CN109651612A - A kind of preparation method of sulfur-bearing high refractive index optical resin - Google Patents
A kind of preparation method of sulfur-bearing high refractive index optical resin Download PDFInfo
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- CN109651612A CN109651612A CN201811526130.3A CN201811526130A CN109651612A CN 109651612 A CN109651612 A CN 109651612A CN 201811526130 A CN201811526130 A CN 201811526130A CN 109651612 A CN109651612 A CN 109651612A
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- refractive index
- sulfur
- necked flask
- high refractive
- optical resin
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- 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
- C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A kind of preparation method of sulfur-bearing high refractive index optical resin, belongs to optical material technical field.The present invention synthesizes a kind of sulfur-bearing monomer of carbon-carbon double bond sealing end using 4,4- dimercapto diphenyl sulfide, acryloyl chloride, then carries out the optical resin that transparent sulfur-bearing high refractive index is made in mikey addition reaction with 4,4- dimercapto diphenyl sulfide monomer.In optical material, refractive index is a critically important index.The existing very high Lorentz-Lorenz molar refraction of sulphur atom has lower dispersion again, and environmental stability is good, nonhazardous, and the adjustable extent of refractive index is big.It is mostly important with sulfidion in the valence state of sulphur atom, so it is to improve one of resin index most efficient method that sulphur atom, which is introduced into macromolecular chain,.Sulphur is introduced into fairly simple convenience in polymer chain, mainly from mercaptan compound, and in macromolecular chain sulphur content it is higher, refractive index is higher.
Description
Technical field
The present invention relates to a kind of preparation methods of sulfur-bearing high refractive index optical resin, belong to optical material field.
Background technique
Important component of the organic resin as optical resin, has been to be concerned by more and more people.In optical material,
Refractive index is a critically important index.The existing very high Lorentz-Lorenz molar refraction of sulphur atom has lower dispersion, environmental stability again
Good, the adjustable extent of nonhazardous, refractive index is big.It is mostly important with sulfidion in the valence state of sulphur atom, so by sulphur original
It is to improve one of resin index most efficient method that son, which is introduced into macromolecular chain,.Sulphur is introduced into fairly simple side in polymer chain
Just, mainly from mercaptan compound, and in macromolecular chain sulphur content it is higher, refractive index is higher.
Summary of the invention
The present invention relates to a kind of preparation methods of sulfur-bearing high refractive index optical resin.4 are utilized its purpose is to provide a kind of,
4- dimercapto diphenyl sulfide, acryloyl chloride synthesize a kind of sulfur-bearing monomer of carbon-carbon double bond sealing end, then are closed by mikey addition reaction
At sulfur-bearing high refractive index optical resin.In the present invention, a kind of sulfur-bearing monomer of both ends carbon-carbon double bond sealing end has been synthesized, then with 4,
4- dimercapto diphenyl sulfide monomer, which carries out mikey addition reaction, can be made transparent sulfur-bearing high refractive index optical resin.
The technical scheme is that a kind of preparation method of sulfur-bearing high refractive index optical resin, includes the following steps:
(1) blender is being housed, 4,4- dimercapto diphenyl sulfide, triethylamine, N, N- is added in the 250mL three-necked flask of condenser pipe
Simultaneously 15min is stirred at room temperature in dimethylformamide, logical nitrogen；
(2) clear solution ice bath is cooled to 0 DEG C, is under nitrogen atmosphere slowly added drop-wise to acryloyl chloride in three-necked flask；
(3) 20h is stirred at room temperature in reaction mixture；
(4) the mixture vacuum distillation after reaction is then removed into volatile matter, and residue is successively used into N, N- dimethyl formyl
Amine and deionized water washing；
(5) organic matter after washing is dried, filtered with anhydrous sodium sulfate, and be concentrated under reduced pressure；
(6) by silica gel column chromatography purification of crude product, use hexane solution as eluant, eluent, obtain colourless low-viscosity (mobile) liquid；
(7) obtained low-viscosity (mobile) liquid is added in 250mL three-necked flask, a certain amount of triethylamine is added；
(8) a certain amount of 4,4- dimercapto diphenyl sulfide is dissolved in n,N-Dimethylformamide, is slowly added drop-wise to above-mentioned three
In mouth flask reaction system, 2h is stirred at room temperature；
(9) in a mold by the obtained solution-cast of reaction, first 70 DEG C of vacuum drying 6h, then 100 DEG C of solidification 3h, last 120
DEG C solidifying 1h can be obtained transparent sulfur-bearing high refractive index optical resin.
Beneficial effects of the present invention: the existing very high Lorentz-Lorenz molar refraction of sulphur atom has lower dispersion, environmental stability again
Good, the adjustable extent of nonhazardous, refractive index is big.It is mostly important with sulfidion in the valence state of sulphur atom, so by sulphur original
It is to improve one of resin index most efficient method that son, which is introduced into macromolecular chain,.Sulphur is introduced into fairly simple side in polymer chain
Just, mainly from mercaptan compound, and in macromolecular chain sulphur content it is higher, refractive index is higher.
