CN115417976B - 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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- CN115417976B CN115417976B CN202211139949.0A CN202211139949A CN115417976B CN 115417976 B CN115417976 B CN 115417976B CN 202211139949 A CN202211139949 A CN 202211139949A CN 115417976 B CN115417976 B CN 115417976B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims description 11
- 238000000034 method Methods 0.000 claims abstract description 17
- 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 6
- 150000002170 ethers Chemical class 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- 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 7
- 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
- 239000002002 slurry Substances 0.000 claims description 6
- 239000002026 chloroform extract Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001556 precipitation Methods 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
- 239000003792 electrolyte Substances 0.000 claims description 4
- 125000001033 ether group Chemical group 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 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
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 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
- 238000001816 cooling Methods 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
- 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
- 150000007529 inorganic bases Chemical class 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 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
- 230000009471 action Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 17
- 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 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229920001940 conductive polymer Polymers 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 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
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 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
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- IEFPJOMUXITDSC-UHFFFAOYSA-N 1-ethyldibenzothiophene Chemical compound S1C2=CC=CC=C2C2=C1C=CC=C2CC IEFPJOMUXITDSC-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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 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
- 238000013459 approach 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
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005227 gel permeation chromatography 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
- 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test 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
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction 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
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BYQADQLDVPAGSR-UHFFFAOYSA-N toluene;hydrobromide Chemical compound Br.CC1=CC=CC=C1 BYQADQLDVPAGSR-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G61/12—Macromolecular compounds containing atoms other than carbon 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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- C08G2261/00—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
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
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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
- C08G2261/32—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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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/54—Physical properties electrochromatic
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08G2261/95—Use in organic luminescent diodes
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1458—Heterocyclic containing sulfur as the only heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1441—Heterocyclic
- C09K2211/1491—Heterocyclic containing other combinations of heteroatoms
Abstract
The invention relates to a hydrophilic red to transparent electrochromic polymer, which has the following structural formula:wherein n is the polymerization degree, and a natural number of 8-100 is taken; r1 and R2 are independently straight-chain ethers of 3-10 carbons, and the number of oxygen atoms is 2-10. The film formed by the polymer can realize the effect of changing red to transparent and contrast under the action of an external electric field>50% of color is switched, the response is rapid, the stability is good, and little contrast attenuation exists after hundreds of color changes; the polymer can be dissolved in an organic solvent, which is beneficial to process treatment and application. The contact angle between the film formed by the polymer and water is smaller than 40 degrees, the hydrophilicity is good, the film is easy to form a film on a conductive substrate in a large area, and the film is firmly combined with the substrate surface.
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 electrochromic materials is that reversible oxidation-reduction reaction can be generated under the action of an external electric field, and the electrochromic materials show the change of appearance color and infrared characteristics, and have 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 being rich in color transformation, high in response speed, high in stability and the like, and therefore becomes a hot spot for research and application in the electrochromic field. However, in the past, the conductive polymer-based electrochromic film is mainly prepared by adopting an electrodeposition method, so that the conductive polymer-based electrochromic film has a large problem in the aspect of large-area stable preparation, and the deposited film can not be dissolved and cannot be further processed, so that the application of the conductive polymer-based electrochromic film is greatly limited.
To achieve the solubility of the conductive polymer, the most common approach is to introduce long chain alkyl groups that allow dissolution of the polymer in an oily solvent such as toluene, chloroform, etc., and carboxylate groups that allow dissolution of the polymer in an aqueous solvent system. Because the aqueous system has relatively poor polymer performance and is easy to react with the electrolyte system, the currently studied soluble polymer is still mainly oily and mainly concentrated in a polypropylene dioxythiophene system (ProDOT), and other systems have relatively few researches and applications. In addition, in order to realize red-to-transparent conversion of one of the three primary colors, the conductive polymer generally needs a higher band gap, and the current common dioxythiophene units all have a lower energy band range, so that the current dioxythiophene units have a certain difficulty in realizing the red electrochromic material, and the partially realized red-to-transparent conversion electrochromic material also has the problems of insufficient stability and the like. Thus, the development of novel red to transparent electrochromic polymers that are solution processable and excellent and stable in performance remains a problem to be solved in the electrochromic field.
