CN107814917A - A kind of intrinsic stretchable electrochromic polymeric compounds of hydrogen bond crosslinks and preparation method thereof - Google Patents
A kind of intrinsic stretchable electrochromic polymeric compounds of hydrogen bond crosslinks and preparation method thereof Download PDFInfo
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- CN107814917A CN107814917A CN201711129752.8A CN201711129752A CN107814917A CN 107814917 A CN107814917 A CN 107814917A CN 201711129752 A CN201711129752 A CN 201711129752A CN 107814917 A CN107814917 A CN 107814917A
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- Prior art keywords
- stretchable
- hydrogen bond
- bond crosslinks
- straight
- hydrogen
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 63
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 63
- 229920000642 polymer Polymers 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title description 6
- 230000008859 change Effects 0.000 claims abstract description 38
- -1 bipyridine diformamide analog Chemical class 0.000 claims abstract description 20
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical class O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 4
- 238000006619 Stille reaction Methods 0.000 claims abstract description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 3
- 230000002950 deficient Effects 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 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
- 125000001544 thienyl group Chemical group 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- SEEOMASXHIJCDV-UHFFFAOYSA-N 3-methyloctane Chemical class CCCCCC(C)CC SEEOMASXHIJCDV-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 46
- 230000015572 biosynthetic process Effects 0.000 abstract description 21
- 238000003786 synthesis reaction Methods 0.000 abstract description 18
- 238000011160 research Methods 0.000 abstract description 8
- 238000013461 design Methods 0.000 abstract description 6
- MUXMPBYMARNJDR-UHFFFAOYSA-N C(=O)N.C(=O)N.N1=CC=CC=C1 Chemical class C(=O)N.C(=O)N.N1=CC=CC=C1 MUXMPBYMARNJDR-UHFFFAOYSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000010408 film Substances 0.000 description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 229920006254 polymer film Polymers 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 125000001246 bromo group Chemical group Br* 0.000 description 9
- 230000006208 butylation Effects 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000002322 conducting polymer Substances 0.000 description 7
- 229920001940 conductive polymer Polymers 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000005700 Stille cross coupling reaction Methods 0.000 description 6
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 6
- 238000005893 bromination reaction Methods 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000031709 bromination Effects 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920000144 PEDOT:PSS Polymers 0.000 description 4
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 4
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 239000008247 solid mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- MLCPSWPIYHDOKG-BUHFOSPRSA-N trans-isoindigo Natural products O=C\1NC2=CC=CC=C2C/1=C1/C2=CC=CC=C2NC1=O MLCPSWPIYHDOKG-BUHFOSPRSA-N 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical class OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- MAWGHOPSCKCTPA-UHFFFAOYSA-N 6-bromo-1h-indole Chemical class BrC1=CC=C2C=CNC2=C1 MAWGHOPSCKCTPA-UHFFFAOYSA-N 0.000 description 2
- GMGLGUFSJCMZNT-UHFFFAOYSA-N BrCCCCCC.BrCCCCCC Chemical compound BrCCCCCC.BrCCCCCC GMGLGUFSJCMZNT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 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
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- CJVCXRMYJNMDTP-UHFFFAOYSA-N pyridine-2,3-dicarboxamide Chemical class NC(=O)C1=CC=CN=C1C(N)=O CJVCXRMYJNMDTP-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- IZUKQUVSCNEFMJ-UHFFFAOYSA-N 1,2-dinitrobenzene Chemical class [O-][N+](=O)C1=CC=CC=C1[N+]([O-])=O IZUKQUVSCNEFMJ-UHFFFAOYSA-N 0.000 description 1
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Chemical class CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 229940049706 benzodiazepine Drugs 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/414—Stille reactions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/54—Physical properties electrochromatic
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses a kind of intrinsic stretchable electrochromic polymeric compounds of hydrogen bond crosslinks, the polymer includes the stretchable group of colour change function group and hydrogen bond crosslinks；With 3,4 ethylenedioxy thiophenes for donor element, five-membered heterocycles either fragrant same clan's compound of electron deficient performance obtains the colour change function group as acceptor groups through Stille coupling reactions or the step of Suzuki coupling reactions one；The stretchable group of the hydrogen bond crosslinks is made up of pyridine diformamide analog derivative or bipyridine diformamide analog derivative.Present invention design synthesizes the intrinsic stretchable electrochromism new material of serial hydrogen bond crosslinks, and the research of synthesis and device for stretchable electrochromic material provides certain theoretical direction and material, technical support.
