CN115417976A - Hydrophilic red to transparent electrochromic polymer and preparation method and application thereof - Google Patents
Hydrophilic red to transparent electrochromic polymer and preparation method and application thereof Download PDFInfo
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- CN115417976A CN115417976A CN202211139949.0A CN202211139949A CN115417976A CN 115417976 A CN115417976 A CN 115417976A CN 202211139949 A CN202211139949 A CN 202211139949A CN 115417976 A CN115417976 A CN 115417976A
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- electrochromic
- transparent
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- 229920000642 polymer Polymers 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims description 10
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 238000000944 Soxhlet extraction Methods 0.000 claims description 3
- 239000002026 chloroform extract Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 239000011630 iodine Chemical group 0.000 claims description 3
- 229910052740 iodine Chemical group 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical group [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 238000006254 arylation reaction Methods 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- MBHINSULENHCMF-UHFFFAOYSA-N n,n-dimethylpropanamide Chemical compound CCC(=O)N(C)C MBHINSULENHCMF-UHFFFAOYSA-N 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 230000005684 electric field Effects 0.000 abstract description 5
- 230000004044 response Effects 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 18
- 229920006254 polymer film Polymers 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 229920001940 conductive polymer Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 3
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 2
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 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 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- RGYLAOMELFKDOL-UHFFFAOYSA-N 2-(2-bromo-3h-thiophen-2-yl)thiophene Chemical compound C=1C=CSC=1C1(Br)CC=CS1 RGYLAOMELFKDOL-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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- MSQDISSCKRBJAN-UHFFFAOYSA-N OC(C(C=C1)=CC=C1C(OCC(Br)Br)=O)=O Chemical compound OC(C(C=C1)=CC=C1C(OCC(Br)Br)=O)=O MSQDISSCKRBJAN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- MKCDXXDWWZVCJG-UHFFFAOYSA-M lithium;4-methyl-1,3-dioxolan-2-one;perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O.CC1COC(=O)O1 MKCDXXDWWZVCJG-UHFFFAOYSA-M 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- BYQADQLDVPAGSR-UHFFFAOYSA-N toluene;hydrobromide Chemical compound Br.CC1=CC=CC=C1 BYQADQLDVPAGSR-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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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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- C08G2261/30—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
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
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- C08G2261/54—Physical properties electrochromatic
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- C08G2261/95—Use in organic luminescent diodes
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Abstract
The invention relates to a hydrophilic red to transparent electrochromic polymer, which has the following structural formula:
wherein n is the degree of polymerization, and is a natural number of 8-100; r1 and R2 are independently straight-chain ether with 3-10 carbons, and the number of oxygen atoms is 2-10. The film formed by the polymer can realize the contrast from red to transparent under the action of an applied electric field>50% color switching, quick response, good stability, almost no contrast attenuation after changing color for hundreds of times; the polymer can be dissolved in an organic solvent, and is beneficial to process treatment and application. The contact angle between the film formed by the polymer and water is less than 40 degrees, the hydrophilicity is good, the large-area film formation on the conductive substrate is easy,and the bonding with the substrate surface is firm.
Description
Technical Field
The invention relates to the technical field of electrochromic polymers, in particular to a hydrophilic red to transparent electrochromic polymer and a preparation method and application thereof.
Background
The principle of the electrochromic material is that reversible redox reaction can occur under the action of an external electric field, changes of appearance color and infrared characteristics are shown, and the electrochromic material has wide application prospects in the fields of intelligent windows, military camouflage and the like. Compared with inorganic electrochromic materials, viologen micromolecule electrochromic materials and the like, the conductive polymer serving as one of the electrochromic materials has the advantages of rich color conversion, high response speed, high stability and the like, and therefore, the conductive polymer becomes a hotspot for research and application in the electrochromic field. However, the conductive polymer-based electrochromic film is mainly prepared by an electrodeposition method, so that the large-area stable preparation of the conductive polymer-based electrochromic film has a great problem, and the deposited film can hardly be dissolved and cannot be further treated, so that the application of the conductive polymer-based electrochromic film is greatly limited.
