CN116874747A - Electrochromic polymer, preparation method thereof and electrochromic polymer film - Google Patents
Electrochromic polymer, preparation method thereof and electrochromic polymer film Download PDFInfo
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- CN116874747A CN116874747A CN202310934003.1A CN202310934003A CN116874747A CN 116874747 A CN116874747 A CN 116874747A CN 202310934003 A CN202310934003 A CN 202310934003A CN 116874747 A CN116874747 A CN 116874747A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 85
- 229920006254 polymer film Polymers 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 23
- 230000008859 change Effects 0.000 claims abstract description 9
- 230000002195 synergetic effect Effects 0.000 claims abstract description 6
- 238000006619 Stille reaction Methods 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 36
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 18
- 229930192474 thiophene Natural products 0.000 claims description 18
- -1 2-octyldodecyl Chemical group 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- LYRCQNDYYRPFMF-UHFFFAOYSA-N trimethyltin Chemical compound C[Sn](C)C LYRCQNDYYRPFMF-UHFFFAOYSA-N 0.000 claims description 10
- 125000005605 benzo group Chemical group 0.000 claims description 9
- CWIXJOXWNHWSTJ-UHFFFAOYSA-N thiadiazole;2h-triazole Chemical compound C=1C=NNN=1.C1=CSN=N1 CWIXJOXWNHWSTJ-UHFFFAOYSA-N 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 8
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 6
- 238000000944 Soxhlet extraction Methods 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical compound BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
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- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
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- 230000035484 reaction time Effects 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 description 20
- 229920001577 copolymer Polymers 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
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- 238000000862 absorption spectrum Methods 0.000 description 7
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical compound C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 description 4
- JOWXBGIZDALBJW-UHFFFAOYSA-N 3h-dioxepine Chemical compound C1OOC=CC=C1 JOWXBGIZDALBJW-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000002036 chloroform fraction Substances 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
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- 239000011521 glass Substances 0.000 description 2
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 238000010129 solution processing Methods 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- XSQSDBVMLJNZKU-UHFFFAOYSA-N 9-(bromomethyl)nonadecane Chemical compound CCCCCCCCCCC(CBr)CCCCCCCC XSQSDBVMLJNZKU-UHFFFAOYSA-N 0.000 description 1
- 235000003392 Curcuma domestica Nutrition 0.000 description 1
- 244000008991 Curcuma longa Species 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000003373 curcuma longa Nutrition 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 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
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 235000013976 turmeric 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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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
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- 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
- 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
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- 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
- 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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- 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
- 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
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
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- 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
- 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
- C08G2261/324—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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
Abstract
An electrochromic polymer, a preparation method thereof and an electrochromic polymer film are provided, wherein the electrochromic polymer comprises the following structural formula:R 1 is a linear alkyl group of 6 or more carbons, R 2 The polymer is branched alkyl with more than 8 carbons, R is branched alkyl with more than 20 carbons, n represents the degree of polymerization, the value of n is a natural number between 8 and 100, and the polymer has visible light to near infrared synergetic color change property and is prepared by Stille coupling.
Description
Technical Field
The present invention relates generally to the field of polymer electrochromic technology, and in particular to an electrochromic polymer, a preparation method thereof and an electrochromic polymer film.
Background
The electrochromic material can generate reversible oxidation-reduction reaction under the action of proper external voltage, and realize reversible conversion between a coloring state and a bleaching state, and has important application prospects in various fields such as intelligent windows, non-emission displays and the like. As one of electrochromic materials, the electrochromic polymer has the advantages of designable color, high response speed, high optical contrast, high coloring efficiency and the like. However, few electrochromic polymers have been reported for co-discoloration from visible to near infrared, and therefore, the development of polymers with broad spectral absorption is of great interest in the electrochromic field.