Disclosure of Invention
First, the technical problem to be solved
In view of the problems existing in the prior art, the invention provides a novel red-to-transparent electrochromic polymer which can be processed in a solution, has excellent performance and better hydrophilicity, can realize high contrast color conversion from red to transparent under the action of an external electric field, has rapid response and good stability, and hardly decays contrast after hundreds of stable discoloration; the polymer can be dissolved in an organic solvent, which is beneficial to further process treatment and application. The contact angle between the film formed by the polymer and water is smaller than 40 degrees, the film has better hydrophilicity, and the film is easier to form a film on a conductive substrate in a large area 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 above purpose, the main technical scheme adopted by the invention comprises the following steps:
in a first aspect, the present invention provides a hydrophilic red to transparent electrochromic polymer having the structural formula:
wherein n represents the polymerization degree, and n is a natural number of 8-100; r1 and R2 are independently straight chain 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: the method comprises the steps of adopting a compound shown in a formula C and a compound shown in a formula B as synthetic monomers, adding the synthetic monomers into an organic solvent, adding organic acid, weak base and palladium catalyst into the organic solvent, and heating under the protection of inert gas to perform arylation coupling polymerization reaction to prepare a red-transparent electrochromic polymer shown in a formula A;
the reaction process is as follows:
wherein n represents the polymerization degree, and n is a natural number of 8-100; r is bromine, chlorine or iodine; r1 and R2 are independently straight chain ether groups of 3 to 10 carbons and wherein the number of oxygen atoms is 2 to 10. The structure of R1 and R2 does not affect the color change properties of the polymer of formula A, e.g., R1 and R2 are preferably 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, the molar ratio of the compound represented by formula C to the compound represented by formula B is controlled to be 1:1.
According to a preferred embodiment of the present invention, the molar ratio of the inorganic weak base to the compound represented by formula B is 2-4:1; the molar ratio of the organic acid to the compound shown in the formula B is 0.08-0.2:1; the molar ratio of the palladium catalyst to the compound shown in the formula B is 0.03-0.05:1.
According to a preferred embodiment of the present invention, wherein the reaction is carried out by heating to 120-140℃for 36-72h.
According to the preferred embodiment of the invention, after the reaction is finished, the reaction solution is cooled to room temperature, is dripped into cold methanol for precipitation, and the precipitate is dried and filtered; and respectively carrying out Soxhlet extraction by using methanol, n-hexane and chloroform, concentrating the chloroform extract, dripping the chloroform extract 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 present invention also relates to the use of a red to transparent electrochromic polymer of formula a in the preparation of electrochromic films and electrochromic devices.
According to the preferred embodiment of the invention, the electrochromic film is prepared by dissolving the red to transparent electrochromic polymer shown in the 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 methylene chloride may 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, and the electrochromic film is a film formed of a red to transparent electrochromic polymer represented by formula a.
(III) beneficial effects
The beneficial effects of the invention are as follows:
the invention takes the molecule with straight-chain ether substituted 2, 5-dibromo-3, 4-propylene dioxythiophene (compound shown as formula C) and structure shown as formula B as synthetic monomer, and takes dioxythiophene as an embedding unit to be introduced into the main chain structure of the polymer shown as formula A, the prepared polymer utilizes the steric hindrance caused by the structure shown as formula B and the electron-withdrawing effect of the benzene ring in the polymer, and combines with the stronger electron-donating side chain group in dioxythiophene to enable the molecule of the polymer to be absorbed in a blue light region to display red; because the long-chain alkyl group is introduced into the molecular structure shown in the formula B, the interaction between molecules is weakened, so that the polymer can be dissolved in an organic solvent such as toluene, methylene dichloride and the like, the soluble treatment of the polymer is facilitated, and the preparation of application processes such as a large-area electrochromic film and the like is facilitated, for example, a spraying or blade coating mode is adopted for film formation. The linear chain ether R1 and R2 carried in the compound shown in the formula C has 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, the good hydrophilicity is shown, the film formation on a conductive substrate is easier to realize, and the bonding strength with the conductive substrate is high.
Experiments prove that after the red-to-transparent electrochromic polymer shown in the formula A is dissolved in an organic solvent to prepare a solution or slurry, the solution or slurry is sprayed or knife-coated to form a film, the conversion from red to transparent with high contrast can be realized, and the method has the characteristics of low driving voltage, high response speed, high stability and the like, and is suitable for manufacturing electrochromic devices. Through tests, the applied step potential of the polymer film is 0V and 1.2V, the residence time of the voltage is 5s and 40s respectively, the transmittance contrast ratio is 62%, and the coloring and fading time is about 1.1s and 6.6s respectively; the electrochemical stability of the polymer is tested, and the square wave potential is scanned for 500 times to still keep good stability, so 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 the red to transparent electrochromic polymer of formula A.
