CN115960120B - Preparation, electrochemical polymerization and application of D-A type monomer based on camphorquinoxaline - Google Patents
Preparation, electrochemical polymerization and application of D-A type monomer based on camphorquinoxaline Download PDFInfo
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- 239000000178 monomer Substances 0.000 title claims abstract description 28
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 11
- 239000012074 organic phase Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 229920006254 polymer film Polymers 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
- 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 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 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
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- SSDDBKANEGGSRG-UHFFFAOYSA-N thiophene;tin Chemical compound [Sn].C=1C=CSC=1 SSDDBKANEGGSRG-UHFFFAOYSA-N 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical compound BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- -1 tetrabutylammonium hexafluorophosphate Chemical compound 0.000 claims description 5
- 238000002484 cyclic voltammetry Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 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
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 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
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 238000010408 sweeping Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 4
- 238000010438 heat treatment Methods 0.000 claims 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims 2
- 229920000642 polymer Polymers 0.000 claims 2
- 238000003756 stirring Methods 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- SQRICDVGYLFTLO-UHFFFAOYSA-N tributyl(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)stannane Chemical group O1CCOC2=C([Sn](CCCC)(CCCC)CCCC)SC=C21 SQRICDVGYLFTLO-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 4
- 229930192474 thiophene Natural products 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
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- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 2
- 241000723346 Cinnamomum camphora Species 0.000 description 2
- 238000006619 Stille reaction Methods 0.000 description 2
- 229960000846 camphor Drugs 0.000 description 2
- 229930008380 camphor Natural products 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 description 2
- 229910000080 stannane Inorganic materials 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 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
- 238000010521 absorption reaction Methods 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
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- 230000001351 cycling effect Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 239000008204 material by function Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 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
Classifications
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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) monomer based on camphorquinoxaline, and belongs to the technical field of organic photoelectric materials. The material takes a camphorquinoxaline structural unit as an electron acceptor, 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 disclosed by the invention is simple in synthetic route, low in cost and easy to obtain raw materials, easy to purify and good in stability, and has potential application value.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a preparation and electrochemical polymerization method of D-A type monomers based on camphorquinoxaline, and application thereof in electrochromic devices.
Background
The application of a current or voltage to a substance causes its redox reaction, the different redox states having different optical absorption and reflection properties, resulting in a macroscopic color change, a phenomenon known as electrochromic. Electrochromic technology belongs to the emerging technical field, and has wide application prospect and market potential.
Electrochromic materials are the most important component in electrochromic devices, and electrochromic materials play a vital role in device performance. Compared with inorganic materials, organic materials are easy to chemically modify and have good processing performance, and are the materials with the most potential to realize large-area production at present. Camphor is a forest chemical with a bicyclo-monoterpene structure, exists in natural Lauraceae plants, and is a natural dominant biomass resource in China. Camphor and its derivatives have wide application in medicine, pesticide and other fields, but have less research in the field of photoelectric functional materials. Therefore, the invention designs and synthesizes a class of electrochromic materials containing camphorquinoxaline. Camphorquinoxalines have a strong electron withdrawing ability and are linked to different electron donating groups to form a series of electron donor-electron acceptor (D-a) type compounds. The compound can be formed into a film through electrochemical polymerization, has excellent electrochromic performance and has potential application value.
Disclosure of Invention
According to the invention, through molecular design, camphorquinoxaline is used as an electron acceptor, a novel D-A type monomer is constructed through Stille coupling reaction, and an 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 camphorquinoxaline compound, which has the advantages of simple preparation operation process, mild reaction conditions, higher yield, simple purification process and high application value.
