CN114907551A - Red electrochromic polymer, preparation method, thin film and device - Google Patents
Red electrochromic polymer, preparation method, thin film and device Download PDFInfo
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- CN114907551A CN114907551A CN202210521261.2A CN202210521261A CN114907551A CN 114907551 A CN114907551 A CN 114907551A CN 202210521261 A CN202210521261 A CN 202210521261A CN 114907551 A CN114907551 A CN 114907551A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000010409 thin film Substances 0.000 title claims description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 229920006254 polymer film Polymers 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 239000010408 film Substances 0.000 claims description 22
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- ZGMKNAXQTFUEIZ-UHFFFAOYSA-N 5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dithiine Chemical compound S1CCSC2=C(Br)SC(Br)=C21 ZGMKNAXQTFUEIZ-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000000944 Soxhlet extraction Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical group [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 235000011181 potassium carbonates Nutrition 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000002026 chloroform extract Substances 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 27
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 9
- 238000005507 spraying Methods 0.000 abstract description 6
- HPGNGICCHXRMIP-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dithiine Chemical compound S1CCSC2=CSC=C21 HPGNGICCHXRMIP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 2
- 125000004434 sulfur atom Chemical group 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229930192474 thiophene Natural products 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
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- 239000007789 gas Substances 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- -1 dodecyloxymethyl propyleneoxythiophene Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
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- 238000013461 design Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 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 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IUFAGWLKBSDNMH-UHFFFAOYSA-N 3-oxo-3-thiophen-3-ylpropanal Chemical compound O=CCC(=O)C=1C=CSC=1 IUFAGWLKBSDNMH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 239000000741 silica gel Substances 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Abstract
The invention discloses a red electrochromic polymer. According to the invention, 3, 4-ethylene dithio thiophene is introduced into a main chain of the propylene dioxythiophene as an embedded unit, different long-chain alkyl groups are introduced into a thiophene side chain structure by utilizing steric hindrance and a certain electron-withdrawing effect caused by sulfur atoms, so that the interaction between molecules is weakened, and the polymer has solubility in organic solvents such as toluene and dichloromethane, and is beneficial to large-area film formation of polymer solution, for example, the film formation is realized by adopting a spraying or blade coating mode; the red electrochromic polymer can realize the conversion from red to transparent states, has the characteristics of low driving voltage, high optical contrast and high stability, and is suitable for the assembly application of electrochromic devices. The invention also discloses a preparation method of the red electrochromic polymer, a polymer film based on the red electrochromic polymer and an electrochromic device.
Description
Technical Field
The invention relates to the technical field of electrochromism, in particular to a red electrochromism polymer, a preparation method, a thin film and a device.
Background
The electrochromic is a phenomenon that under the action of an external electric field, ions and electrons are injected or extracted to generate an oxidation-reduction reaction, and the appearance shows reversible color change. The electrochromic material has wide application prospect in the fields of intelligent windows, military intelligent camouflage and the like. Compared with inorganic metal oxide and viologen organic micromolecule electrochromic materials, the electrochromic polymer has the advantages of easy molecular structure design, rich color conversion, high optical contrast, high response speed, high stability and the like. The development of red to transparent electrochromic materials is also the focus of research on electrochromic polymers, especially red as one of the primary colors of the three primary colors, which has an important influence on the display of the electrochromic materials.
Polyaniline polythiophene and the like of the electrochromic polymer are difficult to dissolve due to a rigid main chain, so that the process is difficult to realize in the aspect of large-area film forming, and therefore, the design and synthesis of a novel electrochromic polymer capable of being processed by solution have important significance for the research and application of electrochromic materials; polymers showing yellow, red and the like generally have higher band gaps, the discoloration stability of the polymers is poor under a high driving potential matched with the band gaps, the discoloration state is generally shown to have residual blue, and the discoloration contrast of the polymers is obviously reduced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a red electrochromic polymer which has the color conversion from red to transparent under the action of an applied electric field and is soluble in solvents such as toluene and dichloromethane, and is beneficial to large-area film formation of a polymer solution.
In order to achieve the purpose, the technical scheme of the invention is as follows: a red electrochromic polymer has the following structural formula:
wherein R is C 12 -C 16 Alkyl of (2) substituted positionR in the above groups are the same or different; n represents a polymerization degree, and n is a natural number of 8 to 100. Further, n is a natural number of 8 to 50. Further, R at the substitution position is the same. Further, C 12 -C 16 The alkyl group of (a) is a straight-chain alkyl group. The main function of the alkyl chain is to increase the solubility of the polymer, at C 12 To C 16 In the range of (1), increasing the number of carbon atoms is advantageous for the solubility of the polymer; and the carbon number of R is less than 12, which is not favorable for the solubility of the polymer in the organic solvent. Compared with branched alkane, the polymer with the linear alkyl R has better electrochromic property.
