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WO2012029675A1 - Procédé de production d'un composé polymère - Google Patents

Procédé de production d'un composé polymère Download PDF

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Publication number
WO2012029675A1
WO2012029675A1 PCT/JP2011/069363 JP2011069363W WO2012029675A1 WO 2012029675 A1 WO2012029675 A1 WO 2012029675A1 JP 2011069363 W JP2011069363 W JP 2011069363W WO 2012029675 A1 WO2012029675 A1 WO 2012029675A1
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group
formula
compound
fluorine atom
substituted
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Japanese (ja)
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上谷　保則
吉村　研
淳 藤原
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住友化学株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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    • 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
    • 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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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • 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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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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    • 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
    • C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
    • 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
    • C08G2261/32—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
    • 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
    • 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
    • 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
    • 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
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
    • 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
    • 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 a method for producing a polymer compound.
  • Organic semiconductor materials are expected to be applied to organic photoelectric conversion elements (organic solar cells, optical sensors, etc.).
  • the functional layer can be manufactured by an inexpensive coating method.
  • organic semiconductor materials that are various polymer compounds for the organic photoelectric conversion element has been studied.
  • an organic semiconductor material for example, 9,9-dioctylfluorene-2,7-diboronic acid ester and 5,5 ′′ ′′-dibromo-3 ′′, 4 ′′ -dihexyl- ⁇ -pentathiophene are polymerized.
  • a polymer compound has been proposed (WO2005 / 092947).
  • an object of the present invention is to provide a method for producing a polymer compound having a large absorbance for light having a long wavelength and a polymer compound having a large absorbance for light having a long wavelength. That is, the present invention is first represented by the formula (4) in which the compound represented by the formula (1) is reacted with the compound represented by the formula (2) or the compound represented by the formula (3). The manufacturing method of the high molecular compound containing a repeating unit is provided.
  • R represents a hydrogen atom, a fluorine atom, an alkyl group optionally substituted with a fluorine atom, an alkoxy group optionally substituted with a fluorine atom, or an aryl group optionally substituted.
  • R may be the same or different
  • Q represents a dihydroxyboryl group or a borate residue
  • two Q may be the same or different.
  • T represents a hydrogen atom, a fluorine atom, an alkyl group optionally substituted with a fluorine atom, an alkoxy group optionally substituted with a fluorine atom, or an optionally substituted group.
  • a plurality of T's may be the same or different, A represents a bromine atom, a chlorine atom or an iodine atom, and two A's may be the same or different.
  • a represents 0 or 1.
  • R and T represent the same meaning as described above.
  • this invention provides the high molecular compound containing the repeating unit represented by Formula (5). (In the formula, R and T have the same meaning as described above.)
  • the present invention provides an organic photoelectric conversion device having a pair of electrodes and a functional layer provided between the electrodes, wherein the functional layer includes an electron-accepting compound and the polymer compound.
  • FIG. 1 is a graph showing an absorption spectrum of polymer compound A.
  • FIG. 2 is a graph showing an absorption spectrum of the polymer compound B.
  • FIG. 3 is a view showing an absorption spectrum of the polymer compound C.
  • This invention contains the repeating unit represented by Formula (4) with which the compound represented by Formula (1), the compound represented by Formula (2), or the compound represented by Formula (3) is made to react.
  • This is a method for producing a polymer compound.
  • R and Q have the same meaning as described above.
  • T and A represent the same meaning as described above.
  • a represents 0 or 1.
  • T and R represent the same meaning as described above.
  • the alkyl group represented by R may be linear or cyclic.
  • a hydrogen atom in the alkyl group may be substituted with a fluorine atom.
  • alkyl group substituted with a fluorine atom examples include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.
  • the alkyl part in the alkoxy group represented by R may be linear or cyclic.
  • alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, Examples include tert-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, and 3,7-dimethyloctyloxy group.
  • a hydrogen atom in the alkoxy group may be substituted with a fluorine atom.
