WO2011066954A1 - π-CONJUGATED POLYMERS CONTAINING FLUOROARYLVINYLEDENE UNITS AND RELATIVE PREPARATION PROCESS - Google Patents
π-CONJUGATED POLYMERS CONTAINING FLUOROARYLVINYLEDENE UNITS AND RELATIVE PREPARATION PROCESS Download PDFInfo
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- WO2011066954A1 WO2011066954A1 PCT/EP2010/007285 EP2010007285W WO2011066954A1 WO 2011066954 A1 WO2011066954 A1 WO 2011066954A1 EP 2010007285 W EP2010007285 W EP 2010007285W WO 2011066954 A1 WO2011066954 A1 WO 2011066954A1
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- Prior art keywords
- alternating
- conjugated polymer
- polymer according
- conjugated
- substituents
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 5
- -1 2-ethylhexyl Chemical group 0.000 claims description 43
- 229920000642 polymer Polymers 0.000 claims description 26
- 125000001424 substituent group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 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 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000001421 myristyl 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])[H] 0.000 claims description 3
- 125000002347 octyl 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])[H] 0.000 claims description 3
- 125000000913 palmityl 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])[H] 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 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 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004079 stearyl 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])[H] 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 150000001875 compounds Chemical class 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000004770 highest occupied molecular orbital Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000003306 harvesting Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 4
- 0 CCCCC(CC)CC(CC(CC)CCCC)(c1cc(*C)ccc1C1=CC2)C1=C[C@@]2C(*C)=Cc(c(F)c(c(F)c1C)F)c1F Chemical compound CCCCC(CC)CC(CC(CC)CCCC)(c1cc(*C)ccc1C1=CC2)C1=C[C@@]2C(*C)=Cc(c(F)c(c(F)c1C)F)c1F 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000306 component Substances 0.000 description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 230000005291 magnetic effect Effects 0.000 description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 3
- 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 3
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 3
- 238000013087 polymer photovoltaic Methods 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000013086 organic photovoltaic Methods 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229960001749 practolol Drugs 0.000 description 2
- 230000003252 repetitive effect Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 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
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 2
- LVJZCPNIJXVIAT-UHFFFAOYSA-N 1-ethenyl-2,3,4,5,6-pentafluorobenzene Chemical group FC1=C(F)C(F)=C(C=C)C(F)=C1F LVJZCPNIJXVIAT-UHFFFAOYSA-N 0.000 description 1
- WJOJBDXFGPXAFX-UHFFFAOYSA-N 2-(2-ethylhexyl)-9H-fluorene-1-carbaldehyde Chemical compound C(C)C(CC1=C(C=2CC3=CC=CC=C3C2C=C1)C=O)CCCC WJOJBDXFGPXAFX-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 230000003340 mental effect Effects 0.000 description 1
- 229920000264 poly(3',7'-dimethyloctyloxy phenylene vinylene) Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
-
- 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
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- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1414—Unsaturated aliphatic units
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- C—CHEMISTRY; METALLURGY
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/148—Side-chains having aromatic units
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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
- C08G2261/30—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
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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
- C08G2261/30—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
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3246—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain 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
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—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
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3327—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms alkene-based
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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
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/91—Photovoltaic applications
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1416—Condensed systems
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- C—CHEMISTRY; METALLURGY
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1483—Heterocyclic containing nitrogen and sulfur as heteroatoms
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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
- H10K30/50—Photovoltaic [PV] devices
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- 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
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to ⁇ -conjugated polymers containing fluoroarylvinylidene units and the relative preparation process.
- the present invention falls within the field of photoactive materials which can be used in the production of photovoltaic devices.
- Photovoltaic devices are devices capable of con- verting the energy of a light radiation into electric energy. At present, most photovoltaic devices which can be used for practical applications exploit the physico- chemical properties of photo-active materials of the inorganic type, in particular high-purity crystalline silicon. As a result of the high production costs of crystalline silicon, scientific research has been orienting its efforts towards the development of alternative organic materials having a conjugated, oligomeric or polymeric structure.
- organic materials having a conjugated structure are characterized by a relative synthesis facility, a low production cost, a reduced weight of the relative photovoltaic device, in addition to allowing the recycling of said polymer at the end of the life- cycle of the device in which it is used.
- the functioning of organic and polymer photovoltaic cells is based on the combined use of an electron acceptor compound and an electron donor compound.
- the most widely-used electron donor and acceptor compounds in devices described in scientific and patent literature are ⁇ -conjugated polymers belonging to the groups of polyparaphenylene vinylenes and polythiophenes , and fullerene derivatives, respectively.