Specific embodiment
Embodiment 1
The synthesis of the sulfur-bearing monomer of both ends carbon-carbon double bond sealing end: blender is being housed, is being added in the 250mL three-necked flask of condenser pipe
9.5g 4,4- dimercapto diphenyl sulfide, 18mL triethylamine, 50mL n,N-Dimethylformamide, logical nitrogen are simultaneously stirred at room temperature
15min；
Clear solution ice bath is cooled to 0 DEG C, is under nitrogen atmosphere slowly added drop-wise to 8.8mL acryloyl chloride in three-necked flask,
20h is stirred at room temperature in reaction mixture；
Then by 70 DEG C of mixture after reaction, -0.1Mpa vacuum distillation removes volatile matter, and residue is successively used 20mL
N,N-dimethylformamide and the washing of 20mL deionized water；
Organic matter after washing is dried, filtered with 10g anhydrous sodium sulfate, and is concentrated under reduced pressure；
By silica gel column chromatography purification of crude product, uses hexane solution as eluant, eluent, obtain colourless low-viscosity (mobile) liquid；
Obtained low-viscosity (mobile) liquid is added in 250mL three-necked flask, the triethylamine of 0.36g is added, by 4,4-, bis- mercapto of 10g
Base diphenyl sulfide is dissolved in 30g n,N-Dimethylformamide, is slowly added drop-wise in above-mentioned three-necked flask, 2h is stirred at room temperature；
The preparation of sulfur-bearing high refractive index optical resin: 10g is taken to cast in Teflon mould the solution that reaction obtains, first
Then 70 DEG C of vacuum drying 6h solidify 3h, last 120 DEG C of solidifications 1h in 100 DEG C of normal pressures, transparent sulfur-bearing height refraction can be obtained
Rate optical resin.
It is 1.7853 that this product, which measures the refractive index at 589nm by elliptic polarization spectrometer, and Abbe number is 38.Can
Transmitance in light-exposed range is 90% or more.280 DEG C of film thermal decomposition temperature or more after solidification.
Claims (2)
1. a kind of preparation method of sulfur-bearing high refractive index optical resin, it is characterised in that include the following steps:
(1) blender is being housed, 4,4- dimercapto diphenyl sulfide, triethylamine, N, N- is added in the 250mL three-necked flask of condenser pipe
Simultaneously 15min is stirred at room temperature in dimethylformamide, logical nitrogen；
(2) clear solution ice bath is cooled to 0 DEG C, is under nitrogen atmosphere slowly added drop-wise to acryloyl chloride in three-necked flask；It will
20h is stirred at room temperature in reaction mixture；
(3) the mixture vacuum distillation after reaction is then removed into volatile matter, and residue is successively used into N, N- dimethyl formyl
Amine and deionized water washing；
(4) organic matter after washing is dried, filtered with anhydrous sodium sulfate, and be concentrated under reduced pressure；
(5) by silica gel column chromatography purification of crude product, use hexane solution as eluant, eluent, obtain colourless low-viscosity (mobile) liquid；
(6) obtained low-viscosity (mobile) liquid is added in 250mL three-necked flask, a certain amount of triethylamine is added；
(7) a certain amount of 4,4- dimercapto diphenyl sulfide is dissolved in n,N-Dimethylformamide, is slowly added drop-wise to above-mentioned step
Suddenly in (6) three-necked flask reaction system, 2h is stirred at room temperature；
(8) in a mold by the obtained solution-cast of reaction, first 70 DEG C of vacuum drying 6h, then 100 DEG C of solidification 3h, last 120
DEG C solidify 1h to get to transparent sulfur-bearing high refractive index optical resin.
2. the preparation method of sulfur-bearing high refractive index optical resin according to claim 1, it is characterised in that specific step is as follows:
The synthesis of the sulfur-bearing monomer of both ends carbon-carbon double bond sealing end: blender is being housed, is being added in the 250mL three-necked flask of condenser pipe
9.5g 4,4- dimercapto diphenyl sulfide, 18mL triethylamine, 50mL n,N-Dimethylformamide, logical nitrogen are simultaneously stirred at room temperature
15min；
Clear solution ice bath is cooled to 0 DEG C, is under nitrogen atmosphere slowly added drop-wise to 8.8mL acryloyl chloride in three-necked flask,
20h is stirred at room temperature in reaction mixture；
Then by 70 DEG C of mixture after reaction, -0.1Mpa vacuum distillation removes volatile matter, and residue is successively used 20mL
N,N-dimethylformamide and the washing of 20mL deionized water；
Organic matter after washing is dried, filtered with 10g anhydrous sodium sulfate, and is concentrated under reduced pressure；
By silica gel column chromatography purification of crude product, uses hexane solution as eluant, eluent, obtain colourless low-viscosity (mobile) liquid；
Obtained low-viscosity (mobile) liquid is added in 250mL three-necked flask, the triethylamine of 0.36g is added, by 4,4-, bis- mercapto of 10g
Base diphenyl sulfide is dissolved in 30g n,N-Dimethylformamide, is slowly added drop-wise in above-mentioned three-necked flask, 2h is stirred at room temperature；
The preparation of sulfur-bearing high refractive index optical resin: 10g is taken to cast in Teflon mould the solution that reaction obtains, first
Then 70 DEG C of vacuum drying 6h solidify 3h in 100 DEG C of normal pressures, last 120 DEG C solidify 1h to get transparent sulfur-bearing high refractive index is arrived
Optical resin.