  • alkoxy group substituted with a fluorine atom examples include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, and a perfluorooctyloxy group.
  • R is an alkyl group or an alkoxy group, from the viewpoint of solubility of the polymer compound in a solvent, the carbon number is preferably 1-20, more preferably 2-18, and more preferably 3-12. More preferably.
  • the aryl group represented by R is an atomic group obtained by removing one hydrogen atom from an unsubstituted aromatic hydrocarbon, having a benzene ring, having a condensed ring, an independent benzene ring or condensed ring 2 Those in which at least two are bonded directly or via a group such as vinylene are also included.
  • the number of carbon atoms of the aryl group is preferably 6 to 60, and more preferably 6 to 30.
  • Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • the aryl group may have a substituent, and examples of the substituent that the aryl group may have include a halogen atom, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms.
  • Etc. the definitions and specific examples of the alkyl group, alkoxy group and aryl group represented by T are the definitions and specific examples of the alkyl group, alkoxy group and aryl group represented by R.
  • Q is a dihydroxyboryl group represented by the following formula Or represents a boric acid ester residue.
  • the boric acid ester residue means a group obtained by removing a hydroxy group from a boric acid diester, and specific examples thereof include a group represented by the following formula.
  • Me represents a methyl group
  • Et represents an ethyl group.
  • Q is preferably a boric acid ester residue.
  • A represents a bromine atom, a chlorine atom or an iodine atom. From the viewpoint of reactivity, a bromine atom is preferable.
  • Examples of the compound represented by the formula (1) in which two Qs are dihydroxyboryl groups include the following compounds.
  • Examples of the compound represented by the formula (1) in which two Qs are boric acid ester residues include the following compounds.
  • the compound represented by the formula (1) in which two Qs are boric acid ester residues is obtained by, for example, dehydrating and condensing the compound represented by the formula (6) with an alcohol or diol in an organic solvent. Can be manufactured. (In the formula, R represents the same meaning as described above.)
  • the slurry-like compound represented by formula (6) disappears, and the reaction solution becomes a uniform solution, so that two Qs are represented by formula (1), which is a borate ester residue. Production of the compound can be confirmed.
  • the reaction solution is concentrated using an evaporator, the residue is washed with a hydrocarbon solvent having a relatively low boiling point, such as hexane, and then filtered, and the two formulas in which Q is a borate ester residue (1 ) Can be obtained.
  • a hydrocarbon solvent having a relatively low boiling point such as hexane
  • Q is a borate ester residue (1 )
  • the alcohol that can be used for the reaction include methanol, ethanol, propanol, 2-propanol, and butanol.
  • the diol that can be used in the reaction include pinacol, catechol, ethylene glycol, and 1,3-propanediol.
  • a dehydrating agent such as anhydrous magnesium sulfate or anhydrous sodium sulfate may be added.
  • the compound represented by the formula (6) is obtained by lithiating the compound represented by the formula (7) with an organolithium compound such as butyllithium (n-BuLi), and then the lithiated compound and trimethyl borate (trimethoxy).
  • a compound represented by the formula (8) is produced by reacting with a boric acid ester such as borane), and the compound represented by the formula (8) can be produced by acid treatment with an acid such as dilute hydrochloric acid. .
  • R represents the same meaning as described above.
  • the lithiation reaction is usually performed in an anhydrous ether solvent such as anhydrous tetrahydrofuran or anhydrous diethyl ether.
  • the reaction temperature is usually ⁇ 80 ° C.
  • the repeating unit represented by Formula (4) is a repeating unit represented by Formula (5).
  • R and T have the same meaning as described above.
  • the amount of the repeating unit represented by the formula (4) is preferably 20 to 100 mol%, more preferably 30 to 100 mol% with respect to the total of all repeating units in the polymer compound. preferable.
  • the polymer compound having a repeating unit represented by the formula (4) preferably has a polystyrene equivalent weight average molecular weight of 10 3 to 10 8 , more preferably 10 3 to 10 7 , and still more preferably 10 3 to 10 6 .
