CN112500557B - Asymmetric donor-acceptor-donor electrochromic polymer based on 5-fluoro-2, 1, 3-benzothiadiazole and application thereof - Google Patents
Asymmetric donor-acceptor-donor electrochromic polymer based on 5-fluoro-2, 1, 3-benzothiadiazole and application thereof Download PDFInfo
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- CN112500557B CN112500557B CN202011239573.1A CN202011239573A CN112500557B CN 112500557 B CN112500557 B CN 112500557B CN 202011239573 A CN202011239573 A CN 202011239573A CN 112500557 B CN112500557 B CN 112500557B
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- benzothiadiazole
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- LNZHAYNBUMVVBK-UHFFFAOYSA-N 5-fluoro-2,1,3-benzothiadiazole Chemical compound C1=C(F)C=CC2=NSN=C21 LNZHAYNBUMVVBK-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229920000642 polymer Polymers 0.000 title abstract description 17
- 229920000547 conjugated polymer Polymers 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- JZIQWUZLPXCCIO-UHFFFAOYSA-N 4,6-dibromo-5-fluoro-2,1,3-benzothiadiazole Chemical compound BrC=1C(=C(C=2C(=NSN2)C1)Br)F JZIQWUZLPXCCIO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- 239000003792 electrolyte Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000004528 spin coating Methods 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- BHFHVALJBJOMHY-UHFFFAOYSA-N 3,6-dibromo-4-fluorobenzene-1,2-diamine Chemical compound NC1=C(C(=C(C=C1Br)F)Br)N BHFHVALJBJOMHY-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- KWEWNOOZQVJONF-UHFFFAOYSA-N 4-fluorobenzene-1,2-diamine Chemical compound NC1=CC=C(F)C=C1N KWEWNOOZQVJONF-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- ARRNBPCNZJXHRJ-UHFFFAOYSA-M hydron;tetrabutylazanium;phosphate Chemical compound OP(O)([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC ARRNBPCNZJXHRJ-UHFFFAOYSA-M 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 238000010898 silica gel chromatography Methods 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- HFRXJVQOXRXOPP-UHFFFAOYSA-N thionyl bromide Chemical compound BrS(Br)=O HFRXJVQOXRXOPP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims 4
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims 4
- 239000012295 chemical reaction liquid Substances 0.000 claims 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000012544 monitoring process Methods 0.000 claims 1
- 230000002787 reinforcement Effects 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 12
- 239000000178 monomer Substances 0.000 abstract description 4
- 238000006619 Stille reaction Methods 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 239000002346 layers by function Substances 0.000 abstract description 2
- 229910001134 stannide Inorganic materials 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 29
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 10
- 230000008859 change Effects 0.000 description 7
- 229920006254 polymer film Polymers 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000004040 coloring Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 230000003446 memory effect Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- -1 stannum compound Chemical class 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- PQGZUSUHCOKSPC-UHFFFAOYSA-E C(CCC)[N+](CCCC)(CCCC)CCCC.P(=O)([O-])([O-])[O-].[F-].[F-].[F-].[F-].[F-].[F-].C(CCC)[N+](CCCC)(CCCC)CCCC.C(CCC)[N+](CCCC)(CCCC)CCCC.C(CCC)[N+](CCCC)(CCCC)CCCC.C(CCC)[N+](CCCC)(CCCC)CCCC.C(CCC)[N+](CCCC)(CCCC)CCCC.C(CCC)[N+](CCCC)(CCCC)CCCC.C(CCC)[N+](CCCC)(CCCC)CCCC.C(CCC)[N+](CCCC)(CCCC)CCCC Chemical compound C(CCC)[N+](CCCC)(CCCC)CCCC.P(=O)([O-])([O-])[O-].[F-].[F-].[F-].[F-].[F-].[F-].C(CCC)[N+](CCCC)(CCCC)CCCC.C(CCC)[N+](CCCC)(CCCC)CCCC.C(CCC)[N+](CCCC)(CCCC)CCCC.C(CCC)[N+](CCCC)(CCCC)CCCC.C(CCC)[N+](CCCC)(CCCC)CCCC.C(CCC)[N+](CCCC)(CCCC)CCCC.C(CCC)[N+](CCCC)(CCCC)CCCC.C(CCC)[N+](CCCC)(CCCC)CCCC PQGZUSUHCOKSPC-UHFFFAOYSA-E 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 1
- PRUZLONTUGFDMT-UHFFFAOYSA-N 2,3-dihydroselenopheno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=C[se]C=C21 PRUZLONTUGFDMT-UHFFFAOYSA-N 0.000 description 1
