CN115975158A - 高透明度电致变色聚合物 - Google Patents
高透明度电致变色聚合物 Download PDFInfo
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- CN115975158A CN115975158A CN202310083647.4A CN202310083647A CN115975158A CN 115975158 A CN115975158 A CN 115975158A CN 202310083647 A CN202310083647 A CN 202310083647A CN 115975158 A CN115975158 A CN 115975158A
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- Prior art keywords
- electrochromic polymer
- heterocyclic
- mcls
- electrochromic
- alkoxy
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- 229920000642 polymer Polymers 0.000 title claims abstract description 99
- 125000003118 aryl group Chemical group 0.000 claims abstract description 60
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 36
- 238000010521 absorption reaction Methods 0.000 claims description 32
- 125000000623 heterocyclic group Chemical group 0.000 claims description 32
- 230000007935 neutral effect Effects 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 125000003545 alkoxy group Chemical group 0.000 claims description 22
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 18
- 125000003282 alkyl amino group Chemical group 0.000 claims description 18
- 125000004688 alkyl sulfonyl alkyl group Chemical group 0.000 claims description 18
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 claims description 18
- 125000005112 cycloalkylalkoxy group Chemical group 0.000 claims description 18
- 125000004446 heteroarylalkyl group Chemical group 0.000 claims description 18
- 125000006517 heterocyclyl carbonyl group Chemical group 0.000 claims description 18
- 125000004415 heterocyclylalkyl group Chemical group 0.000 claims description 18
- 125000005844 heterocyclyloxy group Chemical group 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 17
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 17
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 16
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 16
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 claims description 14
- 125000004414 alkyl thio group Chemical group 0.000 claims description 13
- 125000001072 heteroaryl group Chemical group 0.000 claims description 13
- 229930192474 thiophene Natural products 0.000 claims description 10
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 claims description 9
- 125000006193 alkinyl group Chemical group 0.000 claims description 9
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 9
- 125000000304 alkynyl group Chemical group 0.000 claims description 9
- 125000006310 cycloalkyl amino group Chemical group 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- MABNMNVCOAICNO-UHFFFAOYSA-N selenophene Chemical compound C=1C=C[se]C=1 MABNMNVCOAICNO-UHFFFAOYSA-N 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 abstract description 9
- 230000008859 change Effects 0.000 abstract description 3
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000007787 solid Substances 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 11
