海潮
王利魁
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Jiangnan University
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14Polycondensates modified by chemical after-treatment
    • C08G59/1433Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1483Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing sulfur
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/66Mercaptans

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Abstract

The invention relates to a preparation method of thianthrene structure bromine element high refractive index optical resin, belonging to the technical field of optical materials. Firstly, 4-fluorobenzenethiol and benzylmercaptan are introduced to synthesize 2, 7-bis (phenylethylthio) thianthrene containing sulfydryl, then tetrabromobisphenol a epoxy resin and 2, 7-dimercaptothianthrene are subjected to epoxy-sulfur ' click ' reaction to synthesize epoxy resin with high refractive index, and finally 4' dimercaptodiphenyl sulfide containing S element is used as an epoxy resin curing agent to be cured to obtain the optical resin with high refractive index of bromine element in a thianthrene structure. The product of the invention has excellent optical performance, high refractive index, high light transmittance, and good thermodynamic and mechanical properties. The resin has good application prospect in anti-reflection coatings, optical lenses, optical adhesives, optical packaging materials and the like.

Description

Preparation method of thianthrene structure bromine element high-refractive index optical resin
Technical Field
The invention relates to a preparation method of a thianthrene structure bromine element high-refractive index optical resin, belonging to the technical field of optical materials.
Background
The high-refractive-index optical resin has the advantages of good flexibility, low density, good processability, optical transparency, impact resistance, wear resistance and low cost, and is widely applied to the fields of optical components such as optical adhesives, optical packaging materials, sensors, detectors, optical lenses and the like.
Epoxy resins are the most common and important thermosetting polymers and have been widely used in industry due to their chemical resistance, small shrinkage, good processability and excellent mechanical properties, while the refractive index of the cured products of common epoxy resins is only about 1.57 and does not meet the increasing demand for high performance optical devices. Therefore, the high-refractive-index epoxy resin with excellent performance has wide application prospect in the market.
The thianthracene group is a thermally stable heterocycle that can be incorporated into the conjugated aromatic polymer backbone, improving the mechanical properties and thermal stability of the polymer, and the bent structure of the thianthracene ring can inhibit stacking between polymer chains, which is necessary for high transparency. The sulfur bond (-S-S-) in the thianthrene group can increase the S content of the polymer repeating unit, and the thianthrene has high molar refractive index, small dispersion coefficient and excellent optical and electrochemical properties. Tetrabromobisphenol a structure contains high-content Br element, and the Br element has high molar refractive index, low molar volume and flame retardant property, so that the refractive index of the polymer can be effectively improved.
Disclosure of Invention
The invention aims to overcome the defects and provide the preparation method of the optical epoxy resin with high refractive index, which contains thianthrene structure, sulfur element and bromine element and has excellent performance.
According to the technical scheme, 4-fluorobenzothiophenol and benzylmercaptan are introduced to synthesize 2, 7-bis (phenylethylthio) thianthrene containing sulfydryl, tetrabromobisphenol a epoxy resin and 2, 7-dimercaptothianthrene are subjected to epoxy-sulfur ' click ' reaction to synthesize epoxy resin with high refractive index, and finally 4' -dimercaptodiphenyl sulfide containing S element is used as an epoxy resin curing agent to be cured to obtain the thianthrene structure bromine element high-refractive index optical resin.
Further, the preparation process of the 2, 7-bis (phenethylmercapto) thianthrene comprises the following steps: firstly, 4-fluorobenzene thiol reacts with acetic acid to generate 2, 7-dimercaptothianthrene, then potassium tert-butoxide and benzyl mercaptan hybridize the compound to prepare 2, 7-dibenzylthianthrene, and finally the 2, 7-bis (phenethyl mercapto) thianthrene is prepared through catalytic reaction.