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- WNOOCRQGKGWSJE-UHFFFAOYSA-N 3,4-dihydro-2h-thieno[3,4-b][1,4]dioxepine Chemical compound O1CCCOC2=CSC=C21 WNOOCRQGKGWSJE-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- MABNMNVCOAICNO-UHFFFAOYSA-N selenophene Chemical compound C=1C=C[se]C=1 MABNMNVCOAICNO-UHFFFAOYSA-N 0.000 description 1
- UTUZBCDXWYMYGA-UHFFFAOYSA-N silafluorene Chemical compound C12=CC=CC=C2CC2=C1C=CC=[Si]2 UTUZBCDXWYMYGA-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical compound C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
- G02F1/15165—Polymers
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
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- C08G2261/146—Side-chains containing halogens
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3246—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing nitrogen and sulfur as heteroatoms
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- C08G2261/50—Physical properties
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Abstract
The invention discloses an asymmetric donor-acceptor-donor conjugated polymer based on 5-fluoro-2, 1, 3-benzothiadiazole and application thereof in the electrochromic field. The structural formula of the 5-fluoro-2, 1, 3-benzothiadiazole-based asymmetric donor-acceptor-donor conjugated polymer is shown as follows, and a polymer precursor is obtained by mixing dibromo 5-fluoro-2, 1, 3-benzothiadiazole monomer and Ar stannide and performing Stille reaction, and the polymer precursor is obtained by an electrochemical polymerization method. The conjugated polymer has high intermolecular binding energy and large dipole moment due to the introduction of the asymmetric structure 5-fluoro-2, 1, 3-benzothiadiazole, which is favorable for enhancing interaction of a donor/acceptor, thereby improving optical contrast and color development efficiency of electrochromic, being an excellent electrochromic functional layer, and the constructed flexible electrochromic device has high mechanical stability.
Description
Technical Field
The invention relates to the technical field of organic photoelectricity, in particular to design synthesis of an asymmetric donor-acceptor-donor type polymer based on 5-fluoro-2, 1, 3-benzothiadiazole and application thereof in electrochromic.
Background
Electrochromic materials are characterized in that the doping degree of the electrochromic materials can be regulated and controlled by changing the applied voltage applied to the materials, so that the energy band structure of the materials is changed, the optical absorption performance of the electrochromic materials is changed, and the electrochromic materials are visually represented as the change of the color of thin films of the materials. As the degree of doping (oxidation) increases, electrochromic materials can form polarons and dual-polarized energy levels with lower band gaps between the valence and conduction bands, and the formation of these new energy levels changes the energy required during valence electron transitions, which then appear spectroelectrochemically as changes in absorption peaks. The material has commercialized prospect in various fields such as low-energy display devices, electronic paper, color-changing skin, information storage display and the like, and can be used for updating and functional integration of various wearable electronic equipment.
The evaluation of electrochromic material performance is one of the most important problems, and scientific researchers evaluate electrochromic performance by using the following parameters and indexes:
(1) Optical contrast: (Electrochromic contrast, deltat) optical transmittance (T) between the oxidized (oxidized) and Neutral (Neutral) states of electrochromic materials at a single wavelength ox And T neut . ) The difference is one of important parameters for measuring electrochromic properties of materials. The wavelength is determined according to the absorption spectrum of the material (multiple wavelengths may occur in the same material), that is, the wavelength corresponding to the maximum absorption peak of the material in the oxidized state or the neutral state. The absorption spectrum of the material refers to an absorbance or transmittance curve corresponding to the material under different wavelengths, and the color change of the material is measured by the absorbance of the absorption spectrum.