Designing the donor-acceptor polymer structure is an effective means of achieving broad spectral absorption. Firstly, designing an acceptor structure with strong absorption capacity, and connecting an acceptor with low LUMO energy level with a donor to obtain intramolecular charge transfer with ultra-low band gap, so that the absorption spectrum of a polymer is red shifted to a near infrared region; secondly, designing a donor unit in the polymer, and optimizing the shortwave color change performance of the polymer by regulating and controlling pi-pi transition effect directly related to shortwave absorption; finally, according to an optical compensation mechanism, aiming at absorption trough, an absorption unit with corresponding characteristic optics is introduced into a polymer main chain, so as to achieve the effect of cooperative color change from visible light to near infrared.
In recent years, in the field of organic photovoltaics, thiophene [3,2-b ]]The structure of thiophene (TT) has been widely used, and homopolymers of TT derivatives, such as poly (indacenodithieno [3, 2-b)]Thiophene) (PIDTT) has been demonstrated to have a strong and broad absorption spectrum. On the one hand, the unique coplanar 'trapezoid' structure of the IDTT unit effectively increases the delocalization degree of pi electrons, so that the IDTT unit has high electron enrichment, stronger electron supply capability and higher HOMO energy level. On the other hand, 7- (2-octyldodecyl) benzo (triazole-Thiadiazole) (TNZ) is used as an acceptor unit because a large number of nitrogen atoms are doped in the conjugated ring, and the electron-withdrawing capability of TNZ can be effectively enhanced due to the lack of electricity of the nitrogen atoms, and the conjugated ring beltThe plane regularity is also beneficial to pi electron migration, so that the absorption spectrum is red shifted. Meanwhile, besides the conjugated structure, the long-chain alkyl of the side chain brings good dissolving capacity to the conjugated structure. At the same time, 2,1, 3-benzothiadiazole (TZ) and 3, 3-bis (((2-ethylhexyl) oxy) methyl) -3, 4-dihydro-2H-thieno [3, 4-B)][1,4]Dioxepin (ProDOT (CH) 2 OEtHx) 2 ) The introduction of the light-absorbing material well compensates the absorption trough area of the visible light wave band, thereby effectively realizing wide spectrum absorption. At present, no report of related polymers is available.
Disclosure of Invention
The invention aims at designing and preparing an electrochromic polymer and an electrochromic film comprising the electrochromic polymer, wherein the structure of the electrochromic polymer contains indenodithiophene [3,2-b ]]Thiophene (IDTT), 2,1, 3-benzothiadiazole (TZ), 7- (2-octyldodecyl) benzo (triazole-Thiadiazole) (TNZ), 3-bis (((2-ethylhexyl) oxy) methyl) -3, 4-dihydro-2H-thieno [3, 4-B)][1,4]Dioxepin (ProDOT (CH) 2 OEtHx) 2 ) The unit, the polymer has the characteristic of covering visible light to near infrared cooperative discoloration, and the preparation method mainly synthesizes a novel random quaternary conjugated polymer by a Stille coupling method.
The technical scheme of the invention is that firstly, an electrochromic polymer is provided, and the structural formula of the electrochromic polymer is shown in the following figure:
wherein R is 1 Is a linear alkyl group of 6 or more carbons, R 2 Branched alkyl of 8 or more carbon atoms, R is branched alkyl of 20 or more carbon atoms, n represents the degree of polymerization, n has a natural number of 8 to 100, preferably R in the molecular structure 2 And R is a mono-branched alkyl group, said mono-branched being attached to the backbone at carbon number 2 or 3, the number of carbon atoms of said mono-branched differing from the number of carbon atoms on the backbone by less than or equal to 4, more specifically,
it can be seen that the invention provides structural units comprising indenodithieno [3,2-b ]]Thiophene (IDTT), 2,1, 3-benzothiadiazole (TZ), 7- (2-octyldodecyl) benzo (triazole-Thiadiazole) (TNZ), 3-bis (((2-ethylhexyl) oxy) methyl) -3, 4-dihydro-2H-thieno [3, 4-B)][1,4]Dioxepin (ProDOT (CH) 2 OEtHx) 2 ) A unit having a characteristic of covering a synergistic color change in a range from 400nm to near infrared 900nm of visible light.
