CN114874418A - 基于三氟甲基取代喹喔啉的共轭聚合物及其制备方法和应用 - Google Patents
基于三氟甲基取代喹喔啉的共轭聚合物及其制备方法和应用 Download PDFInfo
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- CN114874418A CN114874418A CN202210444840.1A CN202210444840A CN114874418A CN 114874418 A CN114874418 A CN 114874418A CN 202210444840 A CN202210444840 A CN 202210444840A CN 114874418 A CN114874418 A CN 114874418A
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- Prior art keywords
- conjugated polymer
- trifluoromethyl
- substituted quinoxaline
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- compound
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- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 34
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 125000001567 quinoxalinyl group Chemical class N1=C(C=NC2=CC=CC=C12)* 0.000 title abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 150000003252 quinoxalines Chemical class 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- -1 aromatic heterocycle Chemical group 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 10
- 229940126062 Compound A Drugs 0.000 claims description 10
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 10
- 125000004414 alkyl thio group Chemical group 0.000 claims description 10
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 5
- RWEKWRQKAHQYNE-UHFFFAOYSA-N 7-(bromomethyl)pentadecane Chemical compound CCCCCCCCC(CBr)CCCCCC RWEKWRQKAHQYNE-UHFFFAOYSA-N 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- UWXPRSOEIMNKQW-UHFFFAOYSA-N 1-N,2-N-dibromobenzene-1,2-diamine Chemical compound BrNC1=C(C=CC=C1)NBr UWXPRSOEIMNKQW-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical group OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- KJHQVUNUOIEYSV-UHFFFAOYSA-N ethyl 3,3,3-trifluoro-2-oxopropanoate Chemical compound CCOC(=O)C(=O)C(F)(F)F KJHQVUNUOIEYSV-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- XULHFMYCBKQGEE-MRXNPFEDSA-N 2-Hexyl-1-decanol Natural products CCCCCCCC[C@H](CO)CCCCCC XULHFMYCBKQGEE-MRXNPFEDSA-N 0.000 claims 1
- XULHFMYCBKQGEE-UHFFFAOYSA-N 2-hexyl-1-Decanol Chemical compound CCCCCCCCC(CO)CCCCCC XULHFMYCBKQGEE-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 3
- 230000006698 induction Effects 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 238000013086 organic photovoltaic Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000000370 acceptor Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 229920000144 PEDOT:PSS Polymers 0.000 description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical compound C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- HQOWCDPFDSRYRO-CDKVKFQUSA-N