(2) Coloring efficiency: (CE) refers to the ratio between the change in absorbance per unit area of a conductive polymer film when the conductive polymer film is injected with a certain amount of electricity at a specific wavelength and the charge density of the transmittance conversion that occurs. In general, the values of the coloring efficiency of the same polymer film are constant during oxidation or reduction, irrespective of the thickness of the film. The coloring efficiency calculation formula is:
CE＝ΔOD/Qd ΔOD＝log(T ox /T ref )
wherein DeltaOD is the optical density variation, which means that the polymer film has a specific wavelength lambda max The ratio of the transmittance in the oxidation state to the transmittance in the reduction state; q (Q) d The charge density refers to the amount of charge injected per unit area.
(3) Response time: the (Switchingtime) electrochromic material or device takes the time to complete an oxidation (colored state) or reduction (faded state) conversion process, which corresponds to a colored response time, and a reduction (faded) process, which corresponds to a faded response time. Response time is generally calculated using the time required for a 95% change in transmittance, and the factors affecting conversion time are mainly: the composition of the cell (acid-base nature of the solvent, ion-conducting ability of the supporting electrolyte), the voltage applied during redox, the ease of diffusion of ions in the electrochromic material, etc.
(4) Open optical memory effect: (Open circuit memory) refers to the ability of an electrochromic material to retain an oxidized or reduced state color of the polymer in the absence of an applied external voltage, and is operable to test the optical transmission of the polymer under an applied external pressure for a period of time, and then to switch off the external pressure to test the optical transmission, the change being the memory of the material or device. Related applications have shown that Light Emitting Diodes (LEDs) can maintain displayed content in the event of a power outage. It is worth noting that for electrochromic materials or devices that develop color in solution, the color displayed by the electrochromic materials or devices will fade away quickly due to the ion diffusion or exchange effect, while all-solid electrochromic devices have better memory effect.
The current requirements for electrochromic materials are mainly high optical contrast, high coloring efficiency, short response time, good memory effect, obvious color change, good stability and the like, and the university of Beijing Meng Hong, university of electronic science Gu Chunyang, university of Jiangxi science Xu Jingkun and the like make important contributions in the electrochromic field. Pursuing high-performance electrochromic materials and devices is always an important mission of scientific researchers, and on one hand, the scientific researchers perform performance optimization on the existing invented materials so as to realize performance breakthrough; on the other hand, researchers continue to develop new electrochromic materials in an effort to achieve more efficient, stable electrochromic properties.
In recent years, the use of flexible electronic devices has grown at a remarkable rate, and idtechnex predicts that flexible electronic industry will reach 3010 billion dollars by 2028, which is one of the promising information technologies in the world today. The electrochromic device is used as a component of flexible electronic equipment, and if the device has mechanical properties on the premise of keeping excellent color changing performance, the updating and functional integration of various flexible electronic equipment can be realized. Therefore, the fabrication and practicality of flexible electrochromic devices has become one of the important challenges that needs to be addressed in this field.
Disclosure of Invention
The present invention addresses the deficiencies of the prior art by providing 5-fluoro-2, 1, 3-benzothiadiazole-based asymmetric donor-acceptor-donor electrochromic polymers and their use. The conjugated polymer has asymmetric 5-fluoro-2, 1, 3-benzothiadiazole structure, so that the conjugated polymer has high intermolecular binding energy and large dipole moment, and the interaction between the donor and the acceptor is enhanced, so that the optical contrast and the color development efficiency of electrochromic are improved.