Further, the specific preparation steps of the 2, 7-bis (phenethylmercapto) thianthrene are as follows:
(1) Synthesis of 2, 7-Difluorothiane: adding 4-fluorobenzene thiol into a reaction container, adding a catalyst A, and stirring for reaction; pouring the obtained reaction solution into ice water to form a precipitate, extracting with an extracting agent, drying the extract liquor by adopting a drying agent, and removing the solvent by rotary evaporation to obtain a crude product; adding the crude product and acetic acid into a reaction vessel, heating, continuously adding zinc powder, refluxing the solution, then filtering out excessive zinc from the solution, and adding deionized water into the filtrate to precipitate the product; filtering the product, washing with water, and drying in a vacuum oven to prepare a product 2, 7-difluorothianthrene;
(2) 2, 7-dibenzylthianthrene is synthesized by dissolving potassium tert-butoxide and 2, 7-difluorothianthrene prepared in the step (1) in a solvent A under the atmosphere of nitrogen, and then slowly adding benzylmercaptan into the mixture under ice bath; heating and stirring the mixed solution for reaction to obtain a product; washing the product with deionized water, filtering, precipitating, and vacuum drying at high temperature to obtain a crude product; recrystallizing the crude product by using a solvent B to finally obtain 2, 7-dibenzylthianthrene;
(3) Synthesis of 2, 7-bis (phenethylmercapto) thianthrene: dissolving the 2, 7-dibenzylthiaanthracene prepared in the step (2) in a solvent C, and adding a catalyst B in an ice bath under a nitrogen atmosphere; slowly adding the catalyst C into the mixture, and stirring for reaction; na is mixed with 2 CO 3 Slowly adding the aqueous solution into the reaction mixture to obtain a mixture aqueous solution; extracting impurities in the mixture water solution by using an extracting agent, adding hydrochloric acid into the water solution, and stirring the solution for reaction; filtering the precipitate, and drying in vacuum to obtain 2, 7-di (phenethyl mercapto) thianthrene powder.
Further, the catalyst in the step (1) is A sulfuric acid solution of sulfur trioxide; the extractant is dichloromethane, toluene or ethyl acetate; the drying agent is magnesium sulfate, calcium chloride or magnesium perchlorate;
further, in the step (2), the solvent A is N, N-dimethylformamide or N, N-dimethylacetamide; the solvent B is ethylene glycol monomethyl ether;
further, in the step (3), the solvent C is diethylene glycol dimethyl ether; the extractant is dichloromethane, toluene or ethyl acetate; catalyst B is cyclopentadienyl titanium dichloride, and catalyst C is dibutyl magnesium.
Further, in the step (1), 25.16-37.74g of 4-fluorobenzenethiol is added into a reaction vessel, 300-450mL of catalyst A is added at a time, and the mixture is stirred for reaction; extracting with extractant for 2-4 times; rotary distilling at-0.1-0 MPa and 40-45 deg.c for 1.5-2 hr; adding 500-750mL of acetic acid, heating to 100 ℃, then adding 10-15g of zinc powder, and refluxing the solution for 18-20h; finally, adding 500-750mL of deionized water into the filtrate for precipitation, drying for 48h in a vacuum oven at the temperature of-0.1-0 MPa and 100 ℃;
further, in the step (2), 9.70 to 14.55g of potassium t-butoxide and 7.96 to 11.53g of 2, 7-difluorothianthrene prepared in the step (1) are dissolved in 30 to 45mL of a solvent A; slowly adding 10.2mL of benzyl mercaptan, heating the mixed solution to 60 ℃, and stirring for 28-30h; filtering and precipitating, and then drying at 80 ℃ and-0.1-0 MPa;
further, in the step (3), 2.76 to 4.01g of 2, 7-dibenzylthiaanthracene is dissolved in 20 to 30mL of the solvent C, 0.156 to 0.234g of the catalyst B is added, and 20 to 35mL of the catalyst C is slowly dripped; stirring and reacting for 5-6h.