The invention also provides a preparation method of the electrochromic polymer, which comprises the following steps:
1) Preparation of the polymer by stille coupling: trimethyltin indenodithieno [3,2-B ] thiophene (M1), 4, 7-dibromo-2, 1, 3-benzothiadiazole (M2), 4, 10-dibromo-7- (2-octyldodecyl) benzo (triazole-thiadiazole) (M3), 6, 8-dibromo-3, 3-bis (((2-ethylhexyl) oxy) methyl) -3, 4-dihydro-2H-thieno [3,4-B ] [1,4] dioxacycloheptene (M4), xylene, tris (dibenzylideneacetone) dipalladium and tris (2-methylphenyl) phosphine are added into two ports connected with an atmosphere protection and a condensation pipe above, the air is pumped, the atmosphere protection behavior after the flask is kept, the mixture is cooled to room temperature after the heating reaction, the reaction liquid is dropped into methanol for precipitation, and black precipitate is collected by filtration;
2) Purification of the polymer by soxhlet extraction: wrapping the black brown precipitate with filter paper, placing in a fat extractor, sequentially washing with methanol, n-hexane and chloroform, concentrating chloroform washing solution, dripping into methanol for precipitation, and filtering to collect precipitate to obtain purified electrochromic polymer.
The synthetic route is as follows:
wherein R is 1 Is a linear alkyl group of 6 or more carbons, R 2 Branched alkyl of 8 carbons or more and R is 20Branched alkyl groups having carbon or more, n represents a degree of polymerization, and n is a natural number of 8 to 100; preferably, R in the molecular structure 2 And R is a single branched alkyl group, the single branched alkyl group is connected to the carbon position No. 2 or No. 3 of the main chain, and the difference between the number of carbon atoms of the single branched alkyl group and the number of carbon atoms on the main chain is less than or equal to 4; in particular, the method comprises the steps of,
further, the molar ratio of trimethyltin indenodithiophene [3,2-B ] thiophene (M1) to 4, 7-dibromo-2, 1, 3-benzothiadiazole (M2) in the above step 1 is (3:1) - (5:2), the molar ratio of trimethyltin indenodithiophene [3,2-B ] thiophene (M1) to 4, 10-dibromo-7- (2-octyldodecyl) benzo (triazole-thiadiazole) (M3) is (3:1) - (3:2), and the molar ratio of trimethyltin indenodithiophene [3,2-B ] thiophene (M1): 6, 8-dibromo-3, 3-bis (((2-ethylhexyl) oxy) methyl) -3, 4-dihydro-2H-thieno [3,4-B ] [1,4] dioxacycloheptene (M4) is (3:1) - (11:1).
Further, in the step 1: the molar ratio of trimethylstannodithioindeno [3,2-b ] thiophene (M1) to tris (dibenzylideneacetone) dipalladium is 1: (0.02-0.04); the molar ratio of trimethylstannodithiothieno [3,2-b ] thiophene (M1) to tris (2-methylphenyl) phosphine is 1: (0.1 to 0.2); the amount of xylene was such that the total concentration of the monomers was 0.04mol/L.
Further, the reaction temperature in the step 1 is 100-120 ℃ and the reaction time is 48-96 hours.
Further, the purification process in the step 2 is a soxhlet extraction process, which is sequentially performed with methanol, n-hexane and chloroform, and the chloroform solution is precipitated.
The invention also provides an electrochromic polymer film, which is obtained by spraying or knife coating the electrochromic polymer provided by the invention, and the film thickness of the polymer film is 200-800 nm. The electrochromic polymer capable of absorbing visible light and near infrared wave bands can be formed into a film on the surface of a conductive substrate through solution knife coating and spray coating, the color of the electrochromic polymer is converted from black to transparent, and the electrochromic polymer has the characteristics of low driving voltage, high optical contrast and high stability, and is suitable for assembly application of electrochromic devices.