  • the polymer compound represented by the formula (4) is preferably a conjugated polymer compound.
  • the conjugated polymer compound means a compound in which the main chains of molecules constituting the compound are conjugated.
  • the high molecular compound which has a repeating unit represented by Formula (4) may have repeating units other than the repeating unit represented by Formula (4). Examples of the repeating unit include an arylene group and a heteroarylene group.
  • Examples of the arylene group include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a pyrenediyl group, and a fluorenediyl group.
  • Examples of the heteroarylene group include a flangyl group, a pyrrole diyl group, a pyridinediyl group, and the like.
  • the production method of the present invention is a repetition represented by the formula (4) in which the compound represented by the formula (1) is reacted with the compound represented by the formula (2) or the compound represented by the formula (3). It is a manufacturing method of the high molecular compound containing a unit. Examples of the reaction include a Suzuki coupling reaction.
  • Polymerization by Suzuki coupling reaction can be carried out by using inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, tripotassium phosphate, potassium fluoride, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, water Palladium [tetrakis (triphenylphosphine)], [tris (dibenzylideneacetone)] dipalladium, palladium acetate, bis (triphenylphosphine) palladium dichloride, bis (cyclooctadiene) in the presence of an organic base such as tetraethylammonium oxide Using a palladium complex such as nickel or a nickel complex as a catalyst, triphenylphosphine, tri (2-methylphenyl) phosphine, tri (2-methoxyphenyl) phosphine, Add a ligand such as
  • a solvent is usually used.
  • This solvent may be selected in consideration of the polymerization reaction used, the solubility of the monomer and polymer, and the like. Specifically, tetrahydrofuran, toluene, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, an organic solvent such as a mixed solvent obtained by mixing two or more of these solvents, an organic solvent A mixed solvent having two phases of a phase and an aqueous phase can be mentioned.
  • Solvents used in the Suzuki coupling reaction are organic solvents such as tetrahydrofuran, toluene, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, and mixed solvents in which two or more of these solvents are mixed.
  • a solvent, a mixed solvent having two phases of an organic solvent phase and an aqueous phase is preferable.
  • the reaction solvent is preferably subjected to deoxygenation before the reaction in order to suppress side reactions.
  • the lower limit of the reaction temperature of the production method of the present invention is preferably ⁇ 100 ° C., more preferably ⁇ 20 ° C., and particularly preferably 0 ° C. from the viewpoint of reactivity.
  • the upper limit of the reaction temperature is preferably 200 ° C., more preferably 150 ° C., and particularly preferably 120 ° C. from the viewpoint of the stability of the monomer and the polymer compound.
  • a known method may be used as a method for taking out the polymer compound having the repeating unit represented by the formula (4) from the reaction solution after completion of the reaction.
  • a polymer solution having a repeating unit represented by the formula (4) can be obtained by adding a reaction solution to a lower alcohol such as methanol and filtering and drying the deposited precipitate.
  • the purity of the obtained polymer compound is low, it can be purified by ordinary methods such as recrystallization, continuous extraction with a Soxhlet extractor, column chromatography and the like.
  • the polymerization active group represented by A or Q as an end group remains in the polymer compound. Since the properties such as durability of the obtained organic photoelectric conversion element may be deteriorated, it is preferable to protect the terminal of the polymer compound with a stable group.
  • Examples of the stable group for protecting the terminal include an alkyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkoxy group, an aryl group, an arylamino group, and a monovalent heterocyclic group. Moreover, it replaces with stable group and the hydrogen atom may be located in the terminal. From the viewpoint of enhancing the hole transport property by the terminal group, a group imparting electron donating properties such as an arylamino group is preferable.
  • As the terminal group a group having a conjugated bond continuous with the conjugated structure of the main chain can also be preferably used. Examples of the group include a group bonded to an aryl group or a monovalent heterocyclic group through a carbon-carbon bond.
