CN114853988B - 含噻吩嵌入单元电致变色聚合物、制备方法、薄膜及器件 - Google Patents
含噻吩嵌入单元电致变色聚合物、制备方法、薄膜及器件 Download PDFInfo
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- CN114853988B CN114853988B CN202210532680.6A CN202210532680A CN114853988B CN 114853988 B CN114853988 B CN 114853988B CN 202210532680 A CN202210532680 A CN 202210532680A CN 114853988 B CN114853988 B CN 114853988B
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- electrochromic
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- thiophene
- electrochromic polymer
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229920000642 polymer Polymers 0.000 title claims abstract description 63
- 229930192474 thiophene Natural products 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 28
- 229920006254 polymer film Polymers 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 150000007524 organic acids Chemical class 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
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000009830 intercalation Methods 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 5
- 238000000944 Soxhlet extraction Methods 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002026 chloroform extract Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 230000003287 optical effect Effects 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 11
- 239000010408 film Substances 0.000 description 10
- 230000003595 spectral effect Effects 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 230000004044 response Effects 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- -1 (1-ethyl formate) thiophene-3, 4-dioxypropylenethiophene Chemical class 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical group C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical group COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical group CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000000524 functional group Chemical group 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
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- JSLBLMYJYPZTEB-UHFFFAOYSA-N thiophene-3,4-dicarbonitrile Chemical compound N#CC1=CSC=C1C#N JSLBLMYJYPZTEB-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- VGKLVWTVCUDISO-UHFFFAOYSA-N 3,4-dibromothiophene Chemical compound BrC1=CSC=C1Br VGKLVWTVCUDISO-UHFFFAOYSA-N 0.000 description 1