The second purpose of the present invention is to provide a method for preparing an electrochromic polymer, wherein the electrochromic polymer is the above red electrochromic polymer, and the method comprises the following steps:
mixing 2, 5-dibromo-3, 4-ethylene dithiothiophene, a compound shown as a formula 2, an inorganic weak base, a palladium catalyst and an organic solvent, carrying out polymerization reaction under the protection of inert gas, and carrying out post-treatment after the reaction is finished to obtain an electrochromic polymer shown as a formula 1;
in the formula 2, R is C 12 -C 16 Alkyl group of (1).
The preferable technical proposal is that the organic acid is pivalic acid and/or trimethylacetic acid; the inorganic weak base is potassium carbonate and/or potassium bicarbonate; the palladium catalyst is palladium acetate; the organic solvent is N, N-dimethylacetamide. Thiophene monomers with electron donating substituents in DMAC are advantageous in increasing the reaction rate and the degree of polymerization of the product.
The preferable technical scheme is that the mole ratio of the 2, 5-dibromo-3, 4-ethylene dithiothiophene to the compound shown in the formula 2 in S1 is (2.2-3): 1. too large or too small a molar ratio is unfavorable for polymerization and growth of the molecular chain.
The preferable technical scheme is that the molar ratio of the inorganic weak base to the compound shown in the formula 2 is (1-1.2): 1; the molar ratio of the organic acid to the compound of the formula 2 is (0.08-0.2): 1; the molar ratio of the palladium catalyst to the compound of formula 2 is (0.03-0.05): 1.
the preferable technical scheme is that the temperature of the polymerization reaction is 120-140 ℃, and the reaction time is 36-72 hours.
The preferable technical scheme is that the post-treatment is a Soxhlet extraction process, the Soxhlet extraction is to sequentially extract precipitates obtained by polymerization reaction by using methanol, n-hexane and chloroform, concentrate a chloroform extracting solution, and drip the chloroform concentrated solution into the methanol for precipitation. The methanol and the normal hexane can remove impurities and small molecular substances in the precipitate.
The invention also aims to provide a polymer film which is prepared by coating the solution of the red electrochromic polymer and the organic solvent on a substrate and drying.
The preferable technical scheme is that the film thickness of the polymer film is 80-400 nm. Polymer films less than 80nm can have an effect on film color. When the film thickness of the polymer film is too small, the color contrast is not high, and when the film thickness is too large, the fading state is affected.
The fourth object of the present invention is to provide an electrochromic device, comprising an upper electrode layer, an electrolyte layer, an electrochromic thin film layer and a lower electrode layer which are sequentially stacked, wherein the electrochromic thin film layer is the above-mentioned polymer thin film.
The invention has the advantages and beneficial effects that:
according to the invention, 3, 4-ethylene dithio thiophene is introduced into a main chain of the propylene dioxythiophene as an embedded unit, different long-chain alkyl groups are introduced into a thiophene side chain structure by utilizing steric hindrance and a certain electron-withdrawing effect caused by sulfur atoms, so that the interaction between molecules is weakened, and the polymer has solubility in organic solvents such as toluene and dichloromethane, and is beneficial to large-area film formation of polymer solution, for example, film formation by adopting a spraying or blade coating mode, especially film formation by spraying;
the red electrochromic polymer can realize the conversion from red to transparent states, has the characteristics of low driving voltage, high optical contrast and high stability, and is suitable for the assembly application of electrochromic devices.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a polymer;
FIG. 2 is a spectral absorption curve and a color photograph of a polymer dissolved in methylene chloride;
FIG. 3 is a photograph of the UV-Vis absorption spectra and color shift of a copolymer film at different potentials;
FIG. 4 is a cyclic voltammogram of a copolymer film;
FIG. 5 is a square wave potential cycling curve for a copolymer film;
FIG. 6 is a thermal stability curve for a copolymer;
FIG. 7 is a graph comparing the dissolution of 3, 4-diethyldithiothiophene-3, 4-dioxopropylthiophene polymer with that of 3, 4-diethyldithiothiophene homopolymer.
Detailed Description
The following further describes embodiments of the present invention with reference to examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
The structural formula of the red electrochromic polymer of the embodiment 1 is shown as the formula 1, wherein R is C12 straight-chain alkyl.
