CN115960120A - Preparation, electrochemical polymerization and application of D-A type monomer based on camphor quinoxaline - Google Patents
Preparation, electrochemical polymerization and application of D-A type monomer based on camphor quinoxaline Download PDFInfo
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- 239000000178 monomer Substances 0.000 title claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 17
- -1 camphor quinoxaline Chemical compound 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 14
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- 238000006243 chemical reaction Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 229920006254 polymer film Polymers 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 10
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- VNQXSTWCDUXYEZ-QUBYGPBYSA-N (1S)-(+)-Bornanedione Chemical compound C1C[C@]2(C)C(=O)C(=O)[C@H]1C2(C)C VNQXSTWCDUXYEZ-QUBYGPBYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000009987 spinning Methods 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- SSDDBKANEGGSRG-UHFFFAOYSA-N thiophene;tin Chemical compound [Sn].C=1C=CSC=1 SSDDBKANEGGSRG-UHFFFAOYSA-N 0.000 claims description 5
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical group C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 238000002484 cyclic voltammetry Methods 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 238000003786 synthesis reaction Methods 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 2
- 229930192474 thiophene Natural products 0.000 abstract description 2
- 239000000370 acceptor Substances 0.000 abstract 2
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- 238000000605 extraction Methods 0.000 description 6
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical compound BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
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- 241000723346 Cinnamomum camphora Species 0.000 description 2
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- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 description 2
- 229910000080 stannane Inorganic materials 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical class O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- VPMJBJSLTPBZLR-UHFFFAOYSA-N 3,6-dibromobenzene-1,2-diamine Chemical compound NC1=C(N)C(Br)=CC=C1Br VPMJBJSLTPBZLR-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 241000218195 Lauraceae Species 0.000 description 1
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- 150000001604 bicyclic monoterpene derivatives Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
- UKTDFYOZPFNQOQ-UHFFFAOYSA-N tributyl(thiophen-2-yl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C1=CC=CS1 UKTDFYOZPFNQOQ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses preparation, electrochemical polymerization and application of an electron donor-electron acceptor (D-A) type monomer based on camphor quinoxaline, belonging to the technical field of organic photoelectric materials. The material takes camphor quinoxaline structural units as electron acceptors, and thiophene and derivatives thereof as electron donors. The monomer can be used for preparing a film through electrochemical polymerization and can be used as an electrochromic material. The electrochromic material has the advantages of simple synthetic route, cheap and easily-obtained raw materials, easiness in purification, good stability and potential application value.
Description
1. Field of the invention
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a preparation and electrochemical polymerization method of a D-A type monomer based on camphor quinoxaline, and an application of the D-A type monomer in an electrochromic device.
2. Background of the invention
Applying a current or voltage to a substance causes it to undergo a redox reaction, with different redox states having different optical absorption and reflection properties, resulting in a macroscopic colour change, a phenomenon known as electrochromism. Electrochromic technology belongs to the emerging technical field and has wide application prospect and market potential.
The electrochromic material is the most important component in the electrochromic device, and plays a crucial role in the performance of the device. Compared with inorganic materials, organic materials are easy to chemically modify and have good processing properties, and are the materials which have the greatest potential to realize large-area production at present. Camphor is a forest chemical with a bicyclic monoterpene structure, exists in natural Lauraceae plants, and is a biomass resource with natural advantages in China. Camphor and derivatives thereof have wide application in the fields of medicines, pesticides and the like, but are rarely researched in the field of photoelectric functional materials. Therefore, the invention designs and synthesizes the electrochromic material containing the camphor quinoxaline. The camphorquinoxaline has strong electron-withdrawing ability and is connected with different electron-donating groups to form a series of electron donor-electron acceptor (D-A) type compounds. The compound can form a film through electrochemical polymerization, shows excellent electrochromic performance and has potential application value.
3. Summary of the invention
According to the invention, through molecular design, camphor quinoxaline is taken as an electron acceptor, a novel D-A type monomer is constructed through Stille coupling reaction, and the electrochromic material is prepared through electrochemical polymerization. The electrochromic material has high stability, is easy to synthesize and has potential application value.
The invention also aims to provide a preparation method of the camphor quinoxaline compound, which has the advantages of simple preparation operation process, mild reaction conditions, higher yield, simple purification process and high application value.
