CN114907551B - Red electrochromic polymer, preparation method, film and device - Google Patents
Red electrochromic polymer, preparation method, film and device Download PDFInfo
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- CN114907551B CN114907551B CN202210521261.2A CN202210521261A CN114907551B CN 114907551 B CN114907551 B CN 114907551B CN 202210521261 A CN202210521261 A CN 202210521261A CN 114907551 B CN114907551 B CN 114907551B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229920006254 polymer film Polymers 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006116 polymerization reaction Methods 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
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000002026 chloroform extract Substances 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 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
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 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
- 230000000379 polymerizing effect Effects 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 8
- 125000000217 alkyl group Chemical group 0.000 abstract description 7
- 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
- 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
- 238000005507 spraying Methods 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 2
- 125000004434 sulfur atom Chemical group 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 17
- 229920001577 copolymer Polymers 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010438 heat treatment Methods 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
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003115 supporting electrolyte Substances 0.000 description 2
- -1 thiophene-3, 4-dioxypropylenethiophene Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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
- 230000009286 beneficial effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 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
- 238000004090 dissolution Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 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
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 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
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- 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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- 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
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- 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
- G02F1/153—Constructional details
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- 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
- G02F1/163—Operation of electrochromic cells, e.g. electrodeposition cells; Circuit arrangements therefor
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—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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Abstract
The invention discloses a red electrochromic polymer. According to the invention, 3, 4-ethylenedithiothiophene is introduced into a main chain of propylenedioxythiophene as an embedding unit, and different long-chain alkyl groups are introduced into a thiophene side chain structure by combining with steric hindrance caused by sulfur atoms and a certain electron-withdrawing effect, so that the interaction between molecules is weakened, and the polymer has solubility in organic solvents such as toluene and methylene dichloride, so that the polymer solution can be formed into a film in a large area, for example, a spraying or blade coating mode is adopted; the red electrochromic polymer can realize the conversion from red to transparent state, 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 electrochromic, in particular to a red electrochromic polymer, a preparation method, a film and a device.
Background
Electrochromic refers to a phenomenon that a material undergoes oxidation-reduction reaction through injection or extraction of ions and electrons under the action of an external electric field, and the appearance of the material shows reversible change of color. 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 micromolecular electrochromic materials, the electrochromic polymer has the advantages of easiness in molecular structure design, abundant color conversion, high optical contrast, high response speed, high stability and the like. The development of red to transparent electrochromic materials is also an important issue in electrochromic polymer research, especially red as one of the primary colors of the three primary colors, which has an important impact on the display of electrochromic materials.
The polyaniline polythiophene of the electrochromic polymer is difficult to dissolve due to the rigid main chain, so that the process is difficult to realize in the aspect of large-area film formation, and therefore, the design and synthesis of the novel electrochromic polymer capable of being processed by the solution are of great significance to the research and application of electrochromic materials; polymers showing yellow, red and other colors generally have higher band gaps, the color change stability of the polymers is poor under high driving potential matched with the polymers, the color losing state is usually shown to have residual blue, and the color change contrast of the polymers is obviously reduced.
Disclosure of Invention
One of the purposes of the invention is to overcome the defects existing in the prior art, provide a red electrochromic polymer which has red to transparent color conversion under the action of an external electric field and is favorable for large-area film formation of polymer solution when being dissolved in solvents such as toluene, methylene dichloride and the like.
In order to achieve the above purpose, the technical scheme of the invention is as follows: a red electrochromic polymer having the structural formula:
wherein R is C 12 -C 16 R in the substitution positions 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 in the substitution position is the same. Further, C 12 -C 16 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 Within the scope of (2), increasing the number of carbon atoms is advantageous for polymer solubility; and R has a carbon number lower than 12, which is detrimental to the solubility of the polymer in organic solvents. The polymer wherein R is a linear alkyl group has better electrochromic properties than a branched alkane.
Another object of the present invention is to provide a method for preparing an electrochromic polymer, wherein the electrochromic polymer is the above-mentioned red electrochromic polymer, comprising the steps of:
mixing 2, 5-dibromo-3, 4-ethylene dithio thiophene, a compound shown in a formula 2, 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 in a formula 1;
in the formula 2, R is C 12 -C 16 Is a hydrocarbon group.
