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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- China
- Prior art keywords
- sulfur
- refractive index
- necked flask
- optical resin
- high refractive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 25
- 239000011593 sulfur Substances 0.000 title claims abstract description 24
- 230000003287 optical effect Effects 0.000 title claims abstract description 22
- 239000011347 resin Substances 0.000 title claims abstract description 22
- 229920005989 resin Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 7
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000010898 silica gel chromatography Methods 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000004809 Teflon Substances 0.000 claims description 2
- 229920006362 Teflon® Polymers 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- -1 sulfide ions Chemical class 0.000 abstract description 4
- 238000007259 addition reaction Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 125000004434 sulfur atom Chemical group 0.000 abstract 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract 2
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 239000005864 Sulphur Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005979 thermal decomposition reaction 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
一种含硫高折射率光学树脂的制备方法，属于光学材料技术领域。本发明利用4,4‑二巯基二苯硫醚、丙烯酰氯合成一种碳碳双键封端的含硫单体，然后与4,4‑二巯基二苯硫醚单体进行迈克加成反应制得透明含硫高折射率的光学树脂。在光学材料中，折射率是一个很重要的指标。硫原子既有很高的摩尔折射率又有较低的色散，环境稳定性好，无毒害，折射率的可调范围大。在硫原子的价态中，以二价硫离子最为重要，所以将硫原子引入高分子链中是提高树脂折射率最有效的方法之一。将硫引入聚合物链中比较简单方便，主要是从硫醇化合物出发，而且高分子链中硫的含量越高，折射率越高。A preparation method of a sulfur-containing high refractive index optical resin belongs to the technical field of optical materials. The present invention utilizes 4,4-dimercaptodiphenyl sulfide and acryloyl chloride to synthesize a carbon-carbon double bond-terminated sulfur-containing monomer, and then carries out Mike addition reaction with 4,4-dimercaptodiphenyl sulfide monomer to prepare A transparent sulfur-containing high-refractive-index optical resin is obtained. In optical materials, the refractive index is a very important indicator. Sulfur atom has both high molar refractive index and low dispersion, good environmental stability, no toxicity, and a large adjustable range of refractive index. Among the valence states of sulfur atoms, divalent sulfide ions are the most important, so the introduction of sulfur atoms into the polymer chain is one of the most effective ways to improve the refractive index of resins. The introduction of sulfur into the polymer chain is relatively simple and convenient, mainly starting from thiol compounds, and the higher the content of sulfur in the polymer chain, the higher the refractive index.
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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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| CN201811526130.3A Pending 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 | A kind of preparation method of thianthracene structure bromine element high refractive index optical resin |
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2018
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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 | A kind of preparation method of thianthracene 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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Application publication date: 20190419 |