Description
Technical field
The present invention relates to electrochromic material technical field is related to, the formyl of pyridine -2,6- bis- is based on more particularly, to one kind
The intrinsic stretchable electrochromic polymer of hydrogen bond crosslinks of amine (PDCAs) or bipyridine-diformamide class (DPDCAs) group
Thing material and preparation method thereof
Background technology
Flexible intelligent equipment is the mainstream development direction of current electronic product, and the prospect of marketing is huge, its market scale
Far it will surpass 20,000,000,000 dollars in the year two thousand twenty according to estimates.Electrochromic material is as display device and part wearable electronic
One of critical function material, referring to can be by the double implantation of electronics and ion, extraction or generation oxygen under light current field action
Change reduction reaction, so that a kind of energy-saving material of reversible consecutive variations can occur for its color.This kind of material is in various fields
Show wide application prospect, as Intelligent energy-saving window, blinding free reflective mirror, low energy consumption display device, presentation of information and storage,
Electronic Paper, discoloured skin etc..As the Typical Representative of electronic device of future generation, the development of Flexible Displays and wearable electronic
Requirements at the higher level can be proposed to tensility, developed as early as possible there is an urgent need to researcher and can adapt to certain stress and in shape
The stretchable electrochromic device of excellent properties is maintained in change.
Stretchable electrochromic device is causing concern in recent years, and the preparation of the stretchable electrochromic material of high-performance is
Key issue.Tensility is the key character of electrochromic device of future generation, but the stretchable performance study challenge of device
It is far longer than flexibility, this requires that device can be with reversed torsion, stretching and bending, while its electrochromic property is unaffected, protects
It is fixed to keep steady, thus electrochromic material be preferably in itself elastomer, can high deformation, and discoloration is steady in deformation process
It is fixed.Although conducting polymer has long flexible chain molecular structure in itself, its tensile resistance is compared and metal oxide in theory
It is higher with organic molecule, but the experiment value reported at present is still bad.With deepening continuously and to stretchable device for research
The raising of part performance requirement, the preparation and exploitation of the stretchable electrochromic material of high-performance are that pendulum is important in face of scientific research personnel
One of challenge.
The discovery and research of conjugated polymer interchain hydrogen bond non-covalent, turn into realize conducting polymer high elongation,
The effective ways of self-healing.The formation of hydrogen bond is mostly derived from electrostatic force, and its bond energy is big slightly stronger than Van der Waals force, but active force
Covalent bond and ionic bond are markedly less than with stability.By introducing intermolecular hydrogen bonding, controlled material in conjugated polymer structure
The ratio of middle rigid conjugated structure unit and hydrogen bond crosslinks flexibility carbochain, new intrinsic stretchable, self-healing polymerization is prepared
Thing semiconductor, and it is used for stretchable electrochromic making.Its design concept：Rigid conjugated structure unit crystallinity is high (brilliant
Area), the electric charge transmission of material can be achieved；The flexible carbochain of hydrogen bonds crosslinking is amorphous state (amorphous area), plays emollescence.Draw
When stretching material, hydrogen bond can disconnect absorption mechanical energy, while will not substantially reduce the electronic transport property of polymer；And stress release
When, these keys can recombine again.Although the tensility energy and mechanical endurance of material also have larger room for promotion,
But based on the design concept of interchain hydrogen bond non-covalent, it is anticipated that future can occur the more excellent height of a large amount of performances rapidly and draw
Stretch, selfreparing conducting polymer new material.
Poly- (3,4- ethylenedioxythiophene) class materials Electrochromic excellent performance, stability are good, be design synthesis it is intrinsic can
Stretch the ideal chose of conducting polymer electrochromism new material.Poly- (3,4- ethylenedioxythiophenes) (PEDOT) is conducting polymer
Star's material in thing family, electrical conductivity is very high, reaches as high as 4800S/cm at present；Environmental stability is excellent, adds at 100 DEG C
Hot 1000h electrical conductivity hardly changes；Visible light transmissivity is high (being more than 90%)；Filming performance is good.As electroluminescent change
Color material, analog, derivative based on PEDOT, copolymer (PEDOTs) coloration efficiency are high (up to 1365cm2C-1), response
Time it is short (<1s), good cycling stability (recyclable more than 2,000,000 times), total colouring can be realized.Based on the electroluminescent changes of PEDOTs
The basic research of color material is more ripe, and the electrochromic property of these materials is excellent, portion of material device,
Commercialization, commercialization.As can be seen here, PEDOTs class formations material is that design synthesizes intrinsic stretchable conducting polymer electrochromism
The optimal selection of new material.
The content of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provides a kind of intrinsic stretchable electricity of hydrogen bond crosslinks
Cause electrochromic polymer and preparation method thereof.The present invention is with pyridine-diformamide class (PDCAs) or bipyridine-diformamide class
(DPDCAs) unit is introduced into excellent poly- (BisEDOTs) polymer of electrochromic property as interchain hydrogen bond cross-linked structure
Main chain, design synthesize the intrinsic stretchable electrochromism new material of serial hydrogen bond crosslinks, are the conjunction of stretchable electrochromic material
Into and the research of device certain theoretical direction and material, technical support are provided.