The preferable technical scheme 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 for increasing the reaction rate and degree of polymerization of the product.
The preferable technical scheme is that the molar ratio of the 2, 5-dibromo-3, 4-ethylene dithio thiophene in S1 and the compound of the formula 2 is (2.2-3): 1. too large or too small a molar ratio is detrimental to polymerization and to molecular chain growth.
The preferable technical scheme is that the mol ratio of the inorganic weak base to the compound of the formula 2 is (1-1.2): 1, a step of; the molar ratio of organic acid to compound of formula 2 is (0.08-0.2): 1, a step of; 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, wherein the Soxhlet extraction is a precipitation obtained by sequentially adopting methanol, normal hexane and chloroform for extraction polymerization, concentrating a chloroform extract, and dripping the chloroform concentrate into the methanol for precipitation. Methanol and n-hexane remove impurities and small molecular substances from the precipitate.
The third object of the present invention is to provide a polymer film obtained by coating a substrate with the solution of the above-mentioned red electrochromic polymer and an organic solvent and drying the coated substrate.
The preferable technical proposal is that the film thickness of the polymer film is 80-400 nm. Polymer films less than 80nm have an effect on film color. Too small a film thickness of the polymer film does not have high color contrast, and too large a film thickness affects the fading state.
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 laminated in this order, wherein the electrochromic thin film layer is the polymer thin film described above.
The invention has the advantages and beneficial effects that:
according to the invention, 3, 4-ethylenedithiothiophene is introduced into a main chain of propylenedioxythiophene as an embedding unit, and different long-chain alkyl groups are introduced into a thiophene side chain structure by combining with steric hindrance caused by sulfur atoms and a certain electron-withdrawing effect, so that the interaction between molecules is weakened, and the polymer has solubility in organic solvents such as toluene and methylene dichloride, so that the polymer solution can be formed into a film in a large area, for example, a spraying or blade coating mode is adopted, and particularly, the film is formed by spraying;
the red electrochromic polymer can realize the conversion from red to transparent state, 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 graph of spectral absorption curves and color photographs of a polymer dissolved in methylene chloride;
FIG. 3 is a photograph of ultraviolet-visible absorption spectra and color transition of copolymer films at different potentials;
FIG. 4 is a copolymer film cyclic voltammogram;
FIG. 5 is a graph of square wave potential cycling of copolymer films;
FIG. 6 is a graph of the thermal stability of a copolymer;
FIG. 7 is a graph comparing the dissolution of 3, 4-diethylenedioxythiophene-3, 4-dioxypropylenethiophene polymer with 3, 4-diethylenedioxythiophene homopolymer.
Detailed Description
The following describes the invention in further detail with reference to examples. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
Example 1
The structural formula of the red electrochromic polymer of the embodiment 1 is shown as formula 1, wherein R is C12 linear 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-ethylenedithiothiophene in 20mL of chloroform, placing the solution in a 100mL double-mouth bottle, protecting the bottle by nitrogen, coating the double-mouth bottle with tinfoil paper to achieve a light-shielding effect, and reducing the temperature to 0 ℃; dissolving 0.3mmol of N-bromosuccinimide (NBS) in 10mL of N, N-Dimethylformamide (DMF), slowly injecting the solution into a reaction bottle through a syringe, stirring and reacting for 6h, pouring the reaction solution into water, separating and collecting an organic phase, extracting the water phase twice with 20mL of dichloromethane, combining the organic phases, drying the organic phase with anhydrous magnesium sulfate, loading the mixture on a silica gel column by adopting a dry method, and obtaining white solid with the yield of 73 percent, wherein the eluting agent is dichloromethane/N-hexane (1:1);
the nuclear magnetism 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-ethylenedithiothiophene, 0.1mmol of dodecyloxymethylpropylenedioxythiophene, 0.006mmol of palladium acetate, 0.3mmol of potassium carbonate and 0.03mmol of pivalic acid into a 25mL double-mouth bottle, pumping and ventilating, injecting nitrogen, injecting 15mL of anhydrous N, N-Dimethylacetamide (DMAC), pumping and ventilating again, filling nitrogen, heating to 120 ℃ for reflux reaction for 72h, 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 the chloroform extract to 15mL, dripping the chloroform extract into cold methanol to precipitate to obtain black solid, filtering and drying to obtain the target polymer with the polymerization degree n of 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 linear alkyl.
