ITMI20092150A1 - GREEK-CONJUGATED POLYMERS CONTAINING FLUOROARILVINILEDENIC UNITS AND ITS PREPARATION PROCEDURE - Google Patents
GREEK-CONJUGATED POLYMERS CONTAINING FLUOROARILVINILEDENIC UNITS AND ITS PREPARATION PROCEDURE Download PDFInfo
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- ITMI20092150A1 ITMI20092150A1 IT002150A ITMI20092150A ITMI20092150A1 IT MI20092150 A1 ITMI20092150 A1 IT MI20092150A1 IT 002150 A IT002150 A IT 002150A IT MI20092150 A ITMI20092150 A IT MI20092150A IT MI20092150 A1 ITMI20092150 A1 IT MI20092150A1
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- polymer
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- 229920000547 conjugated polymer Polymers 0.000 title claims description 15
- 238000000034 method Methods 0.000 title description 13
- 238000002360 preparation method Methods 0.000 title description 4
- -1 2-ethylhexyl Chemical group 0.000 claims description 40
- 229920000642 polymer Polymers 0.000 claims description 38
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 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
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 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 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
- 230000003252 repetitive effect Effects 0.000 claims description 3
- 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
- 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
- 125000004435 hydrogen atom Chemical group [H]* 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
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 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
- 230000005855 radiation Effects 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000003306 harvesting Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000006243 chemical 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
- 230000015572 biosynthetic process Effects 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
- 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
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000003507 refrigerant 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
- YAFICFPPTPPVEV-UHFFFAOYSA-N 1-(2,2-dibromoethenyl)-2,3,4,5,6-pentafluorobenzene Chemical group FC1=C(F)C(F)=C(C=C(Br)Br)C(F)=C1F YAFICFPPTPPVEV-UHFFFAOYSA-N 0.000 description 2
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 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
- VYVSCVFABZOIEF-UHFFFAOYSA-N 1-(2,2-dibromoethenyl)-4-fluorobenzene Chemical group FC1=CC=C(C=C(Br)Br)C=C1 VYVSCVFABZOIEF-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
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004907 flux 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
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000264 poly(3',7'-dimethyloctyloxy phenylene vinylene) Polymers 0.000 description 1
- 238000013087 polymer photovoltaic Methods 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- 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
- C08G2261/1414—Unsaturated 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
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/148—Side-chains having aromatic 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
- C08G2261/324—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
- 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
- C08G2261/33—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
- 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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- 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
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
Polimeri pi-coniugati contenenti unità fluoroarilviniledeniche e relativo procedimento di preparazione. Pi-conjugated polymers containing fluoroaryvinyledene units and related preparation process.
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La presente invenzione si riferisce a polimeri piconiugati contenenti unità fluoroarilviniledeniche e al relativo procedimento di preparazione. The present invention relates to piconjugated polymers containing fluoroaryvinyledene units and to the related preparation process.
La presente invenzione si inserisce nel settore dei materiali fotoattivi impiegabili nella fabbricazione di dispositivi fotovoltaici. The present invention is part of the field of photoactive materials that can be used in the manufacture of photovoltaic devices.
I dispositivi fotovoltaici sono dispositivi in grado di convertire l'energia di una radiazione luminosa in energia elettrica. Attualmente, la maggior parte dei dispositivi fotovoltaici utilizzabili per applicazioni pratiche sfrutta le proprietà chimicofisiche di materiali fotoattivi di tipo inorganico, in particolare il silicio cristallino ad elevata purezza. A causa degli elevati costi di produzione del silicio cristallino la ricerca scientifica, tuttavia, sta da tempo orientando i propri sforzi verso lo sviluppo di materiali alternativi di tipo organico aventi struttura coniugata, oligomerica o polimerica. Infatti, a differenza del silicio cristallino ad elevata purezza, i materiali organici aventi struttura coniugata sono caratterizzati da una relativa facilità di sintesi, un basso costo di produzione, un peso ridotto del relativo dispositivo fotovoltaico, oltre a permettere il riciclo di detto polimero al termine del ciclo di vita del dispositivo in cui à ̈ utilizzato. Photovoltaic devices are devices capable of converting the energy of a light radiation into electrical energy. Currently, most photovoltaic devices that can be used for practical applications exploit the chemical-physical properties of photoactive inorganic materials, in particular high purity crystalline silicon. However, due to the high production costs of crystalline silicon, scientific research has for some time been orienting its efforts towards the development of alternative organic materials with conjugated, oligomeric or polymeric structures. In fact, unlike high purity crystalline silicon, organic materials having a conjugated structure are characterized by a relative ease of synthesis, a low production cost, a reduced weight of the relative photovoltaic device, as well as allowing the recycling of said polymer at the end the life cycle of the device in which it is used.
Il funzionamento delle celle fotovoltaiche organiche e polimeriche si basa sull'impiego combinato di un composto accettore di elettroni e di un composto donatore di elettroni. I composti donatori ed accettori di elettroni maggiormente impiegati nei dispositivi descritti nella letteratura scientifica e brevettuale sono, rispettivamente, i polimeri pi-coniugati appartenenti alle classi dei poliparafenilenivinileni e dei politiofeni, e i derivati del fullerene. The operation of organic and polymeric photovoltaic cells is based on the combined use of an electron acceptor compound and an electron donor compound. The electron donor and acceptor compounds most used in the devices described in the scientific and patent literature are, respectively, the pi-conjugated polymers belonging to the classes of polyparaphenylenivinylenes and polythiophenes, and the derivatives of fullerenes.