To achieve solubility of the conductive polymer, the most common method is to introduce a long chain alkyl group that achieves dissolution of the polymer in an oily solvent such as toluene, chloroform, etc. and a carboxylate group that dissolves the polymer in an aqueous solvent system. Because the polymer performance of the aqueous system is relatively poor and the aqueous system is easy to react with the electrolyte system, the currently studied soluble polymer is still mainly oily and mainly focuses on the polypropylene dioxythiophene (ProDOT) system, and other systems are relatively less studied and applied. In addition, in order to realize the red-to-transparent conversion of one of the three primary colors, the conductive polymer generally needs a higher band gap, and the currently common dioxythiophene units all have a lower energy band range, so that the realization of the red electrochromic material has certain difficulty, and the partially realized red-to-transparent conversion electrochromic material also has the problems of insufficient stability and the like. Therefore, the development of novel solution processable, excellent and stable red to transparent electrochromic polymers remains a difficult problem to be solved in the electrochromic field.
Disclosure of Invention
Technical problem to be solved
In view of the problems in the prior art, the invention provides a novel red to transparent electrochromic polymer which is soluble in solution, excellent in performance and better in hydrophilicity, can realize high-contrast color conversion from red to transparent under the action of an external electric field, is quick in response and good in stability, and hardly has contrast attenuation after being stably discolored for hundreds of times; the polymer can also be dissolved in an organic solvent, which is beneficial to further process treatment and application. The contact angle of a film formed by the polymer and water is less than 40 degrees, the film has better hydrophilicity, is easier to form a large-area film on a conductive substrate, and is firmly combined with the substrate. The invention also relates to a preparation method and application of the polymer.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
in a first aspect, the present invention provides a hydrophilic red to transparent electrochromic polymer having the following structural formula:
wherein n represents polymerization degree, and is a natural number of 8-100; r1 and R2 are independently linear ethers of 3 to 10 carbons, and wherein the number of oxygen atoms is 2 to 10.
In a second aspect, the present invention provides a method for preparing a red to transparent electrochromic polymer represented by formula a, the method comprising: taking a compound shown as a formula C and a compound shown as a formula B as synthetic monomers, adding the synthetic monomers into an organic solvent, adding an organic acid, a weak base and a palladium catalyst into the organic solvent, and heating under the protection of inert gas to perform arylation coupling polymerization reaction to prepare a red to transparent electrochromic polymer shown as a formula A;
the reaction process is as follows:
wherein n represents polymerization degree, and n is a natural number of 8-100; r is bromine, chlorine or iodine; r1 and R2 are independently a linear ether group of 3 to 10 carbons, and wherein the number of oxygen atoms is 2 to 10. The structures of R1 and R2 do not influence the color change performance of the polymer shown in the formula A, and preferably, R1 and R2 are the same and are- (OCH) 2 ) 4 -CH 3 。
According to a preferred embodiment of the present invention, wherein the organic acid is pivalic acid or tert-decanoic acid; the inorganic weak base is potassium carbonate, cesium carbonate or potassium acetate; the palladium catalyst is palladium acetate.
According to a preferred embodiment of the present invention, the organic solvent is N, N-dimethylacetamide or N, N-dimethylpropionamide.
According to a preferred embodiment of the present invention, wherein the molar ratio of the compound represented by the formula C to the compound represented by the formula B is controlled to 1.
According to a preferred embodiment of the present invention, wherein the molar ratio of the weak inorganic base to the compound represented by formula B is 2 to 4; the molar ratio of the organic acid to the compound shown in the formula B is 0.08-0.2; the molar ratio of the palladium catalyst to the compound represented by the formula B is 0.03-0.05.
According to the preferred embodiment of the present invention, the reaction is carried out by heating to 120-140 ℃ for 36-72h.
According to the preferred embodiment of the present invention, after the reaction is completed, the reaction solution is cooled to room temperature, the reaction solution is dropped into cold methanol for precipitation, and the precipitate is dried and filtered; and performing Soxhlet extraction with methanol, n-hexane and chloroform respectively, concentrating the chloroform extract, dripping into cold methanol for precipitation, filtering and drying to obtain the red to transparent electrochromic polymer shown in the formula A.
In a third aspect, the invention also relates to the application of the red to transparent electrochromic polymer shown in the formula A in the preparation of electrochromic films and electrochromic devices.
According to a preferred embodiment of the present invention, the electrochromic film is prepared by dissolving the red to transparent electrochromic polymer represented by formula a in an organic solvent to form a solution or slurry, and then coating the solution or slurry on the surface of a conductive substrate or the surface of a smooth plate body and drying. Among them, toluene or dichloromethane can be used as the organic solvent.