The preparation method of the red electrochromic polymer comprises the following steps:
(1) Synthesis of 2, 5-dibromo-3, 4-ethylenedithiothiophene was performed as in example 1;
(2) Synthesis of electrochromic polymers
Placing 0.1mmol of 2, 5-dibromo-3, 4-ethylenedithiothiophene, 0.1mmol of hexacosalkoxy methyl propylene dioxythiophene, 0.006mmol of palladium acetate, 0.3mmol of potassium carbonate and 0.03mmol of pivalic acid into a 25mL double-mouth bottle, pumping and ventilating, injecting nitrogen, injecting 15mL of anhydrous N, N-Dimethylacetamide (DMAC), pumping and ventilating again, filling nitrogen, heating to 120 ℃ for reflux reaction for 72h, cooling to room temperature after the reaction is finished, dripping the reaction liquid into cold methanol for precipitation, and filtering the precipitate for drying; sequentially performing Soxhlet extraction with methanol, n-hexane and chloroform for 24h each time, concentrating chloroform extract to 15mL, dripping into cold methanol to precipitate to obtain black solid, filtering, and drying to obtain target polymer.
The preparation method of the polymer film comprises the following steps:
dissolving the electrochromic polymer in chloroform to prepare a solution of 2mg/ml, filtering out insoluble substances through a filter tip, placing the solution in a spray gun, controlling the air pressure to be 2MPa, spraying the solution on conductive glass, and placing the sprayed solution in a vacuum drying oven at 40 ℃ for later use, wherein the absorbance of the film is about 0.8. 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 of lithium perchlorate propylene carbonate solution.
The nuclear magnetic resonance hydrogen spectrum of the copolymer of example 1 is shown in fig. 1, and the following test was performed on the polymer or polymer film obtained in example 1:
(1) The polymer prepared in example 1 was subjected to solution spectroscopic testing: dissolving polymer in dichloromethane to obtain a concentration of 2×10 -4 mg/mL of solution, solution absorption curve and photograph as shown in FIG. 2, the absorption peak of the copolymer at 459nm, the polymer solution appeared orange-red.
(2) Spectroelectrochemical performance test of polymer films at different voltages:
the three-electrode system is adopted, a platinum wire is a counter electrode, a calibrated silver wire is a reference electrode, the polymer film of the embodiment 1 is a working electrode, and the supporting electrolyte is as follows: 0.1mol/L of lithium perchlorate propylene carbonate solution. The spectrum electrochemical spectrogram and the color-losing and coloring photo of the copolymer film under different applied voltages are shown in figure 3, which shows that the polymer film has obvious electrochromic property; the absorption spectrum of the copolymer has a certain blue shift compared with that of a 3, 4-dioxythiophene homopolymer by adopting 3, 4-ethylenedithiothiophene, and the spectrum absorption of the copolymer can be regulated by regulating the type of the comonomer.
(3) Cyclic voltammetry test the initial redox voltage of the electrochromic polymer is shown in fig. 4, the initial redox voltage of the electrochromic polymer being about 0.5V and 0.36V.
(4) Testing spectral response and stability of copolymer film by step method
As shown in fig. 5, the step potential of P (3, 4-diethylenediothiothiophene-3, 4-dioxypropylenethiophene) was 0V and 1.0V, the voltage residence time was 5s, the maximum transmittance contrast ratio was 21.57%, the electrochromic response time was about 2.4s, and the electrochemical stability of the copolymer was tested, and the square wave potential scan remained good after 100 times of scanning.
(5) The electrochromic polymers were tested for thermal stability (see fig. 6): the thermal decomposition temperature of the polymer is more than 290 ℃, which indicates that the polymer can be applied to working environments with higher temperature.
