WO2013078634A1 - 一种2，7-芴与联噻唑共聚物及其制备方法和包含其的太阳能电池 - Google Patents
一种2，7-芴与联噻唑共聚物及其制备方法和包含其的太阳能电池 Download PDFInfo
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- WO2013078634A1 WO2013078634A1 PCT/CN2011/083204 CN2011083204W WO2013078634A1 WO 2013078634 A1 WO2013078634 A1 WO 2013078634A1 CN 2011083204 W CN2011083204 W CN 2011083204W WO 2013078634 A1 WO2013078634 A1 WO 2013078634A1
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- compound
- fluorene
- palladium
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 14
- SMSLWFZHCONMGQ-UHFFFAOYSA-N 2-(1,3-thiazol-2-yl)-1,3-thiazole Chemical compound C1=CSC(C=2SC=CN=2)=N1 SMSLWFZHCONMGQ-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 229940126062 Compound A Drugs 0.000 claims description 12
- 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 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000006619 Stille reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 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 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000002904 solvent Substances 0.000 description 5
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 2
- 229930182558 Sterol Natural products 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000003432 sterols Chemical class 0.000 description 2
- 235000003702 sterols Nutrition 0.000 description 2
- RXACYPFGPNTUNV-UHFFFAOYSA-N 9,9-dioctylfluorene Chemical compound C1=CC=C2C(CCCCCCCC)(CCCCCCCC)C3=CC=CC=C3C2=C1 RXACYPFGPNTUNV-UHFFFAOYSA-N 0.000 description 1
- 0 CC1(C)OB(c(cc2)cc(C3(C)*)c2-c2c3cc(B3OC(C)(C)C(C)(C)O3)cc2)OC1(C)C Chemical compound CC1(C)OB(c(cc2)cc(C3(C)*)c2-c2c3cc(B3OC(C)(C)C(C)(C)O3)cc2)OC1(C)C 0.000 description 1
- DYOLDBJARBGWQQ-UHFFFAOYSA-N Cc(nc(-c([s]1)nc(C)c1Br)[s]1)c1Br Chemical compound Cc(nc(-c([s]1)nc(C)c1Br)[s]1)c1Br DYOLDBJARBGWQQ-UHFFFAOYSA-N 0.000 description 1
- SJJAGYQGXNRZIQ-UHFFFAOYSA-N SNS.C1=CC=CC2=CC3=CC=CC=C3C=C12 Chemical compound SNS.C1=CC=CC2=CC3=CC=CC=C3C=C12 SJJAGYQGXNRZIQ-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000879 imine group Chemical group 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 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
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/115—Polyfluorene; Derivatives thereof
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
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- 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
- C08G2261/30—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
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
- C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
-
- 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
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3229—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing nitrogen and sulfur as heteroatoms
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- 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
- C08G2261/411—Suzuki reactions
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- 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
- C08G2261/90—Applications
- C08G2261/91—Photovoltaic applications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the invention belongs to the field of organic solar cell materials, and particularly relates to a 2,7-fluorene and bithiazole copolymer, a preparation method thereof and a solar cell comprising the same. Background technique
- the present invention provides a copolymer of 2,7-indole and a bithiazole, which has novel structure, good solubility, excellent film forming performance and high energy. Conversion efficiency, can be used as a solar cell material.
- the present invention also provides a process for the preparation of the copolymer and a solar cell comprising the copolymer. The raw materials used in the preparation method are cheap and easy to obtain, and the synthesis route is simple.
- the invention provides a 2,7-fluorene and bithiazole copolymer of formula (I):
- R l R 2 are both ⁇ C 2 .
- the alkyl group, n is an integer from 10 to 100.
- the same or different as R 2 is selected from CH 3 , C 8 H 17 or C 2 , respectively. H 41 .
- the present invention provides a method for preparing a copolymer of the formula (I) of 2,7-fluorene and a bithiazole, comprising the steps of:
- the compound A and the compound B are added to the organic solvent containing the catalyst, and the molar ratio of the compound A to the compound B is 1:1 to 1.2, and the Suzuki coupling reaction is carried out by heating, and the reaction is terminated after the temperature is lowered to room temperature.
- decyl alcohol was precipitated, extracted by a Soxhlet extractor, and then extracted with decyl alcohol and n-hexane, and then extracted with chloroform until colorless.