Il processo elementare di conversione della luce in corrente elettrica in una cella fotovoltaica polimerica avviene attraverso i seguenti stadi: The elementary process of converting light into electric current in a polymer photovoltaic cell takes place through the following stages:
1. assorbimento di un fotone da parte del composto donatore con formazione di un eccitone, ossia una coppia di trasportatori di carica "elettrone-buca"; 1. absorption of a photon by the donor compound with the formation of an exciton, ie a pair of "electron-hole" charge carriers;
2. diffusione dell'eccitone in una regione del composto donatore in cui può avvenire la sua dissociazione; 2. diffusion of the exciton in a region of the donor compound where its dissociation can take place;
3. dissociazione dell'eccitone nei due trasportatori di carica (elettrone (-) e buca (+)) separati; 3. dissociation of the exciton into the two separate charge carriers (electron (-) and hole (+));
4. trasporto delle cariche così formate al catodo (elettrone, attraverso il composto accettore) e all'anodo (buca, attraverso il composto donatore), con generazione di una corrente elettrica nel circuito del dispositivo. 4. transport of the charges thus formed to the cathode (electron, through the acceptor compound) and to the anode (hole, through the donor compound), with the generation of an electric current in the circuit of the device.
Il processo di fotoassorbimento con formazione dell’eccitone e successiva cessione dell'elettrone al composto accettore comporta il trasferimento di un elettrone dall'orbitale HOMO (Highest Occupied Molecular Orbital) all’orbitale LUMO (Lowest Unoccupied Molecular Orbital) del donatore e, successivamente, il passaggio da questo al LUMO dell'accettore. The process of photoabsorption with formation of the exciton and subsequent transfer of the electron to the acceptor compound involves the transfer of an electron from the HOMO (Highest Occupied Molecular Orbital) orbital to the LUMO (Lowest Unoccupied Molecular Orbital) of the donor and, subsequently, the passage from this to the LUMO of the acceptor.
Poiché l'efficienza di una cella fotovoltaica organica o polimerica dipende dal numero di elettroni liberi che si generano per dissociazione degli eccitoni, una delle caratteristiche strutturali dei composti donatori che più influisce su tale efficienza à ̈ la differenza di energia esistente tra gli orbitali HOMO e LUMO del donatore (cosiddetto band-gap). Da tale differenza dipende, in particolare, la lunghezza d'onda dei fotoni che il composto donatore à ̈ in grado di raccogliere e di convertire efficacemente in energia elettrica (cosiddetto processo di "photon harvesting" o "light harvesting"). Un’altra caratteristica importante à ̈ la mobilità degli elettroni nell’accettore e delle lacune elettroniche nel donatore, che determina la facilità con la quale le cariche elettriche, una volta fotogenerate, raggiungono gli elettrodi. Questa, oltre ad essere una proprietà intrinseca delle molecole, à ̈ anche fortemente influenzata dalla morfologia dello strato fotoattivo, che a sua volta dipende dalla miscibilità reciproca dei componenti e dalla loro solubilità . Infine una ulteriore caratteristica fondamentale à ̈ la resistenza alla degradazione termoossidativa e fotoossidativa dei materiali, che devono essere stabili nelle condizioni di esercizio del dispositivo. Since the efficiency of an organic or polymeric photovoltaic cell depends on the number of free electrons that are generated by dissociation of the excitons, one of the structural characteristics of the donor compounds that most affects this efficiency is the energy difference existing between the HOMO orbitals. and LUMO of the donor (so-called band-gap). In particular, the wavelength of photons that the donor compound is able to collect and efficiently convert into electrical energy depends on this difference (so-called "photon harvesting" or "light harvesting" process). Another important feature is the mobility of the electrons in the acceptor and of the electron gaps in the donor, which determines the ease with which the electrical charges, once photogenerated, 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 mutual miscibility of the components and their solubility. Finally, a further fundamental characteristic is the resistance to thermo-oxidative and photo-oxidative degradation of the materials, which must be stable in the operating conditions of the device.
Al fine di ottenere correnti elettriche accettabili, il band-gap tra HOMO e LUMO non deve essere troppo elevato, ma allo stesso tempo non deve essere troppo basso, perché un band-gap troppo basso penalizzerebbe la tensione ottenibile agli elettrodi del dispositivo. In order to obtain acceptable electrical currents, the band-gap between HOMO and LUMO must not be too high, but at the same time it must not be too low, because too low a band-gap would penalize the voltage obtainable at the device's electrodes.