Technical scheme is as follows：
A kind of intrinsic stretchable electrochromic polymeric compounds of hydrogen bond crosslinks, the polymer include colour change function group and hydrogen bond
The stretchable group of crosslinking.
The colour change function group with 3,4- ethylenedioxy thiophenes for donor element, the five-ring heterocycles class of electron deficient performance
Compound either fragrant same clan's compound obtains as acceptor groups through Stille coupling reactions or the step of Suzuki coupling reactions one
Arrive.
The stretchable group of the hydrogen bond crosslinks is by pyridine-diformamide analog derivative or bipyridine-diformamide class
Derivative forms.
The reaction process of the intrinsic stretchable electrochromic polymeric compounds of hydrogen bond crosslinks is：
Wherein, m ＞ 1；Stretchable unit structure is as shown in A or B, wherein R1For hydrogen-based or methyl,
R2ForWherein R3For hydrogen-based, C1~12Straight or branched alkyl, C1~12Straight chain
Or any one in branched alkoxy, chlorine atom or fluorine atom.
Colour change function unit structure is described in the intrinsic stretchable electrochromic polymeric compounds of hydrogen bond crosslinks：
Any of；
Wherein, X S, Se or O atom；Y is C or N atoms；Z1For O, S, Se, C atom or N-R4, Z2It is former for O, S, Se, C
Son or N-`R4, Z1And Z2It is identical or different；
The R4、`R4It is separately hydrogen-based, C1~12Straight or branched alkyl, C1~12Straight or branched alcoxyl
Any one in base, chlorine atom or fluorine atom；R4、`R4It is identical or different；
R5It is expressed as hydrogen-based, C1~12Straight or branched alkyl, C1~12Straight or branched alkoxyl, chlorine atom or fluorine
Any one in atom；
R6、R7It is separately thienyl, phenyl, pyridine radicals, hydrogen-based, C1~12Straight or branched alkyl, C1~12's
Any one in straight or branched alkoxyl, chlorine atom or fluorine atom, R6、R7It is identical or different；
R8、R9It is separately thienyl, phenyl, any one in pyridine radicals, R8、R9It is identical or different；R10Represent
For any one in H, chlorine atom or fluorine atom.
The branched alkyl is 2- methyl-props alkyl, 2- methyl hexanes base, 2- ethyl hexyls alkyl, 2- ethyl heptanes base, 2-
It is any in hexyl octyl, 2- octyl groups decyl, 2- octyldodecyls, 2- decyls dodecyl, 2- decyl myristyls
It is a kind of.
The present invention is summarized the intrinsic stretchable electrochromic polymeric compounds of serial hydrogen bond crosslinks of synthesis, and it synthesizes road
Line is designed as：
The present invention is summarized as follows using synthesis strategy：With the butylated BisEDOT compounds of tin and five yuan of the rigidity of bromination
Heterocyclic or fragrant class formation are raw material, and palladium chtalyst cross-coupling reaction occurs in toluene to obtain rigid colour change function group
Compound；And then handle the compound bromination, palladium then occurs with the butylated stretchable group (PDCAs or DPDCAs) of tin
Catalyzed coupling reaction, a step obtain the intrinsic stretchable electrochromic polymeric compounds of hydrogen bond crosslinks, can be with by adjusting different rate of charges
Control the tensility energy of Stretchable polymeric.
Wherein as described above, it is Pd (PPh that catalyst, which is tetra-triphenylphosphine palladium,3)4Or bis-triphenylphosphipalladium palladium dichloride is Pd
(PPh3)2Cl2；Solvent is that tetrahydrofuran is one or more in THF, toluene, N,N-dimethylformamide i.e. DMF.
The intrinsic stretchable electrochromic device assembled based on the intrinsic stretchable electrochromic polymeric compounds material of hydrogen bond crosslinks,
Its structure is：Stretchable substrate (SEBS or PDMS or PEDOT:PSS self-supporting films)-conductive layer-ion storage layer-electrolysis
Matter-electrochromic layer-conductive layer-stretchable substrate (SEBS or PDMS or PEDOT:PSS self-supporting films).Such is intrinsic to draw
Stretching electrochromic device not only has good tensility energy, and also good electrochromic property, especially by
Change colour change function group, panchromatic color change can be achieved.
The present invention is beneficial to be had technical effect that：
(1) the intrinsic stretchable electrochromic polymeric compounds material of hydrogen bond crosslinks of the present invention is to be based on intrinsic Stretch material
(PDCAs or DPDCAs) is core, polymer is had good tensility, therefore led in intrinsic stretchable electrochromism
Domain provides certain theory for the synthesis of intrinsic stretchable electrochromic material and the research of intrinsic stretchable electrochromic device
Instruct and material, technical support.