- the chloroform solution was collected and dried to obtain a red powder, and the obtained red color was collected. After the powder is vacuum dried, the copolymer of the formula (I) is obtained.
- R l R 2 are both ⁇ C 2 .
- the alkyl group, n is an integer from 10 to 100.
- the same or different as R 2 is selected from CH 3 , C 8 H 17 or C 2 , respectively. H 41 .
- the catalyst is a mixture of an inorganic base and an organic palladium, or an organic palladium and A mixture of organophosphine ligands.
- the inorganic base is potassium carbonate, sodium carbonate or sodium bicarbonate.
- the organic palladium is bistriphenylphosphine palladium dichloride, tetrakistriphenylphosphine palladium or trisethylenebenzyl acetone dipalladium, and the molar ratio of the organic palladium to the compound A is 1. : 20 ⁇ 100. In a more preferred embodiment, the molar ratio of the organic palladium to the compound A is from 1:40 to 80.
- the organophosphine ligand is tri-tert-butylphosphine, tri-p-phenylenephosphine or 2-bicyclohexylphosphino-2,6-dimethoxybiphenyl.
- the molar ratio of organopalladium to organophosphine ligand in the mixture of organopalladium and organophosphine ligand is from 1:4 to 8.
- the organic solvent is at least one selected from the group consisting of toluene, anthracene, anthracene-dimercaptoamide, and tetrahydrofuran.
- the Suzuki coupling reaction has a reaction temperature of from 70 to 130. C, the reaction time is 12 ⁇ 96 hours.
- the Stille coupling reaction has a reaction temperature of 90 to 100 ° C and a reaction time of 36 to 72 hours.
- the present invention provides a solar cell comprising an anode, an active layer and a cathode which are sequentially laminated, and the electron donor material in the active layer is a copolymer of 2,7-fluorene and a thiazole as described above.
- the invention provides a copolymer of 2,7-fluorene and bithiazole, which has novel structure, and polymerizes 2,7-anthracene and thiazole for the first time to obtain a polymer with good solubility, excellent film forming performance and high energy conversion efficiency.
- polyalkyl fluorene materials have good solubility and processing properties in addition to high thermal stability and chemical stability.
- Thiazole is a typical electron-deficient unit, which contains an electron-withdrawing imine group.
- the bithiazole group in the main chain of the copolymer exhibits high hole mobility.
- the alkyl chain attached to the thiazole can increase the dissolution of the copolymer. performance.
- the invention also provides a preparation method of the copolymer and a sun containing the copolymer
- Fig. 1 is a chart showing the ultraviolet-visible absorption spectrum of poly[4,4'-dioctyl-2,2'-bithiazole-co- 9,9-dioctylfluorene] prepared in Example 1. detailed description
- the monomer A can be synthesized by a method disclosed in the literature (Journal of Advanced Materials, 2007, 19, 2295.) or commercially available, and the monomer B can be obtained. Purchased from the market. It should be noted that many modifications and adaptations may be made by those skilled in the art without departing from the principles of the invention, and such modifications and adjustments are also considered to be within the scope of the invention.
- n is an integer from 10 to 100
- the preparation method is as follows:
- n is an integer from 10 to 100
- the preparation method is as follows:
- the mixed droplets were added to 50 ml of methanol to precipitate. After filtration through a Soxhlet extractor, it was extracted with decyl alcohol and n-hexane successively for 24 h, then extracted with chloroform as a solvent to a colorlessness. The chloroform solution was collected and dried to give a red powder. The product was obtained by suction overnight, yield 58%.
- n is an integer from 10 to 100
- the preparation method is as follows:
- the reaction was stirred for 96 h, and a Suzuki coupling reaction was carried out. After the temperature was lowered to room temperature, the reaction was stopped, and 40 mL of decyl alcohol was precipitated into the flask, which was filtered through a Soxhlet extractor and then extracted with decyl alcohol and n-hexane, respectively, for 24 hours. Then, it was extracted with chloroform as a solvent to a colorlessness. The chloroform solution was collected and dried to give a red solid, which was collected and dried under vacuum at 50 ° C for 24 h to give the product. The yield was 85%.