- 101000817240 Mus musculus Eosinophil cationic protein 1 Proteins 0.000 description 10
- 101000879966 Mus musculus Eosinophil cationic protein 2 Proteins 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
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- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 7
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
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- 125000001424 substituent group Chemical group 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
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- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229940125773 compound 10 Drugs 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 1
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- MCWFWBFCIQXXSJ-UHFFFAOYSA-N 1,5-dibromo-2,4-dihexoxybenzene Chemical compound CCCCCCOC1=CC(OCCCCCC)=C(Br)C=C1Br MCWFWBFCIQXXSJ-UHFFFAOYSA-N 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- QPTWWBLGJZWRAV-UHFFFAOYSA-N 2,7-dibromo-9-H-carbazole Natural products BrC1=CC=C2C3=CC=C(Br)C=C3NC2=C1 QPTWWBLGJZWRAV-UHFFFAOYSA-N 0.000 description 1
- GPSFYJDZKSRMKZ-UHFFFAOYSA-N 3,4-dimethylthiophene Chemical compound CC1=CSC=C1C GPSFYJDZKSRMKZ-UHFFFAOYSA-N 0.000 description 1
- NZWIYPLSXWYKLH-UHFFFAOYSA-N 3-(bromomethyl)heptane Chemical compound CCCCC(CC)CBr NZWIYPLSXWYKLH-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
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- 230000021615 conjugation Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
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- 230000000977 initiatory effect Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
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- 125000001624 naphthyl group Chemical group 0.000 description 1
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- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
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- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
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- 238000004544 sputter deposition Methods 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
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- C09K9/02—Organic tenebrescent materials
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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
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- 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
- C08G61/124—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 nitrogen atom in the ring
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- 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
- C08G61/125—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 oxygen atom in the ring
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- 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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- 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