  • Examples of the arylamino group include a phenylamino group and a diphenylamino group.
  • Examples of the monovalent heterocyclic group include a chenyl group, a pyrrolyl group, a furyl group, a pyridyl group, a quinolyl group, and an isoquinolyl group.
  • the polymer compound having a repeating unit represented by the formula (4) has a high absorbance of light having a long wavelength such as 600 nm light, and is produced using the polymer compound in order to efficiently absorb sunlight.
  • the organic photoelectric conversion element has a large short-circuit current density.
  • the organic photoelectric conversion element of the present invention includes a pair of electrodes, a functional layer between the electrodes, and the functional layer containing a polymer compound containing an electron-accepting compound and a repeating unit represented by the formula (4) To do.
  • a polymer compound containing an electron-accepting compound and a repeating unit represented by the formula (4) are preferable.
  • an electron-accepting compound fullerene and a fullerene derivative are preferable.
  • the high molecular compound containing the repeating unit represented by Formula (5) is preferable.
  • the organic photoelectric conversion element 1.
  • An organic photoelectric conversion element having a pair of electrodes and a functional layer between the electrodes, the functional layer containing an electron-accepting compound and a polymer compound containing a repeating unit represented by the formula (4); 2.
  • An organic photoelectric conversion element in which the electron-accepting compound is a fullerene derivative; Is mentioned.
  • at least one of the pair of electrodes is transparent or translucent.
  • this case will be described as an example. 1 above.
  • the ratio of the electron-accepting compound in the functional layer containing the electron-accepting compound and the polymer compound is 10 to 1000 parts by weight with respect to 100 parts by weight of the polymer compound. It is preferably 20 to 500 parts by weight. In addition, 2.
  • the ratio of the fullerene derivative in the functional layer is preferably 20 to 400 parts by weight with respect to 100 parts by weight of the polymer compound. The amount is more preferably 250 parts by weight, and further preferably 80 to 120 parts by weight.
  • the ratio of the fullerene derivative in the functional layer is preferably 20 to 250 parts by weight, more preferably 40 to 120 parts by weight with respect to 100 parts by weight of the polymer. preferable.
  • the electron-accepting compound and the polymer compound having the repeating unit represented by the formula (4) can efficiently absorb the spectrum of desired incident light. It has an absorption region that can be formed, the heterojunction interface includes many heterojunction interfaces in order to efficiently separate excitons, and has a charge transport property that quickly transports the charges generated by the heterojunction interface to the electrode. This is very important. From such a viewpoint, as the organic photoelectric conversion element, the above 1. , 2.
  • the organic photoelectric conversion element is preferable.
  • the organic photoelectric conversion element is more preferable.
  • an additional layer may be provided between at least one electrode and the functional layer in the element.
  • the additional layer include a charge transport layer that transports holes or electrons.
  • the organic photoelectric conversion element of the present invention is usually formed on a substrate.
  • the substrate may be any substrate that does not chemically change when an electrode is formed and an organic layer is formed. Examples of the material for the substrate include glass, plastic, polymer film, and silicon. In the case of an opaque substrate, the opposite electrode (that is, the electrode far from the substrate) is preferably transparent or translucent.
  • a metal, a conductive polymer, or the like can be used as a material of the pair of electrodes.
  • one of the pair of electrodes is preferably a material having a low work function.
  • metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and those metals
  • An alloy with metal, graphite, a graphite intercalation compound, or the like is used.
  • the alloy examples include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.
  • the material of the transparent or translucent electrode include a conductive metal oxide film and a translucent metal thin film. Specifically, a film formed using a conductive material made of indium oxide, zinc oxide, tin oxide, and indium tin oxide (ITO), indium zinc oxide, etc., which is a composite thereof, NESA Gold, platinum, silver, and copper are used, and ITO, indium / zinc / oxide, and tin oxide are preferable.
  • Examples of the method for producing the electrode include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like.
  • organic transparent conductive films such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode material.