- ⁇ is an integer from 10 to 100
- the preparation method is as follows:
- a Suzuki coupling reaction was performed. After the temperature was lowered to room temperature, the reaction was stopped. 40 mL of sterol was precipitated into the flask, filtered through a Soxhlet extractor, and then extracted with decyl alcohol and n-hexane for 24 h each. Then, it was extracted with chloroform as a solvent, and the chloroform solution was collected and dried to give a red powder, which was collected and dried under vacuum for 50 hr.
- Example 1 Preparation of poly [4, 4 '- dioctyl - 2, 2' - bithiazole 4 CO-, 8- bis (octyloxy) - 2, 7-fluorenyl]
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
本发明提供一种式（I）的2,7-芴与联噻唑共聚物及其制备方法和包含其的太阳能电池。该2,7-芴与联噻唑共聚物的结构式如式（I）所示。其中，R1、R2均为C1~C20的烷基，n为10~100的整数。本发明共聚物结构新颖，溶解性能良好，成膜性能优良，具有较高能量转换效率，可用作太阳能电池材料。本发明还提供了该共聚物的制备方法和包含其的太阳能电池，所述制备方法采用的原材料价廉易得，合成路线简单。
Description
一种 2, 7-芴与联噻唑共聚物及其制备方法和包含其的太阳能电池 技术领域
本发明属于有机太阳能电池材料领域，具体涉及一种 2, 7-芴与联噻唑共聚物 及其制备方法和包含其的太阳能电池。 背景技术
利用廉价材料制备低成本、高效能的太阳能电池一直是光伏领域的研究热点 和难点。 有机半导体材料以其原料易得、 价格低廉、 工艺简单、 稳定性强、 光 伏效应良好等优点备受关注。 自 1992年 N. S. Sariciftci等在 SCIENCE ( N. S Sariciftci, L. Smilowitz, A. J. Heeger, et al. Science, 1992, 258, 1474 )上报道共轭聚 合物与 C6。之间的光诱导电子转移现象后，有机聚合物太阳能电池逐渐成为研究 的热点。 近年来这方面的研究取得了飞速的发展， 但是有机聚合物太阳能电池 仍比无机太阳能电池的转换效率低得多。 为了使有机聚合物太阳能电池得到实 际的应用， 开发具有较高能量转换效率的新型材料仍是这一领域的首要任务。 发明内容
为解决上述有机聚合物太阳能电池低效率的问题， 本发明提供了一种 2, 7- 芴与联噻唑共聚物， 所述共聚物结构新颖， 溶解性能良好， 成膜性能优良， 具 有较高能量转换效率， 可用作太阳能电池材料。 本发明还提供了该共聚物的制 备方法以及包含该共聚物的太阳能电池。 所述制备方法采用的原材料价廉易得， 合成路线简单。
一方面， 本发明提供了一种式 (I)的 2, 7-芴与联噻唑共聚物：
R1 (I) ，
其中， Rl R2均为 ~ C2。的烷基， n为 10 ~ 100的整数。
在优选的实施方案中， 与 R2相同或不同，分别选自 CH3、 C8H17或 C2。H41。 第二方面， 本发明提供了一种 2, 7-芴与联噻唑共聚物式 (I)的制备方法， 包 括如下步骤：
(1) 分别提供如下结构式表示的化合物 A和化合物 B,
为 d C^的烷基；
(2)在无氧环境下， 将化合物 A和化合物 B加入至含有催化剂的有机溶剂 中 , 化合物 A和化合物 B摩尔比为 1:1〜1.2, 加热进行 Suzuki耦合反应， 降至 室温后终止反应， 向所得溶液中加入曱醇沉析， 通过索氏提取器提取之后依次 用曱醇和正己烷抽提， 然后用氯仿抽提至无色， 收集氯仿溶液并旋干， 得到红 色粉末， 收集所得红色粉末真空干燥后即得式 (I)所示共聚物