- the photo-absorption process with the formation of the exciton and subsequent transfer of the electron to the acceptor compound consists in the transfer of an electron from the orbital HOMO (Highest Occupied Molecular Orbital) to the orbital LUMO (Lowest Unoccupied Molecular Orbital) of the donor and subsequently the transfer from this to the LUMO of the acceptor.
- orbital HOMO Highest Occupied Molecular Orbital
- LUMO Low Unoccupied Molecular Orbital
- the efficiency of an organic or polymer photovoltaic cell depends on the number of free electrons which are generated by dissociation of the excitons, one of the structural characteristics of the donor com- pounds which mostly influences said efficiency is the difference in energy existing between the HOMO and LUMO orbitals of the donor (so-called band-gap) .
- the wavelength of the photons which the donor compound is capable of collecting and effectively converting into elec- trie energy depends, in particular, on this difference.
- Another important characteristic is the mobility of the electrons in the acceptor and electronic gaps in the donor, which determines the facility with which the electric charges, once photo-generated, reach the electrodes.
- the band-gap between HOMO and LUMO must not be too high, but at the same time, it must not be too low, as an excessively low band-gap would negatively affect the voltage obtained at the electrodes of the device.
- photovoltaic cells are produced by introducing a thin layer (about 100 nanometers) of a mixture of the acceptor and donor, between two electrodes. To obtain a layer of this type, a solution of the two components is prepared. A photo- active film is then created on the first electrode starting from the solution, using suitable deposition techniques such as "spin-coating” , “ spray-coating” , “ink-jet printing” , etc. Finally, the counter-electrode is deposited on the dried film.
- the donor material most commonly used in the production of polymer solar cells is regioregular poly (3- hexylthiophene) (P3HT) .
- This polymer has interesting electronic and optical characteristics (relatively low band-gap; a good absorption coefficient) , a good solu- bility in the solvents used for producing the photo- voltaic cells and a reasonable mobility of the electronic gaps .
- the polymer MDMO-PPV poly [2- methoxy-5- (3 , 7 -dimethyloctyloxy) -1, 4-phenylene] -alt- (vinylene)
- the polymer P3HT used in combination with acceptor compounds based on fullere- nes, are capable of obtaining maximum conversion efficiencies of solar radiation not higher than 5.4%.
- An objective of the present invention is to overcome the drawbacks revealed by the state of the art.
- An object of the present invention therefore relates to an alternating ⁇ -conjugated polymer comprising: at least one fluoroarylvinylidene electron-acceptor unit A having general formula (I)
- substituents X 1 -X5 are hydrogen atoms, fluorine atoms or an alkyl group containing from 1 to 12 carbon atoms, preferably from 1 to 4 carbon atoms, and with the condition that at least one, preferably at least two, more preferably at least three, of the substituents Xi-X 5 is a fluorine atom or a -CF 2 group, wherein R is H, F or a hydrocarbyl group, possibly fluorinated, having from 1 to 10 carbon atoms, at least one conjugated electron-donor structural unit B connected to the unit A in the points indicated by the dashed lines in general formula (I) .
- the structural units A are preferably substituted with at least three F atoms or three -CF 3 groups .
- the electron-donor structural units B can be selected, for example, from the following list:
- Ri-R 8 substituents are hydrogen atoms
- Ri-Ra alkyl groups are the following: methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, do- decyl, tetradecyl, hexadecyl, octadecyl, eicosyl, 2- ethylhexyl, 2 ethyloctyl, 2-ethyldecyl, 2 -ethyldodecyl , 4 -butylhexyl , 4 -buthyloctyl , 4 -butyldecyl , 4- butyldodecyl , 2-hexyloctyl, 2-hexyldecyl, 4-hexyldecyl , isopropyl, 1-ethylpropyl , 1-butylpentyl , 1 -hexylheptyl , 1-oc
- the ratio between the sum of all the carbon atoms of the alkyl chains variably present in the repetitive base unit of the alternating ⁇ -conjugated polymer and the number of aromatic rings present in the same units is preferably within the range of 2.5 - 12.
- the alternating ⁇ -conjugated polymers object of the present invention preferably have a structure of the repetitive base unit of the type (A-B) n , wherein A and B have the meaning previously defined and n is an integer ranging from 1 to 1,000, preferably from 2 to 500, even more preferably from 3 to 50.
- Each unit A is bound to two B units, the same or different, except for when unit A or unit B represent terminal units of the polymeric chain.
- the terminal unit A or unit B are bound to one unit only, B or A, respectively, and the remaining valence is saturated by a terminal substituent whose structure depends on the preparation method of the polymer and can be easily identified by an expert in the field. In most cases, this substituent is H or Br.