Further, the high refractive index epoxy resin is synthesized as follows: dissolving tetrabromobisphenol a epoxy resin in a solvent A, adding a saturated methanol solution of LiOH, dropwise adding a mixed solution of 2, 7-bis (phenethyl mercapto) thianthrene dissolved in the solvent A while stirring at room temperature, cooling to room temperature after dropwise adding is finished, and distilling to remove impurities to obtain the epoxy resin.
Further, 6.56-9.84g tetrabromobisphenol a epoxy resin is dissolved in 20-30mL solvent A, and 1-2 drops of saturated methanol solution of LiOH are added; then dropwise adding 2.3-3.4g of 2, 7-di (phenethylmercapto) thianthrene solution dissolved in 10-15mL of solvent A;
further, the solvent A is N, N-dimethylformamide or N, N-dimethylacetamide.
Further, the curing process of the epoxy resin is specifically as follows: and adding the synthesized epoxy resin into 4' 4-dimercaptodiphenyl sulfide with the corresponding group ratio, and then placing the mixture in an oven for curing to finally prepare the thianthrene structure bromine element high-refractive-index optical resin.
Further, the epoxy resin curing solution n (epoxy group): the molar ratio of n (-SH) is 1:0.8.
the invention has the beneficial effects that: according to the invention, a series of reactions are carried out to synthesize the high-refractive-index epoxy resin with a thianthrene structure and bromine; the thianthrene structure endows the resin with excellent optical performance and mechanical performance, and the resin has high refractive index, high light transmittance and good thermodynamic performance and mechanical performance. The resin prepared by the method has good application prospects in anti-reflection coatings, optical lenses, optical adhesives, optical packaging materials and the like.
Drawings
FIG. 1 is a graph showing the ultraviolet transmittance of the high refractive index optical resin prepared in example 1.
FIG. 2 thermogravimetric plot of the high refractive index optical resin prepared in example 1.
Detailed Description
Example 1
(1) 2, 7-Difluorothiane synthesis: adding 25.16g of 4-fluorobenzenethiol into a round-bottom flask with a magnetic stirring rod, adding 300mL of sulfuric acid solution of sulfur trioxide with the mass concentration of 40%, reacting for 20 hours, pouring the solution into ice water to form a brown precipitate, extracting with dichloromethane, drying magnesium perchlorate, filtering extract liquid with dichloromethane, removing the solvent by rotary evaporation at 40 ℃ for 2 hours under the pressure of 0.1-0 MPa, and generating a gray solid product. The crude product and 500mL of acetic acid were added to a 1000mL round bottom flask. 10g of zinc powder was added and the solution was refluxed for 18h, then excess zinc was filtered off from the solution and 500mL of water was added to the filtrate to precipitate the product. Filtering the product, washing with water, drying in a vacuum oven at 100 ℃ for 48h under-0.1-0 MPa to obtain 2, 7-difluorothianthrene.
(2) 2, 7-bis (phenethylmercapto) thianthrene synthesis: 9.70g of potassium tert-butoxide, 7.96g of 2, 7-difluorothianthrene were dissolved in 30mL of N, N-dimethylformamide under a nitrogen atmosphere, and the resulting solution was placed in a 100mL round flask and ice-cooled. 10.2mL of benzylthiol was then slowly added to the mixture. The mixed solution was then heated to 60 ℃ and stirred for 28h, and the product was washed with deionized water. Filtering the precipitate and vacuum drying at 80 deg.c and-0.1-0 MPa. The crude product is recrystallized from solvent B to obtain 2, 7-bis (phenethylmercapto) thianthrene.
(3) Synthesis of 2, 7-dimercaptothianthrene: 2.76g of 2, 7-dibenzylthiaanthracene is dissolved in 20mL of diglyme, placed in a 100mL three-necked round flask in a nitrogen atmosphere, ice-bathed, 0.156g of titanocene dichloride is added, and then 20mL of dibutyl magnesium is slowly added to the mixture; after stirring for 5 hours, na with the mass concentration of 5 percent is added 2 CO 3 An aqueous solution was slowly added to the reaction mixture to obtain an aqueous mixture solution. The dichloromethane extracted impurities from the aqueous mixture, and then 37% by mass hydrochloric acid was added to the aqueous solution and the solution was stirred for 1 hour. Filtering the precipitate, and vacuum drying at-0.1-0 MPa and 100 deg.c to obtain 2, 7-dimercaptothianthrene powder.