The invention provides a camphorquinoxaline organic electrochromic material, wherein a camphorgroup is of a right-handed structure, and the structural general formula (I):
Formula (I), R is thiophene electron donor group, specifically one of the following structures:
The structure of the monomer is specifically one of the following structures:
The synthesis method of the camphorquinoxaline electrochromic material comprises the following steps: 4, 7-dibromo-2, 1, 3-benzothiadiazole is reduced into 3, 6-dibromo-1, 2-phenylenediamine by sodium borohydride, then condensed with (+) -camphorquinone, and finally Stille coupling reaction is carried out with thiophene tin reagent to obtain the electrochromic material shown in the formula (I). The method comprises the following steps:
Step (1): dissolving 4, 7-dibromo-2, 1, 3-benzothiadiazole in absolute ethyl alcohol, slowly adding sodium borohydride into the solution at the temperature of 0 ℃ to react for 6 hours at normal temperature, adding water for quenching, extracting with dichloromethane, drying an organic phase with absolute sodium sulfate, and concentrating under reduced pressure to obtain the intermediate 1. (Langmuir, 2009, 25 (9): 5061-5067.)
Step (2): intermediate 1 and (+) -camphorquinone were dissolved in toluene, p-toluene sulfonic acid was added, stirred uniformly at room temperature under nitrogen protection, and then heated to react overnight. And cooling to room temperature after the reaction is finished. After the solvent toluene was spin-dried, water was added to the residue, extraction was performed with methylene chloride, and then the residue was washed with saturated brine, and the organic phase was collected, dried over anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and the obtained solid was separated and purified, and dried under vacuum to obtain intermediate 2. (Tetrahedron letters,2004, 45 (2): 329-333.)
Step (3): intermediate 2 was dissolved in 1, 4-dioxane, thiophene tin reagent, potassium carbonate, tetrakis (triphenylphosphine) palladium were added, stirred uniformly at room temperature under nitrogen protection, and then heated to react overnight. And cooling to room temperature after the reaction is finished. After the solvent toluene was spin-dried, water was added to the residue, extracted with methylene chloride, washed with saturated brine, the organic phase was collected, dried over anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and the obtained solid was separated and purified, and dried under vacuum to obtain camphorquinoxaline D-A type monomers.
The synthesis flow is as follows:
In the step (1), the molar ratio of the 4, 7-dibromo-2, 1, 3-benzothiadiazole to the sodium borohydride is 1:5, the reaction temperature is 25 ℃, and the reaction time is 10-24 hours.
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 mol 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 h.
Dissolving a monomer shown in a formula (I) in a propylene carbonate solvent, taking tetrabutylammonium hexafluorophosphate as an electrolyte, adopting cyclic voltammetry polymerization of-0.6-0.8V, wherein the polymerization sweeping speed is 0.1V/s, the cycle number is 10-30, and obtaining a polymer film after electrochemical polymerization; the initial concentration of the tetrabutylammonium hexafluorophosphate is 0.1mol/L; the initial concentration of the EDOT derivative shown in the formula (I) is 1mmol/L. ITO is a working electrode, a platinum wire is a counter electrode, a silver wire is a reference electrode, and a monomer is polymerized into a film and deposited on the ITO surface.
The electrochemical performance and electrochromic performance of the prepared polymer film are characterized by adopting an electrochemical workstation and ultraviolet-visible-near infrared absorption spectrum. The research shows that the polymer film has good electrochemical oxidation-reduction 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 exceeds 50% at 650nm, and a very fast response speed (response time less than 1 s) is exhibited.
Compared with the prior art, the invention has the advantages that: the novel camphorquinoxaline-based D-A monomer is synthesized, the polymer film is prepared through electrochemical polymerization, and is applied to the electrochromic field, and the camphorquinoxaline-based D-A monomer has potential application prospect in the fields of intelligent windows, displays and the like.
Drawings
FIG. 1 is a cyclic voltammogram of electrochemical polymerization of the monomer CQ-EDOT synthesized in example 1 of the present invention.
FIG. 2 is a graph of the absorption spectra of the CQ-EDOT based polymer film synthesized in example 1 of the present invention at various voltages.
FIG. 3 is a graph of the response time of a CQ-EDOT based polymer film synthesized in example 1 of the present invention.
FIG. 4 is a graph of the cyclic stability of a CQ-EDOT based polymer film synthesized in example 1 of the present invention.