Nel modo più semplice di operare, le celle fotovoltaiche sono fabbricate introducendo tra due elettrodi uno strato sottile (circa 100 nanometri) di una miscela dell'accettore e del donatore. Per realizzare uno strato di questo tipo, viene preparata una soluzione dei due componenti. Successivamente, viene creato un film fotoattivo sul primo elettrodo a partire dalla soluzione, ricorrendo ad opportune tecniche di deposizione come lo "spin-coating", lo "spray-coating", l’"ink-jet printing", etc. Infine, sul film essiccato viene depositato il controelettrodo. In the simplest way, photovoltaic cells are manufactured by introducing a thin layer (about 100 nanometers) of a mixture of the acceptor and donor between two electrodes. To make such a layer, a solution of the two components is prepared. Subsequently, a photoactive film is 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.
Il materiale donatore più comunemente utilizzato nella realizzazione di celle solari polimeriche à ̈ il poli(3-esiltiofene) regioregolare (P3HT). Questo polimero presenta interessanti caratteristiche elettroniche e ottiche (band-gap relativamente basso; buon coefficiente di assorbimento), una buona solubilità nei solventi che vengono impiegati per fabbricare le celle fotovoltaiche e una discreta mobilità delle lacune elettroniche. The most commonly used donor material in the production of polymeric solar cells is regioregular poly (3-hexylthiophene) (P3HT). This polymer has interesting electronic and optical characteristics (relatively low band-gap; good absorption coefficient), a good solubility in the solvents used to manufacture the photovoltaic cells and a fair mobility of the electronic gaps.
Tuttavia, il flusso di fotoni della radiazione solare che giunge sulla superficie della Terra à ̈ massimo per lunghezza d'onda di circa 700 nm, corrispondente a valori di energia intorno a 1,8 eV, significativamente inferiori ai valori di band-gap (generalmente superiori a 2-3 eV) che caratterizzano molti dei materiali polimerici attualmente noti ed utilizzati come composti donatori nei dispositivi fotovoltaici. Pertanto, il processo di light harvesting in questo campo spettrale risulta poco efficiente e solo una frazione dell'energia solare complessiva viene convertita in energia elettrica. Questo à ̈, come detto, uno dei fattori principali che determinano basse efficienze nei dispositivi fotovoltaici. However, the flux of photons of solar radiation reaching the surface of the Earth is maximum for a wavelength of about 700 nm, corresponding to energy values around 1.8 eV, significantly lower than the band-gap values (generally higher than 2-3 eV) that characterize many of the polymeric materials currently known and used as donor compounds in photovoltaic devices. Therefore, the light harvesting process in this spectral range is not very efficient and only a fraction of the total solar energy is converted into electricity. This is, as mentioned, one of the main factors that determine low efficiencies in photovoltaic devices.
A titolo di esempio, tra i polimeri più utilizzati come composti donatori, il polimero MDMO-PPV (poli[2-metossi-5-(3,7-dimetilottilossi)-1,4-fenilen]-alt-(vinilene)) e specialmente il polimero P3HT, utilizzati in combinazione con composti accettori a base di fullereni, sono in grado di realizzare efficienze massime di conversione della radiazione solare non superiori al 5,4%. By way of example, among the polymers most used as donor compounds, the polymer MDMO-PPV (poly [2-methoxy-5- (3,7-dimethyloctyloxy) -1,4-phenylene] -alt- (vinyl)) and especially the P3HT polymer, used in combination with fullerenes-based acceptor compounds, are able to achieve maximum solar radiation conversion efficiencies not exceeding 5.4%.
Per migliorare la resa del processo di light harvesting e, conseguentemente, l'efficienza dei dispositivi fotovoltaici, à ̈ quindi auspicabile individuare nuovi composti donatori in grado di catturare e convertire efficacemente le radiazioni solari, trasportare più efficacemente le cariche agli elettrodi e resistere ai processi di degradazione ossidativa. To improve the performance of the light harvesting process and, consequently, the efficiency of photovoltaic devices, it is therefore desirable to identify new donor compounds capable of effectively capturing and converting solar radiation, more effectively transporting the charges to the electrodes and resisting the processes of oxidative degradation.
Scopo della presente invenzione à ̈ quello di superare gli inconvenienti evidenziati dallo stato della tecnica. The purpose of the present invention is to overcome the drawbacks highlighted by the state of the art.
Oggetto della presente invenzione à ̈ quindi un polimero pi−coniugato alternato comprendente: The object of the present invention is therefore an alternating more conjugated polymer comprising:
- almeno una unità fluoroarilviniledenica elettron-accettrice A di formula generale (I) - at least one electron-accepting fluoroaryvinyledene unit A of general formula (I)
(I) (THE)
in cui i sostituenti X1-X5, uguali o diversi fra loro, sono atomi di idrogeno, atomi di fluoro oppure un gruppo alchilico contenente da 1 a 12 atomi di carbonio, preferibilmente da 1 a 4 atomi di carbonio, e con la condizione che almeno uno, preferibilmente almeno 2, più preferibilmente almeno 3, dei sostituenti X1-X5sia un atomo di fluoro oppure un gruppo -CF2R, in cui R à ̈ H, F o un gruppo idrocarbilico, eventualmente fluorurato, avente da 1 a 10 atomi di carbonio; wherein the substituents X1-X5, the same or different from each other, 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 2, more preferably at least 3, of the substituents X1-X5 is a fluorine atom or a -CF2R group, wherein R is H, F or a hydrocarbyl group, optionally fluorinated, having from 1 to 10 carbon atoms ;
- almeno una unità strutturale coniugata elettrondonatrice B connessa all’unità A nei punti indicati dalle linee tratteggiate nella formula generale (I). - at least one electron donor conjugate structural unit B connected to unit A at the points indicated by the dashed lines in the general formula (I).