- alternating ⁇ - conjugated polymers are particularly preferred: poly [9, 9-bis (2-ethylhexyl) - fluorene—alt- 2- (p- fluorophenyl) -1, 1-vinylidene]
- polymer 1 poly [9 , 9-bis (2 -ethylhexyl) fluorene—al t-2- (pentafluoro-phenyl) -1, 1-vinylidene] (polymer 2) and poly [N-octyl-3 , 7 -phenothiazine—alt-2-
- the above polymer 1 preferably has a value of the n index varying from 3 to 50.
- the above polymer 2 preferably has a value of the n index varying from 3 to 50.
- the alternating ⁇ -conjugated polymer according to the present invention is the following (polymer 3)
- the above polymer 3 preferably has a value of the n index varying from 3 to 50.
- Alternating ⁇ -conjugated polymers of the present invention having structures different from those previously indicated can be obtained by means of processes of the radical-cationic or redox type pertaining to those described or in any case which can be easily inferred by experts on the basis of known methods of organic chemistry.
- the alternating ⁇ -conjugated polymers according to the present invention have favourable physico-chemical properties which allow them to be used as photoactive materials, in particular as electron-donor compounds within photovoltaic devices. They are characterized by band-gap values lower than 3.2 eV and are therefore particularly suitable for exploiting solar radiation with a higher wavelength. Thanks to the thermal oxidative stability conferred by the presence of fluorinated units, these materials can be advantageously used in the production of photovoltaic devices having a longer duration under conditions of high environmental stress and exposure to intense light radiation and with a significant ultraviolet component.
- a further object of the present invention therefore relates to a photovoltaic device comprising any of the alternating ⁇ -conjugated polymers of the present invention .
- the above alternating ⁇ -conjugated polymers can be easily synthesized according to the process schemes previously illustrated.
- the alternating ⁇ -conjugated polymers according to the present invention were characterized by means of UV-Vis-NIR spectroscopy to determine the energy entity of the HOMO-LU O band-gap according to the following procedure.
- the polymer is dissolved in toluene at a concentration of about 10 "4 , transferred to a quartz Suprasil 1.0 cm cuvette and analyzed in transmission by means of a double-beam UV-Vis-NIR spectrophotometer and Perkin Elmer ⁇ 19 double monochromator, within the range of 190-900 nm with a pass-through band of 2.0 nm, a scanning rate of 120 nm/min and step of 1 nm, using an identical cuvette filled with the solvent alone, as reference .
- the band-gap is estimated from the diffuse reflectance spectra by measuring the absorption edge corresponding to the transition from the valence band (VB) to the conduction band (CB) . For determining the edge, the intersection with the axis of the abscissa of the tangent line at the absorption band in the flexpoint was considered.
- the flexpoint ( ⁇ ⁇ , y F ) is determined on the basis of the coordinates of the minimum of the spectrum in first derivative, indicated with ⁇ ' min S y min ⁇
- 3 ⁇ 4DGE VEDGE — h c/ gDGE
- EEDGE 1240 eV / A,EDGE (ntn)
- the reaction mixture was heated to reflux temperature (90°C) and under vigorous stirring for 26 hours.
- the mixture was concentrated to about 30 ml and poured into 400 ml of methanol.
- the precipitate obtained was filtered and washed, in order, with methanol, water and methanol again.
- the product was dissolved in a minimum quantity of toluene and re-precipitated in methanol. 650 mg of yellow-greenish polymer were obtained.
- the optical band-gap measured on the solid film for the copolymer thus obtained is 2.5 eV, HOMO and LUMO values of -5.7 and -2.2 eV, respectively, a weight average molecular weight of 6,400 and a weight loss at 250 °C of less than 1%, determined by means of thermogravimetric analysis in air.
- the mixture was concentrated until dry and poured into 200 ml of methanol.
- the precipitate obtained was filtered and washed, in order, with methanol, water, a mixture of wa- ter/ethanol and finally ethanol .
- the product was dissolved in a minimum quantity of toluene and re-precipitated in methanol. 1,252 mg of grey-coloured polymer were obtained.
- the optical band-gap measured on the solid film for the copolymer thus obtained is 3.1 eV, HOMO and LUMO values of -6.0 and -2.5 eV, respectively, a weight average molecular weight of 6,600 and a weight loss at 250°C of less than 1%, determined by means of thermogravimetric analysis in air.
- the reaction mixture was heated to reflux temperature (90°C) under vigorous stirring for 39 hours .
- the mixture was concentrated until dry and poured into 200 ml of methanol.
- the precipitate obtained was filtered and washed, in order, with methanol, water, a mixture of wa- ter/ethanol and finally methanol.
- the product was dissolved in a minimum quantity of toluene and re-precipitated in methanol. 1,150 mg of brown-greenish-coloured polymer were obtained.