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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
- G02F1/1514—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
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- H10K85/10—Organic polymers or oligomers
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Abstract
一种电致变色聚合物,由包含一个或多个间位共轭的接头(MCLs)以及一个或多个芳香族部分(Ars)的重复单元组成。该一个或多个MCLs中的每一个在MCLs的间位位置处与该一个或多个Ars部分地共轭以形成电致变色聚合物的聚合物主链。该电致变色聚合物可在电致变色器件中经历光学切换和颜色变化,显示出高透明度和高光学对比度。
Description
技术领域
本发明涉及一种新型电致变色聚合物,其包含间位共轭的接头和芳香族部分,在中性状态下该电致变色聚合物在可见光区域呈现高透明度。当该聚合物薄膜被氧化时,其在可见光和近红外区域具有高度吸收性,因此该聚合物薄膜显示着色态。本发明还公开了一种结合了这种具有高光学对比度和高透光率的共轭电致变色聚合物薄膜的装置。
背景技术
电致变色装置可以调节透光率和控制太阳热增益。与通过真空溅射工艺制造的基于无机的电致变色器件相比,基于聚合物的电致变色窗户可以通过卷对卷涂布和层压进行制造。因此,它生产成本低并具有制造灵活性。基于聚合物的电致变色装置通常由共轭电致变色聚合物(ECPs)组成,其具有由sp2杂化碳组成的完全共轭的聚合物主链。传统上,ECPs通常在可见光区域具有强吸收性,因此在其中性状态下着色。当它们被氧化时,它们的吸收转移到近红外(近IR)区域,并且它们在可见光区域变得可透射的。然而,氧化后的聚合物在可见光区域通常仍有微弱的吸收,因此导致残留的颜色。当聚合物膜变厚时,该问题更加严重。因此该问题对聚合物的光学对比度产生负面影响。此外,它限制了电致变色共轭聚合物可以达到的最高光透光率。此外,处于中性状态的传统ECPs会阻挡可见光通过薄膜并允许近红外光通过;但在透射状态下,它允许可见光通过并阻挡近红外光。这种组合对于热管理和控制太阳热增益(SHG)是无效的。SHG描述了太阳辐射通过窗户产品转化为热量的方式。
发明内容
本发明涉及一种新型电致变色聚合物。本发明所公开的电致变色聚合物由一个聚合物主链组成,该聚合物主链包括一个或多个间位共轭的接头(MCLs)以及一个或多个芳香族部分(Ars)。该一个或多个MCLs中的每一个在该一个或多个MCLs的间位位置处与该一个或多个Ars部分地共轭以形成电致变色聚合物的聚合物主链。在一些实施例中,电致变色聚合物是阳极着色的电致变色聚合物(AC-ECP),当其被氧化时着色。
本发明所公开的聚合物主链包括一种重复单元,该重复单元包括一个或多个间位共轭的接头(MCLs)以及一个或多个芳香族部分(Ars)。该一个或多个MCLs中的每一个在该一个或多个MCLs的间位位置处与该一个或多个Ars部分地共轭以形成电致变色聚合物的聚合物主链。在一些实施例中,电致变色聚合物是阳极着色的电致变色聚合物(AC-ECP),当其被氧化时着色。
在一些实施例中,本发明所公开的电致变色聚合物在中性状态下吸收起始波长等于或小于420nm。在一些实施例中,本发明所公开的电致变色聚合物在中性状态下能带隙等于或高于2.9eV并小于4.0eV。在一些实施例中,在中性状态下,最大吸收(该聚合物具有最强光子吸收的波长)小于410nm。在一些实施例中,本发明所公开的电致变色聚合物在中性状态下是无色的,而在氧化状态下它是着色的并可见和近红外吸收的。该被氧化的电致变色聚合物在可见光和/或近红外区域具有大于104cm-1的吸收系数,因此在氧化状态下着色。
尽管它们具有高带隙,但在一些实施例中,本发明所公开的电致变色聚合物相对于Ag/AgCl电极仍然具有在0.1-1.5V(含)的范围内的相对低的氧化电位。
该MCL包括芳香结构或稠合芳香结构或它们的组合中的至少一种。该芳香结构包括苯或杂环结构。该稠合芳香结构包括稠合苯结构、或稠合杂环结构、或苯和杂环的稠合结构。
在一些实施例中,对于本发明所公开的电致变色聚合物,该一个或多个MCLs和该一个或多个Ars以交替的或随机的方式排列,具有以下通式:
在此处的结构中,n是一个大于0的整数,m1、m2、…、mn中的每一个都是大于或等于0的整数,该m1、m2、…、mn中至少一个大于0。该一个或多个MCLs(或该一个或多个Ars)可以彼此相同或不同。
在一些实施例中,该一个或多个MCLs及其间位位置包括下式中的任一种:
其中,每条波浪线代表连接相邻该一个或多个Ars的间位位置;X是S、Se、N、C或O;R1-R12独立地选自以下取代基,包括但不限于氢(hydrogen)、C1-C30烷基(alkyl)、C2-C30烯基(alkenyl)、C2-C30炔基(alkynyl)、C2-C30烷基羰基(alkylcarbonyl)、C1-C30烷氧基(alkoxy)、C3-C30烷氧基烷基(alkoxyalkyl)、C2-C30烷氧基羰基(alkoxycarbonyl)、C4-C30烷氧基羰基烷基(alkoxycarbonylalkyl)、C1-C30烷硫基(alkylthio)、C1-C30氨基羰基(aminylcarbonyl)、C4-C30氨基烷基(aminylalkyl)、C1-C30烷基氨基(alkylaminyl)、C1-C30烷基磺酰基(alkylsulfonyl)、C3-C30烷基磺酰基烷基(alkylsulfonylalkyl)、C6-C18芳基(aryl)、C3-C15环烷基(cycloalkyl)、C3-C30环烷基氨基(cycloalkylaminyl)、C5-C30环烷基烷基氨基(cycloalkylalkylaminyl)、C5-C30环烷基烷基(cycloalkylalkyl)、C5-C30环烷基烷氧基(cycloalkylalkyloxy)、C1-C12杂环基(heterocyclyl)、C1-C12杂环氧基(heterocyclyloxy)、C1-C30杂环烷氧基(heterocyclylalkyloxy)、C1-C30杂环氨基(heterocyclylaminyl)、C5-C30杂环烷基氨基(heterocyclylalkylaminyl)、C2-C12杂环基羰基(heterocyclylcarbonyl)、C3-C30杂环基烷基(heterocyclylalkyl)、C1-C13杂芳基(heteroaryl)或C3-C30杂芳基烷基(heteroarylalkyl)。