Preferibilmente, le unità strutturali A sono sostituite con almeno tre atomi di F o tre gruppi –CF3. Preferably, the structural units A are replaced with at least three F atoms or three groups - CF3.
Le unità strutturali elettron-donatrici B possono essere scelte, ad esempio, fra quelle del seguente elenco: The electron-donor structural units B can be chosen, for example, from those in the following list:
dove i sostituenti Rl-R8, uguali o diversi tra loro, possono essere where the substituents Rl-R8, equal or different from each other, can be
- atomi di idrogeno, - hydrogen atoms,
- gruppi alchilici C1-C37, eventualmente ramificati, - gruppi alcossilici OC1-OC16, a condizione che i sostituenti R1-R8siano legati ad un atomo di carbonio. - C1-C37 alkyl groups, possibly branched, - OC1-OC16 alkoxyl groups, provided that the R1-R8 substituents are bonded to a carbon atom.
Esempi di gruppi alchilici Rl-R8sono i seguenti: metile, etile, propile, butile, esile, ottile, decile, dodecile, tetradecile, esadecile, ottadecile, eicosile, 2-etilesile,2-etilottile, 2-etildecile, 2-etildodecile, 4-butilesile, 4-butilottile, 4-butildecile, 4-butildodecile, 2-esilottile, 2-esildecile, 4-esildecile, isopropile, 1-etilpropile, 1-butilpentile, 1-esileptile, 1-ottilnonile, 1-dodeciltridecile, 1-esadecileptadecile e 1-ottadecilnonadecile. I gruppi butile, esile, ottile, decile, dodecile, 2-etilesile, tetradecile, esadecile, 4-esildecile, 1-ottilnonile sono preferiti. Examples of R1-R8 alkyl groups are the following: methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, 2-ethylhexyl, 2-ethyl octyl, 2-ethyldecyl, 2-ethyldodecyl, 4-butylhexyl, 4-butyloctyl, 4-butyldecyl, 4-butyldodecyl, 2-hexyloctyl, 2-hexyldecyl, 4-hexyldecyl, isopropyl, 1-ethylpropyl, 1-butylpentyl, 1-hexileptyl, 1-octylnonyl, 1-dodecyltridecyl, 1-hexadecylptadecyl and 1-octadecylnonadecyl. The butyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, tetradecyl, hexadecyl, 4-hexyldecyl, 1-octylnonyl groups are preferred.
Al fine di garantire la solubilità dei copolimeri secondo la presente invenzione, preferibilmente il rapporto tra la somma di tutti gli atomi di carbonio delle catene alchiliche variamente presenti nell’unità ripetitiva di base del polimero pi-coniugato alternato ed il numero di anelli aromatici presenti nella medesima unità à ̈ compreso tra 2,5 e 12. In order to ensure the solubility of the copolymers according to the present invention, preferably the ratio between the sum of all the carbon atoms of the alkyl chains variously present in the basic repetitive unit of the alternating pi-conjugated polymer and the number of aromatic rings present in the same unit it is between 2.5 and 12.
I polimeri pi-coniugati alternati oggetto della presente invenzione hanno preferibilmente una struttura dell’unità ripetitiva di base di tipo (A-B)n, dove A e B hanno il significato precedentemente definito e n à ̈ un numero intero variabile da 1 a 1000, preferibilmente da 2 a 500, ancora più preferibilmente tra 3 e 50. The alternating pi-conjugated polymers object of the present invention preferably have a basic repetitive unit structure of type (A-B) n, where A and B have the previously defined meaning and n is an integer variable from 1 to 1000, preferably from 2 to 500, even more preferably between 3 and 50.
Ciascuna unità A à ̈ legata a due unità B, uguali o diverse, tranne quando l’unità A o l’unità B costituiscano unità terminali della catena polimerica. In quest’ultimo caso l’unità A o l’unità B terminali sono legate ad una sola unità B o A, rispettivamente, e la rimanente valenza à ̈ saturata da un sostituente terminale la cui struttura dipende dal metodo di preparazione del polimero ed à ̈ facilmente identificabile dall’esperto dell’arte. Nella maggior parte dei casi detto sostituente à ̈ H oppure Br. Each unit A is linked to two units B, the same or different, except when unit A or unit B constitute terminal units of the polymer chain. In the latter case the terminal unit A or the unit B are linked to a single unit B or A, respectively, and the remaining valence is saturated by a terminal substituent whose structure depends on the method of preparation of the polymer and is easily identifiable by the art expert. In most cases, this substituent is H or Br.