- KWMRVTDUWMBHRV-UHFFFAOYSA-N 3,4-diethylthiophene Chemical compound CCC1=CSC=C1CC KWMRVTDUWMBHRV-UHFFFAOYSA-N 0.000 description 1
- UGIBDPMYKKYHTB-UHFFFAOYSA-N 3,4-difluorothiophene Chemical compound FC1=CSC=C1F UGIBDPMYKKYHTB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 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
- 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
- 230000003044 adaptive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006698 induction Effects 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
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Chemical group CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research 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
- 239000004984 smart glass Substances 0.000 description 1
- JAOZKJMVYIWLKU-UHFFFAOYSA-N sodium 7-hydroxy-8-[(4-sulfonaphthalen-1-yl)diazenyl]naphthalene-1,3-disulfonic acid Chemical compound C1=CC=C2C(=C1)C(=CC=C2S(=O)(=O)O)N=NC3=C(C=CC4=CC(=CC(=C43)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] JAOZKJMVYIWLKU-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- ZWWLLYJRPKYTDF-UHFFFAOYSA-N thiophene-3,4-dicarboxylic acid Chemical compound OC(=O)C1=CSC=C1C(O)=O ZWWLLYJRPKYTDF-UHFFFAOYSA-N 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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- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
- G02F1/15165—Polymers
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- C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
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- C08G2261/1426—Side-chains containing oxygen containing carboxy groups (COOH) and/or -C(=O)O-moieties
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- C08G2261/14—Side-groups
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
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- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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- C08G2261/324—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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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08G2261/54—Physical properties electrochromatic
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- 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