The camphor group of the camphor-quinoxaline organic electrochromic material provided by the invention is of a dextrorotatory structure, and the structural general formula (I) is as follows:
in the formula (I), R is a thiophene electron donating group, and is specifically one of the following structures:
the structure of the monomer is specifically one of the following structures:
the synthesis method of the camphor quinoxaline electrochromic material comprises the following steps: 5363 and reducing 4,7-dibromo-2,1,3 benzothiadiazole into 3,6-dibromo-1,2-phenylenediamine by sodium borohydride, condensing with (+) -camphorquinone, and finally carrying out Stille coupling reaction with a thiophene tin reagent to obtain the electrochromic material shown in the formula (I). The method comprises the following specific steps:
step (1): dissolving 4,7-dibromo-2,1,3 benzothiadiazole in absolute ethyl alcohol, slowly adding sodium borohydride into the absolute ethyl alcohol at 0 ℃, reacting for 6 hours at normal temperature, adding water for quenching, extracting with dichloromethane, drying an organic phase with anhydrous sodium sulfate, and concentrating under reduced pressure to obtain an intermediate 1. (Langmuir, 2009, 25 (9): 5061-5067.)
Step (2): intermediate 1 and (+) -camphorquinone were dissolved in toluene, p-toluenesulfonic acid was added, stirred uniformly at room temperature under nitrogen, then heated and reacted overnight. And cooling to room temperature after the reaction is finished. After the solvent toluene is dried by spinning, water is added into the residue, dichloromethane is used for extraction, then saturated saline solution is used for washing, an organic phase is collected, anhydrous sodium sulfate is added for drying, the organic solvent is removed under reduced pressure, and the obtained solid is separated, purified and dried in vacuum to obtain an intermediate 2. (Tetrahedron letters,2004, 45 (2): 329-333.)
And (3): dissolving the intermediate 2 in 1,4-dioxane, adding a thiophene tin reagent, potassium carbonate and tetrakis (triphenylphosphine) palladium, uniformly stirring under nitrogen protection at room temperature, heating, and reacting overnight. And cooling to room temperature after the reaction is finished. After solvent toluene is dried by spinning, water is added into the residue, dichloromethane is used for extraction, then saturated saline solution is used for washing, organic phase is collected, anhydrous sodium sulfate is added for drying, the organic solvent is removed under reduced pressure, the obtained solid is separated and purified, and vacuum drying is carried out, thus obtaining the camphor quinoxaline D-A type monomer.
The synthetic process comprises the following steps:
in the step (1), the molar ratio of 4,7-dibromo-2,1,3 benzothiadiazole to sodium borohydride is 1: 5, the reaction temperature is 25 ℃, and the reaction time is 10-24 h.
In the step (2), the molar ratio of the intermediate 1 to (+) -camphorquinone is 1: 1, the reaction temperature is 110 ℃, and the reaction time is 6-12 h.
In the step (3), the molar ratio of the intermediate 2 to the thiophene tin reagent is 1: 2-1: 4, the reaction temperature is 65-95 ℃, and the reaction time is 8-12 hours.
Dissolving a monomer shown in a formula (I) in a propylene carbonate solvent, taking tetrabutyl ammonium hexafluorophosphate as an electrolyte, polymerizing by adopting a cyclic voltammetry method of-0.6-0.8V, wherein the polymerization sweep rate is 0.1V/s, the number of cycles is 10-30, and electrochemically polymerizing to obtain a polymer film; the initial concentration of the tetrabutylammonium hexafluorophosphate is 0.1mol/L; the initial concentration of the EDOT derivative represented by the formula (I) is 1mmol/L. ITO is used as a working electrode, a platinum wire is used as a counter electrode, a silver wire is used as a reference electrode, and a monomer is polymerized into a film to be deposited on the surface of the ITO.
And an electrochemical workstation is adopted, and the ultraviolet-visible-near infrared absorption spectrum represents the electrochemical performance and the electrochromic performance of the prepared polymer film. Researches find that the polymer film has good electrochemical redox property, can realize reversible color change from blue to transparent under different voltages, and realizes higher color regulation in a visible light region. The optical contrast at 650nm exceeds 50% and shows a fast response speed (response time less than 1 s).