Particolarmente preferiti sono i seguenti polimeri pi-coniugato alternati: poli[9,9-bis(2-etilesil)-fluorene—alt-2-(p-fluorofenil)-1,1-vinilidene] (polimero 1), poli[9,9-bis(2-etilesil)fluorene—alt-2(pentafluorofenil)-1,1-vinilidene] (polimero 2) e poli[N-ottil-3,7-fenotiazina—alt-2-(pentafluorofenil)-1,1-vinilidene] (polimero 3), per le proprietà di light harvesting mostrate. Particularly preferred are the following alternating pi-conjugate polymers: poly [9.9-bis (2-ethylhexyl) -fluoreneâ € ”alt-2- (p-fluorophenyl) -1,1-vinylidene] (polymer 1), poly [ 9,9-bis (2-ethylhexyl) fluoreneâ € "alt-2 (pentafluorophenyl) -1,1-vinylidene] (polymer 2) and poly [N-octyl-3,7-phenothiazineâ €" alt-2- (pentafluorophenyl ) -1,1-vinylidene] (polymer 3), due to the light harvesting properties shown.
Quando il polimero pi-coniugato alternato secondo la presente invenzione à ̈ il seguente (polimero 1): When the alternating pi-conjugated polymer according to the present invention is the following (polymer 1):
una possibile via per il suo ottenimento à ̈ quella corrispondente al procedimento riportato nel seguente schema A: a possible way to obtain it is the one corresponding to the procedure shown in the following diagram A:
Schema A. Scheme A.
Preferibilmente, il suddetto polimero 1 presenta un valore dell'indice n variabile da 3 a 50 Preferably, the aforesaid polymer 1 has an index value n ranging from 3 to 50
Quando il polimero pi-coniugato alternato secondo la presente invenzione à ̈ il seguente (polimero 2) una possibile via per l’ottenimento à ̈ quella corrispondente al procedimento riportato nel seguente schema B When the alternating pi-conjugated polymer according to the present invention is the following (polymer 2) a possible way to obtain it is the one corresponding to the process reported in the following scheme B
Schema B. Scheme B.
Preferibilmente, il suddetto polimero 2 presenta un valore dell'indice n variabile da 3 a 50. Preferably, the aforesaid polymer 2 has an index value n ranging from 3 to 50.
Quando il polimero pi-coniugato alternato secondo la presente invenzione à ̈ il seguente (polimero 3) When the alternating pi-conjugated polymer according to the present invention is the following (polymer 3)
una possibile via per l’ottenimento à ̈ quella corrispondente al procedimento riportato nel seguente schema C a possible way to obtain it is the one corresponding to the procedure shown in the following diagram C
Schema C. Scheme C.
Preferibilmente, il suddetto polimero 3 presenta un valore dell'indice n variabile da 3 a 50. Preferably, the aforesaid polymer 3 has a value of the index n ranging from 3 to 50.
Polimeri pi-coniugati alternati della presente invenzione aventi strutture diverse da quelle precedentemente indicate sono ottenibili mediante processi di tipo radicalico-cationico o ossidoriduttivo riconducibili a quelli descritti o comunque facilmente desumibili dal tecnico in base alle note metodologie della chimica organica. Alternating pi-conjugated polymers of the present invention having structures different from those indicated above can be obtained by means of radical-cationic or redox processes which can be traced back to those described or in any case easily inferred by the technician based on the known methods of organic chemistry.
I polimeri pi-coniugati alternati secondo la presente invenzione presentano favorevoli proprietà chimico-fisiche che ne permettono il loro impiego come materiali fotoattivi, in particolare come composti elettron-donatori all’interno di dispositivi fotovoltaici. Essi sono caratterizzati da valori di bandgap inferiori a 3,2 eV e pertanto sono particolarmente adatti per sfruttare la radiazione solare a più elevata lunghezza d’onda. Grazie alla stabilità termica e ossidativa conferita dalla presenza di unità fluorurate, questi materiali possono essere utilizzati vantaggiosamente nella realizzazione di dispositivi fotovoltaici aventi una maggiore durata in condizioni di elevato stress ambientale e di esposizione a radiazione luminosa intensa e con una significativa componente ultravioletta. The alternating pi-conjugated polymers according to the present invention have favorable chemical-physical properties which allow their use as photoactive materials, in particular as electron-donor compounds inside photovoltaic devices. They are characterized by bandgap values lower than 3.2 eV and are therefore particularly suitable for exploiting solar radiation at a longer wavelength. Thanks to the thermal and oxidative stability conferred by the presence of fluorinated units, these materials can be used advantageously in the construction of photovoltaic devices having a longer life in conditions of high environmental stress and exposure to intense light radiation and with a significant ultraviolet component.
È quindi un ulteriore oggetto della presente invenzione un dispositivo fotovoltaico comprendente uno qualunque dei polimeri pi-coniugati alternati della presente invenzione. A further object of the present invention is therefore a photovoltaic device comprising any one of the alternating pi-conjugated polymers of the present invention.
Come sarà meglio illustrato nei successivi esempi, i suddetti polimeri pi-coniugati alternati possono essere facilmente sintetizzati secondo gli schemi di procedimento precedentemente illustrati. As will be better illustrated in the following examples, the aforesaid alternating pi-conjugated polymers can be easily synthesized according to the process schemes previously illustrated.