Ri (I) ，
其中， Rl R2均为 ~ C2。的烷基， n为 10 ~ 100的整数。
在优选的实施方案中， 与 R2相同或不同，分别选自 CH3、 C8H17或 C2。H41。 在优选的实施方案中， 催化剂为无机碱与有机钯的混合物， 或者有机钯与
有机膦配体的混合物。
在优选的实施方案中， 无机碱为碳酸钾、 碳酸钠或碳酸氢钠。
在优选的实施方案中， 有机钯为双三苯基膦二氯化钯、 四三苯基膦钯或者 三二亚苄基丙酮二钯， 所述有机钯与所述化合物 A的摩尔比为 1:20〜100。 在更 优选的实施方案中， 所述有机钯与所述化合物 A的摩尔比为 1 :40〜80。
在优选的实施方案中， 有机膦配体为三叔丁基膦、 三对曱苯基膦或 2-双环 己基磷 -2，， 6，-二曱氧基联苯。
在优选的实施方案中， 有机钯与有机膦配体的混合物中有机钯与有机膦配 体的摩尔比为 1:4〜8。
在优选的实施方案中， 所述有机溶剂选自曱苯、 Ν,Ν-二曱基曱酰胺、 四氢 吹喃中的至少一种。
在优选的实施方案中， Suzuki耦合反应的反应温度为 70 ~ 130。C, 反应时 间为 12 ~ 96 小时。
在更优选的实施方案中， Stille耦合反应的反应温度为 90 ~ 100°C, 反应时 间为 36 ~ 72小时。
第三方面， 本发明提供了一种太阳能电池， 包括依次层叠的阳极、 活性层 和阴极， 活性层中的电子给体材质为如前文所述的 2, 7-芴与联噻唑共聚物。
本发明提供一种 2, 7-芴与联噻唑共聚物， 结构新颖， 首次将 2, 7-芴与噻唑聚 合， 得到溶解性能良好、 成膜性能优良且具有较高能量转换效率的聚合物。 聚 烷基芴材料作为新型的光电材料， 除了同样具有较高的热稳定性和化学稳定性 外， 还具有良好的溶解性能和加工性能。 噻唑是一个典型的缺电子单元， 它包 含一个吸电子亚胺基团， 共聚物主链中含有联噻唑基表现出较高的空穴迁移率， 噻唑上连接烷基链可以增加共聚物的溶解性能。
本发明还提供该共聚物的制备方法以及包含该共聚物的太阳
制备方法采用的原材料价廉易得， 合成路线简单。 附图说明
图 1为实施例 1制备的聚 [4, 4' -二辛基- 2, 2' -联噻唑 -co- 9,9-二辛基芴]的 紫外可见吸收光谱图。 具体实施方式
以下所述是本发明的优选实施方式， 其中单体 A可参照文献（ Journal of Advanced Materials (先进材料）， 2007, 19, 2295. )公开的方法合成或者从市场 上购买得到， 单体 B可从市场上购买得到。 应当指出， 对于本技术领域的普通技 术人员来说， 在不脱离本发明原理的前提下， 还可以做出若干改进和调整， 这 些改进和调整也视为在本发明的保护范围内。
实施例 1:
式 (II)的聚 [4, 4' -二辛基 - 2, 2' -联噻唑 -co- 9,9-二辛基芴]:
n为 10 ~ 100的整数,
其制备方法如下:
其中， 提供如下结构式表示的化合物 A和化合物 B,
氮气保护下，将 5,5， -二溴 - 4, 4， -二辛基 - 2, 2， -联噻唑 (165 mg, 0.3 mmol), 2, 7-二硼酸频哪醇酯 -9,9-二辛基芴（193 mg, 0.3 mmol) , 三二亚苄基丙酮二钯 (13.75 mg, 0.015mmol), 2-双环己基磷 -2，， 6，-二曱氧基联苯 (42 mg, 0.1 mmol), 溶 解在 12 mL曱苯中， 再将碳酸钾 (3 mL, 2mol/L)溶液加入到溶液中， 充分通氮气 排空气约 30 min后， 在 90°C搅拌反应 72 h, 进行 Suzuki耦合反应。 降至室温 后停止反应， 向烧瓶中加入 40 mL曱醇沉析， 通过索氏提取器过滤之后依次用 曱醇和正己烷抽提， 各 24 h。 然后以氯仿为溶剂抽提至无色， 收集氯仿溶液并 旋干得到红色粉末， 收集后在真空下 50°C干燥 24 h后即为产物， 产率为 70%。
测试结果为： 分子量（ GPC, THF, R. I): Mn =52.5kDa, MJMn =2.2。
实施例 2:
式 (III)的聚 [4, 4' -二曱基 - 2, 2' -联噻唑 -co- 9,9-二（二十烷）基芴]:
(III)，
n为 10 ~ 100的整数，
制备方法如下：
其中， 提供如下结构式表示的化合物 A和化合物 B,
反应方程式为：
在氮气保护下， 加入 5,5， -二溴- 4, 4， -二曱基 - 2, 2， -联噻唑 (71 mg, 0.2mmol)、 2, 7-二硼酸频哪醇酯 -9,9-二（二十烷基）芴（196 mg, 0.2mmol)和 Ν,Ν- 二曱基曱酰胺溶剂 15ml, 再将碳酸钠 (2 mL, 2mol/L)溶液加入到溶液中， 抽真空 除氧并充入氮气， 然后加入双三苯基膦二氯化钯（ 5 mg, 0.007 mmol ), 加热到 110°C反应 36 h, 进行 Suzuki耦合反应。 冷却至室温后将混合液滴加到 50 ml曱 醇中进行沉降。 通过索氏提取器过滤之后依次用曱醇和正己烷抽提， 各 24 h, 然后以氯仿为溶剂抽提至无色， 收集氯仿溶液并旋干得到红色粉末， 真空泵下
抽过夜得到产物， 产率 58%。
测试结果为： 分子量（ GPC, THF, R. I): Mn = 43.6kDa, MJMn =2.3。
实施例 3:
式 (IV)的聚 [4, 4， -二（二十烷基） - 2, 2， -联噻唑 -co-9,9-二曱基芴]:
n为 10 ~ 100的整数，
制备方法如下：
其中， 提供如下结构式表示的化合物 A和化合物 B,
氮气保护下， 5,5， -二溴 - 4, 4， -二（二十烷基） - 2, 2， -联噻唑 (266 mg, 0.3 mmol), 2, 7-二硼酸频哪醇酯 -9,9-二曱基芴（134 mg, 0.3 mmol)以及 15 mL四 氢呋喃分别加入到 50 mL的两口瓶中， 充分通氮气排空气约 20 min后， 然后将
四三苯基膦 4.巴（ 3.73 mg, 0.003 mmol )加入其中，然后再将碳酸氢钠 (3 mL, 2mol/L) 溶液加入到溶液中， 再充分通氮气排空气约 10 min后， 在 70 搅拌反应 96h, 进行 Suzuki耦合反应。 降至室温后停止反应， 向烧瓶中加入 40 mL曱醇沉析， 通过索氏提取器过滤之后依次用曱醇和正己烷抽提， 各 24 h。 然后以氯仿为溶 剂抽提至无色， 收集氯仿溶液并旋干得到红色固体， 收集后在真空下 50°C干燥 24 h后得到产物。 产率为 85%。
测试结果为： 分子量（ GPC, THF, R. I): Mn =63.4 kDa, MJMn =2.1。
实施例 4:
式 (II)的聚 [4, 4' -二辛基 - 2, 2' -联噻唑 -co- 9,9-二辛基芴]:
η为 10 ~ 100的整数，
其制备方法如下：
其中， 提供如下结构式表示的化合物 Α和化合物 Β,
反应方程式为:
氮气保护下，将 5,5， -二溴 - 4, 4， -二辛基 - 2, 2， -联噻唑(165 11¾, 0.3 1^1101), 2, 7-二硼酸频哪醇酯 -9,9-二辛基芴（193 mg, 0.36 mmol)、 三二亚苄基丙酮二钯 (13.75 mg, 0.015mmol), 2-双环己基磷 -2，， 6，-二曱氧基联苯（ 42 mg, 0.10 mmol )， 溶解在 12 mL曱苯中， 再将碳酸钾 (3 mL, 2mol/L)溶液加入到溶液中， 充分通氮 气排空气约 30 min后， 在 130°C搅拌反应 12 h， 进行 Suzuki耦合反应。 降至室 温后停止反应， 向烧瓶中加入 40 mL曱醇沉析， 通过索氏提取器过滤之后依次 用曱醇和正己烷抽提， 各 24 h。 然后以氯仿为溶剂抽提至无色， 收集氯仿溶液 并旋干得到红色粉末，收集后在真空下 50Ό干燥 24 h后即为产物，产率为 70%。
测试结果为： 分子量（ GPC, THF, R. I): M„ =52.5kDa, MJMn =2.2。
效果实施例
实施例 1制备的聚[ 4, 4' -二辛基- 2, 2' -联噻唑 -co- 4, 8-二 (辛氧基) -2, 7-芴]的 紫外可见吸收光谱图如图 1所示。 由图 1可以看出该共轭聚合物在 350nm ~ 700nm 之间有较大较宽的吸收， 其中最大吸收峰位于 573 nm左右。
Claims
1、 一种 2, 7-芴与联噻唑共聚物， 其特征在于， 结构式如式 (I)所示: 
Ri (I) ，
其中， R2均为 ~ C2。的烷基， n为 10 ~ 100的整数。