The invention is realized by the following technical scheme:
in a first aspect of the invention there is provided an electrochromic polymer of the 5-fluoro-2, 1, 3-benzothiadiazole-based asymmetric donor-acceptor-donor type having the structure:
wherein Ar is thiophene, furan, selenophene, pyrrole, thiazole, benzene, fluorene, carbazole, silafluorene, benzodithiophene, benzodiselenophene, benzodifuran, bithiophene, furan, thienocyclopentadiene, thienopyrrole, thienothilol, 3, 4-ethylenedioxythiophene, 3, 4-propylenedioxythiophene, 3, 4-ethylenedioxyselenophene, 3, 4-ethylenedithiophene or at least one of the derivatives thereof.
Preferably, ar has at least one of the following structures:
wherein R1 is H, C-50 alkyl straight chain or branched chain; p=1 to 3.
In a second aspect of the present invention, there is provided a method for preparing the above-mentioned 5-fluoro-2, 1, 3-benzothiadiazole-based asymmetric donor-acceptor-donor type electrochromic polymer, comprising the steps of:
(1) Mixing dibromo 5-fluoro-2, 1, 3-benzothiadiazole monomer and stannum compound with Ar structure, and performing Stille reaction to obtain a polymerization precursor of conjugated polymer;
(2) And (3) carrying out electrochemical polymerization on the conjugated polymer precursor obtained in the step (1) to obtain the asymmetric donor-acceptor-donor conjugated polymer based on the 5-fluoro-2, 1, 3-benzothiadiazole.
Preferably, in step (1), the molar ratio of dibromo 5-fluoro-2, 1, 3-benzothiadiazole monomer to stannate having Ar structure is 1:2.
Preferably, in step (1), the Stille reaction is: under the protection of nitrogen, dibromo 5-fluoro-2, 1, 3-benzothiadiazole monomer, stannide with Ar structure and tetra-triphenylphosphine palladium are dissolved in N, N-dimethylformamide, and heated to 100 ℃ and refluxed for 12 hours.
Preferably, in step (2), the electrochemical polymerization is: preparing a polymerization precursor with the concentration of 0.01mol/L by taking refined dichloromethane and acetonitrile as electrolyte, and taking tetrabutylammonium phosphate as electrolyte; stirring uniformly, and keeping the solution to polymerize at a constant potential of 1.2V under the nitrogen atmosphere by taking ITO conductive glass as a working electrode, a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode.
In a third aspect of the invention there is provided the use of a conjugated polymer as described above in the manufacture of a flexible electrochromic device.
In a fourth aspect of the invention, a flexible electrochromic device is provided.
Is prepared by the following method:
(1) Curing toluene solution of Styrene Ethylene Butylene Styrene (SEBS), and carrying out surface activation treatment on the cured SEBS substrate to obtain a flexible substrate;
(2) Spin-coating PEDOT PSS aqueous solution on a flexible substrate at 1500 rpm to obtain a PEDOT PSS/SEBS flexible bottom electrode;
(3) Preparing a solution of an asymmetric donor-acceptor-donor conjugated polymer based on 5-fluoro-2, 1, 3-benzothiadiazole by using low-boiling methylene dichloride, and spin-coating the solution onto a PEDOT (polymer electrolyte oxygen demand) PSS/SEBS flexible bottom electrode at 3000 rpm to obtain an electrochromic layer;
(4) Mixing and stirring sulfuric acid, deionized water and polyvinyl alcohol to obtain a transparent stretchable electrolyte; uniformly coating the electrolyte on the electrochromic layer, and allowing the electrolyte to be in a gelatinous state after the solvent volatilizes;
(5) And spin-coating the PEDOT-PSS aqueous solution on the electrolyte layer at 1500 revolutions per minute to obtain the PEDOT-PSS/SEBS flexible top electrode, and obtaining the flexible electrochromic device.
Preferably, in step (3), the asymmetric donor-acceptor-donor type conjugated polymer based on 5-fluoro-2, 1, 3-benzothiadiazole is formulated with low boiling point dichloromethane into a solution with a concentration of 4 to 6 mg/mL.