Detailed Description
Example 1:
Step (1): 3.3g (11.2 mmol) of 4, 7-dibromo-2, 1, 3-benzothiadiazole was dissolved in absolute ethanol, 4.2g (110 mmol) of sodium borohydride was slowly added thereto at 0℃and reacted at room temperature for 6 hours, quenched with water, extracted with methylene chloride, and the organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure to give an intermediate 1(2.9g,98％).1H NMR(600MHz,CDCl3)δ：6.84(s,2H),3.89(s,4H).13C NMR(150MHz,CDCl3)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) of (+) -camphorquinone was added, and the mixture was stirred uniformly at room temperature under nitrogen protection, and then heated under reflux to react overnight. And cooling to room temperature after the reaction is finished. After spin drying toluene as a solvent, adding water to the residue, extracting with dichloromethane, washing with saturated saline, collecting an organic phase, drying with anhydrous sodium sulfate, removing the organic solvent under reduced pressure, separating and purifying the obtained solid, and vacuum drying to obtain intermediate 2 (0.9 g, yield) ：76％).1H NMR(600MHz,CDCl3)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.)
Step (3): 394mg (1 mmol) of intermediate 2 was dissolved in 1, 4-dioxane, 1080mg (2.5 mmol) of tributyl (2, 3-dihydrothieno [3,4-b ] [1,4] dioxan-5-yl) stannane, 1035mg (7.5 mmol) of potassium carbonate, 115mg (0.1 mmol) of tetrakis (triphenylphosphine) palladium were added, stirred uniformly under nitrogen and at room temperature, and then heated under reflux to react overnight. And cooling to room temperature after the reaction is finished. After the solvent was dried by spinning, water was added to the residue, extraction was performed with methylene chloride, and then the residue was washed with saturated brine, and the organic phase was collected, dried over anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and the obtained solid was separated and purified, and dried in vacuo to give 404mg of green solid CQ-EDOT (yield: 78.1%). Melting point ：239.4～240.9℃.1H NMR(600MHz,CDCl3)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, 1.43g (2.5 mmol) of tributyl (2, 2', 3' -tetrahydro- [5,5' -dithieno [3,4-b ] [1,4] dioxin ] -7-yl) stannane, 1035mg (7.5 mmol) of potassium carbonate, 115mg (0.1 mmol) of tetrakis (triphenylphosphine) palladium are added, stirred uniformly under nitrogen and at room temperature, and then heated to reflux and reacted overnight. And cooling to room temperature after the reaction is finished. After the solvent was dried by spinning, water was added to the residue, extraction was performed with methylene chloride, and then the residue was washed with saturated brine, and the organic phase was collected, dried over anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and the obtained solid was separated and purified, and dried in vacuo to give 400mg of red solid CQ-DEDOT (yield: 50.2%). Melting point ：261.6～262.9℃.1H NMR(600MHz,CDCl3)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 was dissolved in 1, 4-dioxane, 312mg (0.168 mmol) of 2-tributylstannylthiophene, 1035mg (7.5 mmol) of potassium carbonate, 112mg (0.1 mmol) of tetrakis (triphenylphosphine) palladium were added, stirred uniformly under nitrogen at room temperature, and then heated under reflux to react overnight. And cooling to room temperature after the reaction is finished. After the solvent was dried by spinning, water was added to the residue, extraction was performed with methylene chloride, and then the residue was washed with saturated brine, and the organic phase was collected, dried over anhydrous sodium sulfate, and then the organic solvent was removed under reduced pressure, and the obtained solid was separated and purified, and dried under vacuum to obtain 300mg of green solid CQ-Th (yield: 75%). Melting point ：231.9～233.2℃.1H NMR(400MHz,CDCl3)δ：8.06(d,J＝8.1Hz,1H),7.99(d,J＝8.1Hz,1H),7.87(dd,J1＝3.8,J2＝1.1Hz,1H),7.81(dd,J1＝3.7,J2＝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 characterization of monomer CQ-EDOT
An electrolyte was prepared by dissolving 0.774g TBAPF 6 in 20mL of propylene carbonate. A monomer solution (1 mmol/L) was prepared by dissolving monomer CQ-EDOT in 10mL of the electrolyte. And (3) carrying out cyclic voltammetry polymerization on the monomer solution at the rate of-0.6-0.8V, wherein the polymerization scanning rate is 0.1V/s, obtaining a polymer film through electrochemical polymerization, and then carrying out dedoping for 60s in the electrolyte at the rate of-0.6V. All subsequent electrochemical tests were performed in the electrolyte.