(4) Synthesis of epoxy resin: 9.84g tetrabromobisphenol a epoxy resin was dissolved in 20mL N, N-dimethylformamide, the solution was placed in a 250mL three-necked flask, and then the above solution was added to the 250mL three-necked flask equipped with a condenser stirrer, and then 1 to 2 drops of a saturated methanol solution of LiOH were added, and then a mixed solution of 2, 7-dimercaptothianthrene dissolved in 10mL N, N-dimethylformamide was added dropwise while stirring at room temperature, after completion of the dropwise addition, the reaction was carried out for 1.5 hours, cooled to room temperature, and impurities were removed by distillation.
(5) Curing of the epoxy resin: adding the epoxy resin synthesized in the step (4) into 4' 4-dimercaptodiphenyl sulfide with the corresponding group ratio, wherein n (epoxy group): n (-SH) is 1:0.8, and then placing the mixture in an oven to be cured for 2.5 hours at 160 ℃ to obtain the high-refractive-index optical material.
The optical material prepared in example 1 was tested, and fig. 1 is a graph of ultraviolet transmittance; it can be seen from fig. 1 that the high refractive polymer synthesized by the experiment has very good light transmittance, and the light transmittance is about 98 in the visible light range. FIG. 2 is a thermogravimetric graph, and it can be seen from FIG. 2 that the main carbon skeleton of the polymer is degraded above 400 ℃, the polymer has good thermal stability, and the refractive index of the polymer is 1.713 through a refractive index test.
Example 2
(1) 2, 7-Difluorothiane synthesis: adding 37.74g of 4-fluorobenzenethiol into a round bottom flask with a magnetic stirring rod, adding 450mL of sulfuric acid solution of sulfur trioxide with the mass concentration of 40%, reacting for 20h, pouring the solution into ice water to form brown precipitate, extracting for 3 times by using dichloromethane, drying magnesium perchlorate and filtering extract liquid by dichloromethane, and carrying out rotary evaporation at 40 ℃ for 2h under the pressure of 0.1-0 MPa to remove the solvent to obtain a gray solid product. The crude product and 750mL of acetic acid were added to a 1000mL round bottom flask. 15g of zinc dust was added and the solution was refluxed for 20h, then excess zinc was filtered off from the solution and 750mL of water was added to the filtrate to precipitate the product. Filtering the product, washing with water, and drying in a vacuum oven at 100 ℃ for 48h to obtain the 2, 7-difluorothianthrene.
(2) 2, 7-bis (phenethylmercapto) thianthrene synthesis: 14.55g of potassium tert-butoxide, 11.53g of 2, 7-difluorothianthrene were dissolved in 45mL of N, N-dimethylformamide under a nitrogen atmosphere, and the resulting solution was placed in a 100mL round flask and ice-cooled. 10.2mL of benzylthiol was then slowly added to the mixture. The mixed solution was then heated to 60 ℃ and stirred for 30h, and the product was washed with deionized water. Filtering the precipitate and vacuum drying at 80 deg.c and-0.1-0 MPa. The crude product is recrystallized by solvent B to obtain 2, 7-bis (phenethylmercapto) thianthrene.
(3) Synthesis of 2, 7-dimercaptothianthrene: dissolving 4.01g of 2, 7-dibenzylthiaanthracene in 20mL of diglyme, placing the solution in a 100mL three-necked round flask, carrying out ice bath under the atmosphere of nitrogen, adding 0.234g of titanocene dichloride, and slowly adding 35mL of dibutyl magnesium into the mixture; after stirring for 6 hours, na was added 2 CO 3 The aqueous solution was slowly added to the reaction mixture to obtain an aqueous mixture solution. Dichloromethane extracted the impurities from the aqueous mixture, hydrochloric acid was added to the aqueous solution and the solution was stirred for 1h. Filtering the precipitate, and vacuum drying at-0.1-0 MPa and 100 deg.c to obtain 2, 7-dimercaptothianthrene powder.