Compared with the prior art, the invention has the advantages that:
1) In the electrochromic polymer provided by the invention, the multipolymer contains indenodithiophene [3,2-b ]]Thiophene (IDTT), 2,1, 3-benzothiadiazole (TZ), 7- (2-octyldodecyl) benzo (triazole-Thiadiazole) (TNZ), 3-bis (((2-ethylhexyl) oxy) methyl) -3, 4-dihydro-2H-thieno [3, 4-B)][1,4]Dioxepin (ProDOT (CH) 2 OEtHx) 2 ) The unit ensures that the electrochromic polymer and the electrochromic polymer film containing the same show wide spectrum absorption behavior, have the synergetic color changing property from visible light coverage to near infrared coverage, can display the conversion from black to transparent color, have high contrast ratio, quick response rate and high stability, and can be applied to electrochromic devices.
2) Each thiophene derivative used in the present invention has alkyl or alkoxy side chains, and on the one hand, the side chain substitution of alkyl or alkoxy is commonly used to increase the solubility of the polymer in organic solvents (such as chloroform), which can give the polymer solution processing capability; on the other hand, alkyl or alkoxy groups of sufficient length are required to be effective due to the low solvency imparted by the rigid backbone of the polymer. The substituents of each monomer in the invention can meet the requirement of solution processing of the polymer.
3) The invention designs a method for synthesizing two novel random quaternary conjugated polymers, utilizes the polymer spectrum absorption principle to realize the preparation of electrochromic polymers covering visible light to near infrared cooperative color change, and has simple preparation process and can be used for large-scale synthesis of electrochromic polymers.
4) The copolymerization mode of the invention is random copolymerization, three donor-acceptor structures exist in the conjugated main chain of the copolymer, and the absorption curve of the polymer can be regulated by adjusting the proportion of each monomer due to the characteristic absorption caused by the structures, so as to obtain a flat high absorption curve.
Drawings
These and/or other aspects and advantages of the present invention will become more apparent and more readily appreciated from the following detailed description of the embodiments of the invention, taken in conjunction with the accompanying drawings, wherein:
FIG. 1 shows nuclear magnetic hydrogen spectrum of a target polymer IDTT-ProDOT-TZ-TNZ-3-1-1-1 obtained in the embodiment of the invention;
FIG. 2 shows nuclear magnetic resonance hydrogen spectra of the target polymer IDTT-ProDOT-TZ-TNZ-2.75-0.25-1-1.5 obtained in the example of the invention;
FIG. 3 is a graph showing the spectral absorption curve of the polymer obtained in the example of the present invention in chloroform;
FIG. 4 is a photograph showing the UV-visible absorption spectrum and color conversion of the copolymer film obtained in the example of the present invention at different potentials, wherein (a) is the UV-visible absorption spectrum of the target polymer IDTT-ProDOT-TZ-TNZ-3-1-1-1; (b) A color conversion photograph of the target polymer IDTT-ProDOT-TZ-TNZ-3-1-1-1; (c) An ultraviolet-visible absorption spectrum of the target polymer IDTT-ProDOT-TZ-TNZ-2.75-0.25-1-1.5; (d) Color conversion photographs of the target polymer IDTT-ProDOT-TZ-TNZ-2.75-0.25-1-1.5;
FIG. 5 is an electrochemical cyclic voltammogram of a copolymer film obtained in an example of the present invention;
FIG. 6 is a graph showing the time transmittance response of a copolymer film obtained according to an embodiment of the present invention;
FIG. 7 is a graph showing the stability of a copolymer film obtained in the examples of the present invention;
FIG. 8 is a graph showing the thermal stability of the copolymer obtained in the example of the present invention.
Detailed Description
The present invention will be described in further detail below with reference to the drawings and detailed description for the purpose of enabling those skilled in the art to understand the invention better.