According to a preferred embodiment of the present invention, the electrochromic device includes an upper electrode layer, an electrolyte layer, an electrochromic film and a lower electrode layer, which are sequentially stacked, the electrochromic film being a film formed of a red to transparent electrochromic polymer represented by formula a.
(III) advantageous effects
The invention has the beneficial effects that:
the invention takes 2, 5-dibromo-3, 4-propylenedioxythiophene (compound shown in formula C) substituted by linear chain ether and molecules with the structure shown in formula B as synthetic monomers, introduces dioxythiophene as an embedding unit into the main chain structure of the polymer shown in formula A, and combines stronger electron-donating side chain groups in dioxythiophene by utilizing steric hindrance caused by the structure shown in formula B and an electron-withdrawing effect of an internal benzene ring of the polymer, so that the molecular absorption of the polymer is positioned in a blue light region to show red; the long-chain alkyl group is introduced into the molecular structure shown in the formula B, so that the interaction between molecules is weakened, the polymer can be dissolved in organic solvents such as toluene, dichloromethane and the like, the soluble liquefaction treatment of the polymer is facilitated, and the application processes such as the preparation of large-area electrochromic films and the like are facilitated, for example, the film forming is realized by adopting a spraying or blade coating mode. The linear ethers R1 and R2 in the compound shown in the formula C have a large number of oxygen atoms, so that the surface tension of the polymer after film formation is obviously increased, the contact angle with water is small, better hydrophilicity is shown, large-area film formation is easier on a conductive substrate, and the bonding firmness with the conductive substrate is high.
Experiments prove that the red-to-transparent electrochromic polymer shown in the formula A prepared by the invention can realize the conversion from red to transparent states with high contrast by spraying or blade coating film after being dissolved in an organic solvent to prepare solution or slurry, has the characteristics of low driving voltage, high response rate, high stability and the like, and is suitable for manufacturing electrochromic devices. Through tests, the applied step potentials of the polymer film are 0V and 1.2V, the voltage residence time is 5s and 40s respectively, the transmittance contrast is 62%, and the coloring time and the fading time are about 1.1s and 6.6s respectively; the electrochemical stability of the polymer is tested, and the good stability is still kept after 500 square wave potential scans, which indicates that the polymer has good stability.
Drawings
FIG. 1 is a molecular structural formula of a red to transparent electrochromic polymer shown in formula A.
FIG. 2 is a nuclear magnetic hydrogen spectrum of a red to transparent electrochromic polymer shown in formula A.
FIG. 3 is a graph showing the molecular weight and distribution of the polymer represented by the formula A measured by gel permeation chromatography, with reference sample being polystyrene, solvent being tetrahydrofuran, and the ordinate being the detected intensity and the abscissa being the retention time.
FIG. 4 is a plot of the spectral absorption of the red to transparent electrochromic polymer of formula A dissolved in chloroform.
FIG. 5 is a photograph of the spectral transmittance curve and color change before and after the color change of the red to transparent electrochromic polymer film shown in formula A.
Fig. 6 is a cyclic voltammogram of the red to transparent electrochromic polymer film shown in formula a.
Fig. 7 is a square wave potential cycling curve for the red to transparent electrochromic polymer film shown in formula a.
Fig. 8 is a photograph of the contact angle of the red to transparent electrochromic polymer film shown in formula a with water.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
Example 1
This example is a method of synthesizing a polymer having the structure shown in formula A:
(1) The synthesis of the molecule of formula B is as follows:
adding 2-bromothiophene, magnesium powder and iodine into tetrahydrofuran, adding zinc chloride, reacting for 4 hours at 0 ℃ to prepare a 2-zinc chloride bithiophene intermediate product, mixing the intermediate product with dibromoethyl terephthalate, and reacting for 12 hours at 10-20 ℃ in tetrahydrofuran by taking tetrakis (triphenylphosphine) palladium as a catalyst to prepare the dibenzothiophene ethyl terephthalate; mixing the ethyl dithienyl terephthalate and 1-magnesium bromide-4-methylbenzene, and introducing HCl into acetic acid to react to prepare the molecule shown in the formula B.
See Chan, s. -h during the reaction; chen, C. -P.; chao, t. -c.; ting, c.; ko, b. — t. macromolecules 2008,41,5519. Only when the reaction material 2-bromothiophene in the reaction process described in this document is replaced by 2-bromobithiophene, the corresponding product TPT described in this document becomes the compound represented by formula B required in the present invention, and is used as a compound monomer for synthesizing the polymer of formula A of the present invention.
