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WO2011158831A1 - Procédé pour la production de composés de masse moléculaire élevée - Google Patents

Procédé pour la production de composés de masse moléculaire élevée Download PDF

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Publication number
WO2011158831A1
WO2011158831A1 PCT/JP2011/063595 JP2011063595W WO2011158831A1 WO 2011158831 A1 WO2011158831 A1 WO 2011158831A1 JP 2011063595 W JP2011063595 W JP 2011063595W WO 2011158831 A1 WO2011158831 A1 WO 2011158831A1
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group
formula
polymer compound
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represented
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邦仁 三宅
剛志 道信
宇平 原
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Sumitomo Chemical Co Ltd
Tokyo Institute of Technology NUC
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Sumitomo Chemical Co Ltd
Tokyo Institute of Technology NUC
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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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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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    • C—CHEMISTRY; METALLURGY
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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
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
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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
    • C08G2261/322—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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    • 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
    • C08G2261/3227—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing only one kind of heteroatoms other than N, O, S, Si, Se, Te
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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
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/94—Applications in sensors, e.g. biosensors
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
    • H10K39/30—Devices controlled by radiation
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    • 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
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
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    • 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
    • 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.
  • a polymer compound having a cyano group has absorption in a long wavelength region, and is expected as a semiconductor material used for organic solar cells and the like.
  • a method for producing a polymer compound having a cyano group a method in which a polymer compound having an alkyne structure and a compound having a cyano group are heated to perform an addition reaction is disclosed (see Non-Patent Document 1).
  • the present invention firstly includes a polymer compound having a structural unit represented by the following formula (I) and a compound represented by the following formula (II) or a compound represented by the following formula (III).
  • a method for producing a polymer compound which is reacted under microwave irradiation to produce a polymer compound having a structural unit represented by the following formula (IV).
  • Ar 3 represents a tetravalent organic group.
  • a 1 and A 2 each independently represent a group represented by ⁇ C (CN) 2 or a group represented by the following formula (V).
  • Ar 3 represents a tetravalent organic group.
  • the present invention provides a polymer compound containing a structural unit represented by the following formula (VI).
  • Ar 4 and Ar 5 each independently represent a divalent heterocyclic group.
  • a 11 and A 22 each independently represent a group represented by ⁇ C (CN) 2 or a group represented by the following formula (VII).
  • Ar 33 represents a tetravalent organic group.
  • the present invention has an anode, a cathode, and an active layer provided between the anode and the cathode, and has an electron donating compound and an electron accepting compound in the active layer.
  • a photoelectric conversion element in which at least one of the compound and the electron-accepting compound is a polymer compound.
  • the present invention provides a solar cell module including a photoelectric conversion element.
  • the present invention provides an image sensor including a photoelectric conversion element.
  • the present invention provides a polymer compound having a structural unit represented by the following formula (I) and a compound represented by the following formula (II) or a compound represented by the following formula (III) under microwave irradiation: To produce a polymer compound having a structural unit represented by the following formula (IV).
  • Ar 3 represents a tetravalent organic group.
  • a 1 and A 2 each independently represent a group represented by ⁇ C (CN) 2 or a group represented by the following formula (V).
  • Ar 3 represents a tetravalent organic group.
  • the polymer compound obtained is a group in which both A 1 and A 2 are represented by ⁇ C (CN) 2 Is a polymer compound having a structural unit represented by the above formula (IV).
  • a polymer compound having a structural unit represented by the above formula (IV) wherein the other of A 1 and A 2 is a group represented by the above formula (V).
  • the tetravalent organic group represented by Ar 3 usually has 6 to 50 carbon atoms.
  • a group having a quinoid structure is preferable.
  • Examples of the group having a quinoid structure include a group represented by the formula (Ar3-1), a group represented by the formula (Ar3-2), And a group represented by the formula (Ar3-3).
  • R 10 , R 11 and R 12 are each independently an alkyl optionally substituted with a hydrogen atom, a halogen atom, a cyano group, a nitro group or a fluorine atom. Represents an alkoxy group which may be substituted with a group or a fluorine atom.