2、 一种 2, 7-芴与联噻唑共聚物的制备方法， 其特征在于， 包括如下步骤:
( 1 ) 分别提供如下结构式表示的化合物 A和化合物 B, 
为 d C^的烷基；
( 2 ) 在无氧环境下， 将化合物 A和化合物 B加入至含有催化剂的有机溶 剂中， 化合物 A和化合物 B摩尔比为 1:1〜1.2, 加热进行 Suzuki耦合反应， 降 至室温后终止反应， 向所得溶液中加入曱醇沉析， 通过索氏提取器提取之后依 次用曱醇和正己烷抽提， 然后用氯仿抽提至无色， 收集氯仿溶液并旋干， 得到 红色粉末， 收集所得红色粉末真空干燥后即得式 (I)所示共聚物 
Ri (I) ，
其中， R2均为 ~ C2。的烷基， n为 10 ~ 100的整数。
3、 如权利要求 2所述的制备方法， 其特征在于， 步骤（2 ) 中所述催化剂 为无机碱与有机钯的混合物， 或者有机钯与有机膦配体的混合物。
4、 如权利要求 3所述的制备方法， 其特征在于， 所述无机碱为碳酸钾、 碳 酸钠或碳酸氢钠。
5、 如权利要求 3所述的制备方法， 其特征在于， 所述有机钯为双三苯基膦 二氯化钯、四三苯基膦钯或者三二亚苄基丙酮二钯，所述有机钯与所述化合物 A 的摩尔比为 1:20〜謂。
6、 如权利要求 3所述的制备方法， 其特征在于， 所述有机膦配体为三叔丁 基膦、 三对曱苯基膦或 2-双环己基磷 -2，， 6，-二曱氧基联苯。
7、 如权利要求 6所述的制备方法， 其特征在于， 所述有机钯与有机膦配体 的混合物中有机钯与有机膦配体的摩尔比为 1:4〜8。
8、 如权利要求 2 所述的制备方法， 其特征在于， 步骤（2 ) 中所述有机溶 剂选自曱苯、 Ν,Ν-二曱基曱酰胺、 四氢呋喃中的至少一种。
9、 如权利要求 2所述的制备方法， 其特征在于， 所述 Stille耦合反应温度 为 70 ~ 130°C, 反应时间为 12 ~ 96 小时。
10、 一种太阳能电池， 包括依次层叠的阳极、 活性层和阴极， 其特征在于， 所述活性层中的电子给体材质为如权利要求 1所述的 2, 7-芴与联噻唑共聚物。
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| PCT/CN2011/083204 WO2013078634A1 (zh) | 2011-11-30 | 2011-11-30 | 一种2，7-芴与联噻唑共聚物及其制备方法和包含其的太阳能电池 |
| US14/347,510 US20140230902A1 (en) | 2011-11-30 | 2011-11-30 | Co-polymer of 2,7-fluorene and bithiazole, method for preparing same and solar battery containing same |
| EP11876702.9A EP2787020A4 (en) | 2011-11-30 | 2011-11-30 | COPOLYMER OF 2,7-FLUORENE AND BITHIAZOL, METHOD OF MANUFACTURING THEREOF AND SOLAR BATTERY THEREWITH |
| CN201180073507.4A CN103797044A (zh) | 2011-11-30 | 2011-11-30 | 一种2,7-芴与联噻唑共聚物及其制备方法和包含其的太阳能电池 |
| JP2014534910A JP2014528501A (ja) | 2011-11-30 | 2011-11-30 | ２，７−フルオレンとビチアゾールとのコポリマー、その調製方法、及び、それを含む太陽電池 |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2014528501A (ja) | 2014-10-27 |
| US20140230902A1 (en) | 2014-08-21 |
| EP2787020A1 (en) | 2014-10-08 |
| EP2787020A4 (en) | 2015-09-09 |
| CN103797044A (zh) | 2014-05-14 |
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