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| CN201811526130.3A CN109651612A (en) | 2018-12-13 | 2018-12-13 | A kind of preparation method of sulfur-bearing high refractive index optical resin |
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| CN201811526130.3A CN109651612A (en) | 2018-12-13 | 2018-12-13 | A kind of preparation method of sulfur-bearing high refractive index optical resin |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112646185A (en) * | 2020-11-30 | 2021-04-13 | 山东益丰生化环保股份有限公司 | Modified polythiol with high refractive index and preparation method thereof |
| CN114181374A (en) * | 2021-12-10 | 2022-03-15 | 江南大学 | Preparation method of thianthrene structure bromine element high-refractive index optical resin |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03109368A (en) * | 1989-09-22 | 1991-05-09 | Nippon Shokubai Kagaku Kogyo Co Ltd | Mew crosslinking thiocarboxylate |
| JPH0477467A (en) * | 1990-07-19 | 1992-03-11 | Mitsui Toatsu Chem Inc | New sulfur-containing aromatic acrylate |
| JPH10171117A (en) * | 1996-12-11 | 1998-06-26 | Toray Ind Inc | Photosensitive paste and production of plasma display |
| JP2002338541A (en) * | 2001-05-21 | 2002-11-27 | Sumitomo Seika Chem Co Ltd | Dielectric forming substance and dielectric film |
| JP2003292508A (en) * | 2002-04-01 | 2003-10-15 | Sumitomo Seika Chem Co Ltd | Curable resin composition |
| CN1946769A (en) * | 2004-04-14 | 2007-04-11 | 出光兴产株式会社 | Sulfur-containing compound, process for producing the same, sulfur-containing polymer, and optical material |
| CN101481360A (en) * | 2009-02-20 | 2009-07-15 | 中山大学 | Sulfur-bearing photo-curing compound and preparation thereof |
| JP2011168526A (en) * | 2010-02-18 | 2011-09-01 | Tokyo Institute Of Technology | Novel (meth)acrylate compound and manufacturing method of the same |
| CN108948256A (en) * | 2018-07-27 | 2018-12-07 | 望江县天长光学科技有限公司 | A kind of preparation method of high refractive index sulfur-bearing optics copolymer resins |
-
2018
- 2018-12-13 CN CN201811526130.3A patent/CN109651612A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03109368A (en) * | 1989-09-22 | 1991-05-09 | Nippon Shokubai Kagaku Kogyo Co Ltd | Mew crosslinking thiocarboxylate |
| JPH0477467A (en) * | 1990-07-19 | 1992-03-11 | Mitsui Toatsu Chem Inc | New sulfur-containing aromatic acrylate |
| JPH10171117A (en) * | 1996-12-11 | 1998-06-26 | Toray Ind Inc | Photosensitive paste and production of plasma display |
| JP2002338541A (en) * | 2001-05-21 | 2002-11-27 | Sumitomo Seika Chem Co Ltd | Dielectric forming substance and dielectric film |
| JP2003292508A (en) * | 2002-04-01 | 2003-10-15 | Sumitomo Seika Chem Co Ltd | Curable resin composition |
| CN1946769A (en) * | 2004-04-14 | 2007-04-11 | 出光兴产株式会社 | Sulfur-containing compound, process for producing the same, sulfur-containing polymer, and optical material |
| CN101481360A (en) * | 2009-02-20 | 2009-07-15 | 中山大学 | Sulfur-bearing photo-curing compound and preparation thereof |
| JP2011168526A (en) * | 2010-02-18 | 2011-09-01 | Tokyo Institute Of Technology | Novel (meth)acrylate compound and manufacturing method of the same |
| CN108948256A (en) * | 2018-07-27 | 2018-12-07 | 望江县天长光学科技有限公司 | A kind of preparation method of high refractive index sulfur-bearing optics copolymer resins |
Non-Patent Citations (1)
| Title |
|---|
| 周淑千等: ""双巯酯基高折射率单体及涂层的制备与性能研究"", 《信息记录材料》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112646185A (en) * | 2020-11-30 | 2021-04-13 | 山东益丰生化环保股份有限公司 | Modified polythiol with high refractive index and preparation method thereof |
| CN112646185B (en) * | 2020-11-30 | 2023-04-28 | 益丰新材料股份有限公司 | Modified polythiol with high refractive index and preparation method thereof |
| CN114181374A (en) * | 2021-12-10 | 2022-03-15 | 江南大学 | Preparation method of thianthrene structure bromine element high-refractive index optical resin |
| CN114181374B (en) * | 2021-12-10 | 2023-02-28 | 江南大学 | Preparation method of thianthrene structure bromine element high-refractive index optical resin |
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