Compared with the prior art, the invention has the advantages that: a novel Camphor-quinoxaline-based D-A type monomer is synthesized, a polymer film is prepared through electrochemical polymerization, and the polymer film is applied to the field of electrochromism and has potential application prospects in the fields of intelligent windows, displays and the like.
Drawings
FIG. 1 is a cyclic voltammogram of electrochemical polymerization of monomeric CQ-EDOT synthesized in example 1 of the present invention.
FIG. 2 is a graph of absorption spectra at different voltages for CQ-EDOT based polymer films synthesized in inventive example 1.
FIG. 3 is a graph of the response time of a CQ-EDOT based polymer film synthesized in inventive example 1.
FIG. 4 is a graph of the cycling stability of a CQ-EDOT based polymer film synthesized in accordance with example 1 of the present invention.
Detailed Description
Example 1:
step (1): 3.3g (11.2 mmol) 4,7-dibromo-2,1,3 benzothiadiazole was dissolved in anhydrous ethanol, 4.2g (110 mmol) sodium borohydride was slowly added thereto at 0 ℃ to react at room temperature for 6h, water was added to quench, dichloromethane was added to quench, the organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure to give intermediate 1 (2.9g, 98%). 1 H NMR(600MHz，CDCl 3 )δ：6.84(s，2H)，3.89(s，4H). 13 C NMR(150MHz，CDCl 3 )δ：133.74，123.27，109.70。(Langmuir，2009，25(9)：5061-5067.)
Step (2): 1g (3.75 mmol) of intermediate 1 was dissolved in 30mL of toluene, 0.62g (3.75 mmol) (+) -camphorquinone was added, and the mixture was stirred uniformly under nitrogen at room temperature, then heated under reflux and reacted overnight. And cooling to room temperature after the reaction is finished. After toluene as a solvent was dried by spinning, water was added to the residue, followed by extraction with dichloromethane, washing with saturated brine, collecting the organic phase, drying with anhydrous sodium sulfate, removing the organic solvent under reduced pressure, and the resulting solid was isolated, purified, and dried under vacuum to obtain intermediate 2 (0.9 g, yield: 76%). 1 H NMR(600MHz，CDCl 3 )8：7.81(s，2H)，3.26(d，J＝2.4Hz，1H)，2.33-2.35(m，1H)，2.07-2.11(m，1H)，1.47(s，3H)，1.43-1.44(m，2H)，1.14(s，3H)，0.62(s，3H)。(Tetrahedron letters，2004，45(2)：329-333.)
And (3): 394mg (1 mmol) of intermediate 2 are dissolved in 1,4-dioxane, 1080mg (2.5 mmol) of tributyl (2,3-dihydrothieno [3,4-b) are added][1，4]Dioxin-5-yl) stannane, 1035mg (7.5 mmol) of potassium carbonate, 115mg (0.1 mmol) of tetrakis (triphenylphosphine) palladium, under nitrogen protection and at room temperature, were uniformly stirred, and then heated under reflux, reacted overnight. After the reaction is finished, cooling to room temperature. After the solvent was dried by spinning, water was added to the residue, followed by extraction with dichloromethane, washing with saturated brine, collecting the organic phase, drying with anhydrous sodium sulfate, removing the organic solvent under reduced pressure, separating and purifying the obtained solid, and drying under vacuum to obtain 404mg of CQ-EDOT as a green solid (yield: 78.1%). Melting point: 239.4-240.9 ℃. 1 H NMR(600MHz，CDCl 3 )δ：8.54(d，J＝8.3Hz，1H)，8.39(d，J＝8.4Hz，1H)，6.51(d，J＝8.5Hz，2H)，4.40-4.33(m，4H)，4.29(m，4H)，3.15(d，J＝4.3Hz，1H)，2.31(m，1H)，2.07(m，1H)，1.52(s，3H)，1.48-1.40(m，2H)，1.13(s，3H)，0.64(s，3H)。
Example 2:
394mg (1 mmol) of intermediate 2 are dissolved in 1,4-dioxane and 1.43g (2.5 mmol) of tributyl (2,2 ',3,3' -tetrahydro- [5,5' -dithieno [3,4-b ] are added][1，4]Dioxin]-7-yl) stannane, 1035mg (7.5 mmol) potassium carbonate, 115mg (0.1 mmol) tetrakis (triphenylphosphine) palladium under nitrogen and stirring at room temperature, then heating to reflux and reacting overnight. After the reaction is finished, cooling to room temperature. After the solvent was dried by spinning, water was added to the residue, followed by extraction with dichloromethane, washing with saturated brine, collecting the organic phase, drying with anhydrous sodium sulfate, removing the organic solvent under reduced pressure, separating and purifying the obtained solid, and drying under vacuum to obtain 400mg of CQ-DEDOT as a red solid (yield: 50.2%). Melting point: 261.6-262.9 ℃. 1 H NMR(600MHz，CDCl 3 )δ：8.62(d，J＝8.4Hz，1H)，8.38(d，J＝8.4Hz，1H)，6.31(d，J＝3.2Hz，2H)，4.40(m，12H)，4.28(m，4H)，3.18(s，1H)，2.30(m，2H)，2.07(m，2H)，1.61(s，3H)，1.14(s，3H)，0.67(s，3H)。
Example 3:
394mg (1 mmol) of intermediate 2 are dissolved in 1,4-dioxane, 312mg (0.168 mmol) of 2-tributylstannyl thiophene, 1035mg (7.5 mmol) of potassium carbonate and 112mg (0.1 mmol) of tetrakis (triphenylphosphine) palladium are added, and the mixture is stirred homogeneously under nitrogen at room temperature and then heated under reflux for reaction overnight. After the reaction is finished, cooling to room temperature. After the solvent was dried, water was added to the residue, followed by extraction with dichloromethane, washing with saturated brine, collecting the organic phase, drying with anhydrous sodium sulfate, removing the organic solvent under reduced pressure, separating and purifying the obtained solid, and drying under vacuum to obtain 300mg of CQ-Th as a green solid (yield: 75%). Melting point: 231.9 to 233.2 ℃. 1 H NMR(400MHz，CDCl 3 )δ：8.06(d，J＝8.1Hz，1H)，7.99(d，J＝8.1Hz，1H)，7.87(dd，J 1 ＝3.8，J 2 ＝1.1Hz，1H)，7.81(dd，J 1 ＝3.7，J 2 ＝1.1Hz，1H)，7.66-7.29(m，2H)，7.22-7.09(m，2H)，3.17(d，J＝4.4Hz，1H)，2.37-2.30(m，1H)，2.15-2.05(m，1H)，1.53(s，3H)，1.47(d，J＝8.7Hz，2H)，1.15(s，3H)，0.66(s，3H)。
Example 4: electrochemical polymerization and electrochromic performance characterization of monomer CQ-EDOT
Mixing 0.774g TBAPF 6 The electrolyte solution was dissolved in 20mL of propylene carbonate to prepare an electrolyte solution. The monomer CQ-EDOT was dissolved in 10mL of the electrolyte solution to prepare a monomer solution (1 mmol/L). The monomer solution is polymerized by cyclic voltammetry at-0.6-0.8V, the polymerization scanning rate is 0.1V/s, a polymer film is obtained by electrochemical polymerization, and then the polymer film is dedoped for 60s at-0.6V in electrolyte. All subsequent electrochemical tests were performed in the electrolyte.
FIGS. 1 to 4 are graphs of electrochemical polymerization CV curves, absorption spectra at different voltages, optical contrast and response time and cycling stability based on the monomer CQ-EDOT. The test result shows that the polymer film prepared by the invention has good electrochemical redox property and excellent stability, and can realize reversible color change from blue to transparent under different voltages. The optical contrast ratio at 667nm is 41.7%, the coloring response time and the fading response time are respectively 0.51s and 0.45s, and the light transmittance is kept about 90% after 400 cycles.