- the optical band-gap measured on the solid film for the copolymer thus obtained is 2.6 eV, a weight average molecular weight of 7,000 and a weight loss at 250°C of less than 3%, determined by means of thermogravimetric analysis in air.
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Abstract
The present invention relates to π- conjugated polymers containing fluoroarylvinylidene units and the relative preparation process. Photovoltaic devices comprising these alternating π-conjugated polymers are also described.
Description
-CO JUGATED POLYMERS CONTAINING FLUOROARYLVINYLEDENE UNITS AND RELATIVE PREPARATION PROCESS
The present invention relates to π-conjugated polymers containing fluoroarylvinylidene units and the relative preparation process.
The present invention falls within the field of photoactive materials which can be used in the production of photovoltaic devices.
Photovoltaic devices are devices capable of con- verting the energy of a light radiation into electric energy. At present, most photovoltaic devices which can be used for practical applications exploit the physico- chemical properties of photo-active materials of the inorganic type, in particular high-purity crystalline silicon. As a result of the high production costs of crystalline silicon, scientific research has been orienting its efforts towards the development of alternative organic materials having a conjugated, oligomeric or polymeric structure. Unlike high-purity crystalline silicon, in fact, organic materials having a conjugated structure are characterized by a relative synthesis facility, a low production cost, a reduced weight of the relative photovoltaic device, in addition to allowing the recycling of said polymer at the end of the life- cycle of the device in which it is used.
The functioning of organic and polymer photovoltaic cells is based on the combined use of an electron acceptor compound and an electron donor compound. The most widely-used electron donor and acceptor compounds in devices described in scientific and patent literature are π-conjugated polymers belonging to the groups of polyparaphenylene vinylenes and polythiophenes , and fullerene derivatives, respectively.
The basic conversion process of light into electric current in a polymer photovoltaic cell takes place through the following steps:
1. absorption of a photon on the part of the donor compound with the formation of an exciton, i.e. a pair of "electron-hole" charge carriers;
2. diffusion of the exciton in a region of the donor compound in which its dissociation can take place;
3. dissociation of the exciton in the two charge carriers (electron (-) and hole (+) ) separated;
4. transporting of the charges thus formed to the cathode (electron, through the acceptor compound) and anode (hole, through the donor compound) , with the generation of an electric current in the circuit of the device .
The photo-absorption process with the formation of the exciton and subsequent transfer of the electron to
the acceptor compound consists in the transfer of an electron from the orbital HOMO (Highest Occupied Molecular Orbital) to the orbital LUMO (Lowest Unoccupied Molecular Orbital) of the donor and subsequently the transfer from this to the LUMO of the acceptor.
As the efficiency of an organic or polymer photovoltaic cell depends on the number of free electrons which are generated by dissociation of the excitons, one of the structural characteristics of the donor com- pounds which mostly influences said efficiency is the difference in energy existing between the HOMO and LUMO orbitals of the donor (so-called band-gap) . The wavelength of the photons which the donor compound is capable of collecting and effectively converting into elec- trie energy (so-called "photo harvesting" or "light- harvesting" process) depends, in particular, on this difference. Another important characteristic is the mobility of the electrons in the acceptor and electronic gaps in the donor, which determines the facility with which the electric charges, once photo-generated, reach the electrodes. This, in addition to being an intrinsic property of the molecules, is also strongly influenced by the morphology of the photoactive layer, which in turn depends on the reciprocal miscibility of the com- ponents and their solubility. Finally, a further funda-
mental characteristic is the resistance to thermo- oxidative and photo-oxidative degradation of the materials, which must be stable under the operating conditions of the device.
In order to obtain acceptable electric currents, the band-gap between HOMO and LUMO must not be too high, but at the same time, it must not be too low, as an excessively low band-gap would negatively affect the voltage obtained at the electrodes of the device.
In the simplest way of operating, photovoltaic cells are produced by introducing a thin layer (about 100 nanometers) of a mixture of the acceptor and donor, between two electrodes. To obtain a layer of this type, a solution of the two components is prepared. A photo- active film is then created on the first electrode starting from the solution, using suitable deposition techniques such as "spin-coating" , " spray-coating" , "ink-jet printing" , etc. Finally, the counter-electrode is deposited on the dried film.
The donor material most commonly used in the production of polymer solar cells is regioregular poly (3- hexylthiophene) (P3HT) . This polymer has interesting electronic and optical characteristics (relatively low band-gap; a good absorption coefficient) , a good solu- bility in the solvents used for producing the photo-
voltaic cells and a reasonable mobility of the electronic gaps .