其中,R13,R14和R15各自独立地选自以下取代基,包括但不限于氢(hydrogen)、C1-C30烷基(alkyl)、C2-C30烯基(alkenyl)、C2-C30炔基(alkynyl)、C2-C30烷基羰基(alkylcarbonyl)、C1-C30烷氧基(alkoxy)、C3-C30烷氧基烷基(alkoxyalkyl)、C2-C30烷氧基羰基(alkoxycarbonyl)、C4-C30烷氧基羰基烷基(alkoxycarbonylalkyl)、C1-C30烷硫基(alkylthio)、C1-C30氨基羰基(aminylcarbonyl)、C4-C30氨基烷基(aminylalkyl)、C1-C30烷基氨基(alkylaminyl)、C1-C30烷基磺酰基(alkylsulfonyl)、C3-C30烷基磺酰基烷基(alkylsulfonylalkyl)、C6-C18芳基(aryl)、C3-C15环烷基(cycloalkyl)、C3-C30环烷基氨基(cycloalkylaminyl)、C5-C30环烷基烷基氨基(cycloalkylalkylaminyl)、C5-C30环烷基烷基(cycloalkylalkyl)、C5-C30环烷基烷氧基(cycloalkylalkyloxy)、C1-C12杂环基(heterocyclyl)、C1-C12杂环氧基(heterocyclyloxy)、C1-C30杂环烷氧基(heterocyclylalkyloxy)、C1-C30杂环氨基(heterocyclylaminyl)、C5-C30杂环烷基氨基(heterocyclylalkylaminyl)、C2-C12杂环基羰基(heterocyclylcarbonyl)、C3-C30杂环基烷基(heterocyclylalkyl)、C1-C13杂芳基(heteroaryl)或C3-C30杂芳基烷基(heteroarylalkyl)。
在一些实施例中,基于噻吩的单元包含下式
或以上的任意组合,
其中,X是S、Se、N、C或O;R15-R18中的每一个独立地选自以下取代基,包括但不限于氢(hydrogen)、C1-C30烷基(alkyl)、C2-C30烯基(alkenyl)、C2-C30炔基(alkynyl)、C2-C30烷基羰基(alkylcarbonyl)、C1-C30烷氧基(alkoxy)、C3-C30烷氧基烷基(alkoxyalkyl)、C2-C30烷氧基羰基(alkoxycarbonyl)、C4-C30烷氧基羰基烷基(alkoxycarbonylalkyl)、C1-C30烷硫基(alkylthio)、C1-C30氨基羰基(aminylcarbonyl)、C4-C30氨基烷基(aminylalkyl)、C1-C30烷基氨基(alkylaminyl)、C1-C30烷基磺酰基(alkylsulfonyl)、C3-C30烷基磺酰基烷基(alkylsulfonylalkyl)、C6-C18芳基(aryl)、C3-C15环烷基(cycloalkyl)、C3-C30环烷基氨基(cycloalkylaminyl)、C5-C30环烷基烷基氨基(cycloalkylalkylaminyl)、C5-C30环烷基烷基(cycloalkylalkyl)、C5-C30环烷基烷氧基(cycloalkylalkyloxy)、C1-C12杂环基(heterocyclyl)、C1-C12杂环氧基(heterocyclyloxy)、C1-C30杂环烷氧基(heterocyclylalkyloxy)、C1-C30杂环氨基(heterocyclylaminyl)、C5-C30杂环烷基氨基(heterocyclylalkylaminyl)、C2-C12杂环基羰基(heterocyclylcarbonyl)、C3-C30杂环基烷基(heterocyclylalkyl)、C1-C13杂芳基(heteroaryl)
或C3-C30杂芳基烷基(heteroarylalkyl)。Y是任意一个或多个Ars、或芳香结构、或稠合的芳香结构、或以上的任意组合。
在一些实施例中,基于噻吩的单元中的X是O。
在一些实施例中,本发明所公开的电致变色聚合物包含下式
附图描述
本技术的各种实施例的某些特征在所附权利要求书中具体阐述。通过参考阐述利用本发明原理的说明性实施例的以下详细描述以及以下附图,将更好地理解本技术的特征和优点。为了说明本发明的目的,附图示出了本发明的一个或多个实施例的多方面。然而,应当理解,本发明不限于附图中所示的精确配置和手段。
图1(A)-(B)是显示本发明所公开的ECP(图1(A))与传统的ECP(图1(B))相比不同的颜色变化机理图。
图2是根据一个实施例提供的使用示例ECP-1的示例性固态器件的CV数据。
图3是根据一个实施例提供的使用示例ECP-1的示例性固态器件在545nm处的切换动力学。
图4是根据一个实施例提供的使用示例ECP-1的薄膜在不同电压下的吸收光谱。
图5是根据一个实施例提供的使用示例ECP-2的示例性固态器件的CV数据。
图6是根据一个实施例提供的使用示例ECP-2的示例性固态器件在550nm处的切换动力学。
图7是根据一个实施例提供的使用示例ECP-2的薄膜在不同电压下的吸收光谱。
图8是根据一个实施例提供的使用示例ECP-6的0.1mg/ml二氯甲烷溶液在不同电压下的吸收光谱。
图9是根据一个实施例提供的使用示例ECP-7的0.1mg/ml二氯甲烷溶液在不同电压下的吸收光谱。
具体实施方式
在以下描述中,阐述了某些具体细节以提供对本发明的各种实施例的透彻理解。然而,本领域普通技术人员将理解,可以在没有这些细节的情况下实施本发明。此外,虽然这里公开了本发明的各种实施例,但是根据本领域普通技术人员的公知常识,在本发明的范围内可以做出许多适配和修改。这些修改包括对本发明的任何方面的已知等效物的替换,以便以基本上相同的方式实现相同的结果。除非上下文另外要求,否则在整个说明书和权利要求书中,词语“包括”及其变体(例如“包括”和“包含”)应以开放的、包含性的含义来解释,即为“包括但不限于”。另外,除非上下文另有明确规定,否则单数形式的“一个”,“一种”和“该”包括复数个所指对象。
在整个说明书中,对“一个实施例”或“实施例”的引用意味着结合该实施例描述的特定特征、结构或特性包括在本发明的至少一个实施例中。因此,在说明书各处出现的短语“在一个实施例中”或“在实施例中”不一定都指代相同的实施例,而是指在某些情况下。此外,一个或多个实施例中的特定特征、结构或特性可以以任何合适的方式组合。
本发明涉及一种新型电致变色聚合物。本发明公开的电致变色聚合物由一个聚合物主链组成,该聚合物主链包括一个或多个间位共轭的接头(MCLs)以及一个或多个芳香族部分(Ars)。该一个或多个MCLs中的每一个在该一个或多个MCLs的间位位置处与该一个或多个Ars部分地共轭以形成电致变色聚合物的聚合物主链。在一些实施例中,本发明公开的电致变色聚合物由一种重复单元组成,该重复单元包括一个或多个MCLs以及一个或多个Ars,其间位共轭通过使用MCLs引入到聚合物主链。在一些实施例中,这种电致变色聚合物称为阳极着色的共轭电致变色聚合物(AC-ECP),当其被氧化时着色。