  • the four R 10 may be the same or different.
  • Six R 11 may be the same or different.
  • Six R 12 may be the same or different.
  • halogen atom represented by R 10 to R 12 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the alkyl group represented by R 10 to R 12 usually has 1 to 20 carbon atoms.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group, and an octyl group.
  • a hydrogen atom in the alkyl group may be substituted with a fluorine atom.
  • the alkoxy group represented by R 10 to R 12 usually has 1 to 20 carbon atoms. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a heptyloxy group, a hexyloxy group, and an octyloxy group.
  • a hydrogen atom in the alkoxy group may be substituted with a fluorine atom.
  • Examples of the compound represented by the formula (III) include a compound represented by the following formula (III-1), a compound represented by the following formula (III-2), and a compound represented by the following formula (III-3). Compounds.
  • R 311 , R 321 and R 331 may each independently be substituted with a hydrogen atom, a halogen atom, a cyano group, a nitro group or a fluorine atom. It represents an alkyl group which may be substituted with an alkoxy group or a fluorine atom.
  • R 311 may be the same or different.
  • the eight R 321s may be the same or different.
  • the six R 331s may be the same or different.
  • halogen atom, alkyl group and alkoxy group represented by R 311 , R 321 and R 331 are the same as those of the halogen atom, alkyl group and alkoxy group represented by R 10 and the same examples. is there.
  • the hydrogen atom in the alkyl group represented by R ⁇ 311> , R ⁇ 321> , R ⁇ 331> and the alkoxy group may be substituted with a fluorine atom.
  • the polymer compound having the structural unit represented by formula (I) is a polymer compound having the structural unit represented by formula (I) in the main chain, and has the structural unit represented by formula (IV).
  • the polymer compound is preferably a polymer compound having a structural unit represented by the formula (IV) in the main chain.
  • the polymer compound having the structural unit represented by the formula (I) further includes at least one selected from the group consisting of an arylene group, a divalent heterocyclic group, a vinylene group, and a divalent group containing a metal atom.
  • a polymer compound having a group is preferable. Definition of an arylene group, divalent heterocyclic group, and divalent group containing a metal atom, specific examples are definitions of an arylene group, divalent heterocyclic group, and divalent group containing a metal atom described in detail below. The same as the specific example.
  • arylene group divalent heterocyclic group, vinylene group, and divalent group containing a metal atom
  • an arylene group and a divalent heterocyclic group are more preferable, and a divalent heterocyclic group is more preferable.
  • the polymer compound having a structural unit represented by the formula (I) is a polymer compound having a structural unit represented by the following formula (I-2).
  • the polymer compound having a structural unit represented by IV) is a polymer compound having a structural unit represented by the following formula (IV-2). That is, a preferred embodiment of the production method of the present invention is represented by a polymer compound having a structural unit represented by the following formula (I-2) and a compound represented by the formula (II) or the formula (III).
  • Ar 6 and Ar 7 each independently represent an arylene group, a divalent heterocyclic group, a vinylene group or a divalent group containing a metal atom.
  • Ar 8 and Ar 9 each independently represent an arylene group, a divalent heterocyclic group, a vinylene group or a divalent group containing a metal atom.
  • a 3 and A 4 represent the same meaning as A 1 and A 2 described above.
  • the arylene group represented by Ar 6 , Ar 7 , Ar 8 and Ar 9 is an atom obtained by removing two hydrogen atoms bonded to an aromatic ring from an aromatic carbocyclic compound which may have a substituent. Means a group. The number of carbon atoms in the arylene group is usually 6-60. Examples of the arylene group include a phenylene group, a naphthalenediyl group, and a fluorenediyl group.
  • Examples of the substituent that the arylene group represented by Ar 6 , Ar 7 , Ar 8, and Ar 9 may have include a halogen atom, a cyano group, a nitro group, an alkyl group that may be substituted with a fluorine atom, and fluorine
  • An alkoxy group which may be substituted with an atom is exemplified.