(4) Synthesis of epoxy resin: 6.56g tetrabromobisphenol a epoxy resin is dissolved in 30mL N, N-dimethylformamide, the solution is placed in a 250mL three-necked flask, then the above solution is added into the 250mL three-necked flask equipped with a condenser stirrer, then 1-2 drops of a saturated methanol solution of LiOH are added, then a mixed solution of 2, 7-dimercaptothianthrene dissolved in 15mL N, N-dimethylformamide is added dropwise while stirring at room temperature, after completion of the dropwise addition, the reaction is carried out for 1.5 hours, the reaction is cooled to room temperature, and impurities are removed by distillation.
(5) Curing of the epoxy resin: adding the epoxy resin synthesized in the step (4) into 4' 4-dimercaptodiphenyl sulfide with the corresponding group ratio, wherein n (epoxy group): n (-SH) is 1:0.8, and then placing the mixture in an oven to be cured for 2.5 hours at 160 ℃ to obtain the high-refractive-index optical material.

Claims (7)

1. A preparation method of a thianthrene structure bromine element high-refractive index optical resin is characterized by comprising the following steps: introducing 4-fluorobenzenethiol and benzylmercaptan to synthesize mercapto 2, 7-bis (phenylethylmercapto) thianthrene, performing epoxy-sulfur ' click ' reaction on tetrabromobisphenol a epoxy resin and 2, 7-dimercaptothianthrene to synthesize high-refractive-index epoxy resin, and finally curing by using S-element-containing 4' 4-dimercaptodiphenyl sulfide as an epoxy resin curing agent to obtain thianthrene-structured bromine element high-refractive-index optical resin;
the specific preparation steps of the 2, 7-di (phenethyl mercapto) thianthrene are as follows:
(1) Synthesis of 2, 7-Difluorothiane: adding 25.16-37.74g of 4-fluorobenzenethiol into a reaction container, adding 300-450mL of catalyst A at one time, and stirring for reaction; extracting with extractant for 2-4 times; rotary distilling at-0.1-0 MPa and 40-45 deg.c for 1.5-2 hr; adding 500-750mL of acetic acid, heating to 100 ℃, then adding 10-15g of zinc powder, and refluxing the solution for 18-20h; finally, adding 500-750mL of deionized water into the filtrate for precipitation, drying for 48h in a vacuum oven at 100 ℃ under the pressure of-0.1-0 MPa, and preparing a product 2, 7-difluorothianthrene;
(2) Synthesis of 2, 7-dibenzylthianthrene by dissolving 9.70 to 14.55g of potassium t-butoxide and 7.96 to 11.53g of 2, 7-difluorothianthrene prepared in step (1) in 30 to 45mL of a solvent A under a nitrogen atmosphere; slowly adding 10.2mL of benzyl mercaptan, heating the mixed solution to 60 ℃, and stirring for 28-30h; filtering the precipitate, and drying at 80 deg.C and-0.1-0 MPa to obtain crude product; recrystallizing the crude product by using a solvent B to finally obtain 2, 7-dibenzylthianthrene;
(3) Synthesis of 2, 7-bis (phenethylmercapto) thianthrene: 2.76-4.01g of 2, 7-dibenzyl thiaanthracene prepared in the step (2) is dissolved in 20-30mL of solvent C, 0.156-0.234g of catalyst B is added, and 20-35mL of catalyst C is slowly dripped; stirring and reacting for 5-6h; na is mixed with 2 CO 3 Slowly adding the aqueous solution into the reaction mixture to obtain a mixture aqueous solution; extracting impurities in the mixture water solution by using an extracting agent, adding hydrochloric acid into the water solution, and stirring the solution for reaction; filtering the precipitate, and drying in vacuum to obtain 2, 7-di (phenethyl mercapto) thianthrene powder;
the high refractive index epoxy resin is synthesized by the following method: dissolving 6.56-9.84g of tetrabromobisphenol a epoxy resin in 20-30mL of solvent A, and adding 1-2 drops of saturated methanol solution of LiOH; then dropwise adding 2.3-3.4g of 2, 7-di (phenethylmercapto) thianthrene solution dissolved in 10-15mL of solvent A; after the dropwise addition, the mixture was cooled to room temperature, and impurities were removed by distillation to obtain an epoxy resin.