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1458—Heterocyclic containing sulfur as the only heteroatom
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Abstract
本发明公开了一种含噻吩嵌入单元电致变色聚合物。本发明将强吸电基噻吩作为嵌入单元,引入至二氧噻吩主链中,利用其强吸电子作用以及一定的空间位阻,电致变色聚合物具有黄色、红色至透明态的可逆转换;含噻吩嵌入单元电致变色聚合物具有驱动电压低、光学对比度高、稳定性高的特点,适用于电致变色器件的组装应用。本发明还公开了一种电致变色聚合物的制备方法、薄膜和器件。
Description
技术领域
本发明涉及电致变色技术领域,具体涉及含噻吩嵌入单元电致变色聚合物、制备方法、薄膜及器件。
背景技术
电致变色是指材料在外加电场作用下,通过离子与电子的注入或抽出,发生氧化还原反应,外观表现为颜色可逆变化的现象。电致变色材料在智能窗、防眩目后视镜、自适应伪装等领域有广阔的应用前景,发展新型变色性能优异的电致变色聚合物也一直是电致变色领域的研究热点,特别是具有高带隙结构的聚合物。
目前,调整聚合物带隙以及光谱吸收的方法主要有两种,一种是调节电子诱导效应,另一种是调节共轭效应。其中,电子诱导效应是将吸电子或富电子的基团引入聚合物中,通过调控主链的π电子密度,对带隙及光谱吸收进行调控。共轭效应则是利用基团的立体性,调节共轭链的共平面性进行调控。
显示黄色、橙色、红色等颜色需要聚合物具有较高的带隙,而实现较困难。Reynolds等将苯环、甲氧基苯、咔唑等基团引入至二氧噻吩主链,利用苯环等破坏二氧噻吩主链的共平面性,达到增加带隙的目标,使聚合物显示为黄色、橙色等(Macromolecules,47,5462),但上述基团的引入会使聚合物的稳定性急剧下降。另外,强吸电基噻吩由于其强吸电子作用导致其均聚物虽然具有较高的带隙,但因变色电位较高,稳定性仍较差。
发明内容
本发明的目的之一在于克服现有技术中存在的缺陷,提供一种含噻吩嵌入单元电致变色聚合物,具有驱动电压低、光学对比度高、稳定性高的特点。
为了实现上述目的,本发明的技术方案为:含噻吩嵌入单元电致变色聚合物,结构式如下:
式1中,R1各自独立为F、CN、COOC2H5,R各自独立为C8-C16的烷基;n表示聚合度,n为8~100的自然数,进一步的,n为8~50的自然数。进一步的,式1中两个R所表示的官能团相同,和/或两个R1所表示的官能团也相同。碳原子数过小不利于聚合物在有机溶剂的溶解度,不利于成膜。
本发明的目的之二在于提供一种含噻吩嵌入单元电致变色聚合物的制备方法,包括以下步骤:
式2所示化合物、式3所示化合物、无机弱碱、钯类催化剂、有机酸和有机溶剂混合,惰性气体保护条件下聚合反应,反应结束后经后处理得式1所示电致变色聚合物;
式2中R为各自独立为C8-C16的烷基,式3中R1各自独立为F、CN、COOC2H5。
优选的技术方案为,所述有机酸为选自三甲基乙酸和特戊酸中的至少一种;所述无机弱碱为碳酸钠和碳酸钾中的至少一种;所述钯类催化剂为乙酸钯;所述有机溶剂为N,N-二甲基乙酰胺。
优选的技术方案为,式2所示化合物与式3所示化合物的摩尔比为(0.9~1.1):1。摩尔比过大或过小不利于聚合,不利于聚合物分子链的增长。
优选的技术方案为,无机弱碱与式3所示化合物的摩尔比为(1~1.6):1;有机酸与式3所示化合物的摩尔比为(0.1~0.25):1;钯类催化剂与式3所示化合物的摩尔比为(0.02~0.04):1。
优选的技术方案为,所述聚合反应的温度为120~140℃,反应时间为36~72h。
优选的技术方案为,所述后处理为索氏提取过程,所述索氏提取为依次采用甲醇、正已烷、甲苯、氯仿提取聚合反应所得沉淀,氯仿提取液浓缩,并将氯仿浓缩液滴入甲醇中进行沉淀。
本发明的目的之三在于提供一种聚合物薄膜,所述聚合物薄膜由上述的含噻吩嵌入单元电致变色聚合物和有机溶剂的溶液涂布于基材并干燥制得。
优选的技术方案为,聚合物薄膜的膜厚为150~600nm。膜厚过小颜色对比度不高,过大例如大于400nm,则薄膜太厚,影响褪色状态。
本发明的目的之四在于提供一种电致变色器件,包括依次层叠的上电极层、电解质层、电致变色薄膜层和下电极层,所述电致变色薄膜层为上述的电致变色薄膜。进一步的,所述电致变色器件包括但不限于电子设备状态检测设备、电致变色智能窗、防眩目后视镜、电致变色自适应伪装设备。
本发明的优点和有益效果在于:
本发明将强吸电基噻吩作为嵌入单元,引入至二氧噻吩主链中,利用其强吸电子作用以及一定的空间位阻,电致变色聚合物具有黄色、红色至透明态的可逆转换;
含噻吩嵌入单元电致变色聚合物具有驱动电压低、光学对比度高、稳定性高的特点,适用于电致变色器件的组装应用。
附图说明
图1是实施例1电致变色聚合物的核磁氢谱;
图2是实施例2电致变色聚合物的核磁氢谱;
图3是实施例3电致变色聚合物的核磁氢谱;
图4是实施例1-3电致变色聚合物溶于二氯甲烷的光谱吸收曲线和颜色照片;
图5是实施例2电致变色聚合物薄膜在不同电位下的紫外-可见吸收光谱与颜色变换照片;
图6是实施例3电致变色聚合物薄膜在不同电位下的紫外-可见吸收光谱与颜色变换照片;
图7是实施例2电致变色聚合物薄膜计时透光率响应和稳定性曲线;