FIG. 3 is a graph showing the molecular weight and distribution of the polymer of formula A measured by gel permeation chromatography, wherein the reference sample is polystyrene, the solvent is tetrahydrofuran, and the ordinate indicates the detected intensity and the abscissa indicates the residence time.
FIG. 4 is a spectral absorption curve of the red to transparent electrochromic polymer of formula A dissolved in chloroform.
FIG. 5 is a graph of spectral transmittance curves versus color shift of a red to transparent electrochromic polymer film of formula A before and after discoloration.
FIG. 6 is a cyclic voltammogram of a red to transparent electrochromic polymer film of formula A.
FIG. 7 is a square wave potential cycling curve of a red to transparent electrochromic polymer film of formula A.
Fig. 8 is a photograph of the contact angle of the red to transparent electrochromic polymer film of formula a with water.
Detailed Description
The invention will be better explained by the following detailed description of the embodiments with reference to the drawings.
Example 1
This example is a method of synthesizing a polymer of the structure shown in formula a:
(1) The synthesis method of the molecule shown in the formula B is as follows:
adding 2-bromothiophene, magnesium powder and iodine into tetrahydrofuran, adding zinc chloride, reacting for 4 hours at 0 ℃ to obtain a 2-bromothiophene intermediate product, mixing the intermediate product with ethyl dibromoterephthalate, and reacting for 12 hours at 10-20 ℃ in tetrahydrofuran with tetrakis (triphenylphosphine) palladium as a catalyst to obtain ethyl dibenzothiophene; dibenzothiophene ethyl terephthalate is mixed with 1-magnesium bromide-4 methylbenzene, HCl is introduced into acetic acid, and the molecule shown in the formula B is prepared.
See Chan, s. -h. during the reaction; chen, c. -p.; chao, t. -c.; ting, c.; ko, B. -T.macromolecules 2008,41,5519. The corresponding product TPT described in this document is changed to the compound of formula B required for the present invention, and is used as a monomer for synthesizing the polymer of formula A of the present invention, only by replacing 2-bromothiophene as a reaction raw material in the reaction process described in this document with 2-bromothiophene.
(2) Synthesis of target Polymer of Structure represented by formula A
Placing 0.1mmol of 2, 5-dibromo-3, 4-propylenedioxythiophene with the following structure, 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 into a 25mL double-mouth bottle, pumping and ventilating to inject nitrogen, injecting 15mL of anhydrous N, N-Dimethylacetamide (DMAC), pumping and ventilating to fill nitrogen again, heating to 140 ℃ for 48 hours, cooling to room temperature after the reaction is finished, dripping the reaction liquid into cold methanol for precipitation, and filtering the precipitate for drying; and respectively carrying out Soxhlet extraction with methanol, n-hexane and chloroform for 24 hours, concentrating chloroform extract to 15mL, dripping into cold methanol to precipitate to obtain red solid, filtering and drying to obtain the target polymer with the structure shown in formula A.
Wherein, the specific structure of the straight-chain ether branched chain on the 2, 5-dibromo-3, 4-propylenedioxythiophene can be customized and introduced through the ether exchange reaction step in the process of synthesizing the 3, 4-propylenedioxythiophene, and 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 nuclear magnetic resonance hydrogen spectrum of the target polymer is shown in fig. 2. The molecular weight and distribution diagram of the target polymer of the structure shown in formula A are shown in FIG. 3, wherein the reference sample is polystyrene, the solvent is tetrahydrofuran, the ordinate is the detected intensity, and the abscissa is the residence time. The polymer of formula a was measured to have a molecular weight Mn of 20044 daltons, a Mw of 57626 daltons and a PDI of 2.87498.
The polymer of the structure represented by formula a prepared in this example was subjected to solution spectroscopic testing: dissolving the polymer with the structure shown in the formula A in chloroform to prepare the polymer with the concentration of 1 x 10 -4 mg/mL of solution, the absorption curves of the solutions are shown in FIG. 4, the polymer absorption peaks are located at 546nm, respectively, and the polymer solution appears red.
Example 2
This example is a polymer film formed using a molecule of formula a:
the polymer with the structure shown in the formula A and prepared in the example 1 is dissolved in toluene to prepare a solution with the concentration of 4mg/mL, 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, the solution is sprayed on conductive glass, the absorbance of the film is about 1.0, and the solution is placed in a vacuum drying oven for vacuum drying at the temperature of 40 ℃ for later use after the spraying.