2. The method for preparing a high refractive index optical resin of a bromine element in a thianthrene structure according to claim 1, which comprises the following steps: the catalyst in the step (1) is sulfuric acid solution of A sulfur trioxide; the extractant is dichloromethane, toluene or ethyl acetate; the drying agent is magnesium sulfate, calcium chloride or magnesium perchlorate.
3. The method for preparing a high refractive index optical resin of a bromine element in a thianthrene structure according to claim 1, which comprises the following steps: in the step (2), the solvent A is N, N-dimethylformamide or N, N-dimethylacetamide; the solvent B is ethylene glycol monomethyl ether.
4. The method for preparing a high refractive index optical resin of a bromine element in a thianthrene structure according to claim 1, which comprises the following steps: in the step (3), the solvent C is diglyme; the extractant is dichloromethane, toluene or ethyl acetate; catalyst B is cyclopentadienyl titanium dichloride, and catalyst C is dibutyl magnesium.
5. The method for preparing a thianthrene-structured bromine-element-containing high-refractive-index optical resin according to claim 1, wherein the method comprises the steps of: the solvent A is N, N-dimethylformamide or N, N-dimethylacetamide.
6. The method for preparing the thianthrene structural bromine element high refractive index optical resin according to claim 1, wherein the curing process of the epoxy resin is specifically as follows: adding the synthesized epoxy resin into 4' 4-dimercaptodiphenyl sulfide with the corresponding group ratio, and then placing the mixture in an oven for curing to finally prepare the high-refractive-index optical resin of the bromine element with the thianthrene structure.
7. The method for preparing a high refractive index optical resin of a bromine element in a thianthrene structure according to claim 6, which comprises the following steps: the epoxy resin curing solution n (epoxy group): the molar ratio of n (-SH) is 1:0.8.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102432829A (en) * 2011-08-02 2012-05-02 华南理工大学 Sulphur-containing optical epoxy resin and preparation method thereof
CN109651612A (en) * 2018-12-13 2019-04-19 江南大学 A kind of preparation method of sulfur-bearing high refractive index optical resin
CN112625217A (en) * 2020-12-23 2021-04-09 江南大学 Preparation method of sulfur-containing fluorene-containing structure high-refractive-index optical resin

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI367900B (en) * 2007-10-09 2012-07-11 Ind Tech Res Inst Encapsulant composition for a light-emitting diode

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102432829A (en) * 2011-08-02 2012-05-02 华南理工大学 Sulphur-containing optical epoxy resin and preparation method thereof
CN109651612A (en) * 2018-12-13 2019-04-19 江南大学 A kind of preparation method of sulfur-bearing high refractive index optical resin
CN112625217A (en) * 2020-12-23 2021-04-09 江南大学 Preparation method of sulfur-containing fluorene-containing structure high-refractive-index optical resin

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Synthesis and characterization of thianthrene-based epoxy with high refractive index over 1.7;Xiaojuan Zhao,et al.;《PHOSPHORUS, SULFUR, AND SILICON》;20170905;第193卷(第1期);第33-40页 *
Thianthrene as an activating group for the synthesis of poly(aryl ether thianthrene)s by nucleophilic aromatic substitution;JOSEPH B. EDSON,et al.;《Journal of Polymer Science: Part A: Polymer Chemistry》;20041231;第6353-6363页 *

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