图8是实施例3电致变色聚合物薄膜计时透光率响应和稳定性曲线;
图9是实施例3电致变色聚合物薄膜的电化学稳定曲线(100次循环伏安扫描);
图10是实施例3电致变色聚合物薄膜的电化学稳定曲线(第1次和第100次循环伏安扫描)。
具体实施方式
下面结合实施例,对本发明的具体实施方式作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案,而不能以此来限制本发明的保护范围。
实施例1
实施例1的含噻吩嵌入单元电致变色聚合物结构式见式1,其中R1均为CN,R均为C12烷基。
含氟取代基噻吩嵌入单元的电致变色聚合物的制备:
1.1溴代反应制备2,5-二溴-二烷氧基甲基丙撑二氧噻吩
将0.1mmol的二烷氧基甲基丙撑二氧噻吩溶于20mL氯仿置于100mL双口瓶,氮气保护,用锡箔纸包覆双口瓶,达到避光的效果,将0.3mmol的NBS(N-溴代丁二酰亚胺)溶于10mL的N,N-二甲基甲酰胺(DMF),通过注射器缓慢注入至反应瓶中,搅拌反应36h,将反应液倒入水中,分液收集有机相,水相用20mL二氯甲烷萃取两次,合次有机相,用无水硫酸镁干燥,采用干法上样过硅胶柱,淋洗剂为二氯甲烷/正已烷(2:1),得到白色固体,产率为73%;对应的核磁氢谱1H-NMR(400MHz,CDCl3):δ3.93(s,4H),1.45-1.15(m,20H),0.90(t,6H,J=7.0Hz)。
1.2 3,4-二氰基噻吩单体的制备:
将3,4-二溴噻吩5.04g、氰化亚铜5.38g和DMF8ml加入250ml三颈烧瓶中,氮气氛围下160℃搅拌回流24h,然后将溶液冷却至室温,向该混合物中加入含有氯化铁16g的1.0M盐酸溶液100ml,在65℃下搅拌1h,用二氯甲烷萃取数次,再用6M的盐酸溶液洗涤数次,饱和碳酸钠溶液洗两次,水洗两次,浓缩,将粗产物通过柱色谱纯化得到白色絮状固体。产率为67%。1H NMR(400MHz,CDCl3):δ8.00(s)。
1.3聚合反应
0.1mmol的2,5-二溴-二烷氧基甲基丙撑二氧噻吩、0.1mmol的3,4-二氰基噻吩、0.006mmol的醋酸钯、0.3mmol的碳酸钾、0.03mmol的特戊酸置于25mL双口瓶中,抽换气注入氮气,注入15mL无水DMF,再抽换气充满氮气,加热至120℃回流反应72h,反应结束冷却至室温,将反应液滴入至冷甲醇中进行沉淀,过滤沉淀物进行干燥。
1.3聚合反应所得沉淀的后处理
分别以甲醇、正已烷和氯仿进行索氏提取,每一次提取时间为24h,将氯仿提取液进行浓缩至15mL,再滴入至冷甲醇中沉淀得到黑色固体,过滤干燥即得到目标聚合物。经检测聚合物的聚合度为10-20。
实施例2
实施例2的含噻吩嵌入单元电致变色聚合物结构式见式1,其中R1均为COOC2H5,R均为C12烷基。
含甲酸乙酯基取代基噻吩嵌入单元的电致变色聚合物的制备:
2.1溴代反应制备2,5-二溴-二烷氧基甲基丙撑二氧噻吩同实施例1;
2.2 3,4-二甲酸乙酯基噻吩单体的制备:
将3,4-二羧基噻吩溶解在乙醇中,加入1ml硫酸,将混合物加热回流过夜,然后冷却至室温,加入碳酸钾2g,过滤,旋蒸除去溶剂,将粗产物通过柱色谱纯化(石油醚:乙酸乙酯=6:1),得到黄色油状液体,产率为75%。1H NMR(400MHz,CDCl3):δ1.3-1.5(m,10H)3.31(s,4H),7.82(s,2H)。
2.3聚合反应
0.1mmol的2,5-二溴-二烷氧基甲基丙撑二氧噻吩、0.1mmol的3,4-二甲酸乙酯基噻吩、0.006mmol的醋酸钯、0.3mmol的碳酸钾、0.03mmol的特戊酸置于25mL双口瓶中,抽换气注入氮气,注入15mL无水DMF,再抽换气充满氮气,加热至120℃回流反应72h,反应结束冷却至室温,将反应液滴入至冷甲醇中进行沉淀,过滤沉淀物进行干燥。
2.3聚合反应所得沉淀的后处理
分别以甲醇、正已烷和氯仿进行索氏提取,每一次提取时间为24h,将氯仿提取液进行浓缩至15mL,再滴入至冷甲醇中沉淀得到黑色固体,过滤干燥即得到目标聚合物。经检测聚合物的聚合度为10-20。
实施例3
实施例3的含噻吩嵌入单元电致变色聚合物结构式见式1,其中R1均为F,R均为C12H25。
含甲酸乙酯基取代基噻吩嵌入单元的电致变色聚合物的制备:
2.1溴代反应制备2,5-二溴-二烷氧基甲基丙撑二氧噻吩同实施例1;
2.2聚合反应
0.1mmol的2,5-二溴-二烷氧基甲基丙撑二氧噻吩、0.1mmol的3,4-二氟噻吩、0.006mmol的醋酸钯、0.3mmol的碳酸钾、0.03mmol的特戊酸置于25mL双口瓶中,抽换气注入氮气,注入15mL无水DMF,再抽换气充满氮气,加热至120℃回流反应72h,反应结束冷却至室温,将反应液滴入至冷甲醇中进行沉淀,过滤沉淀物进行干燥。
2.3聚合反应所得沉淀的后处理
分别以甲醇、正已烷和氯仿进行索氏提取,每一次提取时间为24h,将氯仿提取液进行浓缩至15mL,再滴入至冷甲醇中沉淀得到黑色固体,过滤干燥即得到目标聚合物。经检测聚合物的聚合度为10-20。
实施例1-3所得电致变色聚合物薄膜的制备:
将聚合物溶于氯仿中,配制2mg/ml的溶液,通过滤嘴过滤出不溶物后转入喷枪中,控制气压为2MPa,在导电玻璃上进行喷涂,喷涂后置于真空干燥箱中40℃真空烘干待用。薄膜吸光度为0.8左右。
实施例1-3聚合物薄膜的厚度控制在150-600nm区间内。