CCCCCCc1ccc(cc1)C1(c2cc3-c4sc5cc(\C=C6/C(=O)c7ccccc7C6=C(C#N)C#N)sc5c4C(c3cc2-c2sc3cc(C=C4C(=O)c5ccccc5C4=C(C#N)C#N)sc3c12)(c1ccc(CCCCCC)cc1)c1ccc(CCCCCC)cc1)c1ccc(CCCCCC)cc1 Chemical compound CCCCCCc1ccc(cc1)C1(c2cc3-c4sc5cc(\C=C6/C(=O)c7ccccc7C6=C(C#N)C#N)sc5c4C(c3cc2-c2sc3cc(C=C4C(=O)c5ccccc5C4=C(C#N)C#N)sc3c12)(c1ccc(CCCCCC)cc1)c1ccc(CCCCCC)cc1)c1ccc(CCCCCC)cc1 HQOWCDPFDSRYRO-CDKVKFQUSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical compound CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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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- 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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
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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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- C08G2261/1412—Saturated aliphatic units
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- C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/334—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing heteroatoms
- C08G2261/3342—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing heteroatoms derived from cycloolefins containing heteroatoms
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- C08G2261/40—Polymerisation processes
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- C08G2261/514—Electron transport
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Abstract
本发明涉及基于三氟甲基取代喹喔啉的共轭聚合物及其制备方法和在有机光伏器件中的应用。所述基于三氟甲基取代喹喔啉的共轭聚合物通过三氟甲基取代喹喔啉与共轭芳香环及其衍生物单元共聚而成。本发明具有合成方法简单、产率高、成本较低的优势；同时，三氟甲基具有强吸电子诱导效应、亲脂性以及稳定的C‑F键，将其引入到共轭聚合物中，与传统给体材料相比，其光伏性能提升更为显著，具有良好的商业化前景。
Description
技术领域
本发明涉及光电技术领域，具体涉及一种基于三氟甲基取代喹喔啉的共轭聚合物及其制备方法和应用。
背景技术
随着人类的发展，传统化石能源被不断消耗，环境污染也日益严重，世界能源体系面临“更多能源”需求和“更低碳排放”的双重挑战。而太阳能是取之不尽、用之不竭的清洁能源，因此研究和利用有机太阳能电池也被认为是解决能源危机的最有效方法之一。
有机太阳能电池能量转换效率的上限主要是由活性层材料决定的，活性层材料由给体和受体两个部分组成。目前，构建高效的聚合物给体光伏材料普遍是通过D(给电子单元)-A(受电子单元)共聚的分子设计策略，首先，选定好主链中的给电子单元与吸电子单元，再通过侧链工程和官能团取代等方法可以对材料的光伏性能进行细致的调控，最后达到一个较高的能量转换效率。2017年，侯剑辉课题组[Liu D,Zhao W,Zhang S,Ye L, ZhengZ,Cui Y,Chen Y,Hou J.Macromolecules,2015,48:5172–5178]以含噻吩共轭侧链的苯并二噻吩(BDT)为给电子单元，以喹喔啉(Qx)为吸电子单元，设计合成了三个不同氟取代形式的聚合物给体PBQ-OF、PBQ-QF和PBQ-4F。通过在吸电子的喹喔啉单元上引入强吸电子官能团氟原子方法，可以调控分子能级，以达到获得更高的开路电压的目的。
近年来，越来越多性能优异的受体材料，如Y6、ITIC，以及它们的衍生物被不断开发，然而给体材料的研究进展相对较为落后。对于理想的聚合物给体材料，其分子设计中的重要的原则是与对应的受体材料有着极为良好的互补吸收，达到能最大程度的转换太阳光能目的，从而保证光伏器件拥有一个较高的光电流上限。因此，为了进一步提高器件的能量转换效率(PCE)，开发能与这些受体吸收互补、能级匹配、在共混薄膜中可以形成纳米级的稳定形貌的新型给体材料也显得越来越重要。然而目前的高效聚合物给体材料如PM6和D18，其分子结构复杂、合成路线冗长、产率低；且聚合物给体材料的氟化方式普遍是在芳香环上直接引入氟原子，已经难以满足实际使用的需求。