(2) present invention by intrinsic Stretchable polymeric introduce colour change function group, make polymer realize it is intrinsic can
While tensile property, the panchromatic change of polymer color is realized；Simultaneously by changing colour change function group, polymerization can be adjusted
Thing absorption spectrum, and then change the electrochromic property (response time, transmitance etc.) of polymer.
(3) the intrinsic stretchable electrochromic polymeric compounds material of hydrogen bond crosslinks of the present invention obtains through chemical polymerization, compared to more electric
Chemical polymerization obtains polymer has smaller structure defect in theory, and polymer is spun into stretchable electricity by spin coating method
On extremely, soaked with anhydrous methylene chloride or acetonitrile, wash the monomer of film surface and the polymer that some degree of polymerization are relatively low off, after
In being dried in vacuum tank.Layer of gel electrolyte is applied between two films, in being dried in vacuum tank.Finally device is sealed with UV glue
Dress, by whole device sealing to completely cut off air.The device architecture of assembling is stretchable substrate (SEBS or PDMS or PEDOT:PSS
Self-supporting film)-conductive layer-ion storage layer-electrolyte-electrochromic layer-conductive layer-stretchable substrate (SEBS or PDMS
Or PEDOT:PSS self-supporting films).
(4) ultraviolet specrophotometer is utilized, passes through the voltage of electrochemical workstation regulation application on the working electrode (s, record
The variation tendency of polymer absorption spectrum under different voltages, that is, the spectroelectrochemistry collection of illustrative plates of polymer is obtained；Secondly utilize
Polymer film is doped at a particular wavelength under square wave current potential and goes doped transmission to determine for ultraviolet-uisible spectrophotometer
Rate, so as to calculate optical contrast, response time etc.；Ultraviolet-uisible spectrophotometer record for when m- transmittance curve,
Electrochemical workstation record for time current curve, can also calculate coloration efficiency according to this two curves.
(5) ultraviolet specrophotometer is utilized, passes through the voltage of electrochemical workstation regulation application on the working electrode (s, record
The variation tendency of absorption spectrum of the polymer under different voltages and different stretch length, that is, obtained polymer is stretching shape
Spectroelectrochemistry collection of illustrative plates under state.Secondly polymer film is determined under square wave current potential specific using ultraviolet-uisible spectrophotometer
It is doped and go doped transmitance under wavelength and specific tensile elongation, so as to calculate optical contrast, response time etc.；
Ultraviolet-uisible spectrophotometer record for when m- transmittance curve, electrochemical workstation record for time current curve,
The coloration efficiency under specific tensile elongation can be also calculated according to this two curves.
Note：Coloration efficiency：Refer to electrochromic material under given wavelength, the change of absorbance is with causing whole electronics to be noted
Ratio when entering or extracting out.
For a kind of electrochromic material, coloration efficiency is an important parameter for evaluating material property.Coloring effect
The coloration efficiency of rate research conducting polymer will combine the electrochemistry and spectrum change process of electrochromic film, and its calculation formula is such as
Under：
CE=Δs OD/Qd (1)
Wherein, the change (Δ OD) of optical contrast ratio refers in a specific wavelength λmaxUnder, electrochemical oxidation and reductive polymerization
During thing film, corresponding transmitance value (transmitance T when polymer film is dopedoxWith transmitance T during middle conditionred) ratio,
Calculated by below equation：
Δ OD=log (Tox/Tred) (2)
The color for absorbing position and determining polymer of polymer, there is weight for preparing a variety of colors electrochromic polymeric compounds
Meaning is wanted, the response time is equally the important parameter of electrochromic material, and it is disclosed during doping, and Doped ions enter
The speed of main polymer chain.
Brief description of the drawings
Fig. 1 is the intrinsic stretchable electrochromic polymeric compounds of hydrogen bond crosslinks of the different indigoid of embodiment 1 in MeCN-
BmimPF6(0.1mol·L-1) in system, the color change figure before and after film stretching；
Fig. 2 is the intrinsic stretchable electrochromic polymeric compounds of hydrogen bond crosslinks of the different indigoid of embodiment 1 in MeCN-
BmimPF6(0.1mol·L-1) in system, film spectroelectrochemistry figure in an unstretched state；
Fig. 3 is the intrinsic stretchable electrochromic polymeric compounds of hydrogen bond crosslinks of the different indigoid of embodiment 1 in MeCN-
BmimPF6(0.1mol·L-1) in system, spectroelectrochemistry figure after film stretching 50%；
Fig. 4 is the intrinsic stretchable electrochromic polymeric compounds of hydrogen bond crosslinks of the different indigoid of embodiment 1 in MeCN-
BmimPF6(0.1mol·L-1) in system, m- transmittance curve when after film stretching 50%；
Embodiment
With reference to the accompanying drawings and examples, the present invention is specifically described.