Preferably, in the step (4), sulfuric acid, deionized water and polyvinyl alcohol are mixed according to the mass ratio of 5:50: 45.
The beneficial effects of the invention are as follows:
the conjugated polymer of the invention has higher intermolecular binding energy and larger dipole moment due to the introduction of the asymmetric structure 5-fluoro-2, 1, 3-benzothiadiazole, which is beneficial to enhancing interaction of a donor/acceptor, thereby improving optical contrast and color development efficiency of electrochromic, being an excellent electrochromic functional layer, and the constructed flexible electrochromic device has higher mechanical stability.
Drawings
FIG. 1 is a spectroelectrochemical diagram.
FIG. 2 is a kinetic graph.
Fig. 3 is a diagram of a flexible electrochromic device.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the present application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
In order to enable those skilled in the art to more clearly understand the technical solutions of the present application, the technical solutions of the present application will be described in detail below with reference to specific embodiments. If experimental details are not specified in the examples, the conditions are generally conventional or recommended by the reagent company; reagents, consumables, etc. used in the examples described below are commercially available unless otherwise specified.
Example 1
Preparation of 5-fluoro-2, 1, 3-benzothiadiazole-based asymmetric donor-acceptor-donor type conjugated polymer precursor (Structure c, DT48 FBT)
The chemical reaction flow is shown as follows, and specific reaction steps and reaction conditions are as follows:
(1) Preparation of Compound (a)
In a two-necked flask, 3, 4-diamino-1-fluorobenzene (3.47 g,27.5 mmol) was dissolved in 30ml of 48% HBr solution, 8.81g (55.1 mmol) of liquid bromine was slowly added dropwise, and the flask was transferred to an oil bath and heated slowly to 95 ℃. The reaction was carried out overnight and monitored by TLC for reverse reactionThe reaction was cooled to room temperature, the reaction solution was poured into ice water, the reaction solution was neutralized to pH 8-9 with solid sodium carbonate, extracted three times with ethyl acetate (3X 20 mL), the organic phase was washed once with saturated brine, dried over anhydrous magnesium sulfate for 24 hours, filtered and evaporated by rotary evaporation to give a crude product, which was separated by silica gel column chromatography to give 2.66g of brown solid with a yield of 44%. 1 HNMR(400MHz,DMSO-d 6 ,ppm),δ7.42(s,1H),6.05(s,2H),5.16(s,2H).
(2) Preparation of Compound (b)
In a two-necked flask, 2, 5-dibromo-3, 4-diamino-1-fluorobenzene (1.0 g, 3.7 mmol) was added to 15mL of chloroform, and dibromosulfoxide (2.25 g, 18.9 mmol) was slowly added dropwise under nitrogen protection and ice bath conditions, and after the dropwise addition was completed, stirring was continued for 2 hours, and the mixture was transferred to room temperature and stirred for 2 hours, and then heated to 75℃and stirred overnight. TLC monitored the reaction was completed, the reaction system was cooled to room temperature, poured into ice water, saturated aqueous sodium carbonate solution was neutralized to pH 8-9, extracted three times with ethyl acetate (3X 20 mL), the organic phase was washed once with saturated brine, dried over anhydrous sodium sulfate for 24 hours, and rotary distilled to give a crude product, which was separated by column chromatography to give 0.57g of yellow solid with a yield of 52%. 1 H NMR(400MHz,CDCl 3 ,ppm),δ8.45(s,1H)； 13 C NMR(100MHz,DMSO-d 6 ,ppm):155.14,150.16,145.14,136.46,111.69.