The preparation method of the red electrochromic polymer comprises the following steps:
(1) synthesis of 2, 5-dibromo-3, 4-ethylenedithiothiophene
Dissolving 0.1mmol of 3, 4-ethylene dithio-thiophene in 20mL of chloroform, placing the solution in a 100mL double-mouth bottle, protecting the solution with nitrogen, coating the double-mouth bottle with tinfoil paper to achieve the effect of avoiding light, and reducing the temperature to 0 ℃; dissolving 0.3mmol of N-bromosuccinimide (NBS) in 10mL of N, N-Dimethylformamide (DMF), slowly injecting into a reaction bottle through a syringe, stirring for reacting for 6h, pouring the reaction solution into water, separating the solution to collect an organic phase, extracting the water phase twice with 20mL of dichloromethane, combining the organic phases, drying with anhydrous magnesium sulfate, loading the solution onto a silica gel column by a dry method, wherein the eluent is dichloromethane/N-hexane (1: 1), so as to obtain a white solid with the yield of 73%;
the nuclear magnetic hydrogen spectrum of the compound prepared by the step 1 H NMR(400MHz,CDCl 3 ,δ,ppm):3.22(s,4H)。
(2) Synthesis of electrochromic polymers
Placing 0.1mmol of 2, 5-dibromo-3, 4-ethylene dithiothiophene, 0.1mmol of dodecyloxymethyl propyleneoxythiophene, 0.006mmol of palladium acetate, 0.3mmol of potassium carbonate and 0.03mmol of pivalic acid in a 25mL double-mouth bottle, pumping and exchanging gas, injecting nitrogen gas, injecting 15mL of anhydrous N, N-Dimethylacetamide (DMAC), pumping and exchanging gas, filling nitrogen gas, heating to 120 ℃, refluxing for reaction for 72 hours, cooling to room temperature after the reaction is finished, dropping the reaction liquid into cold methanol for precipitation, filtering the precipitate, and drying; and then respectively carrying out Soxhlet extraction by using methanol, n-hexane and chloroform, wherein the extraction time is 24h each time, concentrating the chloroform extract to 15mL, then dripping into cold methanol to precipitate to obtain a black solid, filtering and drying to obtain the target polymer, wherein the polymerization degree n is 8-20.
Example 2
The structural formula of the red electrochromic polymer of the embodiment 2 is shown in a formula 1, wherein R is C16 straight-chain alkyl.
The preparation method of the red electrochromic polymer comprises the following steps:
(1) synthesis of 2, 5-dibromo-3, 4-ethylenedithiothiophene the same as in example 1;
(2) synthesis of electrochromic polymers
Placing 0.1mmol of 2, 5-dibromo-3, 4-ethylene dithio-thiophene, 0.1mmol of hexacosanyloxymethyl propyleneoxythiophene, 0.006mmol of palladium acetate, 0.3mmol of potassium carbonate and 0.03mmol of pivalic acid in a 25mL double-neck bottle, pumping gas, injecting nitrogen, injecting 15mL of anhydrous N, N-Dimethylacetamide (DMAC), pumping gas, filling nitrogen, heating to 120 ℃, refluxing for reaction for 72 hours, cooling to room temperature after the reaction is finished, dropping the reaction liquid into cold methanol for precipitation, filtering the precipitate, and drying; and sequentially carrying out Soxhlet extraction with methanol, n-hexane and chloroform for 24h each time, concentrating the chloroform extract to 15mL, dripping into cold methanol to precipitate to obtain a black solid, filtering and drying to obtain the target polymer.
The NMR spectrum of the obtained copolymer is shown in FIG. 2.
The polymer film was prepared as follows:
the electrochromic polymer of the embodiment is dissolved in chloroform to prepare a solution of 2mg/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, spraying is carried out on conductive glass, the absorbance of a film is about 0.8, and the sprayed solution is placed in a vacuum drying oven to be dried in vacuum at 40 ℃ for standby. 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: 0.2mol/L lithium perchlorate propylene carbonate solution.
The nmr spectrum of the copolymer of example 1 is shown in fig. 1, and the polymer or polymer film obtained in example 1 is subjected to the following tests:
(1) the polymer prepared in example 1 was subjected to solution spectroscopic testing: the polymer was dissolved in dichloromethane and formulated to a concentration of 2 x 10 -4 The absorption curve and the photograph of the solution of mg/mL are shown in FIG. 2, the absorption peak of the copolymer is 459nm, and the polymer solution is orange red.
(2) The polymer film is subjected to spectrum electrochemical performance tests under different voltages:
a three-electrode system is adopted, a platinum wire is used as a counter electrode, a calibrated silver wire is used as a reference electrode, the polymer film in example 1 is used as a working electrode, and a supporting electrolyte is as follows: 0.1mol/L lithium perchlorate propylene carbonate solution. The spectroelectrochemical spectrogram and the color loss coloring photograph of the copolymer film under different applied voltages are shown in figure 3, which shows that the polymer film has obvious electrochromic performance; 3, 4-ethylene dithio thiophene is adopted, the absorption spectrum of the copolymer has a certain blue shift compared with that of a 3, 4-dioxy trimethylene thiophene homopolymer, and the spectral absorption of the copolymer can be adjusted by regulating the kind of the comonomer.