I seguenti esempi di realizzazione sono forniti a scopo illustrativo della presente invenzione e non devono essere intesi in senso limitativo dell’ambito di protezione. The following embodiments are provided for illustrative purposes of the present invention and must not be construed as limiting the scope of protection.
I polimeri pi-coniugati alternati secondo la presente invenzione sono stati caratterizzati mediante spettroscopia UV-Vis-NIR per determinare l’entità energetica del band-gap HOMO-LUMO secondo la seguente procedura. The alternating pi-conjugated polymers according to the present invention were characterized by UV-Vis-NIR spectroscopy to determine the energy entity of the HOMO-LUMO band-gap according to the following procedure.
Il polimero à ̈ disciolto in toluene ad una concentrazione di circa 10<-4>M, trasferito in una cuvetta in quarzo Suprasil da 1.0 cm ed analizzato in trasmissione mediante uno spettrofotometro UV-Vis-NIR a doppio raggio e doppio monocromatore Perkin Elmer λ 19, nell’intervallo 190–900 nm con banda passante di 2,0 nm, velocità di scansione di 120 nm/min e step di 1 nm, utilizzando come riferimento una identica cuvetta riempita con il solo solvente. The polymer is dissolved in toluene at a concentration of about 10 <-4> M, transferred into a 1.0 cm Suprasil quartz cuvette and analyzed in transmission by means of a double beam UV-Vis-NIR spectrophotometer and double monochromator Perkin Elmer Î »19, in the range 190â €“ 900 nm with 2.0 nm bandwidth, scanning speed of 120 nm / min and 1 nm step, using as reference an identical cuvette filled with solvent only.
Dagli spettri in riflettanza diffusa viene stimato il band-gap misurando l’edge di assorbimento corrispondente alla transizione dalla banda di valenza (VB) a quella di conduzione (CB). Per la determinazione dell’edge, si à ̈ fatto ricorso all’intersezione con l’asse delle ascisse della retta tangente alla banda di assorbimento nel punto di flesso. 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). To determine the edge, we resorted to the intersection with the abscissa axis of the straight line tangent to the absorption band at the inflection point.
Il punto di flesso (λF, yF) viene determinato in base alle coordinate del minimo dello spettro in derivata prima, indicate con λ’mined y’min. The inflection point (Î »F, yF) is determined on the basis of the coordinates of the minimum of the spectrum in first derivative, denoted by λ â € ™ mined yâ € ™ min.
L’equazione della retta tangente allo spettro UV-Vis nel punto di flesso (λF, yF) à ̈: The equation of the tangent line to the UV-Vis spectrum at the inflection point (Î »F, yF) is:
y = y’minλ yF– y’minλ’miny = yâ € ™ minÎ »yFâ €“ yâ € ™ minÎ »â € ™ min
Infine, dalla condizione di intersezione con l’asse delle ascisse ψ = 0, si ricava: Finally, from the condition of intersection with the abscissa axis ψ = 0, we obtain:
λEDGE= (y’minλ’min- yF)/ y’minÎ »EDGE = (yâ € ™ minλ â € ™ min- yF) / yâ € ™ min
Pertanto, misurando le coordinate del minimo dello spettro in derivata prima ed il corrispondente valore di assorbanza yFdallo spettro UV-Vis, per sostituzione si ricava direttamente λEDGE. 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, Î »EDGE is directly obtained by substitution.
L’energia corrispondente à ̈: The corresponding energy is:
EEDGE= hÎ1⁄2EDGE= h c/λEDGEEEDGE = hÎ1⁄2EDGE = h c / Î »EDGE
ove h = 6,626 10<-34>J s where h = 6.626 10 <-34> J s
c = 2,998 10<8>m s<-1>c = 2,998 10 <8> m s <-1>
ossia EEDGE= 1,988 10<-16>J/λEDGE(nm). that is EEDGE = 1.988 10 <-16> J / Î »EDGE (nm).
Ricordando, infine, che 1 J = 6,2410<18>eV, si ha: EEDGE= 1240 eV / λEDGE(nm) Finally, remembering that 1 J = 6.2410 <18> eV, we have: EEDGE = 1240 eV / Î »EDGE (nm)
ESEMPIO 1 EXAMPLE 1
Polimero pi-coniugato alternato poli[9,9-bis(2-etilesil)fluorene—alt-2-(p-fluorofenil)-1,1-vinilidene], (polimero 1). Polymer pi-conjugated alternating poly [9.9-bis (2-ethylhexyl) fluoreneâ € ”alt-2- (p-fluorophenyl) -1,1-vinylidene], (polymer 1).