如图1所示,传统的共轭ECPs(图1(B))是完全共轭的,在可见光区域具有很强的吸收,因此在它们的中性状态下着色,而当被氧化(氧化状态)时,它们的吸收移向近红外区域,变得透射的。然而,氧化后的聚合物在可见光区域仍有微弱的吸收,导致残留的颜色。相反地,如图1(A)中的本发明所公开的ECP的一个示例所示,在中性状态下ECP在450nm以上的波长基本没有吸收,在氧化状态下在可见光范围和近红外范围内有多个吸收峰,表明在可见光范围内的着色和近红外吸收。本发明所公开的电致变色聚合物允许可见光和近红外光的同时通过或阻挡,在一个实施例中,这在用于管理太阳热增益的电致变色窗户中非常有用。本发明所公开的电致变色聚合物在中性状态下是透明的,并且在氧化状态下着色和吸收红外线,这些对实现高光学对比度、高透光率和协同的太阳热增益是非常需要的。
本发明公开的电致变色聚合物在中性状态下在可见光区域是透明的,在氧化状态下是有色的。例如,本发明所公开的电致变色聚合物在中性状态下在可见光范围(例如,450-750nm)中可以具有至少60%的透光率。在一些实施例中,本发明所公开的ECPs在中性状态下在450-750nm范围内具有至少65%、70%、75%、80%、85%、90%、92%、95%、98%或更高的透光率。在一些实施例中,本发明所公开的电致变色聚合物在中性状态下的可见光范围内是透明的。在氧化状态下,本发明所公开的电致变色聚合物在可见光范围(例如,约360至750nm)和近红外范围(例如,约750至1600纳米)具有吸收性,从而着色并能够吸收近红外光。
本发明所公开的电致变色聚合物具有UV吸收性和能带隙。能带隙是电子的价带和导带之间的能量差。它是将电子激发到导带中可以参与传导的状态所需的最小能量变化。吸收起始是在高于该波长下该聚合物不具有光子吸收。能带隙可以计算为1240/吸收起始波长。在一些实施例中,在中性状态下本发明所公开的电致变色聚合物在等于或小于450nm处具有吸收起始。在一些实施例中,在中性状态下本发明所公开的电致变色聚合物的吸收起始在等于或小于440nm,430nm,420nm,410nm,405nm,or 400nm处。在一些实施例中,在中性状态下,最大吸收(该聚合物具有最强光子吸收的波长)小于420nm。在一些实施例中,在中性状态下,最大吸收小于410nm or 405nm or 400nm。在一些实施例中,本发明所公开的电致变色聚合物在中性状态下具有能带隙等于或高于2.8eV并小于4.0eV。在一些实施例中,本发明所公开的电致变色聚合物在中性状态下具有能带隙等于或高于2.9,3.0or 3.1eV并小于4.0eV。在一些实施例中,本发明所公开的电致变色聚合物在中性状态下是无色的(例如,在400-750nm或410-750nm或420-750nm没有吸收)或黄色的(例如,在400-500nm,或410-500nm或420-500nm,或400-480nm,或410-480nm或420-480nm,或400-450nm,或410-450nm或420-450nm有拖尾吸收),并且在氧化状态下是着色的、在可见和近红外有吸收的。氧化的电致变色聚合物在可见和/或近红外区域具有大于104cm-1的吸收系数,因此在氧化状态下着色。
由于在中性状态下在可见光范围内基本没有吸光度,而在氧化状态下在可见光范围内有高吸光度,与常规ECPs相比,本发明所公开的电致变色聚合物表现出高光学对比度和高透光率。尽管它们具有高带隙,但在一些实施例中,本发明所公开的电致变色聚合物相对于Ag/AgCl电极在0.1-1.5V(含)的范围内具有相对低的氧化电位。在一些实施例中,本发明所公开的电致变色聚合物相对于Ag/AgCl电极在0.1-1V(含)的范围内具有相对低的氧化电位。相对低的氧化电位可以有利于ECPs的循环耐久性。因此,本发明所公开的电致变色聚合物可以成功地应用到具有良好循环稳定性/可靠性和高光学对比度的器件中。
该MCL包含芳香结构或稠合芳香结构或它们的组合中的至少一种。芳香结构包括苯或杂环结构。稠合芳香结构包括稠合苯结构或稠合杂环结构或稠合苯和杂环结构。在一些实施例中,MCL包含苯、或萘、或五元杂环、或苯稠合的五元杂环、或这些结构的组合中的至少一种。也可以将侧链或芳族侧链引入到MCL以调整其性能,例如溶解度或可加工性或稳定性。
在一些实施例中,该一个或多个MCLs和该一个或多个Ars以交替或随机的方式排列,其通式为:
在此处的结构中,n是一个大于0的整数,m1、m2、…、mn中的每一个都是等于或大于0的整数,该m1、m2、…、mn中至少一个大于0。该一个或多个Ars为芳香族部分,可以包含一个或多个芳香结构。该一个或多个MCLs(或该一个或多个Ars)可以彼此相同或不同。
通过使用一个或多个MCLs在聚合物主链中引入间位共轭。一个或多个MCLs中的每一个通过经由其间位位置与该一个或多个Ar(s)连接而部分地共轭在聚合物主链中。例如,间位位置是MCLs的芳香结构或稠合芳香结构的两个位置。当间位位置连接时,来自芳香结构或稠合芳香结构的π电子不能通过p轨道完全离域到另一个相邻连接的单元。
在一些实施例中,该MCLs的芳香结构包含苯结构或五元杂环结构,并且该MCLs的芳香结构在间位位置(即该芳香结构的1-和3-位)上被取代。在一些实施例中,该MCLs的稠合芳香结构包含萘,并且稠合芳香结构在间位位置(即该萘的1-和3-、或1-和4-、或1-和6-位)上被取代。在一些实施例中,该MCLs的稠合芳香结构包含与五元杂环稠合的苯,并且稠合芳香结构在间位位置(即该杂环稠合的苯上的1-和3-、或1-和5-位)上被取代。
该一个或多个MCLs的示例结构及其间位位置可以包括以下结构其中之一:
其中,X是S、Se、N、C或O;R1-R12分别独立选自以下取代基,包括但不限于氢(hydrogen)、C1-C30烷基(alkyl)、C2-C30烯基(alkenyl)、C2-C30炔基(alkynyl)、C2-C30烷基羰基(alkylcarbonyl)、C1-C30烷氧基(alkoxy)、C3-C30烷氧基烷基(alkoxyalkyl)、C2-C30烷氧基羰基(alkoxycarbonyl)、C4-C30烷氧基羰基烷基(alkoxycarbonylalkyl)、C1-C30烷硫基(alkylthio)、C1-C30氨基羰基(aminylcarbonyl)、C4-C30氨基烷基(aminylalkyl)、C1-C30烷基氨基(alkylaminyl)、C1-C30烷基磺酰基(alkylsulfonyl)、C3-C30烷基磺酰基烷基(alkylsulfonylalkyl)、C6-C18芳基(aryl)、C3-C15环烷基(cycloalkyl)、C3-C30环烷基氨基(cycloalkylaminyl)、C5-C30环烷基烷基氨基(cycloalkylalkylaminyl)、C5-C30环烷基烷基(cycloalkylalkyl)、C5-C30环烷基烷氧基(cycloalkylalkyloxy)、C1-C12杂环基(heterocyclyl)、C1-C12杂环氧基(heterocyclyloxy)、C1-C30杂环烷氧基(heterocyclylalkyloxy)、C1-C30杂环氨基(heterocyclylaminyl)、C5-C30杂环烷基氨基(heterocyclylalkylaminyl)、C2-C12杂环基羰基(heterocyclylcarbonyl)、C3-C30杂环基烷基(heterocyclylalkyl)、C1-C13杂芳基(heteroaryl)或C3-C30杂芳基烷基(heteroarylalkyl);波浪线代表间位位置所在位置。