(3) Cyclic voltammetry testing of initial redox voltage of electrochromic polymers
As shown in fig. 4, the initial redox voltage of the electrochromic polymer was approximately 0.5V and 0.36V.
(4) Step method for testing spectral response and stability of copolymer film
As shown in FIG. 5, the step potentials of P (3, 4-diethyldithiothiophene-3, 4-dioxotrimethylene thiophene) are 0V and 1.0V, the voltage residence time is 5s, the maximum transmittance contrast is 21.57%, the electrochromic response time is about 2.4s, the electrochemical stability of the copolymer is tested, and the good stability is still maintained after 100 square-wave potential scans.
(5) The thermal stability of the electrochromic polymer was tested (see fig. 6): the thermal decomposition temperature of the polymer is more than 290 ℃, which shows that the polymer can be applied to a working environment with higher temperature.
(6) Testing of the solubility of electrochromic polymers:
as shown in FIG. 7, the solubility of example P (3, 4-diethyldithiothiophene-3, 4-dioxotrimethylene thiophene) can be up to 10mg/ml, as compared with the solubility of 3, 4-diethyldithiothiophene-3, 4-dioxotrimethylene thiophene polymer (a) and 3, 4-diethyldithiothiophene homopolymer (b) in methylene chloride.
The 3, 4-ethylenedithiothiophene homopolymer has low solubility and can be dissolved in DMF, DMSO and the like, but the production requirement of spray coating film formation cannot be met, and the solubility of P (3, 4-diethylenedithiothiophene-3, 4-dioxotrimethylene thiophene) in methylene chloride and the like of the examples 1 and 2 meets the production requirement of spray coating film formation.
The embodiment shows that the color and the absorption spectrum of the copolymer film prepared by the invention can be regulated and controlled by the type of the comonomer, the copolymer film can realize the conversion from red to transparent, and has the characteristics of low driving potential, high color change rate, 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 above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, it is possible to make various improvements and modifications without departing from the technical principle of the present invention, and these improvements and modifications should also be considered as the protection scope of the present invention.
Claims (10)
1. A red electrochromic polymer is characterized in that the structural formula is as follows:
wherein R is C 12 -C 16 The R in the substituent positions of the alkyl groups of (1) are the same or different; n represents a polymerization degree, and n is a natural number of 8 to 100.
2. A method for preparing an electrochromic polymer, wherein the electrochromic polymer is the red electrochromic polymer according to claim 1, comprising the steps of:
mixing 2, 5-dibromo-3, 4-ethylene dithiothiophene, a compound shown as a formula 2, an inorganic weak base, a palladium catalyst and an organic solvent, carrying out polymerization reaction under the protection of inert gas, and carrying out post-treatment after the reaction is finished to obtain an electrochromic polymer shown as a formula 1;
in the formula 2, R is C 12 -C 16 Alkyl group of (1).
3. The method for preparing an electrochromic polymer according to claim 2, wherein the organic acid is pivalic acid and/or trimethylacetic acid; the inorganic weak base is potassium carbonate and/or potassium bicarbonate; the palladium catalyst is palladium acetate; the organic solvent is N, N-dimethylacetamide.
4. The method for preparing an electrochromic polymer according to claim 2, wherein the molar ratio of 2, 5-dibromo-3, 4-ethylenedithiothiophene to the compound of formula 2 in S1 is (2.2 to 3): 1.
5. the preparation method of the electrochromic polymer as claimed in claim 2, wherein the molar ratio of the inorganic weak base to the compound of formula 2 is (1-1.2): 1; the molar ratio of the organic acid to the compound of the formula 2 is (0.08-0.2): 1; the molar ratio of the palladium catalyst to the compound of formula 2 is (0.03-0.05): 1.
6. the method for preparing an electrochromic polymer according to claim 2, wherein the temperature of the polymerization reaction is 120 to 140 ℃ and the reaction time is 36 to 72 hours.
7. The method for preparing electrochromic polymer according to claim 2, wherein the post-treatment is a soxhlet extraction process, the soxhlet extraction process comprises the steps of sequentially extracting precipitates obtained through polymerization reaction by using methanol, n-hexane and chloroform, concentrating a chloroform extract, and dripping the chloroform concentrate into methanol for precipitation.
8. A polymer film obtained by applying a solution of the red electrochromic polymer according to claim 1 and an organic solvent to a substrate and drying the solution.
9. The electrochromic film according to claim 1, wherein the polymer film has a film thickness of 80 to 400 nm.
10. An electrochromic device comprising an upper electrode layer, an electrolyte layer, an electrochromic thin film layer and a lower electrode layer which are sequentially laminated, wherein the electrochromic thin film layer is the polymer thin film according to claim 8 or 9.
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