In un pallone a tre colli da 250 ml munito di agitatore magnetico e refrigerante a ricadere sono stati introdotti sotto atmosfera inerte, nell’ordine: In a 250 ml three-necked flask equipped with a magnetic stirrer and reflux refrigerant, the following were introduced under an inert atmosphere, in the order:
- 1289 mg (2,696 mmoli) di acido 9,9-bis(2’-etilesil)-2,7-diboronico; - 1289 mg (2.696 mmoles) of 9,9-bis (2â € ™ -ethylhexyl) -2,7-diboronic acid;
- 755 mg (2,696 mmoli) di p-fluoro-β,βdibromostirene (1,1-dibromo-2-(p-fluorofenil)etilene), disciolti in circa 20 ml di toluene deareato; - 755 mg (2.696 mmoles) of p-fluoro-β, βdibromostyrene (1,1-dibromo-2- (p-fluorophenyl) ethylene), dissolved in about 20 ml of deaerated toluene;
- 250 mg di Aliquat 336 (5,9 mmoli) disciolti in circa 50 ml di toluene deareato; - 250 mg of Aliquat 336 (5.9 mmoles) dissolved in approximately 50 ml of deaerated toluene;
- 12 ml di carbonato di potassio 1,036 M (12,4 mmoli) (acqua deareata); - 12 ml of 1.036 M potassium carbonate (12.4 mmoles) (deaerated water);
- 66 mg (0,054 mmoli) di palladio (0) tetrakis(trifenilfosfina). - 66 mg (0.054 mmol) of palladium (0) tetrakis (triphenylphosphine).
La miscela di reazione à ̈ stata riscaldata a riflusso (90°C) e sotto intensa agitazione per 26 ore. The reaction mixture was heated to reflux (90 ° C) and under intense stirring for 26 hours.
Al termine del periodo indicato, la miscela à ̈ stata concentrata sino a circa 30 ml e versata in 400 ml di metanolo. Il precipitato ottenuto à ̈ stato filtrato e lavato, nell’ordine, con metanolo, acqua e ancora metanolo. At the end of the indicated period, the mixture was concentrated up to about 30 ml and poured into 400 ml of methanol. The precipitate obtained was filtered and washed, in order, with methanol, water and more methanol.
Il prodotto à ̈ stato disciolto in una quantità minima di toluene e riprecipitato in metanolo. Sono stati ottenuti 650 mg di polimero di colore giallo tendente al verdastro. The product was dissolved in a minimum quantity of toluene and re-precipitated in methanol. 650 mg of yellow to greenish polymer were obtained.
Il band gap ottico misurato sul film solido per il copolimero così ottenuto à ̈ di 2,5 eV, valori di HOMO e LUMO rispettivamente di -5,7 e -2,2 eV, un peso molecolare medio ponderale di 6400 ed una e una perdita in peso a 250°C inferiore all’1%, determinata mediante analisi termogravimetrica in aria. The optical band gap measured on the solid film for the copolymer thus obtained is 2.5 eV, HOMO and LUMO values respectively of -5.7 and -2.2 eV, a weight average molecular weight of 6400 and one e a weight loss at 250 ° C of less than 1%, determined by thermogravimetric analysis in air.
Schematicamente, la reazione avvenuta à ̈ la seguente: Schematically, the reaction that took place is the following:
ESEMPIO 2 EXAMPLE 2
Polimero pi-coniugato alternato poli[9,9-bis(2-etilesil)fluorene—alt-2-(pentafluorofenil)-1,1-vinilidene], (polimero 2) Polymer pi-conjugated alternating poly [9,9-bis (2-ethylhexyl) fluoreneâ € ”alt-2- (pentafluorophenyl) -1,1-vinylidene], (polymer 2)
In un pallone a tre colli da 250 ml munito di agitatore magnetico e refrigerante a ricadere sono stati introdotti sotto atmosfera inerte, nell’ordine: In a 250 ml three-necked flask equipped with a magnetic stirrer and reflux refrigerant, the following were introduced under an inert atmosphere, in the order:
- 1143 mg (2,39 mmoli) di acido 9,9-bis(2’-etilesil)-2,7-diboronico; - 1143 mg (2.39 mmoles) of 9,9-bis (2â € ™ -ethylhexyl) -2,7-diboronic acid;
- 841 mg (2,39 mmoli) di pentafluoro-β,βdibromostirene (1,1-dibromo-2-(pentafluorofenil)etilene) disciolti in circa 20 ml di toluene deareato; - 221 mg di Aliquat 336 (5,2 mmoli) disciolti in circa 50 ml di toluene deareato; - 841 mg (2.39 mmoles) of pentafluoro-β, βdibromostyrene (1,1-dibromo-2- (pentafluorophenyl) ethylene) dissolved in about 20 ml of deaerated toluene; - 221 mg of Aliquat 336 (5.2 mmoles) dissolved in approximately 50 ml of deaerated toluene;
- 10,8 ml di carbonato di potassio 1,033 M (11,1 mmoli) (acqua deareata) - 10.8 ml of 1.033 M potassium carbonate (11.1 mmol) (deaerated water)
- 58 mg (0,047 mmoli) di palladio (0) tetrakis(trifenilfosfina.) - 58 mg (0.047 mmol) of palladium (0) tetrakis (triphenylphosphine.)
La miscela di reazione à ̈ stata riscaldata a riflusso (90°C) e sotto intensa agitazione per 33 ore. The reaction mixture was heated to reflux (90 ° C) and under intense stirring for 33 hours.
Al termine del periodo indicato, la miscela à ̈ stata concentrata a secco e versata in 200 ml di metanolo. Il precipitato ottenuto à ̈ stato filtrato e lavato, nell’ordine, con metanolo, acqua, una miscela acqua/etanolo e infine etanolo. At the end of the indicated period, the mixture was concentrated to dryness and poured into 200 ml of methanol. The precipitate obtained was filtered and washed, in order, with methanol, water, a water / ethanol mixture and finally ethanol.