该一个或多个Ars可以包括但不限于分别具有下式的基于噻吩的单元、基于呋喃的单元、基于硒吩的单元或基于吡咯的单元中的任一种:
在上述结构中,R13,R14和R15各自独立地选自以下取代基,包括但不限于氢(hydrogen)、C1-C30烷基(alkyl)、C2-C30烯基(alkenyl)、C2-C30炔基(alkynyl)、C2-C30烷基羰基(alkylcarbonyl)、C1-C30烷氧基(alkoxy)、C3-C30烷氧基烷基(alkoxyalkyl)、C2-C30烷氧基羰基(alkoxycarbonyl)、C4-C30烷氧基羰基烷基(alkoxycarbonylalkyl)、C1-C30烷硫基(alkylthio)、C1-C30氨基羰基(aminylcarbonyl)、C4-C30氨基烷基(aminylalkyl)、C1-C30烷基氨基(alkylaminyl)、C1-C30烷基磺酰基(alkylsulfonyl)、C3-C30烷基磺酰基烷基(alkylsulfonylalkyl)、C6-C18芳基(aryl)、C3-C15环烷基(cycloalkyl)、C3-C30环烷基氨基(cycloalkylaminyl)、C5-C30环烷基烷基氨基(cycloalkylalkylaminyl)、C5-C30环烷基烷基(cycloalkylalkyl)、C5-C30环烷基烷氧基(cycloalkylalkyloxy)、C1-C12杂环基(heterocyclyl)、C1-C12杂环氧基(heterocyclyloxy)、C1-C30杂环烷氧基(heterocyclylalkyloxy)、C1-C30杂环氨基(heterocyclylaminyl)、C5-C30杂环烷基氨基(heterocyclylalkylaminyl)、C2-C12杂环基羰基(heterocyclylcarbonyl)、C3-C30杂环基烷基(heterocyclylalkyl)、C1-C13杂芳基(heteroaryl)或C3-C30杂芳基烷基(heteroarylalkyl)。
基于噻吩的单元的示例可以包括但不限于下式
或以上的任意组合。
在上述结构中,X为S、Se、N、C或O;R15-R18中的每一个独立地选自以下取代基,包括但不限于氢(hydrogen)、C1-C30烷基(alkyl)、C2-C30烯基(alkenyl)、C2-C30炔基(alkynyl)、C2-C30烷基羰基(alkylcarbonyl)、C1-C30烷氧基(alkoxy)、C3-C30烷氧基烷基(alkoxyalkyl)、C2-C30烷氧基羰基(alkoxycarbonyl)、C4-C30烷氧基羰基烷基(alkoxycarbonylalkyl)、C1-C30烷硫基(alkylthio)、C1-C30氨基羰基(aminylcarbonyl)、C4-C30氨基烷基(aminylalkyl)、C1-C30烷基氨基(alkylaminyl)、C1-C30烷基磺酰基(alkylsulfonyl)、C3-C30烷基磺酰基烷基(alkylsulfonylalkyl)、C6-C18芳基(aryl)、C3-C15环烷基(cycloalkyl)、C3-C30环烷基氨基(cycloalkylaminyl)、C5-C30环烷基烷基氨基(cycloalkylalkylaminyl)、C5-C30环烷基烷基(cycloalkylalkyl)、C5-C30环烷基烷氧基(cycloalkylalkyloxy)、C1-C12杂环基(heterocyclyl)、C1-C12杂环氧基(heterocyclyloxy)、C1-C30杂环烷氧基(heterocyclylalkyloxy)、C1-C30杂环氨基(heterocyclylaminyl)、C5-C30杂环烷基氨基(heterocyclylalkylaminyl)、C2-C12杂环基羰基(heterocyclylcarbonyl)、C3-C30杂环基烷基(heterocyclylalkyl)、C1-C13杂芳基(heteroaryl)或C3-C30杂芳基烷基(heteroarylalkyl)。Y是一个或多个Ars,或芳香结构,或稠合芳香结构,或以上的任意组合。
在一些实施例中,基于噻吩的单元中的X是O。
通过将间位共轭引入电致变色聚合物主链中,沿聚合物主链的电子共轭被中断并因此导致高带隙(>2.0eV)。所以本发明所公开的电致变色聚合物在中性状态下表现出高度透射性(或甚至透明)。ECP的氧化导致较低的带隙(<1.5eV),聚合物的吸光度从紫外区红移到可见光和近红外区。因此,聚合物变得高度着色。
该一个或多个Ars可能包括一个或多个芳香结构或稠合芳香结构。通过控制Ars的类型和数量,可以容易地调整本发明所公开的电致变色聚合物的氧化还原电位,同时在中性状态下在可见光范围内保持高度透明。例如,可以在主链上引入更多的富电子单元(例如二氧噻吩),使聚合物更容易被氧化,从而降低其起始电位并提高其电化学稳定性和电致变色循环稳定性。本发明所公开的电致变色聚合物的氧化还原电位也可以通过改变MCLs上的取代基(例如,引入烷氧基侧链)来调整。本发明所公开的电致变色聚合物可溶解在溶剂中,例如甲苯或对二甲苯,该溶剂可以用于溶液可加工的膜制造工艺。通过控制聚合物溶液的浓度,可以获得厚度可控的聚合物薄膜。此外,优异的溶解性使得本发明所公开的电致变色聚合物可以与各种制造工艺兼容,例如旋涂、喷涂和滴涂。易于制造的工艺使其具有更广的应用前景。
示例如下所示。
实施例
示例1ECP-1
在一些实施例中,本发明所公开的ECP-1包含式
ECP-1通过首先制备含咔唑的反应单元,然后和一种二聚体单元聚合而成。具体步骤如下:
步骤1-1:制备含咔唑的反应单元(化合物2)
将3,6-二溴咔唑溶解在DMF中。随后,加入1.2eq NaH,并将混合物搅拌2个小时。然后将1.2eq化合物1加入反应中,将混合物搅拌过夜。然后加水到反应中沉淀出固体。过滤悬浮液以获得所需产物化合物2,该产物是白色固体。
步骤1-2:聚合:含咔唑的反应单元和一个二聚体单元聚合