  • the number of carbon atoms and specific examples of the alkyl group and alkoxy group are the same as the number of carbon atoms and specific examples of the alkyl group and alkoxy group represented by R 10 .
  • the divalent heterocyclic group represented by Ar 6 , Ar 7 , Ar 8 and Ar 9 is an atomic group obtained by removing two heterocyclic hydrogen atoms from a heterocyclic compound which may have a substituent. Means. The number of carbon atoms in the heterocyclic group is usually 2-50. Specific examples of the divalent heterocyclic group include carbazole diyl group, thiophene diyl group, thiazole diyl group, pyrrole diyl group, and pyridine diyl group. As the divalent heterocyclic group, an aromatic heterocyclic group is preferable, and a thiophenediyl group is more preferable.
  • Examples of the substituent that the divalent heterocyclic group represented by Ar 6 , Ar 7 , Ar 8, and Ar 9 may have may be substituted with a halogen atom, a cyano group, a nitro group, or a fluorine atom.
  • Examples thereof include an alkyl group and an alkoxy group which may be substituted with a fluorine atom.
  • the number of carbon atoms and specific examples of the alkyl group and alkoxy group are the same as the number of carbon atoms and specific examples of the alkyl group and alkoxy group represented by R 10 .
  • Examples of the divalent group containing a metal atom represented by Ar 6 , Ar 7 , Ar 8 and Ar 9 include a group represented by the following formula (IX).
  • M represents a metal atom.
  • R 9 represents an alkyl group which may be substituted with a fluorine atom. Six R 9 may be the same or different.
  • the divalent group containing a metal atom is preferably a divalent group containing a transition metal atom, and the transition metal atom is more preferably a platinum atom, a gold atom, a palladium atom, or a mercury atom.
  • the number of carbon atoms and specific examples of the alkyl group represented by R 9 are the same as the number of carbon atoms and specific examples of the alkyl group represented by R 10 .
  • a preferred embodiment of the divalent group containing a metal atom is a group represented by the following formula (IX-2).
  • R 1 represents an alkyl group which may be substituted with a fluorine atom.
  • Six R 1 may be the same or different.
  • the alkyl group represented by R 1 usually has 1 to 20 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group, and an octyl group.
  • a hydrogen atom in the alkyl group may be substituted with a fluorine atom.
  • Ar 6 , Ar 7 , Ar 8 and Ar 9 are preferably an arylene group or a divalent heterocyclic group, and more preferably a divalent heterocyclic group.
  • the polymer compound having the structural unit represented by the formula (I-2) may further have other repeating units.
  • Examples of other repeating units (divalent groups) include repeating units represented by the following formulas (B-1) to (B-15).
  • R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 and R 34 each independently represent a hydrogen atom or a substituent.
  • Six R 21 may be the same or different.
  • 5 is R 22 may be the same or different.
  • Six R 23 may be the same or different.
  • Four R 24 may be the same or different.
  • Two R 25 may be the same or different.
  • Four R 27 may be the same or different.
  • the three R 28 may be the same or different.
  • Four R 29 may be the same or different.
  • Two R 30 may be the same or different.
  • Four R 31 may be the same or different.
  • Two R 32 may be the same or different.
  • Two R 33 may be the same or different.
  • Two R 34 may be the same or different.
  • Examples of the substituent represented by R 21 to R 34 include a halogen atom, a cyano group, a nitro group, an alkyl group which may be substituted with a fluorine atom, and an alkoxy group which may be substituted with a fluorine atom. It is done.
  • the number of carbon atoms and specific examples of the alkyl group and alkoxy group are the same as the number of carbon atoms and specific examples of the alkyl group and alkoxy group represented by R 10 described above.
  • the polymer compound having the structural unit represented by the formula (I) preferably has a polystyrene-equivalent number average molecular weight of 10 3 to 10 8 , and more preferably 10 4 to 10 7 .
  • a polymer compound having a structural unit represented by formula (I), a compound represented by formula (II) or a compound represented by formula (III), and a solvent are mixed.