The flow of photons of solar radiation which reaches the surface of the Earth, however, is maximum for a wavelength of about 700 nm, corresponding to energy values of around 1.8 eV, much lower than the band- gap values (generally higher than 2-3 eV) which characterize many of the polymeric materials currently known and used as donor compounds in photovoltaic devices . The light harvesting process of this spectral field is consequently not very efficient and only a fraction of the overall solar energy is converted into electric energy. As already mentioned, this is one of the main factors which cause low efficiencies in photovoltaic devices .
Among the polymers most widely-used as donor compounds, for example, the polymer MDMO-PPV (poly [2- methoxy-5- (3 , 7 -dimethyloctyloxy) -1, 4-phenylene] -alt- (vinylene) ) and especially the polymer P3HT, used in combination with acceptor compounds based on fullere- nes, are capable of obtaining maximum conversion efficiencies of solar radiation not higher than 5.4%.
In order to improve the yield of the light harvesting process and consequently the efficiency of photo- voltaic devices, it is consequently fundamental to find
new donor compounds capable of effectively capturing and converting solar radiations, transporting the charges to the electrodes more efficiently and resisting oxidative degradation processes.
An objective of the present invention is to overcome the drawbacks revealed by the state of the art.
An object of the present invention therefore relates to an alternating π-conjugated polymer comprising: at least one fluoroarylvinylidene electron-acceptor unit A having general formula (I)
(I)
wherein the substituents X1-X5, the same or different, are hydrogen atoms, fluorine atoms or an alkyl group containing from 1 to 12 carbon atoms, preferably from 1 to 4 carbon atoms, and with the condition that at least one, preferably at least two, more preferably at least three, of the substituents Xi-X5 is a fluorine atom or a -CF2 group, wherein R is H, F or a hydrocarbyl group, possibly fluorinated, having from 1 to 10 carbon atoms,
at least one conjugated electron-donor structural unit B connected to the unit A in the points indicated by the dashed lines in general formula (I) .
The structural units A are preferably substituted with at least three F atoms or three -CF3 groups .
The electron-donor structural units B can be selected, for example, from the following list:
-8-
C1-C37 alkyl groups, possibly branched,
OC1-OC16 alkoxy groups on the condition that the substituents Ri-Rs are bonded to a carbon atom.
Examples of Ri-Ra alkyl groups are the following: methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, do- decyl, tetradecyl, hexadecyl, octadecyl, eicosyl, 2- ethylhexyl, 2 ethyloctyl, 2-ethyldecyl, 2 -ethyldodecyl , 4 -butylhexyl , 4 -buthyloctyl , 4 -butyldecyl , 4- butyldodecyl , 2-hexyloctyl, 2-hexyldecyl, 4-hexyldecyl , isopropyl, 1-ethylpropyl , 1-butylpentyl , 1 -hexylheptyl , 1-octylnonyl , 1-dodecyltridecyl , 1-hexadecylheptadecyl and 1-octadecylnonadecyl . The groups butyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, tetradecyl, hexadecyl, 4-hexyldecyl, 1-octylnonyl, are preferred.
In order to guarantee the solubility of the copolymers according to the present invention, the ratio between the sum of all the carbon atoms of the alkyl chains variably present in the repetitive base unit of the alternating π-conjugated polymer and the number of aromatic rings present in the same units is preferably within the range of 2.5 - 12.
The alternating π-conjugated polymers object of the present invention preferably have a structure of the repetitive base unit of the type (A-B)n, wherein A and B
have the meaning previously defined and n is an integer ranging from 1 to 1,000, preferably from 2 to 500, even more preferably from 3 to 50.
Each unit A is bound to two B units, the same or different, except for when unit A or unit B represent terminal units of the polymeric chain. In this latter case, the terminal unit A or unit B are bound to one unit only, B or A, respectively, and the remaining valence is saturated by a terminal substituent whose structure depends on the preparation method of the polymer and can be easily identified by an expert in the field. In most cases, this substituent is H or Br.
The following alternating π- conjugated polymers are particularly preferred: poly [9, 9-bis (2-ethylhexyl) - fluorene—alt- 2- (p- fluorophenyl) -1, 1-vinylidene]
(polymer 1) , poly [9 , 9-bis (2 -ethylhexyl) fluorene—al t-2- (pentafluoro-phenyl) -1, 1-vinylidene] (polymer 2) and poly [N-octyl-3 , 7 -phenothiazine—alt-2-
(pentaf luorophenyl) -1, 1-vinylidene] (polymer 3) , for the light harvesting properties shown.
When the alternating π-conjugated polymer according to the present invention is the following (polymer 1) :
Scheme A
The above polymer 1 preferably has a value of the n index varying from 3 to 50.
When the alternating π-conjugated polymer according to the present invention is the following (polymer 2) :
a possible method for obtaining it is that corresponding to the process indicated in the following scheme B :
Scheme B .