因此，亟需找到一种技术方案，来解决现有技术存在的缺陷。
发明内容
本发明针对目前直接在喹喔啉结构上引入单个氟原子的技术缺陷，设计了一种合成简单、产率高、成本低的新型宽带隙聚合物给体材料，其通过制备三氟甲基取代喹喔啉类的共轭聚合物，从而引入氟原子，在简化制备方法的同时，显著改善了聚合物的光伏特性。
本发明的一个目的在于，提供一种基于三氟甲基取代喹喔啉的共轭聚合物，所述基于三氟甲基取代喹喔啉的共轭聚合物具有以下结构通式：
其中，
Ar基团选自芳香环、芳香杂环，芳香环衍生物、芳香杂环衍生物；
X1和X2独立地选自卤素原子、氢原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基、硝基、直链或支链结构的C1-C30烷基、直链或支链结构的C1-C30烷氧基、直链或支链结构的C1-C30烷硫基、直链或支链结构的C1-C30硅烷基；
R选自直链或支链结构的C1-C30烷基、C1-C30烷氧基、C1-C30烷硫基或C1-C30硅烷基；
n为自然数。
进一步地，所述Ar基团选自以下结构中的任一种：
其中，
R1选自直链或支链结构的C1-C30烷基、C1-C30烷氧基、C1-C30烷硫基或C1-C30 硅烷基；
X3选自卤素原子或氢原子。
进一步地，所述X1和X2独立地选自氢原子或氟原子。
进一步地，n为20-200的自然数。
进一步地，所述基于三氟甲基取代喹喔啉的共轭聚合物选自如下结构：
其中，R1和R2独立地选自直链或支链结构的C1-C30烷基、C1-C30烷氧基、C1-C30 烷硫基或C1-C30硅烷基。
进一步地，所述基于三氟甲基取代喹喔啉的共轭聚合物选自如下结构：
如上式，优选地，本发明的基于三氟甲基取代喹喔啉的共轭聚合物的共聚单体，其喹喔啉环上的烷氧基链要选择Y型支化的长烷基链，这样做的目的在于，极大地提升聚合物的溶液可加工性，从而增加聚合物的成膜性，
本发明的另一个目的在于，提供上述基于三氟甲基取代喹喔啉的共轭聚合物的制备方法，所述基于三氟甲基取代喹喔啉的共轭聚合物的制备方法包括如下步骤：
含三氟甲基的喹喔啉前驱体的制备：
二溴-邻苯二胺或其衍生物，与三氟丙酮酸乙酯溶于溶剂中，室温下反应，然后加热回流反应，得到白色固体；然后将所述白色固体、1-溴-2-己基癸烷和碳酸钾溶于溶剂中，加热搅拌，反应完毕后提纯，得到所述含三氟甲基的喹喔啉前驱体；
产物的制备：
在惰性气体保护下，将化合物A与化合物B加入溶剂中，在催化剂作用下进行偶联反应，得到产物；其中化合物A、化合物B的结构式如下：
其中，
X1和X2独立地选自氢原子或氟原子；
Y为硼酸酯基团或三烷基锡基团；
Z为卤素原子；
R为直链或支链结构的C1-C30烷基、C1-C30烷氧基、C1-C30烷硫基或C1-C30硅烷基。
进一步地，所述催化剂选自四(三苯基膦)钯、氯化钯和醋酸钯中的一种或多种。
进一步地，所述化合物A和所述化合物B的摩尔比为1:(0.8-1.5)。
进一步地，所述共聚反应的温度为110-200℃，时间为0.25-72h。
特别地，
当化合物A为芳烃二硼酸化合物或芳烃二硼酸酯化合物，化合物B为芳烃二卤化物时，采用Suzuki法制备基于三氟甲基取代的喹喔啉类共轭聚合物；
所述Suzuki法反应条件如下：
溶剂选自四氢呋喃和甲苯中的至少一种；
催化剂为四(三苯基膦)钯；
所述催化剂的加入量为化合物A与化合物B总摩尔量的0.01％-10％；
反应温度为110℃-200℃，反应时间为0.25-72h。
当化合物A为三烷基锡代芳烃化合物，化合物B为芳烃二卤化物时，采用Stille法制备基于三氟甲基取代的喹喔啉类共轭聚合物；
所述Stille法反应条件如下：
溶剂选自四氢呋喃、甲苯、氯苯和二甲基甲酰胺中的至少一种；
催化剂选自四(三苯基膦)钯、氯化钯和醋酸钯种的至少一种；
所述催化剂的加入量为化合物A与化合物B总摩尔量的0.01％-10％；
反应温度为110-200℃，反应时间为0.25-72h。
本发明的另一个目的在于，提供上述基于三氟甲基取代喹喔啉的共轭聚合物在有机太阳能电池中的应用。
与现有技术相比，本发明具有如下有益效果：
1.本发明制备的新型宽带隙聚合物给体材料具有合成方法简单、产率高、成本较低的优势；
2.本发明制备的基于三氟甲基取代喹喔啉的共轭聚合物中，三氟甲基具有强吸电子诱导效应、亲脂性以及稳定的C-F键，将其引入到共轭聚合物中，与传统给体材料相比，其光伏性能提升更为显著，具有良好的商业化前景。
具体实施方式
为了更清楚地说明本发明的技术方案，列举如下实施例，但本发明并不局限于此。
下述实施例中所使用的实验方法如无特殊说明，均为常规方法；下述实施例中所用的试剂、材料等，如无特殊说明，均可从商业途径得到。
实施例1
一种基于三氟甲基取代喹喔啉的共轭聚合物P1，其结构式如下所示：
其制备方法如下：
(1)单体M1的合成
将化合物1(797.7mg，3mmol)溶解在甲苯(40mL)中，在室温下搅拌并缓慢滴加三氟丙酮酸乙酯(680.4mg，4mmol)。反应1h后，将有白色固体从溶液中沉淀出来。将反应混合物在室温下搅拌30min，然后在装有分水器的烧瓶中回流2h，在真空下浓缩反应液，得到白色固体化合物2(929.8mg，产率：83.3％)，且无需进一步纯化。
将化合物2(929.8mg，2.5mmol)、碳酸钾(414.6mg，3.0mmol)和1-溴-2-己基癸烷(916.2mg，3.0mmol)溶解在N,N-二甲基甲酰胺溶液(30mL)中。将混合物回流12h，然后冷却至室温并倒入饱和NH4Cl溶液中，用石油醚萃取并用去离子水洗涤。合并的有机层用无水MgSO4干燥，浓缩并通过柱色谱法使用石油醚/二氯甲烷纯化，得到无色油状物 M1。(1.31g，2.2mmol，产率：88％)。1H NMR(600MHz,CHCl3-d)δ7.95(d,J＝8.2Hz, 1H),7.82(d,J＝8.2Hz,1H),4.62(d,J＝5.4Hz,2H),1.94(hept,J＝5.9Hz,1H),1.53–1.37 (m,8H),1.35–1.24(m,16H),0.90(td,J＝7.0,2.8Hz,6H).