Example 1
A method for preparing electrochromic polymer covering visible light to near infrared synergetic discoloration, comprising the following steps:
(1) Synthesis of 4, 10-dibromo-7- (2-octyldodecyl) benzo (triazole-thiadiazole) (TNZ-Br), the synthetic route is shown in the following figure:
synthesis of the compound of formula 1: fuming nitric acid (6 g,0.095 mol) was added dropwise to a two-necked flask containing trifluoromethanesulfonic acid (50 g,0.333 mol), followed by rapid formation of 2CF at 0deg.C 3 SO 3 H/HNO 3 Solid, 4, 7-dibromobenzo-2, 1, 3-thiadiazole (6 g, 0.020mol) is directly added, and the mixture is heated and stirred at 55 ℃ for reaction for 48 hours; the mixture was poured into 500mL of ice-water mixture and filtered, and the precipitate was washed with pure water; vacuum drying at 80deg.C for more than 8 hr to obtain pale yellow solid, which is compound shown in formula 1, with 86% yield.
Synthesis of the compound of formula 2: the compound of formula 1 (3 g,7.8 mmol) and iron powder (3 g,54 mmol) were placed in acetic acid (110 mL) and heated at 80deg.C for 6h; after cooling to room temperature, the mixture was poured into 500mL of ice-water mixture, and the precipitate was filtered and washed; vacuum drying at 80deg.C for more than 8 hr to obtain yellowish green solid, which is compound shown in formula 2, with 65% yield.
Synthesis of compounds of formula 3: in a dry 25mL round bottom flask was added the compound described by formula 2 (700 mg,2.20 mmol) and glacial acetic acid (4 mL). Sodium nitrite (167 mg,2.42 mmol) was dissolved in deionized water (8 ml), and the sodium nitrite solution was added dropwise to the reaction mixture using a constant pressure dropping funnel, and stirred at room temperature for 30 minutes. After the reaction was completed, the solid was collected by suction filtration using a 0.45 μm nylon membrane and dried to obtain a brown yellow precipitate, i.e., the compound of formula 3 in 77% yield, which was continued to the next step without further purification.
Synthesis of compounds of formula 4: to a solution containing anhydrous DMF (10 mL) and compound 3 of formula 3 (500 mg,1.49 mmol) was added triethylamine (0.25 mL) dropwise. The reaction was stirred at room temperature for 20 minutes and the color of the solution changed from turmeric to dark red, indicating the formation of anions. Subsequently, 9- (bromomethyl) nonadecane (646 mg,1.79 mmol) was added dropwise to the reaction vessel. The reaction was stirred at room temperature under argon overnight. The reaction was monitored by Thin Layer Chromatography (TLC) (dichloromethane: ethyl acetate=4:1)Is completed. The crude product is extracted by a separating funnel in ethyl acetate and deionized water. The organic fraction was collected, washed with deionized water, then brine, and MgSO 4 Drying and filtering. The filtrate was collected and the solvent was removed by rotary evaporation. The crude product was subjected to column chromatography (silica gel, dichloromethane: ethyl acetate=4:1) and finally dried under vacuum to give a dark red viscous liquid, i.e. the compound of formula 4, in 24% yield. 1 HNMR(400MHz,CDCl 3 )δ:5.30(s,1H),4.83(d,J＝7.2Hz,1H),2.17(s,2H),1.56(s,6H),1.40–1.13(m,28H),0.86(dd,J＝12.2,5.9Hz,6H).
(2) Synthesis of electrochromic polymers covering visible to near infrared synergistic discolouration
Electrochromic polymer 1: substitution of trimethyltin monomer IDTT-SnMe 3 (0.1 mmol) and in each case 0.033mmol of bromomonomers ProDOT (CH) 2 OEtHx) 2 Br, TZ-Br and TNZ-Br (i.e., the compounds represented by formula 4) were charged into a 50mL two-necked flask. Then tris (dibenzylideneacetone) dipalladium (Pd 2 (dba) 3 ) (0.002 mmol), triorthophenylphosphine (P (tol) 3 ) (0.004 mmol) was added to the flask and the mixture was degassed by three freeze/pump/thaw cycles to fill with argon. Then, 5mL of Xylene (Xylene) was injected into the flask, the mixture was degassed and refilled with argon. The mixture was heated at 118℃for 48h. After cooling to room temperature, the mixture was added dropwise to cold methanol and cooled in a refrigerator for 30min, the precipitate was collected by filtration, washed sequentially with methanol and n-hexane using Soxhlet extraction, and finally washed with chloroform. The chloroform fraction was collected, concentrated by rotary evaporator and reprecipitated again in cold methanol. Finally, the target polymer was collected by filtration and dried in vacuo, the target polymer being IDTT-ProDOT-TZ-TNZ-3-1-1-1 (3-1-1-1 in the target polymer representation represents IDTT: proDOT (CH) in the starting material 2 OEtHx) 2 -Br: TZ-Br: the molar ratio of TNZ-Br is 3:1:1: 1) The yield was 64%. 1 H NMR(400MHz,CDCl 3 )δ:8.57(s,1H),7.54(s,2H),7.25(d,J＝44.9Hz,16H),7.12(s,5H),5.30(s,2H),2.59(d,J＝18.4Hz,10H),1.55(s,28H),1.24(t,J＝17.3Hz,41H),0.85(dd,J＝17.3,12.8Hz,18H).