(3) Preparation of Compound (c)
Dibromo 5-fluoro-2, 1, 3-benzothiadiazole (0.40 mmol), 2-tributyltin thiophene (0.30 g,0.8 mmol), and catalyst tetra triphenylphosphine palladium (0.028 g,0.04 mmol) were added to a 50mL three-neck flask under nitrogen protection, N-dimethylformamide (20 mL) was stirred well, heated to reflux at 100deg.C for 12h, and TLC monitored for reaction. After the reaction, pouring the product into a proper amount of water, extracting with dichloromethane three times (3×20), merging organic phases, washing with distilled water twice, drying with anhydrous magnesium sulfate for 24 hours, filtering, rotary steaming to obtain a crude product, separating with a silica gel chromatographic column to obtain a red product, and obtaining the yield: 71%. 1 H NMR(400MHz,CDCl 3 ,ppm),δ8.07(d,1H),7.92(d,1H),7.64(d,1H),7.13(d,1H),7.05(d,1H),2.72(m,4H),1.73(m,4H),1.42(m,12H),0.94(m,6H)； 13 C NMR(100MHz,DMSO-d 6 ,ppm):159.73,157.71,153.33,149.58,144.36,143.34,137.52,137.50,132.13,132.09,131.39,131.32,129.68,125.67,125.58,122.84,122.78,122.57,116.58,116.32,111.11,110.99,31.73,31.70,30.56,30.52,30.50,30.41,29.09,29.06,22.66,22.65,14.13。
Example 2
Electrochemical polymerization of 5-fluoro-2, 1, 3-benzothiadiazole asymmetric donor-acceptor-donor conjugated polymer precursors to corresponding polymers
The chemical reaction flow is shown as follows, and specific reaction steps and reaction conditions are as follows:
under the protection of nitrogen, dissolving 5-fluoro-2, 1, 3-benzothiadiazole asymmetric donor-acceptor-donor type conjugated polymer precursor prepared in the example 1 in 5mL of refined dichloromethane, 5mL of acetonitrile serving as electrolyte to prepare a polymerization precursor with the concentration of 0.01mol/L and 0.1mol/L of tetrabutylammonium phosphate hexafluoride serving as electrolyte; stirring uniformly, continuously introducing nitrogen to protect for 20 minutes, keeping the solution under the nitrogen atmosphere, taking ITO conductive glass as a working electrode, taking a platinum sheet as a counter electrode, taking Ag/AgCl as a reference electrode, and depositing on the ITO conductive glass under a constant potential of 1.2V to obtain the 5-fluoro-2, 1, 3-benzothiadiazole asymmetric donor-acceptor-donor conjugated polymer.
Example 3
Use of the Polymer Material obtained in example 2 in the electrochromic field
The following examples illustrate the 5-fluoro-2, 1, 3-benzothiadiazole asymmetric donor-acceptor-donor type conjugated polymers provided by the present invention and their application processes in the electrochromic field, but the present invention is not limited to the examples.
(1) Spectroelectrochemical
Depositing the polymer prepared in the example 2 on ITO conductive glass to form a polymer film, and placing the ITO conductive glass covered with the polymer film in a three-electrode electrolytic cell, wherein the electrolytic cell is provided with acetonitrile solution containing tetrabutylammonium phosphate hexafluoride; wherein the working electrode is ITO conductive glass attached with a polymer film, the counter electrode is a platinum sheet, and the reference electrode is an Ag/AgCl electrode. The electrochemical spectrum of the polymer is obtained by regulating the voltage applied to the working electrode through an electrochemical workstation by utilizing a constant potential method and recording the change trend of the absorption spectrum of the polymer under different voltages by utilizing an ultraviolet-visible spectrometer, wherein the spectrum electrochemical spectrum is shown in figure 1. Three absorption peaks appear in fig. 2, namely a thiophene absorption peak, a pi-pi absorption peak of 5-fluoro-2, 1, 3-benzothiadiazole-thiophene and a polaron absorption peak of a material at 370nm, 550nm and 750nm, respectively, and the intensity of the 550nm absorption peak of the polymer is weakened or even disappeared with increasing voltage, and a new absorption peak generated by polaron absorption appears gradually in the near infrared region. The isosbestic point of the spectrum is about 620nm, which indicates that the polymer can be switched back and forth between the oxidation state and the reduction state without obstruction, and has better oxidation-reduction performance.