Embodiment 1
A kind of intrinsic stretchable electrochromic polymeric compounds of hydrogen bond crosslinks based on different indigoid, are made as follows：
(1) stretchable group PDCAs is synthesized
(1a) with 2,6- pyridinedicarboxylic acids (10.03g, 0.06mol) for raw material, it is anti-with oxalyl chloride (22.85g, 0.18mol)
2,6- pyridine dimethyl chlorides should be generated；
(1b) 2,6- pyridines dimethyl chloride (2.98g, 0.18mol) and 2- ethamine EDOT (6.00g, 0.32mol) Yu Sanyi
One-step synthesis PDCA short chains in amine (6mL) and CH2Cl2 (36mL) mixed solution,
(1c) PDCA short chains (1.3g, 3.37mmol) and LDA (3.37mL, 6.74mmol), tributyltin chloride (2.19g,
Tin butylation PDCAs can be obtained by 6.74mmol) reacting, after separating-purifying, to be used after.
(2) donor groups BisEDOT is synthesized
(2a) with EDOT (7.50g, 50mmol) for raw material, THF (50mL) is solvent, with n-BuLi (53mL,
85.00mmol) reacted at -78 DEG C two hours, add CuCl2 afterwards and react 12 hours, generate BisEDOT；
(2b) BisEDOT (1.5g, 5.0mol) reacts two hours with n-BuLi (4.0mL, 6.3mmol) at -78 DEG C,
Tributyltin chloride (2.05g, 6.3mmol) is added afterwards to react 12 hours, generates the butylated BisEDOT of tin, for future use.
(3) different indigoid is the synthesis of the intrinsic Stretchable polymeric of hydrogen bond crosslinks of colour change function group
(3a) is with 6- bromo indoles -2,3- diketone (6.0g, 13.4mmol) and 6- bromo indole -2- ketone (6.4g, 13.4mmol)
For raw material, two bromos 3,3 '-di- indole dione are synthesized in next step in the acid condition of acetic acid and hydrochloric acid mixed solution；
(3b) two bromo 3,3 '-di- indole dione (2.0g, 4.5mmol) are dissolved in DMF (50.0mL), and potassium carbonate provides
In weakly alkaline environment, it will be obtained on the N atoms on hexyl bromide 1 bromohexane (1.6g, 9.6mmol) introducing lactam nucleus with strengthening dissolubility
IDOH (hexyl isoindigo is blue or green)；
(3c) in toluene solution, by IDOH (0.6g, 1.0mmol) and tin butylation BisEDOT (2.8g, 5.0mmol)
Stille cross-coupling reactions synthesis BisEDOT- occurs under tetra-triphenylphosphine palladium (0.12g, 10%mmol) catalytic environment
IDOH (hexyl isoindigo is blue or green)-BisEDOT monomers,
(3d) handles BisEDOT-IDOH (hexyl isoindigos in CH2Cl2 solution, with NBS (0.09g, 0.4mmol) bromination
It is blue or green)-BisEDOT monomers (0.2g, 0.2mmol), two bromo BisEDOT-IDOH (hexyl isoindigo is blue or green)-BisEDOT is obtained, to treat
After use.
(4) synthesis based on IDOH classes for the intrinsic Stretchable polymeric of hydrogen bond crosslinks of colour change function group
(4a) tin butylation PDCAs (0.61g, 0.85mmol) and two bromo BisEDOT-IDOH (hexyl isoindigo is blue or green)-
BisEDOT (0.2g, 0.17mmol) is with Pd2 (dba) 3 (0.04g, 5%mmol), P (o-tal) 3 (0.12g, 40mmol%)
For catalyst, using chlorobenzene as solvent environment in hydrogen bond crosslinks sheet of the Stille cross-coupling reactions synthesis based on different indigoid occurs
Levy Stretchable polymeric material blends；
Mixture is carried out recrystallization experiment by (4b) in petroleum ether, separates out solid, then by obtained solid mixture according to
It is secondary washed with ether, acetone after dry, obtain the intrinsic Stretchable polymeric material of hydrogen bond crosslinks based on different indigoid.
Embodiment 2
A kind of intrinsic stretchable electrochromic polymeric compounds of hydrogen bond crosslinks based on benzotriazole, make as follows
：
(1) stretchable group PDCAs is synthesized
(1a) with 2,6- pyridinedicarboxylic acids (10.03g, 0.06mol) for raw material, it is anti-with oxalyl chloride (22.85g, 0.18mol)
2,6- pyridine dimethyl chlorides should be generated；
(1b) 2,6- pyridines dimethyl chloride (2.98g, 0.18mol) and 2- ethamine EDOT (6.00g, 0.32mol) Yu Sanyi
One-step synthesis PDCA short chains in amine (6mL) and CH2Cl2 (36mL) mixed solution,
(1c) PDCA short chains (1.3g, 3.37mmol) and LDA (3.37mL, 6.74mmol), tributyltin chloride (2.19g,
Tin butylation PDCAs can be obtained by 6.74mmol) reacting, after separating-purifying, to be used after.