Polymer film Performance test
A three-electrode system with a polymer film as a working electrode, a platinum wire as a counter electrode and a calibrated silver wire as a reference electrode is adopted to support a lithium perchlorate propylene carbonate solution with electrolyte of 0.1mol/L, and the following tests are carried out:
(1) Testing of spectroelectrochemical properties of Polymer films at different voltages
The transmittance spectra and photographs of the polymer films before and after discoloration are shown in FIG. 5. As can be seen from the illustration, the polymer film formed by the molecules shown in the formula A has obvious electrochromic performance, the film shows red color (neutral state) before an electric field is applied, the film shows transparent (oxidized state) after the electric field is applied, and the film can show a high-contrast red-to-transparent change range, especially almost completely transparent in a fading state, and the transmittance contrast is higher than 50%.
(2) The initial redox voltage of 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) Testing spectral response and stability of copolymer film by step method
As shown in FIG. 7, the polymer films were applied at step potentials of 0V and 1.2V, dwell times of 5s and 40s, respectively, transmittance contrast ratio of 62%, and coloring and fading times of about 1.1s and 6.6s, respectively. The electrochemical stability of the polymer is tested, and the polymer still maintains good stability after 500 times of square wave potential scanning.
(4) The electrochromic polymers were tested for surface affinity: the contact angle of the surface of the polymer film formed by the molecule shown in the test formula A with water is about 34.6 degrees and less than 40 degrees as shown in FIG. 8, which shows that the polymer film formed by the molecule shown in the test formula A has good hydrophilicity. The hydrophilicity is mainly brought about by the large number of oxygen atoms contained in the straight chain ether branches on the propylenedioxythiophene. The branched chain can not only not affect the color-changing performance of the polymer and the film thereof, but also can effectively improve the polarity of the soluble electrochromic polymer due to the existence of a large number of oxygen atoms and the formation of hydrogen bond combination with other materials, thereby being easier to form a film on a conductive substrate in a large area and being more beneficial to the injection and extraction of doped ions.
As can be seen from the above test, the electrochromic polymer with the structure shown in the formula A prepared by the invention can realize the 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 types of the existing red high-performance electrochromic materials, and can be applied to the fields of electrochromic display, self-adaptive camouflage and the like; meanwhile, the film has good hydrophilicity and certain polarity, so that the film is easier to form a film on a conductive substrate in a large area, and the film can be firmly combined with the conductive substrate.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A hydrophilic red to transparent electrochromic polymer characterized by the following structural formula:
wherein n represents the polymerization degree, and n is a natural number of 8-100; r1 and R2 are independently straight chain ethers of 3 to 10 carbons and wherein the number of oxygen atoms is 2 to 10.
2. A method for preparing a red to transparent electrochromic polymer represented by formula a, the method comprising: the method comprises the steps of adopting a compound shown in a formula C and a compound shown in a formula B as synthetic monomers, adding the synthetic monomers into an organic solvent, adding organic acid, weak base and palladium catalyst into the organic solvent, and heating under the protection of inert gas to perform arylation coupling polymerization reaction to prepare a red-transparent electrochromic polymer shown in a formula A;
the reaction process is as follows:
wherein n represents the polymerization degree, and n is a natural number of 8-100; r is bromine, chlorine or iodine; r1 and R2 are independently straight chain ether groups of 3 to 10 carbons and wherein the number of oxygen atoms is 2 to 10.
3. The process 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 t-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 preparation method according to claim 2, wherein the molar ratio of the compound represented by formula C to the compound represented by formula B is controlled to be 1:1.
6. The process according to claim 2, wherein the molar ratio of the weak inorganic base to the compound of formula B is 2-4:1; the molar ratio of the organic acid to the compound shown in the formula B is 0.08-0.2:1; the molar ratio of the palladium catalyst to the compound shown in the formula B is 0.03-0.05:1.
7. The preparation method according to claim 2, wherein the reaction is carried out by heating to 120-140 ℃ for 36-72 hours.
8. The preparation method according to claim 2, wherein after the reaction is completed, cooling to room temperature, dropping the reaction solution into cold methanol for precipitation, drying and filtering the precipitate; and respectively carrying out Soxhlet extraction by using methanol, n-hexane and chloroform, concentrating the chloroform extract, dripping the chloroform extract into cold methanol for precipitation, filtering and drying to obtain the red-to-transparent electrochromic polymer shown in the formula A.
9. Use of a red to transparent electrochromic polymer according to formula a of 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 of 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 formed by red to transparent electrochromic polymers shown in a formula A.
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