Il prodotto à ̈ stato disciolto in una quantità minima di toluene e riprecipitato in metanolo. Sono stati ottenuti 1252 mg di polimero di colore grigio. The product was dissolved in a minimum quantity of toluene and re-precipitated in methanol. 1252 mg of gray colored polymer were obtained.
Il band gap ottico misurato sul film solido per il copolimero così ottenuto à ̈ di 3,1 eV, valori di HOMO e LUMO rispettivamente di -6,0 e -2,5 eV, un peso molecolare medio ponderale di 6600 ed una e una perdita in peso a 250°C inferiore all’1%, determinata mediante analisi termogravimetrica in aria. The optical band gap measured on the solid film for the copolymer thus obtained is 3.1 eV, HOMO and LUMO values respectively of -6.0 and -2.5 eV, a weight average molecular weight of 6600 and one e a weight loss at 250 ° C of less than 1%, determined by thermogravimetric analysis in air.
Schematicamente, la reazione avvenuta à ̈ la seguente: Schematically, the reaction that took place is the following:
ESEMPIO 3 EXAMPLE 3
Polimero pi-coniugato alternato poli[N-ottil-3,7-fenotiazina—alt-2-(pentafluorofenil)-1,1-vinilidene], (polimero 3). Polymer pi-conjugated alternating poly [N-octyl-3,7-phenothiazineâ € ”alt-2- (pentafluorophenyl) -1,1-vinylidene], (polymer 3).
In un pallone a tre colli da 250 ml munito di agitatore magnetico e refrigerante a ricadere sono stati introdotti sotto atmosfera inerte, nell’ordine: In a 250 ml three-necked flask equipped with a magnetic stirrer and reflux refrigerant, the following were introduced under an inert atmosphere, in the order:
- 1021 mg (2,558 mmoli) di acido N-ottilfenotiazo-3,7-diboronico; - 1021 mg (2,558 mmoles) of N-octylphenothiazo-3,7-diboronic acid;
- 900 mg (2,39 mmoli) di pentafluoro-β,βdibromostirene (1,1-dibromo-2-(pentafluorofenil)etilene) disciolti in circa 20 ml di toluene deareato; - 900 mg (2.39 mmoles) of pentafluoro-β, βdibromostyrene (1,1-dibromo-2- (pentafluorophenyl) ethylene) dissolved in about 20 ml of deaerated toluene;
- 238 mg di Aliquat 336 (5,6 mmoli) disciolti in circa 50 ml di toluene deareato; - 238 mg of Aliquat 336 (5.6 mmoles) dissolved in about 50 ml of deaerated toluene;
- 11,5 ml di carbonato di potassio 1,033 M (11,9 mmoli) (acqua deareata) - 11.5 ml of 1.033 M potassium carbonate (11.9 mmol) (deaerated water)
- 61 mg (0,050 mmoli) di palladio(0)tetrakis-(trifenilfosfina) - 61 mg (0.050 mmol) of palladium (0) tetrakis- (triphenylphosphine)
La miscela di reazione à ̈ stata riscaldata a riflusso (90°C) e sotto intensa agitazione per 39 ore. The reaction mixture was heated to reflux (90 ° C) and under intense stirring for 39 hours.
Al termine del periodo indicato, la miscela à ̈ stata concentrata a secco e versata in 200 ml di metanolo. Il precipitato ottenuto à ̈ stato filtrato e lavato, nell’ordine, con metanolo, acqua, una miscela acqua/etanolo e infine metanolo. At the end of the indicated period, the mixture was concentrated to dryness and poured into 200 ml of methanol. The precipitate obtained was filtered and washed, in order, with methanol, water, a water / ethanol mixture and finally methanol.
Il prodotto à ̈ stato disciolto in una quantità minima di toluene e riprecipitato in metanolo. Sono 5 stati ottenuti 1150 mg di polimero di colore marrone leggermente tendente al verdastro. The product was dissolved in a minimum quantity of toluene and re-precipitated in methanol. 5 1150 mg of slightly greenish brown colored polymer were obtained.
Il band gap ottico misurato su film solido per il copolimero così ottenuto à ̈ di 2,6 eV, un peso molecolare medio ponderale di 7000 e una perdita in 0 peso a 250°C inferiore al 3%, determinata mediante analisi termogravimetrica in aria. The optical band gap measured on solid film for the copolymer thus obtained is 2.6 eV, a weight average molecular weight of 7000 and a 0 weight loss at 250 ° C of less than 3%, determined by thermogravimetric analysis in air .
Schematicamente, la reazione avvenuta à ̈ la seguente: Schematically, the reaction that took place is the following:
5 5
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| PCT/EP2010/007285 WO2011066954A1 (en) | 2009-12-04 | 2010-11-30 | π-CONJUGATED POLYMERS CONTAINING FLUOROARYLVINYLEDENE UNITS AND RELATIVE PREPARATION PROCESS |
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
Non-Patent Citations (2)
| Title |
|---|
| 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 * |
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