Electrochromic polymer 2: substitution of trimethyltin monomer IDTT-SnMe 3 (0.1 mmol) and 0.009mmol of bromomonomer ProDOT (CH) 2 OEtHx) 2 Br, 0.036mmol of TZ-Br and 0.055mmol of TNZ-Br (i.e., the compound represented by formula 4) were charged into a 50mL two-necked flask. Then tris (dibenzylideneacetone) dipalladium (Pd 2 (dba) 3 ) (0.002 mmol), triorthophenylphosphine (P (tol) 3 ) (0.004 mmol) was added to the flask and the mixture was degassed by three freeze/pump/thaw cycles to fill with argon. Then, 5mL of Xylene (Xylene) was injected into the flask, the mixture was degassed and refilled with argon. The mixture was heated at 118℃for 48h. After cooling to room temperature, the mixture was added dropwise to cold methanol and cooled in a refrigerator for 30min, the precipitate was collected by filtration, washed sequentially with methanol and n-hexane using Soxhlet extraction, and finally washed with chloroform. The chloroform fraction was collected, concentrated by rotary evaporator and reprecipitated again in cold methanol. Finally, the target polymer is collected by filtration and dried in vacuum, and the target polymer is
IDTT-ProDOT-TZ-TNZ-2.75-0.25-1-1.5 (2.75-0.25-1-1.5 in the target polymer formula represents IDTT: proDOT (CH) in the raw material 2 OEtHx) 2 -Br: TZ-Br: the molar ratio of TNZ-Br was 2.75:0.25:1:1.5 With a yield of 60%. 1 H NMR(400MHz,CDCl 3 )δ8.57(s,1H),7.55(s,2H),7.25(d,J＝51.0Hz,16H),7.13(s,9H),2.57(s,10H),1.57(s,20H),1.43(s,3H),1.39–1.13(m,50H),1.03(s,2H),0.93–0.75(m,22H)。
The nuclear magnetic resonance hydrogen spectra of the electrochromic polymer 1 and the electrochromic polymer 2 obtained are shown in fig. 1 and fig. 2, respectively.
Example 2
The polymer prepared in example 1 was subjected to solution spectroscopy and electrochemical performance testing. Dissolving polymer in chloroform to obtain a concentration of 2×10 -4 mg/mL of solution, the solution absorption curves are shown in FIG. 3, and the polymer solutions are all black. The solutions of both polymers have a broad absorption range and are in the form of solutions, as measured by UV-visible spectrophotometrySeveral high absorption peaks are exhibited, which are the result of pi electron transitions and intramolecular charge transfer interactions. Wherein, the absorption peaks corresponding to the target polymer IDTT-ProDOT-TZ-TNZ-3-1-1-1 shown in FIG. 3 (a) are respectively at 474nm, 613nm and 840 nm. The absorption peaks corresponding to the target polymer IDTT-ProDOT-TZ-TNZ-2.75-0.25-1-1.5 shown in FIG. 3 (b) are at 468nm, 610nm and 849nm, respectively.