(2) Kinetic stability study of Polymer films
And measuring the transmittance of the polymer film in an oxidation state and a reduction state under a specific wavelength by using an ultraviolet-visible spectrophotometer, so as to calculate the optical contrast, influence time and the like. The ultraviolet-visible spectrophotometer records a time-transmittance curve, the electrochemical workstation records a time-current curve, and the coloring efficiency can be calculated according to the two curves. FIG. 2 is a graph showing the dynamic stability study of the 5-fluoro-2, 1, 3-benzothiadiazole asymmetric donor-acceptor-donor type conjugated polymer prepared in example 2 at 550nm with square wave potential interval of 10s. The transmittance value of the polymer was about 14%, and after 100s of scanning, the transmittance was maintained at 10%.
Example 4
Preparation of Flexible electrochromic device Using Polymer Material obtained in example 2 as an example
(1) Pouring toluene solution of SEBS into a flat culture dish for solidification; with ultraviolet-ozone (UV-O) 3 ) And (3) carrying out surface activation treatment on the cured SEBS substrate by using a plasma cleaning machine to obtain the flexible substrate.
(2) Spin-coating the PEDOT PSS aqueous solution on the stretchable substrate SEBS at 1500 revolutions per minute by using a spin coater to obtain the PEDOT PSS/SEBS flexible bottom electrode.
(3) The 5-fluoro-2, 1, 3-benzothiadiazole asymmetric donor-acceptor-donor type conjugated polymer prepared in example 2 was prepared into a solution having a concentration of 5mg/mL with low boiling point methylene chloride and spin-coated onto the polishing plate at 3000 rpm to obtain an electrochromic layer with a small image pattern on the polishing plate.
(4) Sulfuric acid, deionized water and polyvinyl alcohol are mixed according to the mass ratio of 5:50:45 is mixed and stirred to prepare a transparent stretchable electrolyte. And uniformly coating the electrolyte on the electrochromic layer in a vacuum glove box, and volatilizing the solvent until the electrolyte is in a gelatinous state.
(5) And spin-coating the PEDOT-PSS aqueous solution on the electrolyte layer at 1500 revolutions per minute to obtain the PEDOT-PSS/SEBS flexible top electrode, and obtaining the flexible electrochromic device.
The flexible electrochromic device can be bent, has good toughness and can maintain electrochromic performance, so the flexible electrochromic device has high mechanical stability (as shown in figure 3).
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the same, but rather, various modifications and variations may be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.
Claims (1)
1. A flexible electrochromic device comprising a conjugated polymer of the 5-fluoro-2, 1, 3-benzothiadiazole asymmetric donor-acceptor-donor type, characterized in that it is prepared by the following method:
(1) Solidifying the toluene solution of the SEBS, and carrying out surface activation treatment on the solidified SEBS substrate to obtain a flexible substrate;
(2) Spin-coating PEDOT PSS on the flexible substrate obtained in the step (1) in a water-soluble manner to obtain a PEDOT PSS/SEBS flexible bottom electrode;
(3) Preparing a solution of an asymmetric donor-acceptor-donor conjugated polymer based on 5-fluoro-2, 1, 3-benzothiadiazole by using low-boiling methylene dichloride, and spin-coating the solution onto the PEDOT PSS/SEBS flexible bottom electrode obtained in the step (2) to obtain an electrochromic layer; the concentration of the solution is 4-6 mg/mL;
the structural formula of the 5-fluoro-2, 1, 3-benzothiadiazole-based asymmetric donor-acceptor-donor conjugated polymer is as follows:
the 5-fluoro-2, 1, 3-benzothiadiazole-based asymmetric donor-acceptor-donor type conjugated polymer is prepared by the following method:
1) 3, 4-diamino-1-fluorobenzene 3.47g (27.5 mmol) is dissolved in 30mL48% HBr solution in a two-mouth flask, 8.81g (55.1 mmol) liquid bromine is slowly dripped, the flask is transferred into an oil bath pot and is slowly heated to 95 ℃, the reaction is carried out overnight, TLC monitors that the reaction is complete, the reaction system is cooled to room temperature, the reaction liquid is poured into ice water, sodium carbonate is used as a reinforcement until the pH value of the reaction liquid is 8-9, the reaction liquid is extracted three times by ethyl acetate, an organic phase is washed once by saturated saline solution, anhydrous magnesium sulfate is dried for 24h, filtered and steamed by a rotary way to obtain a crude product, and brown solid 2, 5-dibromo-3, 4-diamino-1-fluorobenzene is obtained by silica gel column chromatography;
2) In a two-neck flask, 1.0g of 2, 5-dibromo-3, 4-diamino-1-fluorobenzene is added into 15mL of chloroform, 2.25g of dibromosulfoxide is slowly dripped under the conditions of nitrogen protection and ice bath, stirring is continued for 2h after dripping is finished, the mixture is transferred to room temperature for stirring for 2h, the temperature is raised to 75 ℃ for stirring overnight, TLC monitors that the reaction is finished, the reaction system is cooled to room temperature, the mixture is poured into ice water, saturated sodium carbonate aqueous solution is neutralized to pH 8-9, ethyl acetate is extracted for three times, an organic phase is washed once with saturated saline, anhydrous sodium sulfate is dried for 24h, crude products are obtained by rotary evaporation, and yellow solid dibromo 5-fluoro-2, 1, 3-benzothiadiazole is obtained by column chromatography separation;
3) Under the protection of nitrogen, adding dibromo 5-fluoro-2, 1, 3-benzothiadiazole, 0.30g of 2-tributyltin thiophene and 0.028g of catalyst tetra-triphenylphosphine palladium into a 50mL three-neck flask to ensure that the concentration of the dibromo 5-fluoro-2, 1, 3-benzothiadiazole is 0.40mmol, adding 20mL of N, N-dimethylformamide, stirring uniformly, heating and refluxing at 100 ℃ for 12h, TLC monitoring reaction, pouring the product into proper water after reaction, extracting with dichloromethane for three times to combine organic phases, washing with distilled water for two times, drying with anhydrous magnesium sulfate for 24h, filtering, steaming in a rotating way to obtain a crude product, and separating with a silica gel chromatographic column to obtain a red product 5-fluoro-2, 1, 3-benzothiadiazole asymmetric donor-acceptor-donor type conjugated polymer precursor;
4) Under the protection of nitrogen, dissolving the 5-fluoro-2, 1, 3-benzothiadiazole asymmetric donor-acceptor-donor type conjugated polymer precursor prepared in the step 3) in 5mL of refined dichloromethane, preparing a polymerization precursor solution with the concentration of 0.01mol/L by taking 5mL of acetonitrile as electrolyte, and taking 0.1mol/L of tetrabutylammonium phosphate as electrolyte; stirring uniformly, continuously introducing nitrogen to protect for 20 minutes, keeping the solution under the nitrogen atmosphere, taking ITO conductive glass as a working electrode, taking a platinum sheet as a counter electrode, taking Ag/AgCl as a reference electrode, and depositing on the ITO conductive glass under a constant potential of 1.2V to obtain the 5-fluoro-2, 1, 3-benzothiadiazole asymmetric donor-acceptor-donor conjugated polymer;
(4) Mixing and stirring sulfuric acid, deionized water and polyvinyl alcohol to obtain a transparent stretchable electrolyte; uniformly coating the electrolyte on the electrochromic layer obtained in the step (3), and obtaining an electrolyte layer after the solvent volatilizes and the electrolyte is in a gelatinous state; sulfuric acid, deionized water and polyvinyl alcohol according to the mass ratio of 5:50:45 mixing;
(5) And (3) spin-coating the PEDOT/PSS aqueous solution on the electrolyte layer obtained in the step (4) to obtain the flexible electrochromic device.
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