(2) donor groups BisEDOT is synthesized
(2a) with EDOT (7.50g, 50mmol) for raw material, THF (50mL) is solvent, with n-BuLi (53mL,
85.00mmol) reacted at -78 DEG C two hours, add CuCl2 afterwards and react 12 hours, generate BisEDOT；
(2b) BisEDOT (1.5g, 5.0mol) reacts two hours with n-BuLi (4.0mL, 6.3mmol) at -78 DEG C,
Tributyltin chloride (2.05g, 6.3mmol) is added afterwards to react 12 hours, generates the butylated BisEDOT of tin, for future use.
(3) synthesis of BisEDOT-BTzH (hexyl BTA)-BisEDOT rigidity colour change function groups
(3a) with 3,4- dinitro benzenes (0.32g, 3.0mmol) for raw material, with natrium nitrosum (0.30g, 3.3mmol) in ice
Reaction generation benzotriazole in acetic acid (12ml)；
(3b) benzotriazole (0.26g, 2.2mmol) is with hexyl bromide 1 bromohexane (0.413g, 2.5mmol) in DMF (30ml)
Reaction obtains hexyl BTA (BTzH), and the introducing of N atoms can increase the dissolubility of material；
(3c) with BTzH (0.30g, 1.5mmol), bromine (0.56g, 3.5mmol) is raw material, and hydrobromic acid (10ml) is molten
Bromination BTzH is made in agent, single step reaction；
(3d) with bromination BTzH (0.52g, 1.45mmol), tin butylation BisEDOT (4.15g, 7.25mmol) is raw material,
Toluene (50ml) is solvent, and tetra-triphenylphosphine palladium (0.12g, 10%mmol) catalysis is lower to occur the synthesis of Stille cross-coupling reactions
BisEDOT-BTzH (hexyl BTA)-BisEDOT polymer precursors；
(3e) with BisEDOT-BTzH (hexyl BTA)-BisEDOT polymer precursors (1.9g, 2.5mmol),
NBS (0.89g, 5mmol) is raw material, is reacted in dichloromethane (50ml) and obtains two bromo BisEDOT-BTzH (hexyl benzos
Triazole)-BisEDOT, to be used after.
(4) synthesis based on BTzH classes for the intrinsic Stretchable polymeric of hydrogen bond crosslinks of colour change function group
(4a) is by tin butylation PDCAs (0.61g, 0.85mmol) and the two bromo BisEDOT-BTzH (nitrogen of hexyl benzo three
Azoles)-BisEDOT (0.156g, 0.17mmol) is in Pd2(dba)3(0.04g, 5%mmol), P (o-tal)3(0.12g,
40mmol%) be catalyst, using chlorobenzene as solvent environment in occur Stille cross-coupling reactions synthesize based on the nitrogen of benzo three
The intrinsic stretchable electrochromic polymeric compounds material of hydrogen bond crosslinks of azole.
(4b) polymer treatment mode is：Pour the mixture into a large amount of volume petroleum ethers, solid polymer can be separated out
Mixture, dried after solid mixture is washed with ether, acetone successively afterwards, obtain the hydrogen bond based on benzotriazole and hand over
Join intrinsic stretchable electrochromic polymeric compounds material.
Embodiment 3
A kind of intrinsic stretchable electrochromic polymeric compounds of hydrogen bond crosslinks based on the oligomeric species of PEDOT, as follows
It is made：
(1) stretchable group PDCAs is synthesized
(1a) with 2,6- pyridinedicarboxylic acids (10.03g, 0.06mol) for raw material, it is anti-with oxalyl chloride (22.85g, 0.18mol)
2,6- pyridine dimethyl chlorides should be generated；
(1b) 2,6- pyridines dimethyl chloride (2.98g, 0.18mol) and 2- ethamine EDOT (6.00g, 0.32mol) Yu Sanyi
One-step synthesis PDCA short chains in amine (6mL) and CH2Cl2 (36mL) mixed solution,
(1c) PDCA short chains (1.3g, 3.37mmol) and LDA (3.37mL, 6.74mmol), tributyltin chloride (2.19g,
Tin butylation PDCAs can be obtained by 6.74mmol) reacting, after separating-purifying, to be used after.
(2) donor groups BisEDOT is synthesized
(2a) with EDOT (7.50g, 50mmol) for raw material, THF (50mL) is solvent, with n-BuLi (53mL,
85.00mmol) reacted at -78 DEG C two hours, add CuCl2 afterwards and react 12 hours, generate BisEDOT；
(2b) BisEDOT (1.5g, 5.0mol) reacts two hours with n-BuLi (4.0mL, 6.3mmol) at -78 DEG C,
Tributyltin chloride (2.05g, 6.3mmol) is added afterwards to react 12 hours, generates the butylated BisEDOT of tin, for future use.