(2) Synthesis of target Polymer having Structure represented by formula A
Placing 0.1mmol of 2, 5-dibromo-3, 4-propylenedioxythiophene with the structure as shown in the specification, 0.1mmol of molecules shown in a formula B, 0.004mmol of palladium acetate, 0.25mmol of potassium carbonate and 0.01mmol of pivalic acid in a 25mL double-neck bottle, pumping gas, injecting nitrogen, injecting 15mL of anhydrous N, N-Dimethylacetamide (DMAC), pumping gas, filling nitrogen, heating to 140 ℃, reacting for 48 hours, cooling to room temperature after the reaction is finished, dropping the reaction liquid into cold methanol for precipitation, filtering the precipitate, and drying; and then respectively carrying out Soxhlet extraction by using methanol, n-hexane and chloroform, wherein the extraction time is 24h each time, concentrating the chloroform extract to 15mL, then dripping into cold methanol to precipitate to obtain a red solid, filtering and drying to obtain the target polymer with the structure shown in the formula A.
Wherein, the specific structure of the linear ether branched chain on the 2, 5-dibromo-3, 4-propylenedioxythiophene can be introduced in a customized manner through the ether exchange reaction step in the process of synthesizing the 3, 4-propylenedioxythiophene, for example, the branched chain structure introduced in the embodiment is- (OCH) 2 ) 4 -CH 3 。
FIG. 1 is a schematic diagram showing the molecular structure of the target polymer prepared in this example. The NMR spectrum of the target polymer is shown in FIG. 2. As shown in FIG. 3, the molecular weight and the distribution of the target polymer having the structure represented by formula A are measured by gel permeation chromatography, the reference sample is polystyrene, the solvent is tetrahydrofuran, the ordinate of the graph is the detected intensity, and the abscissa of the graph is the retention time. The molecular weight of the polymer of formula a was measured to be Mn 20044 daltons, mw 57626 daltons, and PDI 2.87498.
The polymer having the structure shown in formula a prepared in this example was subjected to solution spectroscopic measurement: dissolving the polymer with the structure shown in the formula A in chloroform to prepare the polymer with the concentration of 1 × 10 -4 The absorption curve of the solution of mg/mL is shown in FIG. 4, the absorption peaks of the polymers are respectively at 546nm, and the polymer solution is red.
Example 2
This example is the formation of a polymer film using a molecule of formula a:
the polymer with the structure shown in the formula A and prepared in example 1 is dissolved in toluene to prepare 4mg/mL solution, insoluble substances are filtered out through a filter tip, the solution is placed in a spray gun, the air pressure is controlled to be 2MPa, spraying is carried out on conductive glass, the absorbance of a film is about 1.0, and the sprayed solution is placed in a vacuum drying oven to be dried in vacuum at 40 ℃ for later use.
Polymer film Performance testing
The following tests were carried out using a three-electrode system with a polymer film as the working electrode, a platinum wire as the counter electrode, and a calibrated silver wire as the reference electrode, and a lithium perchlorate propylene carbonate solution with a supporting electrolyte of 0.1 mol/L:
(1) Testing the spectroelectrochemical performance of the polymer film under different voltages
The transmittance spectra and photographs of the polymer film before and after discoloration are shown in FIG. 5. As can be seen from the figure, the polymer film formed by the molecules shown in the formula A has obvious electrochromic performance, the film displays red (neutral state) before an electric field is applied, the film is transparent (oxidation state) after the electric field is applied, and the film can display a high-contrast red to transparent change range, particularly the film is almost completely transparent in a fading state, and the transmittance contrast is higher than 50%.
(2) The initial redox voltage of the electrochromic polymer was measured by cyclic voltammetry as shown in fig. 6, and the initial oxidation potential of the polymer film formed by the molecule of formula a was 0.63V.
(3) Step method for testing spectral response and stability of copolymer film
As shown in fig. 7, the polymer film was applied with step potentials of 0V and 1.2V, voltage dwell times of 5s and 40s, respectively, transmittance contrast of 62%, and coloration and discoloration times of about 1.1s and 6.6s, respectively. The electrochemical stability of the polymer is tested, and the polymer still keeps good stability after being scanned for 500 times by square wave potential.