Preparing a polymer film: dissolving polymer in chloroform to prepare 5mg/ml solution, filtering out insoluble substances through a filter tip, placing into a spray gun, controlling the air pressure to be 2MPa, spraying on conductive glass, and placing into a vacuum drying oven for vacuum drying at 40 ℃ after spraying, wherein the absorbance of the film is about 1.0. 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, and the supporting electrolyte is as follows: 0.1mol/L of lithium perchlorate propylene carbonate solution.
The copolymer films were subjected to spectroelectrochemical performance tests at different voltages. The three-electrode system was used, an ITO glass plate (size: 1 cm. Times.5 cm) carrying an electrochromic polymer film was used as a working electrode, and a silver wire was used as a quasi-reference electrode (according to Fc/Fc) + Calibration) and platinum wire as counter electrode, the electrolyte solution was lithium perchlorate/propylene carbonate (LiClO) at a concentration of 0.1M 4 PC) solution. The spectroelectrochemical spectrograms and the color-loss coloring photos of the two copolymer films under different applied voltages are shown in fig. 4, and it is easy to see that the two electrochromic films have obvious electrochromic transition. And the polymer film has a certain red shift relative to the spectrum of the solution due to the stacking of pi-pi bonds. With the continuous rise of the voltage, the polymer film can realize the transition from the high absorption state which basically covers 400-900 nm to the transparent state.
The electrochemical properties of the copolymer were tested by cyclic voltammetry, as shown in figure 5, both polymers having relatively high oxidation potentials. Wherein IDTT-ProDOT-TZ-TNZ-3-1-1-1 shows an oxidation peak at 1.01V, a double reduction peak at 0.94V and 0.60V, IDTT-ProDOT-TZ-TNZ-2.75-0.25-1-1.5 shows an oxidation peak at 1.02V, and a double reduction peak at 0.72V and 0.47V, both of which have reversible redox activities, with a reversible change in color.
Response time refers to the time required for a material to achieve 95% of its maximum transmittance difference. The response time and the cycling stability of the polymer are tested by adopting an ultraviolet-visible spectrophotometer and an electrochemical workstation in a combined way, a three-electrode system is connected with the electrochemical workstation, a quartz cuvette is placed in the ultraviolet-visible spectrophotometer, and the transmittance change of the polymer film at the wavelength of maximum transmittance is synchronously measured while voltage is applied to the polymer film. The test results are shown in FIGS. 6 and 7, respectively, with the IDTT-ProDOT-TZ-TNZ-3-1-1-1 setting a double potential step in the square wave cycle at 470nm of: 1.2V and 0V, with durations of 80s and 20s, respectively. The initial optical contrast of IDTT-ProDOT-TZ-TNZ-3-1-1-1 was 46.6%, and after 120 cycles of square wave, the optical contrast was reduced to 43.6%; the IDTT-ProDOT-TZ-TNZ-2.75-0.25-1-1.5 set a double potential step in the square wave cycle at 466nm of: 1.0V and 0V, with durations of 60s and 40s, respectively. The initial optical contrast of IDTT-ProDOT-TZ-TNZ-2.75-0.25-1-1.5 was 42.8%, and after 560 cycles of square wave, the optical contrast was reduced to 32.5%. Furthermore, in the switching response process, the coloring time (t) c ) For 9.5s, the fading time (t b ) 44.5s; the coloration time (t) of IDTT-ProDOT-TZ-TNZ-2.75-0.25-1-1.5 c ) For 6.3s, the fading time (t b ) 27.0s.
The results of testing the thermal stability of electrochromic polymer films are shown in fig. 8: the thermal decomposition temperatures of the polymers are all higher than 300 ℃, which indicates that the polymers can be applied to working environments with higher temperatures.
As can be seen from the above examples, the color and absorption spectrum of the copolymer film prepared by the invention can be regulated and controlled by the types of the comonomers, the copolymer film can realize the cooperative color change from visible light to near infrared, and the copolymer film has the characteristics of high optical contrast, high coloring efficiency, good stability and the like, and the prepared copolymer film can be applied to the fields of electrochromic display, self-adaptive camouflage and the like.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (10)
1. An electrochromic polymer, characterized in that the molecular structure thereof comprises the following structure:
wherein R is 1 Is a linear alkyl group of 6 or more carbons, R 2 Branched alkyl of 8 carbons or more, R is branched alkyl of 20 carbons or more, n represents the degree of polymerization, and n has a natural number of 8 to 100.