  • a material used for the charge transport layer as the additional layer that is, the hole transport layer or the electron transport layer
  • an electron donating compound and an electron accepting compound described later can be used, respectively.
  • As a material used for the buffer layer as an additional layer halides or oxides of alkali metals or alkaline earth metals such as lithium fluoride can be used.
  • fine particles of an inorganic semiconductor such as titanium oxide can be used.
  • the organic thin film containing the high molecular compound which has a repeating unit represented by Formula (4) can be used, for example.
  • the thickness of the organic thin film is usually 1 nm to 100 ⁇ m, preferably 2 nm to 1000 nm, more preferably 5 nm to 500 nm, and further preferably 20 nm to 200 nm.
  • the organic thin film may contain the high molecular compound which has a repeating unit represented by Formula (4) individually by 1 type, or may contain it in combination of 2 or more types.
  • another high molecular compound or a low molecular compound can also be mixed and used as an electron-donating compound in an organic thin film.
  • the electron-donating compound that the organic thin film may contain in addition to the polymer compound having the repeating unit represented by the formula (4) include, for example, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligos.
  • Thiophene and derivatives thereof polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof Derivatives, polythienylene vinylene and its derivatives.
  • Examples of the electron accepting compound include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, and fluorenone derivatives.
  • diphenyldicyanoethylene and derivatives thereof diphenoquinone derivatives, 8-hydroxyquinoline and metal complexes of derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and its derivatives, polyfluorene and its derivatives, fullerene and derivatives thereof such as C 60, carbon nanotube And phenanthroline derivatives such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, and fullerene and derivatives thereof are particularly preferable.
  • the electron-donating compound and the electron-accepting compound are relatively determined from the energy levels of these compounds.
  • Fullerenes and derivatives thereof include C 60 , C 70 , C 84 and derivatives thereof.
  • a fullerene derivative represents a compound in which at least a part of fullerene is modified.
  • Examples of the fullerene derivative include a compound represented by the formula (I), a compound represented by the formula (II), a compound represented by the formula (III), and a compound represented by the formula (IV).
  • R a is an alkyl group, aryl group, heteroaryl group or group having an ester structure. A plurality of R a may be the same or different.
  • R b represents an alkyl group or an aryl group, and a plurality of R b may be the same or different.
  • the definitions and specific examples of the alkyl group and aryl group represented by R a and R b are the same as the definitions and specific examples of the alkyl group and aryl group represented by R.
  • the heteroaryl group represented by Ra usually has 3 to 60 carbon atoms, and examples thereof include a chenyl group, a pyrrolyl group, a furyl group, a pyridyl group, a quinolyl group, and an isoquinolyl group.
  • Examples of the group having an ester structure represented by Ra include a group represented by the formula (V).
  • u1 represents an integer of 1 to 6
  • u2 represents an integer of 0 to 6
  • R c represents an alkyl group, an aryl group, or a heteroaryl group.
  • the definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R c are the same as the definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R a .
  • Specific examples of the C 60 derivative include the following.
  • Specific examples of the C 70 derivative include the following.
  • the organic thin film may be produced by any method, for example, a method by film formation from a solution containing a polymer compound having a repeating unit represented by formula (4), or vacuum deposition.
  • An organic thin film may be formed by a method.
  • Examples of the method for producing an organic thin film by film formation from a solution include a method of producing an organic thin film by applying the solution on one electrode and then evaporating the solvent.
  • the solvent used for film formation from a solution is not particularly limited as long as it dissolves the polymer compound.
  • the solvent examples include hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, Examples thereof include halogenated hydrocarbon solvents such as bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, chlorobenzene, dichlorobenzene, and trichlorobenzene, and ether solvents such as tetrahydrofuran and tetrahydropyran.
  • hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicycl
  • the polymer compound can usually be dissolved in the solvent in an amount of 0.1% by weight or more.
  • spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic method Coating methods such as a printing method, an offset printing method, an ink jet printing method, a dispenser printing method, a nozzle coating method, a capillary coating method can be used, and a spin coating method, a flexographic printing method, an ink jet printing method, and a dispenser printing method are preferable.
  • the organic photoelectric conversion element By irradiating light such as sunlight from a transparent or translucent electrode, the organic photoelectric conversion element generates a photovoltaic force between the electrodes and can be operated as an organic thin film solar cell. It can also be used as an organic thin film solar cell module by integrating a plurality of organic thin film solar cells. In addition, by applying light from a transparent or translucent electrode in a state where a voltage is applied between the electrodes, a photocurrent flows and it can be operated as an organic photosensor. It can also be used as an organic image sensor by integrating a plurality of organic photosensors.
  • the polystyrene equivalent weight average molecular weight of the polymer compound was determined by size exclusion chromatography (SEC). Column: TOSOH TSKgel SuperHM-H (2) + TSKgel SuperH2000 (4.6 ml.d. ⁇ 15 cm); Detector: RI (SHIMADZU RID-10A); Mobile phase: Tetrahydrofuran (THF) Synthesis Example 1 Synthesis of Compound (2) In a 100 ml three-necked flask equipped with a Dimroth condenser in a nitrogen atmosphere, Adv. Funct. Mater. 2007, Vol.
  • Synthesis Example 2 Synthesis of Compound (3)
  • 0.74 g (1.2 mmol) of compound (2), 0.29 g (2.5 mmol) of pinacol, and 30 ml of chloroform were added at room temperature (25 ° C.) to form a slurry reaction.
  • the mixture was stirred while heating to reflux until the solution became a homogeneous solution.
  • 1.0 g of anhydrous magnesium sulfate was added to the reaction solution, and the mixture was further stirred while heating under reflux for 4 hours. After stirring, the mixture was filtered, and the filtrate was concentrated with an evaporator.
  • the reaction solution was allowed to stand, and a separated toluene layer was obtained.
  • the toluene layer was washed twice with 10 mL of water, twice with 10 mL of 3 wt% aqueous acetic acid and twice with 10 mL of water, and the obtained toluene layer was poured into methanol to obtain a deposited precipitate. This precipitate was dried under reduced pressure and then dissolved in toluene.
  • the obtained toluene solution was filtered to remove insoluble matters, and then passed through an alumina / silica gel column for purification. The obtained toluene solution was concentrated under reduced pressure and then poured into methanol to obtain a generated precipitate.
  • Example 2 Synthesis of polymer compound B Monomer synthesized by a method described in 312 mg (0.395 mmol) of Compound (3) in a reaction vessel in an argon atmosphere, Journal of Materials Chemistry, 2002, No. 12, pages 2887-2892 200 mg (0.436 mmol) of A, 128 mg of trioctylmethylammonium chloride (trade name Aliquat 336 (registered trademark), manufactured by Sigma-Aldrich Co.) and 26 mL of toluene were added, and the solution obtained using argon was sufficiently bubbled. Deaerated.
  • the polymer obtained above was dissolved in 30 mL of orthodichlorobenzene, 10 ml of a 9.1 wt% sodium diethyldithiocarbamate aqueous solution was added, and the reaction solution was refluxed for 5 hours. After completion of the reflux, the reaction solution was cooled to around room temperature (25 ° C.). Thereafter, the reaction solution was allowed to stand to obtain a separated orthodichlorobenzene layer.
  • the orthodichlorobenzene layer was washed twice with 10 mL of water, twice with 10 mL of 3 wt% acetic acid water, and further twice with 10 mL of water, and the resulting orthodichlorobenzene layer was poured into methanol to obtain a deposited precipitate. did.
  • the precipitate was dried under reduced pressure and then dissolved in orthodichlorobenzene.
  • the obtained orthodichlorobenzene solution was filtered to remove insolubles, and then the filtrate was passed through an alumina / silica gel column for purification.