(6) Testing the solubility of electrochromic polymers:
as shown in FIG. 7, the solubility of the 3, 4-diethylenedithioxy thiophene-3, 4-dioxypropylenethiophene polymer (a) and the 3, 4-diethylenedithioxy thiophene homopolymer (b) in methylene chloride was compared, and the solubility of example P (3, 4-diethylenedithioxy thiophene-3, 4-dioxypropylenethiophene) was as high as 10mg/ml.
The 3, 4-ethylene dithiothiophene homopolymer has lower solubility, can be dissolved in DMF, DMSO and the like, but does not meet the production requirements of spray film formation, while the solubility of the P (3, 4-diethylene dithiothiophene-3, 4-dioxypropylene thiophene) of the embodiment 1 and the embodiment 2 in methylene dichloride and the like meets the production requirements of spray film formation.
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 conversion from red to transparent, and the copolymer film has the characteristics of low driving potential, high color-changing 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 foregoing is merely a preferred embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the scope of the invention.
Claims (10)
1. A red electrochromic polymer characterized by the following structural formula:
wherein R is C 12 -C 16 R in the substitution positions 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 of claim 1, comprising the steps of:
mixing 2, 5-dibromo-3, 4-ethylene dithiothiophene, a compound shown in a formula 2, inorganic weak base, a palladium catalyst, organic acid and an organic solvent, carrying out polymerization reaction under the protection of inert gas, and carrying out aftertreatment after the reaction is finished to obtain an electrochromic polymer shown in the formula 1;
in the formula 2, R is C 12 -C 16 Is a hydrocarbon group.
3. The method of preparing electrochromic polymer according to claim 2, characterized in 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.
4. The method for producing electrochromic polymer according to claim 2, wherein the molar ratio of 2, 5-dibromo-3, 4-ethylenedithiothiophene in S1, the compound of formula 2 is (2.2 to 3): 1.
5. the method of preparing electrochromic polymer according to claim 2, characterized in that the molar ratio of the inorganic weak base to the compound of formula 2 is (1-1.2): 1, a step of; the molar ratio of organic acid to compound of formula 2 is (0.08-0.2): 1, a step of; the molar ratio of the palladium catalyst to the compound of formula 2 is (0.03-0.05): 1.
6. the method for preparing electrochromic polymer according to claim 2, wherein the polymerization temperature is 120-140 ℃ and the reaction time is 36-72 hours.
7. The method for preparing electrochromic polymer according to claim 2, wherein the post-treatment is a soxhlet extraction process, wherein the soxhlet extraction is a precipitation obtained by sequentially extracting and polymerizing methanol, n-hexane and chloroform, concentrating a chloroform extract, and dripping the chloroform concentrate into the methanol for precipitation.
8. A polymer film prepared by applying the solution of the red electrochromic polymer according to claim 1 and an organic solvent to a substrate and drying.
9. The polymer film according to claim 8, wherein the film thickness of the polymer film is 80 to 400nm.
10. An electrochromic device comprising an upper electrode layer, an electrolyte layer, an electrochromic film layer and a lower electrode layer, which are laminated in this order, wherein the electrochromic film layer is the polymer film according to claim 8 or 9.
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| WO2020262443A1 (en) * | 2019-06-28 | 2020-12-30 | 出光興産株式会社 | Conductive oligomer, conductive composition, conductive aid, and condenser electrode, transparent electrode, battery electrode, or capacitor electrode formed using said conductive composition |
| CN114853987A (en) * | 2022-04-12 | 2022-08-05 | 上海戎科特种装备有限公司 | Electrochromic copolymer containing dioxythiophene and 9,9' -spirobifluorene structure, preparation method thereof and polymer film |
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| WO2020262443A1 (en) * | 2019-06-28 | 2020-12-30 | 出光興産株式会社 | Conductive oligomer, conductive composition, conductive aid, and condenser electrode, transparent electrode, battery electrode, or capacitor electrode formed using said conductive composition |
| CN114853987A (en) * | 2022-04-12 | 2022-08-05 | 上海戎科特种装备有限公司 | Electrochromic copolymer containing dioxythiophene and 9,9' -spirobifluorene structure, preparation method thereof and polymer film |
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