Claims (7)
1. A D-A type monomer based on camphor quinoxaline is characterized in that camphor groups are of dextrorotatory structures and have the following chemical general formula:
wherein, -R is any one of the following structures:
2. the method for synthesizing a camphorquinoxaline-based D-a type monomer according to claim 1, comprising the steps of:
(1) Intermediate 1 was prepared as described in literature (Langmuir, 2009, 25 (9): 5061-5067);
(2) Dissolving the intermediate 1 and (+) -camphorquinone in toluene, adding a small amount of p-toluenesulfonic acid (PTSA) for catalysis, uniformly stirring under the protection of nitrogen, heating and reacting overnight. After the reaction is finished, cooling to room temperature. After the solvent toluene is dried by spinning, adding water into the reaction solution, extracting by dichloromethane, washing by saturated saline solution, collecting the organic phase, adding anhydrous sodium sulfate, drying, removing the organic solvent under reduced pressure, separating and purifying the obtained solid, and drying in vacuum to obtain an intermediate 2. (Tetrahedron letters,2004, 45 (2): 329-333.)
(3) Dissolving the intermediate 2 in toluene, adding a thiophene tin reagent, potassium carbonate and tetrakis (triphenylphosphine) palladium, uniformly stirring at room temperature under the protection of nitrogen, then heating, and reacting overnight. And cooling to room temperature after the reaction is finished. And (3) after solvent toluene is spin-dried, adding water into the reaction solution, extracting with dichloromethane, washing with saturated saline solution, collecting an organic phase, adding anhydrous sodium sulfate, drying, removing the organic solvent under reduced pressure, separating and purifying the obtained solid, and drying in vacuum to obtain the target monomer.
3. The organic electrochromic material with camphorquinoxaline according to claim 2, wherein in the synthesis method: in the step (1), excessive sodium borohydride is added dropwise at 0 ℃, the reaction temperature is 25 ℃, and the reaction time is 10-24 h.
4. The camphorquinoxaline-based D-a type monomer of claim 2, wherein in the synthesis process: in the step (2), the molar ratio of the intermediate 1 to the (+) -camphorquinone is 1: 1, the reaction temperature is 110 ℃, and the reaction time is 6-12 h.
5. The camphorquinoxaline-based D-a type monomer according to claim 2, wherein in the synthesis process: in the step (2), the molar ratio of the intermediate 2 to the thiophene tin reagent is 1: 2-1: 4, the reaction temperature is 65-95 ℃, and the reaction time is 8-12 hours.
6. The electrochemical polymerization of a class of camphorquinoxaline-based D-a type monomers as claimed and their use in electrochromic devices.
7. The electrochemical polymerization of a type D-A monomer based on camphorquinoxaline and its application in electrochromic device according to claim 6, characterized by comprising the following steps:
dissolving a monomer shown in a formula (I) in a propylene carbonate solvent, taking tetrabutyl ammonium hexafluorophosphate as an electrolyte, polymerizing by adopting a cyclic voltammetry method of-0.6-0.8V, wherein the polymerization sweep rate is 0.1V/s, the number of cycles is 10-30, and electrochemically polymerizing to obtain a polymer film; the initial concentration of the tetrabutylammonium hexafluorophosphate is 0.1mol/L; the initial concentration of the monomer shown in the formula (I) is 1mmol/L. Indium Tin Oxide (ITO) transparent conductive glass is used as a working electrode, a platinum wire is used as a counter electrode, a silver wire is used as a reference electrode, and a monomer is polymerized into a film to be deposited on the surface of the ITO.
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| CN111233840A (en) * | 2018-11-28 | 2020-06-05 | 北京鼎材科技有限公司 | Quinoxaline derivative and application thereof in organic light-emitting device |
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| CN110066287A (en) * | 2019-03-05 | 2019-07-30 | 浙江工业大学 | A kind of EDOT- quinoxaline-EDOT derivative and the preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| T. SUZUKI: "Preparation, properties, and X-ray structures of 5, 5‘-bi(8-aminoquinoxalyl)s: novel Wurster-type electron donors with a heterobiaryl skeleton", 《TETRAHEDRON LETTERS》, vol. 45, 31 December 2004 (2004-12-31), pages 329 - 333, XP002476074, DOI: 10.1016/j.tetlet.2003.10.151 * |
| 卜俊文: "樟脑基喹喔啉类化合物的合成及其生物活性", 《CHIN． J． SYN． CHEM．》, vol. 28, no. 7, 31 December 2020 (2020-12-31), pages 584 - 593 * |
| 汪文源: "基于给体-受体型三苯胺喹喔啉类电致变色材料的合成及性能研究", 《CHIN. J. ORG. CHEM.》, vol. 10, 31 December 2020 (2020-12-31), pages 2513 - 2519 * |
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