(4) Testing of the surface affinity of electrochromic polymers: the contact angle of the surface of the polymer film formed by the molecules shown in formula A with water is measured, as shown in FIG. 8, to be about 34.6 degrees and less than 40 degrees, which indicates that the polymer film formed by the molecules shown in formula A has good hydrophilicity. The hydrophilicity is mainly brought about by the large number of oxygen atoms contained in the linear ether branches of the propylenedioxythiophene. The branched chain does not influence the color-changing performance of the polymer and the thin film thereof, and simultaneously, due to the existence of a large number of oxygen atoms, hydrogen bond combination is easy to form between the branched chain and other materials, and the polarity of the soluble electrochromic polymer can be effectively improved, so that the branched chain is easier to form a film on a conductive substrate in a large area, and is more beneficial to the injection and extraction of doped ions.
The tests show that the electrochromic polymer with the structure shown in the formula A can realize conversion from red to transparent, has the characteristics of high contrast, low driving potential, high color change rate, high coloring efficiency, good stability and the like, can make up the problem of insufficient varieties of the conventional red high-performance electrochromic materials, and can be applied to the fields of electrochromic display, self-adaptive camouflage and the like; meanwhile, the conductive film has better hydrophilicity and certain polarity, so that a large-area film is more easily formed on the conductive substrate, and the conductive film can be firmly combined with the conductive substrate.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A hydrophilic red to transparent electrochromic polymer characterized by the structural formula:
wherein n represents polymerization degree, and n is a natural number of 8-100; r1 and R2 are independently linear ethers of 3 to 10 carbons, and wherein the number of oxygen atoms is 2 to 10.
2. A preparation method of a red to transparent electrochromic polymer shown as a formula A is characterized by comprising the following steps: taking a compound shown as a formula C and a compound shown as a formula B as synthetic monomers, adding the synthetic monomers into an organic solvent, adding an organic acid, a weak base and a palladium catalyst into the organic solvent, and heating under the protection of inert gas to perform arylation coupling polymerization reaction to prepare a red to transparent electrochromic polymer shown as a formula A;
the reaction process is as follows:
wherein n represents polymerization degree, and n is a natural number of 8-100; r is bromine, chlorine or iodine; r1 and R2 are independently a linear ether group of 3 to 10 carbons, and wherein the number of oxygen atoms is 2 to 10.
3. The method according to claim 2, wherein in the compound of formula C, R1 and R2 are the same and are- (OCH) 2 ) 4 -CH 3 。
4. The method according to claim 2, wherein the organic acid is pivalic acid or tert-decanoic acid; the inorganic weak base is potassium carbonate, cesium carbonate or potassium acetate; the palladium catalyst is palladium acetate; the organic solvent is N, N-dimethylacetamide or N, N-dimethylpropionamide.
5. The production method according to claim 2, wherein the molar ratio of the compound represented by the formula C to the compound represented by the formula B is controlled to 1.
6. The preparation method according to claim 2, wherein the molar ratio of the inorganic weak base to the compound represented by formula B is 2 to 4; the molar ratio of the organic acid to the compound shown in the formula B is 0.08-0.2; the molar ratio of the palladium catalyst to the compound represented by the formula B is 0.03-0.05.
7. The method of claim 2, wherein the reaction is carried out by heating to 120-140 ℃ for 36-72h.
8. The process according to claim 2, wherein the reaction mixture is cooled to room temperature after the completion of the reaction, and the reaction mixture is dropped into cold methanol to precipitate, and the precipitate is dried and filtered; and then respectively carrying out Soxhlet extraction by using methanol, n-hexane and chloroform, concentrating the chloroform extract, dripping into cold methanol for precipitation, filtering and drying to obtain the red to transparent electrochromic polymer shown in the formula A.
9. Use of the red to transparent electrochromic polymer of formula a according to claim 1 for the preparation of electrochromic films and electrochromic devices.
10. The use according to claim 9, wherein the electrochromic film is prepared by dissolving the red to transparent electrochromic polymer shown in formula a in an organic solvent to form a solution or slurry, and then coating the solution or slurry on the surface of a conductive substrate or the surface of a smooth plate body and drying;
the electrochromic device comprises an upper electrode layer, an electrolyte layer, an electrochromic film and a lower electrode layer which are sequentially stacked, wherein the electrochromic film is a film formed by a red to transparent electrochromic polymer shown in a formula A.
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