(3) synthesis of PentaEDOT rigidity colour change function group
(3a) with EDOT (1.42g, 40.0mmol) for raw material, with NBS (4.09g, 23.0mmol) for bromating agent, in THF
In (50.0mL), a step generates two bromo EDOT；
(3b) is by two bromo EDOT (1.3g, 4.0mmol) and tin butylation BisEDOT (5.0g, 8.74mmol) in toluene
In environment, with tetra-triphenylphosphine palladium (0.12g, 10%mmol) for catalyst, the step of Stille cross-coupling reactions one occurs and obtains
PentaEDOT monomers；
(3c) with NBS (0.09g, 0.4mmol) for bromating agent, bromine substitution PentaEDOT (0.14g, 0.2mmol) is through bromination
Reaction obtains two bromo PentaEDOT, to be used after.
(4) PentaEDOT is the synthesis of the intrinsic Stretchable polymeric of hydrogen bond crosslinks of colour change function group
(4a) collects tin butylation PDCAs (0.61g, 0.85mmol) and two bromo PentaEDOT in toluene solution
(0.36g, 0.42mmol) is in Pd2(dba)3(0.04g, 5%mmol), P (o-tal)3(0.12g, 40mmol%) is catalysis
Agent, using chlorobenzene as solvent environment in occur the synthesis of Stille cross-coupling reactions the hydrogen bond crosslinks based on PEDOT classes be intrinsic to draw
Stretch electrochromic polymeric compounds material.
(4b) mixture carries out recrystallization experiment in petroleum ether, obtains solid mixture, and solid mixture is used successively
Dried after ether, acetone washing, obtain the intrinsic stretchable electrochromic polymeric compounds material of hydrogen bond crosslinks based on PEDOT classes.
Test case：
The intrinsic stretchable electrochromic polymeric compounds of hydrogen bond crosslinks based on different indigoid made from the embodiment of the present invention 1 are molten
Solution (3mg/mL) into toluene, it is spun on the PET (polyethylene terephthalate) after UV surface processing, rotating speed
2000RMP.Made annealing treatment after high temperature of 120 DEG C in vacuum drying oven, the thin polymer film stablized, afterwards to polymer thin
Film carries out electrochromic property test and stretchable performance test：
(1) electro-chemical test
Using electrochemical workstation three-electrode system, stretchable electrochromic polymeric compounds intrinsic to hydrogen bond crosslinks are doped
To go to adulterate experiment test, test voltage is that -0.5V goes to adulterate, and+1.5V is doping voltage, under doping and dedoping state, its
Color changes significantly, the change from dirty-green to bluish violet.After being stretched 50%, under identical voltage of transformation, its film
Color still there is obvious color change.As a result it is as shown in Figure 1.
(2) spectrum test under unstretched state：
It will be carried out based on the spectrogram under the intrinsic Stretchable polymeric film stretching unstretched state of IDOH class hydrogen bond crosslinks
Test, voltage change respectively from -0.5V, -0.3V, -0.1V, 0.1V, 0.3V, 0.5V, 0.7V, 0.9V, 1.1V, 1.3V, 1.5V,
Its spectrum change situation is tested successively, and test result is as shown in Figure 2.
It can be learnt by Fig. 2：- 0.5V voltages go dopant states under, two obvious absworption peaks be present in polymer, point
Not between 400nm and 600~700nm, now polymer film shows dirty-green；Absworption peak before being raised with voltage by
Fade mistake, and new absworption peak (500nm~600nm) occurs, and now bluish violet is presented in polymer film color.
(3) spectrum test under 50% state is stretched
Surveyed the spectrogram under 50% state is stretched based on the intrinsic Stretchable polymeric film of IDOH class hydrogen bond crosslinks
Examination, voltage change respectively from -0.5V, -0.3V, -0.1V, 0.1V, 0.3V, 0.5V, 0.7V, 0.9V, 1.1V, 1.3V, 1.5V, according to
Secondary its spectrum change situation of test.Test result is as shown in Figure 3.
It can be learnt by Fig. 3：- 0.5V voltages go dopant states under, two obvious absworption peaks be present in polymer, point
Not between 400nm and 600~700nm, now polymer film shows dirty-green；Absworption peak before being raised with voltage by
Fade mistake, and new absworption peak (500nm~600nm) occurs, and now bluish violet is presented in polymer film color.
From spectrally it was found that stretching before and after Polymer absorption peak position value do not change substantially, illustrate that polymer is being drawn
Do not occur the phenomenon of rupture of conjugated chain during stretching, it is preferable to illustrate that the intrinsic Stretchable polymeric of IDOH class hydrogen bond crosslinks has
Tensility.