2. The electrochromic polymer of claim 1 wherein R in said molecular structure 2 And R is a single branched alkyl group, the single branched alkyl group is connected to the carbon number 2 or the carbon number 3 of the main chain, and the difference between the number of the carbon atoms of the single branched alkyl group and the number of the carbon atoms on the main chain is less than or equal to 4.
3. The electrochromic polymer of claim 1 wherein, in said molecular structure
4. The electrochromic polymer of claim 1, wherein said electrochromic polymer has a synergistic color change characteristic covering the range from visible 400nm to near infrared 900 nm.
5. A method for preparing an electrochromic polymer according to any one of claims 1 to 4, comprising the steps of:
1) Preparation of the polymer by stille coupling: trimethyltin indenodithieno [3,2-B ] thiophene (M1), 4, 7-dibromo-2, 1, 3-benzothiadiazole (M2), 4, 10-dibromo-7- (2-octyldodecyl) benzo (triazole-thiadiazole) (M3), 6, 8-dibromo-3, 3-bis (((2-ethylhexyl) oxy) methyl) -3, 4-dihydro-2H-thieno [3,4-B ] [1,4] dioxacycloheptene (M4), xylene, tris (dibenzylideneacetone) dipalladium and tris (2-methylphenyl) phosphine were added to two ports with atmosphere protection and a condenser tube attached above, the air was evacuated, the atmosphere protection behavior in the flask was maintained, and the mixture was heated to react. After the reaction is finished, cooling to room temperature, dripping the reaction liquid into methanol for precipitation, and filtering and collecting black precipitate;
2) Purification of the polymer by soxhlet extraction: wrapping black precipitate with filter paper, placing in a fat extractor, sequentially washing with methanol, n-hexane and chloroform, concentrating chloroform washing solution, dripping into methanol for precipitation, and filtering to collect precipitate to obtain purified electrochromic polymer.
6. The method for preparing electrochromic polymer according to claim 5, wherein the molar ratio of trimethyltin indenodithiophene [3,2-B ] thiophene (M1) to 4, 7-dibromo-2, 1, 3-benzothiadiazole (M2) in step 1 is (3:1) - (5:2), the molar ratio of trimethyltin indenodithiophene [3,2-B ] thiophene (M1) to 4, 10-dibromo-7- (2-octyldodecyl) benzo (triazole-thiadiazole) (M3) is (3:1) - (3:2), and the molar ratio of trimethyltin indenodithiophene [3,2-B ] thiophene (M1): 6, 8-dibromo-3, 3-bis (((2-ethylhexyl) oxy) methyl) -3, 4-dihydro-2H-thieno [3,4-B ] [1,4] dioxaheptene (M4) is (3:1) - (11:1).
7. The method of preparing electrochromic polymer according to claim 5, wherein in step 1: the molar ratio of trimethylstannodithioindeno [3,2-b ] thiophene (M1) to tris (dibenzylideneacetone) dipalladium is 1: (0.02-0.04); the molar ratio of trimethylstannodithiothieno [3,2-b ] thiophene (M1) to tris (2-methylphenyl) phosphine is 1: (0.1 to 0.2); the amount of xylene was such that the total concentration of the monomers was 0.04mol/L.
8. The method for preparing electrochromic polymer according to claim 4, wherein the temperature of the mixture heating reaction in the step 1 is 100-120 ℃ and the reaction time is 48-96 hours.
9. The method for preparing electrochromic polymer according to claim 5, wherein the purification process in step 2 is a Soxhlet extraction process, which comprises sequentially extracting with methanol, n-hexane, and chloroform, and precipitating the chloroform solution.
10. An electrochromic polymer film, characterized in that the polymer film is obtained from the electrochromic polymer according to any one of claims 1 to 4 by spraying or doctor blading, and the film thickness of the polymer film is 200 to 800nm.
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