  • the obtained orthodichlorobenzene solution was concentrated under reduced pressure, poured into methanol, and the resulting precipitate was recovered.
  • the weight average molecular weight in terms of polystyrene of the polymer compound C was 1.1 ⁇ 10 5 .
  • Measurement Example 1 Measurement of absorbance of organic thin film Polymer compound A was dissolved in o-dichlorobenzene at a concentration of 0.5% by weight to prepare a coating solution. The obtained coating solution was applied onto a glass substrate by spin coating. The coating operation was performed at 23 ° C. Then, it baked for 5 minutes on 120 degreeC conditions in air
  • Table 1 shows the absorbance at 600 nm and 700 nm.
  • Measurement Example 2 Measurement of Absorbance of Organic Thin Film An organic thin film was prepared in the same manner as in Measurement Example 1 except that polymer compound B was used instead of polymer compound A, and the absorption spectrum of the organic thin film was measured. The measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm and 700 nm. Comparative Example 1 Measurement of Absorbance of Organic Thin Film An organic thin film was prepared in the same manner as in Measurement Example 1 except that the polymer compound C was used in place of the polymer compound A, and the absorption spectrum of the organic thin film was measured. The measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm and 700 nm.
  • a PEDOT: PSS solution (CleviosP VP AI4083 manufactured by HC Starck Co., Ltd.) is applied onto the ITO film by spin coating, and heated at 120 ° C. for 10 minutes in the atmosphere to thereby form a hole injection layer having a thickness of 50 nm. It was created.
  • the coating solution 1 was applied onto the hole injection layer by spin coating to obtain a functional layer of an organic thin film solar cell.
  • the film thickness of the functional layer was 100 nm.
  • the organic thin film solar cell was produced by vapor-depositing calcium with a film thickness of 4 nm with a vacuum evaporation machine, and vapor-depositing aluminum with a film thickness of 100 nm.
  • the degree of vacuum at the time of vapor deposition was 1 to 9 ⁇ 10 ⁇ 3 Pa in all cases.
  • the shape of the organic thin film solar cell thus obtained was a square of 2 mm ⁇ 2 mm.
  • the resulting organic thin-film solar cell is measured by irradiating with constant light using a solar simulator (trade name OTENTO-SUN II: AM1.5G filter, irradiance 100 mW / cm 2 , manufactured by Spectrometer Co., Ltd.), and a generated current And the voltage was measured to obtain the photoelectric conversion efficiency.
  • the photoelectric conversion efficiency was 3.87%
  • the short-circuit current density was 8.5 mA / cm 2
  • the open-circuit voltage was 0.91 V
  • the fill factor (FF) was 0.50.
  • the method for producing a polymer compound of the present invention is useful for producing a polymer compound having a large absorbance of light having a long wavelength.

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Abstract

La présente invention concerne un procédé de production d'un composé polymère contenant un motif répétitif représenté par la formule (4), dans lequel un composé représenté par la formule (1) est mis à réagir avec un composé représenté par la formule (2) ou un composé représenté par la formule (3). Un composé polymère qui présente une absorbance élevée de la lumière de grande longueur d'onde peut être produit par ce procédé. (Dans la formule (1), R représente un atome d'hydrogène, un atome de fluor, un groupe alkyle qui peut être substitué par un atome de fluor, un groupe alcoxy qui peut être substitué par un atome de fluor ou un groupe aryle éventuellement substitué; et Q représente un groupe dihydroxyboryle ou un résidu d'ester d'acide borique). (Dans la formule (4), a représente 0 ou 1; R est tel que défini ci-dessus; et T représente un atome d'hydrogène, un atome de fluor, un groupe alkyle qui peut être substitué par un atome de fluor, un groupe alcoxy qui peut être substitué par un atome de fluor ou un groupe aryle éventuellement substitué).
PCT/JP2011/069363 2010-09-03 2011-08-22 Procédé de production d'un composé polymère WO2012029675A1 (fr)

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