(4) polymer film transmission measurement
Enter the transmittance curve under 50% state is stretched based on the intrinsic Stretchable polymeric film of IDOH class hydrogen bond crosslinks
Row test, voltage change changes between -0.5V and 1.5V, tests it under 1000nm wavelength, during doping and dedoping state
The situation of change of polymer film transmitance；Wherein time interval is 20s.Test result is as shown in Figure 4.It can be learnt by Fig. 4：
Under the state of oxidation (dopant states), the transmitance of polymer film is 43.5%, under reducing condition (going dopant states), polymer
The transmitance of film is 56.5%, in doping voltage and is gone in the transfer process of doping voltage, the transmitance of polymer film is tieed up substantially
Hold 13% or so.
Claims (6)
1. a kind of intrinsic stretchable electrochromic polymeric compounds of hydrogen bond crosslinks, it is characterised in that the polymer includes colour change function base
Group and the stretchable group of hydrogen bond crosslinks.
2. polymer according to claim 1, it is characterised in that the colour change function group is with 3,4- ethylenedioxy thiophenes
For donor element, five-membered heterocycles either fragrant same clan's compound of electron deficient performance is as acceptor groups, warp
Stille coupling reactions or the step of Suzuki coupling reactions one obtain.
3. polymer according to claim 1, it is characterised in that the stretchable group of the hydrogen bond crosslinks is by pyridine-diformazan
Amide derivatives or bipyridine-diformamide analog derivative composition.
4. polymer according to claim 1, it is characterised in that the reaction process of the polymer is：
Wherein, m ＞ 1；Stretchable unit structure is as shown in A or B, wherein R1For hydrogen-based or methyl,
R2ForWherein R3For hydrogen-based, C1~12Straight or branched alkyl, C1~12Straight chain or branch
Any one in chain alkoxy, chlorine atom or fluorine atom.
5. polymer according to claim 4, it is characterised in that the colour change function unit structure is：
Any of；
Wherein, X S, Se or O atom；Y is C or N atoms；Z1For O, S, Se, C atom or N-R4, Z2For O, S, Se, C atom or
N-`R4, Z1And Z2It is identical or different；
The R4、`R4It is separately hydrogen-based, C1~12Straight or branched alkyl, C1~12Straight or branched alkoxyl,
Any one in chlorine atom or fluorine atom；R4、`R4It is identical or different；
R5It is expressed as hydrogen-based, C1~12Straight or branched alkyl, C1~12Straight or branched alkoxyl, chlorine atom or fluorine atom
In any one；
R6、R7It is separately thienyl, phenyl, pyridine radicals, hydrogen-based, C1~12Straight or branched alkyl, C1~12Straight chain
Or any one in branched alkoxy, chlorine atom or fluorine atom, R6、R7It is identical or different；
R8、R9It is separately thienyl, phenyl, any one in pyridine radicals, R8、R9It is identical or different；R10Be expressed as H,
Any one in chlorine atom or fluorine atom.
6. the polymer according to claim 4 or 5, it is characterised in that the branched alkyl is 2- methyl-props alkyl, 2- first
Base hexyl, 2- ethyl hexyls alkyl, 2- ethyl heptanes base, 2- hexyls octyl, 2- octyl groups decyl, 2- octyldodecyls,
Any one in 2- decyls dodecyl, 2- decyl myristyls.
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| CN109651601A (en) * | 2018-12-03 | 2019-04-19 | 江西科技师范大学 | A kind of stretchable conducting polymer of novel hydrogen bond crosslinks and synthetic method |
| CN110376817A (en) * | 2019-06-25 | 2019-10-25 | 西安交通大学 | A kind of flexible full-solid electrochromic device and its control method based on amberplex |
| CN111072932A (en) * | 2019-12-19 | 2020-04-28 | 南京宜凯瑞新材料有限公司 | Black to transparent cross-linked electrochromic polymer and preparation method thereof |
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2017
- 2017-11-15 CN CN201711129752.8A patent/CN107814917B/en active Active
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| JIN YOUNG OH ET AL.: "Intrinsically stretchable and healable semiconducting polymer for organic transistors", 《NATURE》 * |
| SHOULI MING ET AL.: "Thiadiazolo[3,4‑c]pyridine as an Acceptor toward Fast-Switching Green Donor−Acceptor-Type Electrochromic Polymer with Low Bandgap", 《ACS APPLIED MATERIALS & INTERFACES》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651601A (en) * | 2018-12-03 | 2019-04-19 | 江西科技师范大学 | A kind of stretchable conducting polymer of novel hydrogen bond crosslinks and synthetic method |
| CN110376817A (en) * | 2019-06-25 | 2019-10-25 | 西安交通大学 | A kind of flexible full-solid electrochromic device and its control method based on amberplex |
| CN111072932A (en) * | 2019-12-19 | 2020-04-28 | 南京宜凯瑞新材料有限公司 | Black to transparent cross-linked electrochromic polymer and preparation method thereof |
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| CN107814917B (en) | 2020-09-22 |
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