The above polymer 2 preferably has a value of the n index varying from 3 to 50.
When the alternating π-conjugated polymer according to the present invention is the following (polymer 3)
a possible method for obtaining it is that corre-
285
sponding to the process indicated in the following scheme C:
Scheme C.
The above polymer 3 preferably has a value of the n index varying from 3 to 50.
Alternating π-conjugated polymers of the present invention having structures different from those previously indicated can be obtained by means of processes of the radical-cationic or redox type pertaining to those described or in any case which can be easily inferred by experts on the basis of known methods of organic chemistry.
The alternating π-conjugated polymers according to the present invention have favourable physico-chemical properties which allow them to be used as photoactive materials, in particular as electron-donor compounds within photovoltaic devices. They are characterized by band-gap values lower than 3.2 eV and are therefore
particularly suitable for exploiting solar radiation with a higher wavelength. Thanks to the thermal oxidative stability conferred by the presence of fluorinated units, these materials can be advantageously used in the production of photovoltaic devices having a longer duration under conditions of high environmental stress and exposure to intense light radiation and with a significant ultraviolet component.
A further object of the present invention therefore relates to a photovoltaic device comprising any of the alternating π-conjugated polymers of the present invention .
As will be better illustrated in the following examples, the above alternating π-conjugated polymers can be easily synthesized according to the process schemes previously illustrated.
The following embodiment examples are provided for illustrative purposes of the present invention and should not be considered as limiting its protection scope.
The alternating π-conjugated polymers according to the present invention were characterized by means of UV-Vis-NIR spectroscopy to determine the energy entity of the HOMO-LU O band-gap according to the following procedure.
The polymer is dissolved in toluene at a concentration of about 10"4 , transferred to a quartz Suprasil 1.0 cm cuvette and analyzed in transmission by means of a double-beam UV-Vis-NIR spectrophotometer and Perkin Elmer λ 19 double monochromator, within the range of 190-900 nm with a pass-through band of 2.0 nm, a scanning rate of 120 nm/min and step of 1 nm, using an identical cuvette filled with the solvent alone, as reference .
The band-gap is estimated from the diffuse reflectance spectra by measuring the absorption edge corresponding to the transition from the valence band (VB) to the conduction band (CB) . For determining the edge, the intersection with the axis of the abscissa of the tangent line at the absorption band in the flexpoint was considered.
The flexpoint (λΡ, yF) is determined on the basis of the coordinates of the minimum of the spectrum in first derivative, indicated with λ' min S y min ·
The equation of the tangent line at the UV-Vis spectrum in the flexpoint ( Fl yF) is:
y = y' min + yF _ y' min λ' min
Finally, from the intersection condition with the axis of the abscissa ψ = 0, the following is obtained: EDGE = (y'min λ' min - yF)/y'min
Therefore, by measuring the coordinates of the minimum of the spectrum in first derivative and the corresponding absorbance value yF from the UV-Vis spectrum, λΕϋσΕ is obtained directly by substitution.
The corresponding energy is :
¾DGE = VEDGE — h c/ gDGE
wherein h = 6.626 10"34 J s
c = 2.998 108 m s"1 i.e. EEDGE = 1.988 10~16 J/λEDGE(nm).
Finally, remembering that 1 J = 6.24 1018 eV, the following is obtained:
EEDGE = 1240 eV / A,EDGE (ntn)
EXAMPLE 1
Alternating π- conjugated polymer poly [9, 9-bis (2- ethylhexyl) fluorene—alt- 2- (p- fluorophenyl) -1, 1-vinyl- idene] , (polymer 1)
The following products were introduced, in order, into a 250 ml three-necked flask equipped with a magnetic stirrer and reflux condenser, in an inert atmos- phere:
1,289 mg (2.696 mmoles) of 9,9-bis(2'- ethylhexyl) -2 , 7-diboronic acid;
755 mg (2.696 mmoles) of p- fluoro-β,β- dibromostyrene (1, l-dibromo-2- (p- fluorophenyl) ethylene) , dissolved in about 20 ml of
deaerated toluene;
- 250 mg of Aliquat 336 (5.9 mmoles) dissolved in about 50 ml of deaerated toluene;
12 ml of potassium carbonate 1.036 M (12.4 mmoles) (deaerated water) ;
66 mg (0.054 mmoles) of palladium (0) tetrakis (triphenylphosphine) .
The reaction mixture was heated to reflux temperature (90°C) and under vigorous stirring for 26 hours.
At the end of the period indicated, the mixture was concentrated to about 30 ml and poured into 400 ml of methanol. The precipitate obtained was filtered and washed, in order, with methanol, water and methanol again.
The product was dissolved in a minimum quantity of toluene and re-precipitated in methanol. 650 mg of yellow-greenish polymer were obtained.