  • the solvent may be a solvent that can dissolve the entire amount of the compound used in the reaction or a solvent that can dissolve a partial amount of each of the compounds used in the reaction. You may heat the obtained solution in the range below the thermal decomposition temperature of the high molecular compound which has a structural unit represented by Formula (IV), irradiating a microwave.
  • the frequency of the microwave used for the reaction is not particularly limited, and is usually 1000 MHz to 5000 MHz, preferably 2000 MHz to 4000 MHz.
  • the microwave may be a continuous wave or a pulse wave. Further, the microwave may be a single mode or a multimode. If necessary, the reaction may be performed while heating or cooling from the outside. At that time, a reflux tube may be attached to the reaction vessel, and the reaction may be performed while boiling the solvent. Moreover, you may react under pressurization.
  • the reaction time is usually 1 minute to 7 days.
  • the reaction may be carried out in air or in an inert atmosphere.
  • the reaction is preferably carried out under an inert atmosphere such as N 2 gas or argon gas.
  • the ratio of the compound represented by formula (II) or the compound represented by formula (III) used in the reaction to 1 mol part of the structural unit represented by formula (I) is 0.1 mol part or more. .
  • an excess amount of the compound represented by the formula (II) or the compound represented by the formula (III) is a polymer compound having a structural unit represented by the formula (IV) Can be separated using techniques such as sublimation, reprecipitation, and chromatography.
  • the production method of the present invention is excellent in reactivity and is represented by the formula (IV) even if the polymer compound having the structural unit represented by the formula (I) has a substituent having a large steric hindrance.
  • the polymer compound having a structural unit can be produced in high yield.
  • the preferable aspect of the manufacturing method of this invention is a manufacturing method of the high molecular compound containing the structural unit represented by following formula (VI). That is, a preferred embodiment of the production method of the present invention comprises a polymer compound having a structural unit represented by formula (I) and a compound represented by formula (II) or a compound represented by formula (III).
  • the polymer compound containing the structural unit represented by the following formula (VI) of the present invention is highly yielded by a production method similar to the production method of the polymer compound having the structural unit represented by the formula (IV) already described. Can be manufactured at a rate.
  • Ar 4 and Ar 5 each independently represent a divalent heterocyclic group.
  • a 11 and A 22 each independently represent a group represented by ⁇ C (CN) 2 or a group represented by the following formula (VII).
  • Ar 33 represents a tetravalent organic group.
  • the divalent heterocyclic group represented by Ar 4 and Ar 5 means an atomic group obtained by removing two heterocyclic hydrogen atoms from a heterocyclic compound which may have a substituent.
  • the number of carbon atoms in the heterocyclic group is usually 2-50.
  • Specific examples of the divalent heterocyclic group include carbazole diyl group, thiophene diyl group, thiazole diyl group, pyrrole diyl group, and pyridine diyl group.
  • the divalent heterocyclic group represented by Ar 4 and Ar 5 is preferably an aromatic heterocyclic group, more preferably a thiophenediyl group.
  • Examples of the substituent that the divalent heterocyclic group represented by Ar 4 and Ar 5 may have include a halogen atom, a cyano group, a nitro group, an alkyl group optionally substituted with a fluorine atom, and a fluorine atom.
  • the alkoxy group which may be substituted is mentioned.
  • the number of carbon atoms and specific examples of the alkyl group and alkoxy group are the same as the number of carbon atoms and specific examples of the alkyl group and alkoxy group represented by R 10 .
  • the tetravalent organic group represented by Ar 33 is the same as the tetravalent organic group represented by Ar 3 described above.
  • a preferred embodiment of the structural unit represented by the formula (VI) is a structural unit in which A 11 and A 22 are a group represented by the formula (VII).
  • Specific examples of Ar 33 include groups exemplified as the tetravalent organic group represented by Ar 3 described above.
  • the tetravalent organic group represented by Ar 33 is preferably a group having a quinoid structure.
  • the polymer compound of the present invention may further contain a structural unit represented by the following formula (I).