将化合物2(1eq)、化合物3(1eq)、K2CO3(2.6eq.)、PivOH(0.3eq.)and Pd(OAc)2(0.02eq.)添加到Schlenk管中。然后将Schlenk管置于真空下(3-5分钟)并把氮气重新充入管中。以上描述的步骤反复三次。然后将氮气脱气的溶剂二甲基乙酰胺(DMAc)添加到管中,将混合物加热至120℃并持续14小时。然后将混合物转移到甲醇中沉淀出未纯化的聚合物固体。过滤以获得固体并将固体再次溶解在氯仿中并用水洗涤三次。将氯仿溶液加入到大量的甲醇中从而沉淀得到聚合物。过滤悬浮液以获得所需产物聚合物ECP-1。
所得的ECP-1具有约为0.75V(vs.Ag/AgCl)的氧化电位和高于3.0eV的能带隙。将其制成固态电致变色器件(ECD),其中ECP-1作为电致变色层,在PEGDA中的0.2M的LiTFSI作为电解质,并且VOx作为离子存储层。固态ECD可以在-0.5V至1.5V之间稳定切换(图2)。如图4所示,ECP-1中性态和氧化态吸收光谱显示,其为405nm并且为320nm。固态ECD是高度透明的,在中性状态下具有高达93%的透光率(图3),当ECP-1被氧化时转换成亮蓝色,在约614nm处有一个吸收峰和在900-1100nm附近的近红外区域显示出另外一个更宽的吸收带(图4)。固态ECD的光学对比度约为75%(图3)。
示例2ECP-2
在一些实施例中,本发明所公开的ECP-2包含下式
ECP-2是通过先制备一个苯衍生物的反应单元,然后将其与无环二氧噻吩(AcDOT)单元聚合来合成的。具体步骤如下:
步骤2-1:通过两个步骤制备一个包含苯的反应单元(化合物4)
将化合物5和对甲苯磺酸溶解在乙腈中。随后,加入N-溴代琥珀酰亚胺,并将混合物搅拌过夜。过滤悬浮液以获得所需产物。产物化合物6是白色固体。
化合物6在N2下溶解在DMF中。向溶液中加入K2CO3,将反应混合物搅拌15分钟,然后加入2-乙基己基溴。将反应混合物在100℃搅拌过夜。停止反应并冷却至室温。真空除去溶剂,将残余物溶解在乙醚中。有机相用水洗涤,水相用乙酸乙酯萃取。干燥合并的有机相,真空除去挥发物。粗品通过小硅胶柱,真空干燥溶剂,得到化合物4,为黄色油状物。
步骤2-2:聚合:聚合方法与步骤1-2类似,这里不同的反应单元是苯衍生物的反应单元(化合物4)和结构如下的AcDOT单元(化合物8)
所得的ECP-2具有约为0.95V的氧化电位(vs.Ag/AgCl)和高于3.1eV的能带隙。ECP-2被制成固态ECD,其中ECP-2作为电致变色层,在PEGMEA中的1M的LiPF6作为电解质,并且VOx用作离子存储层。固态ECD可以在-0.6V至1.7V之间稳定切换(图5)。ECP-2的中性态和氧化态吸收光谱,以为410nm和为350nm,在图7中示出。固态ECD显示出高透明度,在中性状态下550nm处的透光率高达94%(图6),当ECP-2被氧化时呈现鲜红色,在546nm附近有一个吸收峰,另一个更宽的吸收带在约800-1100nm波长处(图7)。固态ECD的光学对比度为87%(图6)。
示例3ECP-3
在一些实施方案中,本发明所公开的ECP-3包含式
ECP-3是通过制备一个含苯的反应单元,然后将其与ProDot单元聚合合成的。具体步骤如下:步骤3-1:同步骤2-1
步骤3-2:聚合:聚合方法与步骤1-2类似,这里不同的反应单元是含苯的反应单元(化合物4)和结构如下的3,4-亚乙基二氧噻吩(EDOT,化合物9)
示例4ECP-4
在一些实施例中,本发明所公开的ECP-4包含式
ECP-4是通过制备含萘的反应单元,然后将其与AcDOT单元聚合而合成的。具体步骤如下:步骤4-1:通过两个步骤制备含萘的反应单元(化合物10)
在-78℃的条件下用15分钟向化合物11的二氯甲烷溶液中滴加溴的二氯甲烷溶液。将反应混合物在-78℃搅拌2小时,然后逐渐升温至室温并在室温下再保持2小时。过量的溴用饱和亚硫酸钠水溶液淬灭并在室温下搅拌2小时。用二氯甲烷萃取后,将合并的有机层用盐水洗涤,硫酸钠干燥,真空浓缩。
在N2条件下将化合物12溶解在DMF中,向溶液中加入K2CO3,并将反应混合物搅拌15分钟,然后加入2-乙基溴化乙烷。将反应混合物在100℃搅拌过夜。停止反应并冷却至室温。真空除去溶剂,将残余物溶解在乙醚中。有机相用水洗涤,水相用乙酸乙酯萃取。合并的有机相真空干燥。步骤4-2:聚合:聚合方法与步骤1-2类似,这里不同的反应单元是含萘反应单元(化合物10)和AcDOT(化合物8)。
示例5ECP-5
在一些示例中,本发明所公开的ECP-5包含下式
ECP-5通过与步骤1-2类似的聚合方法合成而得,这里不同的反应单元是1,5-二溴-2,4-双(己氧基)苯和3,4-二甲基噻吩。
在一些示例中,本发明所公开的ECP包含下式
其中,n和m是大于0的整数,a和b是大于或等于0的整数并a和b中至少一个大于0。
在一些实施例中,本发明所公开的ECP的吸收起始波长小于400nm。在一个实施例中,具有分子式的ECP-6溶液具有如图8所示。在一个实施例中,具有分子式的ECP-7溶液具有如图9所示。ECP-6和ECP-7都可以被制作成薄膜并表现出跟溶液类似的吸收光谱。
在另一方面,本发明所公开的聚合物可以具有荧光发射并且可以应用于荧光产品。
前述描述是为了说明和描述的目的而提供的。其并非旨在详尽无遗或将本公开限制为所公开的精确形式。本发明所公开的广度和范围不应受到任何上述示例性实施例的限制。对于本领域的技术人员来说,许多修改和变化将是显而易见的。这些修改和变化包括所公开特征的任何相关组合。选择和描述实施例是为了最好地解释本发明所公开的原理及其实际应用,从而使本领域的其他技术人员能够理解本公开的各种实施例以及适用于预期的特定用途的各种修改。本发明所公开的范围旨在由以下权利要求及其等同物来定义。
Claims (15)
1.一种电致变色聚合物,其特征在于,由以下组成:
一个聚合物主链,所述聚合物主链包括一个或多个间位共轭的接头(MCLs)以及一个或多个芳香族部分(Ars),
所述一个或多个MCLs中的每一个在所述一个或多个MCLs的间位位置处与所述一个或多个Ars部分地共轭,
所述的电致变色聚合物在中性状态下吸收起始波长等于或小于420nm。
2.根据权利要求1所述的电致变色聚合物,其特征在于,所述电致变色聚合物在中性状态下最大吸收值(max)小于410nm。
3.根据权利要求1所述的电致变色聚合物,其特征在于,所述电致变色聚合物在中性状态下呈现无色。
4.根据权利要求1所述的电致变色聚合物,其特征在于,所述电致变色聚合物在氧化状态下在可见和/或近红外波长处有吸收波长。
5.如权利要求4所述的电致变色聚合物,其特征在于,所述电致变色聚合物在氧化状态下的吸收系数大于104cm-1。
6.根据权利要求1所述的电致变色聚合物,其特征在于,所述电致变色聚合物相对于Ag/AgCl电极具有在0.1-1.5V(含)范围内的氧化电位。
7.根据权利要求1所述的电致变色聚合物,其特征在于,所述一个或多个MCLs包含芳香结构或稠合芳香结构中的至少一种。