The optical band-gap measured on the solid film for the copolymer thus obtained is 2.5 eV, HOMO and LUMO values of -5.7 and -2.2 eV, respectively, a weight average molecular weight of 6,400 and a weight loss at 250 °C of less than 1%, determined by means of thermogravimetric analysis in air.
Schematically, the reaction which took place is the
following :
EXAMPLE 2
Alternating π-conjugated polymer poly [9 , 9-bis (2- ethylhexyl) fluorene—alt-2- (pentafluorophenyl) -1,1- vinyl-idene] , (polymer 2)
The following products were introduced, in order, into a 250 ml three-necked flask equipped with a magnetic stirrer and reflux condenser, in an inert atmos- phere:
- 1,143 mg (2.39 mmoles) of 9 , 9-bis (2 ' -ethylhexyl) - 2 , 7-diboronic acid;
841 mg (2.39 mmoles) of pentafluoro-β,β- dibromostyrene (1, l-dibromo-2- (pentafluorophenyl) - ethylene) dissolved in about 20 ml of deaerated toluene ;
- 221 mg of Aliquat 336 (5.2 mmoles) dissolved in about 50 ml of deaerated toluene;
10.8 ml of potassium carbonate 1.033 M (11.1 mmoles) (deaerated water)
58 mg (0.047 mmoles) of palladium (0) tetrakis ( triphenylphosphine . )
The reaction mixture was heated to reflux temperature (90°C) and under vigorous stirring for 33 hours .
At the end of the period indicated, the mixture was concentrated until dry and poured into 200 ml of methanol. The precipitate obtained was filtered and washed, in order, with methanol, water, a mixture of wa- ter/ethanol and finally ethanol .
The product was dissolved in a minimum quantity of toluene and re-precipitated in methanol. 1,252 mg of grey-coloured polymer were obtained.
The optical band-gap measured on the solid film for the copolymer thus obtained is 3.1 eV, HOMO and LUMO values of -6.0 and -2.5 eV, respectively, a weight average molecular weight of 6,600 and a weight loss at 250°C of less than 1%, determined by means of thermogravimetric analysis in air.
Schematically, the reaction which took place is the following :
EXAMPLE 3
Alternating π- conjugated polymer poly [N-octyl-3 , 7-
phenothiazine—alt-2- (pentafluorophenyl) -1, 1- vinylidene] , (polymer 3)
The following products were introduced, in order, into a 250 ml three-necked flask equipped with a mag- netic stirrer and reflux condenser, in an inert atmosphere :
- 1,021 mg (2.558 mmoles) of N-octylphenothiazo- 3 , 7-diboronico acid;
900 mg (2.39 mmoles) of pentafluoro-β,β- dibromostyrene ( 1 , l-dibromo-2-
(pentafluorophenyl) ethylene) dissolved in about 20 ml of deaerated toluene;
- 238 mg of Aliquat 336 (5.6 mmoles) dissolved in about 50 ml of deaearated toluene;
- 11.5 ml of potassium carbonate 1.033 M (11.9 mmoles) (deaerated water)
- 61 mg (0.050 mmoles) di palladium ( 0 ) tetrakis- ( triphenylphosphine)
The reaction mixture was heated to reflux temperature (90°C) under vigorous stirring for 39 hours .
At the end of the period indicated, the mixture was concentrated until dry and poured into 200 ml of methanol. The precipitate obtained was filtered and washed, in order, with methanol, water, a mixture of wa-
ter/ethanol and finally methanol.
The product was dissolved in a minimum quantity of toluene and re-precipitated in methanol. 1,150 mg of brown-greenish-coloured polymer were obtained.
The optical band-gap measured on the solid film for the copolymer thus obtained is 2.6 eV, a weight average molecular weight of 7,000 and a weight loss at 250°C of less than 3%, determined by means of thermogravimetric analysis in air.
Schematically, the reaction which took place is the following :
Claims
1. An alternating π-conjugated polymer comprising: a fluoroarylvinylidene electron-acceptor unit A having general formula (I)
(I)
wherein the substituents Xi-X5, the same or different, are hydrogen atoms, fluorine atoms or an alkyl group containing from 1 to 12 carbon atoms, preferably from 1 to 4 carbon atoms, and with the condition that at least one, preferably at least two, more preferably at least three, of the substituents X1-X5 is a fluorine atom or a -CF2R group, wherein R is H, F or a hydrocarbyl group, possibly fluorinated, having from 1 to 10 carbon atoms, at least one conjugated electron-donor structural unit B connected to the A unit in the points indicated by the dashed lines in general formula (I) .
2. The alternating π-conjugated polymer according to claim 1, wherein the average number of A units in the polymer ranges from 2 to 1,000, preferably from 5 to 1,000.