FIGS. 1-4 are graphs of electrochemical polymerization CV curves based on monomer CQ-EDOT, absorption spectra at different voltages, optical contrast and response time, and cycling stability. The test result shows that the polymer film prepared by the invention has good electrochemical oxidation-reduction property and excellent stability, and can realize reversible color change from blue to transparent under different voltages. The optical contrast at 667nm is 41.7%, the response time of coloring and fading is 0.51s and 0.45s respectively, and the color-changing film has better stability, and the light transmittance is kept to be about 90% after 400 times of circulation.
Claims (6)
1. A D-A monomer based on camphorquinoxaline is characterized in that a camphorgroup has a right-handed structure and has the following chemical formula:
Wherein, -R is:
2. A method for synthesizing a class of camphorquinoxaline-based D-a monomers according to claim 1, comprising the steps of:
(1) Dissolving 4, 7-dibromo-2, 1, 3-benzothiadiazole in absolute ethyl alcohol, adding sodium borohydride for reaction, adding water for quenching, extracting with dichloromethane, drying an organic phase with absolute sodium sulfate, and concentrating under reduced pressure to obtain an intermediate 1;
(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, reacting overnight, cooling to room temperature after the reaction is finished, spin-drying solvent toluene, adding water into the reaction liquid, extracting with dichloromethane, washing with saturated saline, collecting an organic phase, adding anhydrous sodium sulfate for drying, removing the organic solvent under reduced pressure, separating and purifying the obtained solid, and vacuum drying to obtain an intermediate 2;
(3) Dissolving the intermediate 2 in 1, 4-dioxane, adding thiophene tin reagent, potassium carbonate and tetra (triphenylphosphine) palladium, uniformly stirring at room temperature under the protection of nitrogen, heating, reacting overnight, cooling to room temperature after the reaction is finished, spin-drying solvent toluene, adding water into the reaction solution, extracting with dichloromethane, washing with saturated saline water, collecting an organic phase, adding anhydrous sodium sulfate for drying, removing the organic solvent under reduced pressure, separating and purifying the obtained solid, and vacuum drying to obtain a target monomer; wherein the thiophene tin reagent is tributyl (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin-5-yl) stannane.
3. The method for synthesizing camphorquinoxaline-based D-A type monomers according to claim 2, wherein in the step (1), sodium borohydride is excessively added and dropwise added at 0 ℃ at a reaction temperature of 25 ℃ for a reaction time of 10 to 24 hours.
4. The method for synthesizing camphorquinoxaline-based D-A type monomers according to claim 2, wherein in the step (2), the molar ratio of the intermediate 1, (+) -camphorquinone is 1:1, the reaction temperature is 110 ℃, and the reaction time is 6 to 12 hours.
5. The method for synthesizing camphorquinoxaline-based D-A type monomers according to claim 2, wherein 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 h.
6. Use of an electrochemical polymer of a class of camphorquinoxaline based D-a monomers in electrochromic devices according to claim 1, wherein the electrochemical polymer is prepared by:
Dissolving a monomer shown in a formula (I) in a propylene carbonate solvent, taking tetrabutylammonium hexafluorophosphate as an electrolyte, adopting cyclic voltammetry polymerization of-0.6-0.8V, wherein the polymerization sweeping speed is 0.1V/s, the cycle number is 10-30, and obtaining a polymer film after electrochemical polymerization; 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, the indium tin oxide 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 the monomer is polymerized into a film and deposited on the surface of the indium tin oxide.
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