(2)P1的合成
将0.2mmol化合物M1和0.2mmol化合物M2加入反应釜中，再加入0.0006mmol 催化剂Pd2(dba3)和0.0024mmolP(o-tol)3，然后将反应釜抽至真空后通入氮气，重复三次，每次通入氮气5min。将混合物溶于5mL氯苯中，在回流温度下反应48h。冷却至室温后，将聚合物溶液缓慢沉析到入100mL甲醇中，将沉析出的固体聚合物在索氏提取器内依次用甲醇、正己烷、二氯甲烷和三氯甲烷洗脱。最后用三氯甲烷溶解后沉析到甲醇中，过滤、真空干燥24h，得到蓝黑色固体粉末的聚合物P1(GPC：Mn＝34.5KDa，PDI＝2.2)。
实施例2
一种基于三氟甲基取代喹喔啉的共轭聚合物P2，其结构式如下所示：
(1)单体M2的合成：
同实施例1的化合物2的制备，仅将化合物1邻苯二胺等物质的量地替换为化合物3，最后得到淡黄色油状物M2。1H NMR(600MHz,Chloroform-d)δ4.61(d,J＝5.4Hz,2H),1.94(hept,J＝6.1Hz,1H),1.53–1.37(m,8H),1.35–1.24(m,16H),0.90(td,J＝6.9,3.1Hz,6H).
(2)P2的合成：
同实施例1中P1的制备，仅将单体M1等物质的量地替换为实施例2中的含三氟甲基的喹喔啉前驱体M2(GPC：Mn＝36.5KDa，PDI＝2.3)。
对比例1
(1)单体M3的合成
取化合物1和乙醛酸各5mmol，室温下溶于30mL的乙酸中。将此悬浊液加热至 40℃搅拌10min，然后冷却至室温继续搅拌3h。将悬浊液中的固体抽滤并干燥得到白色固体(4.95mmol，产率99.0％)。将此白色固体(4.95mmol)、叔丁醇钾(t-BuOK，5.94mmol) 和1-溴-2-己基癸烷(4.95mmol)溶于甲醇中，将此混合液加热回流12h，然后冷却至室温。将混合液倒入饱和氯化铵(NH4Cl)溶液中，然后用二氯甲烷进行萃取并水洗有机相。将有机相用无水硫酸镁固体进行干燥，之后过滤除去硫酸镁。然后用旋转蒸发仪除去有机溶剂，将残渣用干法制样，用硅胶柱分离得到无色油状液体化合物M3(4.66mmol，产率 94.1％)。
(2)对比例1聚合物的合成
同实施例1中P1的制备，仅将单体M1等物质的量地替换为对比例1中的单体 M3(GPC：Mn＝19.6KDa，PDI＝2.3)。
测试例
将上述实施例1-2和对比例1所制备的聚合物作为活性层材料用于有机太阳能电池器件中进行性能测试，器件结构为：ITO(135nm)/PEDOT:PSS(40nm)/活性层(100 nm)/PDINN(5nm)/Ag(100nm)，其中PEDOT:PSS为阳极修饰层，PDINN为阴极修饰层。
上述太阳能电池器件的制备与表征：首先，将含ITO玻璃基底依次使用丙酮、去离子水、丙酮和异丙醇进行超声清洗，之后将其烘干并使用紫外臭氧进行处理。然后将PEDOT:PSS水溶液旋涂在ITO的表面制备一层PEDOT:PSS薄膜，之后将其于150℃干燥 15min以除去PEDOT:PSS薄膜中的水。然后将给体聚合物与Y6小分子受体以质量比为 1:1.2混合溶解在氯仿溶液中，制备为18mg/mL的光活性层溶液。再将所述光活性层溶液旋涂在PEDOT:PSS薄膜上，并在80℃下热退火5min调控其微观形貌。然后将PDINN 的甲醇溶液旋涂在光活性层上，作为阴极修饰层。然后在真空环境下(约5.0×10-5Pa)将高纯度金属Ag蒸镀沉积在PDINN层上作为阴极。
对上述器件进行光伏性能测试，测试结果均在100mW cm-2(1个太阳,AM1.5G光谱)的太阳模拟灯条件下测试获得。
测试结果如表1所示：
表1实施例1-2和对比例1聚合物的光伏性能测试
根据表1可以得出，向材料中引入三氟甲基，可以降低其LUMO能级，从而达到显著提升器件开路电压的效果，有效增强了器件的光伏性能，大大提高了能量转换效率，有利于降低有机太阳能电池器件的成本。