3. The alternating π-conjugated polymer according to claim 1 or 2, wherein the conjugated electron-donor structural units B are selected from the following group :
-25-
C1-C37 alkyl groups, possibly branched,
- OC1-OC16 alkoxy groups on the condition that the substituents Ri-R8 are bonded to a carbon atom.
4) The alternating π-conjugated polymer according to claim 3, wherein the substituents Ri-Re in the above- mentioned structures are selected from the following group of substituents: methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, 2-ethylhexyl, 2 ethyloctyl, 2- ethyldecyl, 2-ethyldodecyl , 4 -butylhexyl , 4- buthyloctyl, 4 -butyldecyl , 4 -butyldodecyl , 2- hexyloctyl, 2-hexyldecyl, 4 -hexyldecyl , isopropyl, 1- ethylpropyl, 1-butylpentyl, 1-hexylheptyl , 1- octylnonyl, 1-dodecyltridecyl , 1-hexadecylheptadecyl and 1-octadecylnonadecyl.
5. The alternating π-conjugated polymer according to any of the previous claims, wherein the structure of the repeating base unit is represented by the formulae (A-B)n wherein A and B have the meaning specified above and n is an integer ranging from 1 to 1,000, preferably from 2 to 500.
6. The alternating π-conjugated polymer according to any of the previous claims, wherein the ratio between the sum of all the carbon atoms of the alkyl chains present in the repeating base unit and the number of aromatic rings present in the same unit, ranges from 3.5 to 12.
7. The alternating π-conjugated polymer according to claim 1, having the following structure:
8. The alternating π-conjugated polymer according to claim 1, having the following structure
wherein n ranges from 3 to 50.
9. The alternating π-conjugated polymer according to claim 1, having the following structure:
wherein n ranges from 3 to 50.
10. A photovoltaic device comprising an alternating π- conjugated polymer according to any of the claims from 1 to 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI2009A002150 | 2009-12-04 | ||
| ITMI2009A002150A IT1396648B1 (en) | 2009-12-04 | 2009-12-04 | GREEK-CONJUGATED POLYMERS CONTAINING FLUOROARILVINILEDENIC UNITS AND ITS PREPARATION PROCEDURE |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014188376A1 (en) | 2013-05-23 | 2014-11-27 | Eni S.P.A. | Stabilized photoactive composition and use thereof |
| WO2015068102A1 (en) | 2013-11-05 | 2015-05-14 | Eni S.P.A. | Inverted polymer solar cells and process for producing the same |
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| JP2004010703A (en) * | 2002-06-05 | 2004-01-15 | Konica Minolta Holdings Inc | Organic electroluminescent element material and organic electroluminescent element and display using the same |
| US20040147701A1 (en) * | 2003-01-29 | 2004-07-29 | Michael Redecker | Molecular chemical compounds with structures allowing electron displacement and capable of emitting photoluminescent radiation, and photoluminescence quenching device employing the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004010703A (en) * | 2002-06-05 | 2004-01-15 | Konica Minolta Holdings Inc | Organic electroluminescent element material and organic electroluminescent element and display using the same |
| US20040147701A1 (en) * | 2003-01-29 | 2004-07-29 | Michael Redecker | Molecular chemical compounds with structures allowing electron displacement and capable of emitting photoluminescent radiation, and photoluminescence quenching device employing the same |
Non-Patent Citations (2)
| Title |
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| ANDREW C GRIMSDALE ET AL: "Synthesis of Light-Emitting Conjugated Polymers for Applications in Electroluminescent Devices", CHEMICAL REVIEWS, ACS,WASHINGTON, DC, US LNKD- DOI:10.1021/CR000013V, vol. 109, 1 February 2009 (2009-02-01), pages 897 - 1091, XP009133687, ISSN: 0009-2665 * |
| GURGE R M ET AL: "LIGHT EMITTING PROPERTIES OF FLUORINE-SUBSTITUTED POLY(1,4-PHENYLENE VINYLENES)", MACROMOLECULES, AMERICAN CHEMICAL SOCIETY, US LNKD- DOI:10.1021/MA970693C, vol. 30, no. 26, 29 December 1997 (1997-12-29), pages 8286 - 8292, XP000729177, ISSN: 0024-9297 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014188376A1 (en) | 2013-05-23 | 2014-11-27 | Eni S.P.A. | Stabilized photoactive composition and use thereof |
| WO2015068102A1 (en) | 2013-11-05 | 2015-05-14 | Eni S.P.A. | Inverted polymer solar cells and process for producing the same |
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| IT1396648B1 (en) | 2012-12-14 |
| ITMI20092150A1 (en) | 2011-06-05 |
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