实施例1-3所得电致变色聚合物薄膜参与电致变色器件的组装
采用以上电致变色聚合物薄膜为工作电极、铂丝为对电极、标定过的银丝为参比电极的三电极体系,支持电解质为0.2mol/L的高氯酸锂丙烯碳酸酯溶液。
实施例1所得聚合物的核磁共振氢谱见图1,实施例2所得聚合物的核磁共振氢谱见图2,实施例3所得聚合物的核磁共振氢谱见图3;对实施例1-3制得的聚合物、聚合物薄膜或者电致变色器件进行以下测试:
(1)实施例1制备的聚合物进行溶液光谱测试:
将实施例的聚合物溶于二氯甲烷,配制成浓度为2*10-4mg/mL的溶液,溶液光谱吸收曲线和照片如图2所示,图中曲线与电致变色聚合物的对应关系为:
(a)P(3,4-二(1-甲酸乙酯基)噻吩-3,4-二氧丙撑噻吩)——实施例2,吸收峰为432nm,聚合物溶液呈现为橙黄色;
(b)P(3,4-二氟代噻吩-3,4-二氧丙撑噻吩)——实施例3,吸收峰为488nm,聚合物溶液呈现为红褐色;
(c)P(3,4-二氰基噻吩-3,4-二氧丙撑噻吩)——实施例1吸收峰为590nm,聚合物溶液呈现为蓝色。
(2)对聚合物薄膜进行不同电压下的光谱电化学性能测试:
采用三电极体系,铂丝为对电极,标定过的银丝为参比电极,聚合物薄膜为工作电极,支持电解质为:0.1mol/L的高氯酸锂丙烯碳酸酯溶液。
图5为实施例2聚合物薄膜在不同外加电压下的光谱电化学谱图和失色着色照片;图6为实施例3共聚物薄膜在不同外加电压下的光谱电化学谱图和失色着色照片;采用强吸电基噻吩作为嵌入单元,聚合物的吸收光谱较3,4-二氧丙撑噻吩均聚物有一定的蓝移,通过调控共聚单体种类可对共聚物的光谱吸收实现调节。
3,4-二氧丙撑噻吩均聚物聚合物在波长530nm附近有强吸收,在570nm附近有一个肩峰吸收,在这两个吸收峰的综合作用下,其溶液显紫红色。
(3)阶跃法测试聚合物薄膜的光谱响应与稳定性能
图7为实施例2聚合物薄膜的光谱响应与稳定性能;图7所示,P(3,4-二甲酸乙酯基噻吩-3,4-二氧丙撑噻吩)的阶跃电位为0V和1.8V,电压驻留时间为15s,透过率对比度为33.67%,失色和着色的响应时间为4.2s左右;
图8是实施例3聚合物薄膜的光谱响应与稳定性能;图8所示,P(3,4-二氟代噻吩-3,4-二氧丙撑噻吩)的阶跃电位为0V和1.0V,电压驻留时间为15s,透过率对比度为27.68%,失色和着色的响应时间为3.7s左右;
与实施例1相比,实施例2和3的聚合物薄膜光谱响应与稳定性能较优。
(4)电致变色聚合物薄膜的电化学稳定性测试
图9为实施例3电致变色聚合物薄膜100次循环伏安扫描结果,图10为图9中第一次和第100次循环伏安扫描结果,电致变色聚合物薄膜循环伏安扫描100次依然保持稳定性。
与实施例1和2相比,实施例3电致变色聚合物薄膜的电化学稳定性较优。
由以上可知,电致变色聚合物的颜色和吸收光谱可通过共聚单体种类进行调控,共聚物薄膜可实现有色至透明的变换,并且具有驱动电位低、变色速率快、着色效率高、稳定性好等特点,制备的共聚物薄膜在电致变色显示、自适应伪装等领域可应用。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.含噻吩嵌入单元电致变色聚合物,其特征在于,结构式如下:
式1中,R1各自独立为F、CN、COOC2H5,R各自独立为C8-C16
的烷基;n表示聚合度,n为8~100的自然数。
2.权利要求1所述的含噻吩嵌入单元电致变色聚合物的制备方法,其特征在于,包括以下步骤:
式2所示化合物、式3所示化合物、无机弱碱、钯类催化剂、有机酸和有机溶剂混合,惰性气体保护条件下聚合反应,反应结束后经后处理得式1所示电致变色聚合物;
式2中R为各自独立为C8-C16的烷基,式3中R1各自独立为F、CN、COOC2H5。
3.根据权利要求2所述的含噻吩嵌入单元电致变色聚合物的制备方法,其特征在于,所述有机酸为特戊酸;所述无机弱碱为碳酸钾;所述钯类催化剂为乙酸钯;所述有机溶剂为N,N-二甲基乙酰胺。
4.根据权利要求2所述的含噻吩嵌入单元电致变色聚合物的制备方法,其特征在于,式2所示化合物与式3所示化合物的摩尔比为(0.9~1.1):1。
5.根据权利要求2所述的含噻吩嵌入单元电致变色聚合物的制备方法,其特征在于,无机弱碱与式3所示化合物的摩尔比为(1~1.6):1;有机酸与式3所示化合物的摩尔比为(0.1~0.25):1;钯类催化剂与式3所示化合物的摩尔比为(0.02~0.04):1。
6.根据权利要求2所述的含噻吩嵌入单元电致变色聚合物的制备方法,其特征在于,所述聚合反应的温度为120~140℃,反应时间为36~72h。
7.根据权利要求2所述的含噻吩嵌入单元电致变色聚合物的制备方法,其特征在于,所述后处理为索氏提取过程,所述索氏提取为依次采用甲醇、正已烷、甲苯、氯仿提取聚合反应所得沉淀,氯仿提取液浓缩,并将氯仿浓缩液滴入甲醇中进行沉淀。
8.聚合物薄膜,其特征在于,所述聚合物薄膜由权利要求1所述的含噻吩嵌入单元电致变色聚合物和有机溶剂的溶液涂布于基材并干燥制得。
9.根据权利要求8所述的聚合物薄膜,其特征在于,聚合物薄膜的膜厚为150~600nm。
10.电致变色器件,其特征在于,包括依次层叠的上电极层、电解质层、电致变色薄膜层和下电极层,所述电致变色薄膜层为权利要求8或9中任意一项所述的电致变色薄膜。
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