对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的，本发明的范围由所附权利要求而不是上述说明限定，因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。
此外，应当理解，虽然本说明书按照实施方式加以描述，但并非每个实施方式仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施例中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。
Claims (10)
1.基于三氟甲基取代喹喔啉的共轭聚合物，其特征在于，所述基于三氟甲基取代喹喔啉的共轭聚合物具有以下结构通式：
其中，
Ar基团选自芳香环、芳香杂环，芳香环衍生物、芳香杂环衍生物；
X1和X2独立地选自卤素原子、氢原子、烯基、炔基、芳基、羟基、氨基、羰基、羧基、酯基、氰基、硝基、直链或支链结构的C1-C30烷基、直链或支链结构的C1-C30烷氧基、直链或支链结构的C1-C30烷硫基、直链或支链结构的C1-C30硅烷基；
R选自直链或支链结构的C1-C30烷基、C1-C30烷氧基、C1-C30烷硫基或C1-C30硅烷基；
n为自然数。
2.根据权利要求1所述基于三氟甲基取代喹喔啉的共轭聚合物，其特征在于，所述Ar基团选自以下结构中的任一种：
其中，
R1选自直链或支链结构的C1-C30烷基、C1-C30烷氧基、C1-C30烷硫基或C1-C30硅烷基；
X3选自卤素原子或氢原子。
3.根据权利要求1所述基于三氟甲基取代喹喔啉的共轭聚合物，其特征在于，所述X1和X2独立地选自氢原子或氟原子。
4.根据权利要求1所述基于三氟甲基取代喹喔啉的共轭聚合物，其特征在于，n为20-200的自然数。
5.根据权利要求1所述基于三氟甲基取代喹喔啉的共轭聚合物，其特征在于，所述基于三氟甲基取代喹喔啉的共轭聚合物选自如下结构：
其中，R1和R2独立地选自直链或支链结构的C1-C30烷基、C1-C30烷氧基、C1-C30烷硫基或C1-C30硅烷基。
6.权利要求1-5任一项所述基于三氟甲基取代喹喔啉的共轭聚合物的制备方法，其特征在于，所述基于三氟甲基取代喹喔啉的共轭聚合物的制备方法包括如下步骤：
含三氟甲基的喹喔啉前驱体的制备：
二溴-邻苯二胺或其衍生物，与三氟丙酮酸乙酯溶于溶剂中，室温下反应，然后加热回流反应，得到白色固体；然后将所述白色固体、1-溴-2-己基癸烷和碳酸钾溶于溶剂中，加热搅拌，反应完毕后提纯，得到所述含三氟甲基的喹喔啉前驱体；
产物的制备：
在惰性气体保护下，将化合物A与化合物B加入溶剂中，在催化剂作用下进行偶联反应，得到产物；其中化合物A、化合物B的结构式如下：
其中，
X1和X2独立地选自氢原子或氟原子；
Y为硼酸酯基团或三烷基锡基团；
Z为卤素原子；
R为直链或支链结构的C1-C30烷基、C1-C30烷氧基、C1-C30烷硫基或C1-C30硅烷基。
7.根据权利要求6所述基于三氟甲基取代喹喔啉的共轭聚合物的制备方法，其特征在于，所述白色固体与2-己基-1-癸醇的摩尔比为1:(0.9-1.2)。
8.根据权利要求6所述基于三氟甲基取代喹喔啉的共轭聚合物的制备方法，其特征在于，所述化合物A和所述化合物B的摩尔比为1:(0.8-1.5)。
9.根据权利要求5所述基于三氟甲基取代喹喔啉的共轭聚合物的制备方法，其特征在于，所述共聚反应的温度为110-200℃，时间为0.25-72h。
10.权利要求1-5任一项所述基于三氟甲基取代喹喔啉的共轭聚合物在有机太阳能电池中的应用。
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