8.根据权利要求7所述的电致变色聚合物,其特征在于,所述一个或多个MCLs包含芳香结构,其中所述芳香族结构包括苯或杂环结构。
9.根据权利要求7所述的电致变色聚合物,其特征在于,所述一个或多个MCLs包含稠合芳香结构,其中所述稠合芳香结构包括稠合苯结构,或稠合杂环结构,或苯和杂环的稠合结构。
11.根据权利要求1所述的电致变色聚合物,其特征在于,所述一个或多个MCLs中的每一个及其相应的间位位置包含以下其中一个化学式:
其中X是S、Se、N、C或O;R1-R12各自独立地选自氢(hydrogen)、C1-C30烷基(alkyl)、C2-C30烯基(alkenyl)、C2-C30炔基(alkynyl)、C2-C30烷基羰基(alkylcarbonyl)、C1-C30烷氧基(alkoxy)、C3-C30烷氧基烷基(alkoxyalkyl)、C2-C30烷氧基羰基(alkoxycarbonyl)、C4-C30烷氧基羰基烷基(alkoxycarbonylalkyl)、C1-C30烷硫基(alkylthio)、C1-C30氨基羰基(aminylcarbonyl)、C4-C30氨基烷基(aminylalkyl)、C1-C30烷基氨基(alkylaminyl)、C1-C30烷基磺酰基(alkylsulfonyl)、C3-C30烷基磺酰基烷基(alkylsulfonylalkyl)、C6-C18芳基(aryl)、C3-C15环烷基(cycloalkyl)、C3-C30环烷基氨基(cycloalkylaminyl)、C5-C30环烷基烷基氨基(cycloalkylalkylaminyl)、C5-C30环烷基烷基(cycloalkylalkyl)、C5-C30环烷基烷氧基(cycloalkylalkyloxy)、C1-C12杂环基(heterocyclyl)、C1-C12杂环氧基(heterocyclyloxy)、C1-C30杂环烷氧基(heterocyclylalkyloxy)、C1-C30杂环氨基(heterocyclylaminyl)、C5-C30杂环烷基氨基(heterocyclylalkylaminyl)、C2-C12杂环基羰基(heterocyclylcarbonyl)、C3-C30杂环基烷基(heterocyclylalkyl)、C1-C13杂芳基(heteroaryl)或C3-C30杂芳基烷基(heteroarylalkyl);每条波浪线代表其中的一个间位位置。
12.根据权利要求1所述的电致变色聚合物,其特征在于,所述一个或多个Ars中的每一个包含分别具有下式的基于噻吩的单元、基于呋喃的单元、基于硒吩的单元或基于吡咯的单元中的一种:
其中R13,R14和R15各自独立地选自氢(hydrogen)、C1-C30烷基(alkyl)、C2-C30烯基(alkenyl)、C2-C30炔基(alkynyl)、C2-C30烷基羰基(alkylcarbonyl)、C1-C30烷氧基(alkoxy)、C3-C30烷氧基烷基(alkoxyalkyl)、C2-C30烷氧基羰基(alkoxycarbonyl)、C4-C30烷氧基羰基烷基(alkoxycarbonylalkyl)、C1-C30烷硫基(alkylthio)、C1-C30氨基羰基(aminylcarbonyl)、C4-C30氨基烷基(aminylalkyl)、C1-C30烷基氨基(alkylaminyl)、C1-C30烷基磺酰基(alkylsulfonyl)、C3-C30烷基磺酰基烷基(alkylsulfonylalkyl)、C6-C18芳基(aryl)、C3-C15环烷基(cycloalkyl)、C3-C30环烷基氨基(cycloalkylaminyl)、C5-C30环烷基烷基氨基(cycloalkylalkylaminyl)、C5-C30环烷基烷基(cycloalkylalkyl)、C5-C30环烷基烷氧基(cycloalkylalkyloxy)、C1-C12杂环基(heterocyclyl)、C1-C12杂环氧基(heterocyclyloxy)、C1-C30杂环烷氧基(heterocyclylalkyloxy)、C1-C30杂环氨基(heterocyclylaminyl)、C5-C30杂环烷基氨基(heterocyclylalkylaminyl)、C2-C12杂环基羰基(heterocyclylcarbonyl)、C3-C30杂环基烷基(heterocyclylalkyl)、C1-C13杂芳基(heteroaryl)或C3-C30杂芳基烷基(heteroarylalkyl)。
13.根据权利要求12所述的电致变色聚合物,其特征在于,所述一个或多个Ars中的每一个包含一个基于噻吩的单元,其中所述基于噻吩的单元包含下式中的一种:
其中X是S、Se、N、C或O;R15-R18中的每一个独立地选自氢(hydrogen)、C1-C30烷基(alkyl)、C2-C30烯基(alkenyl)、C2-C30炔基(alkynyl)、C2-C30烷基羰基(alkylcarbonyl)、C1-C30烷氧基(alkoxy)、C3-C30烷氧基烷基(alkoxyalkyl)、C2-C30烷氧基羰基(alkoxycarbonyl)、C4-C30烷氧基羰基烷基(alkoxycarbonylalkyl)、C1-C30烷硫基(alkylthio)、C1-C30氨基羰基(aminylcarbonyl)、C4-C30氨基烷基(aminylalkyl)、C1-C30烷基氨基(alkylaminyl)、C1-C30烷基磺酰基(alkylsulfonyl)、C3-C30烷基磺酰基烷基(alkylsulfonylalkyl)、C6-C18芳基(aryl)、C3-C15环烷基(cycloalkyl)、C3-C30环烷基氨基(cycloalkylaminyl)、C5-C30环烷基烷基氨基(cycloalkylalkylaminyl)、C5-C30环烷基烷基(cycloalkylalkyl)、C5-C30环烷基烷氧基(cycloalkylalkyloxy)、C1-C12杂环基(heterocyclyl)、C1-C12杂环氧基(heterocyclyloxy)、C1-C30杂环烷氧基(heterocyclylalkyloxy)、C1-C30杂环氨基(heterocyclylaminyl)、C5-C30杂环烷基氨基(heterocyclylalkylaminyl)、C2-C12杂环基羰基(heterocyclylcarbonyl)、C3-C30杂环基烷基(heterocyclylalkyl)、C1-C13杂芳基(heteroaryl)或C3-C30杂芳基烷基(heteroarylalkyl);Y是任何一个或多个Ars,或芳香结构,或稠合芳香结构或以上任何两者组合。
14.根据权利要求13所述的电致变色聚合物,其特征在于,所述基于噻吩的单元中的X为O。
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