  • the number average molecular weight in terms of polystyrene of the polymer compound of the present invention is preferably 10 3 to 10 8 .
  • the polymer compound having a structural unit represented by formula (VI) is preferably a polymer compound having a structural unit represented by formula (VI) in the main chain.
  • the polymer compound produced by the production method of the present invention is useful as a material for an active layer for a photoelectric conversion element.
  • the photoelectric conversion element of the present invention has an anode, a cathode, and an active layer provided between the anode and the cathode, and has an electron donating compound and an electron accepting compound in the active layer.
  • At least one of the functional compound and the electron-accepting compound includes a repeating unit represented by the formula (VI).
  • a preferred embodiment of the structural unit represented by the formula (VI) is a structural unit in which A 11 and A 22 are a group represented by ⁇ C (CN) 2 , and A 11 and A 22 is a structural unit which is a group represented by the formula (VII).
  • the anode, the active layer, the electron-donating compound and the electron-accepting compound that constitute the active layer, the cathode, and other components that are formed as necessary will be described in detail below.
  • Basic form of photoelectric conversion element As a basic form of the photoelectric conversion element, a pair of electrodes, at least one of which is transparent or translucent, an electron donating compound (p-type organic semiconductor) and an electron accepting compound (n-type organic semiconductor, etc.) It has a bulk hetero active layer or p / n stacked active layer formed from an organic composition.
  • the generated electrons and holes can be taken out as electric energy (current) by moving to the electrodes.
  • the photoelectric conversion efficiency is increased because it has absorption in a long wavelength region and can convert a wide range of wavelengths.
  • the photoelectric conversion element is usually formed on a substrate.
  • the substrate may be any substrate that does not chemically change when the electrodes are formed and the organic layer is formed. Examples of the material for the substrate include glass, plastic, polymer film, and silicon.
  • the opposite electrode that is, the electrode far from the substrate
  • the transparent or translucent electrode material examples include a conductive metal oxide film and a translucent metal thin film. Specifically, it is formed using indium oxide, zinc oxide, tin oxide, and conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), and NESA that are composites thereof. A film formed using gold, platinum, silver, copper, or the like is used, and a film formed using ITO, IZO, or tin oxide is preferable.
  • the electrode forming method include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.
  • the transparent or translucent electrode may be an anode or a cathode.
  • the other electrode may not be transparent, and as the electrode material of the electrode that is not transparent, a metal, a conductive polymer, or the like can be used.
  • the electrode material include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like.
  • alloys thereof or one or more metals selected from the group consisting of one or more metals and gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin Alloy, graphite, graphite intercalation compound, polyaniline and its derivatives, polythiophene and its derivatives.
  • the alloy 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.
  • An additional intermediate layer (such as a charge transport layer) other than the active layer may be used as a means for improving the photoelectric conversion efficiency.
  • the material used for the intermediate layer include alkali metal or alkaline earth metal halides or oxides such as lithium fluoride, and specifically lithium fluoride.
  • fine particles of inorganic semiconductors such as titanium oxide, a mixture of PEDOT (poly (3,4-ethylenedioxythiophene)) and PSS (poly (4-styrenesulfonate)) (PEDOT: PSS), etc. are used for the intermediate layer. It may be used as a material.
  • the active layer contained in the photoelectric conversion element can contain a polymer compound containing a structural unit represented by the formula (VI) as at least one of an electron donating compound and an electron accepting compound.
  • the electron-donating compound and the electron-accepting compound are relatively determined from the HOMO or LUMO energy levels of these compounds.
  • the electron donating compound may be a low molecular compound or a high molecular compound.
  • the electron donating compound is preferably a polymer compound.
  • Examples of the electron donating compound include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, and aromatic amines in side chains or main chains.
  • polysiloxane derivatives polyaniline and derivatives thereof, polythiophene and derivatives thereof, polymer compounds having thiophene as a partial skeleton, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, and polythienylene vinylene and derivatives thereof.
  • the electron-donating compound examples include polythiophene (polythiophene and derivatives thereof) which may have a substituent, a structure including a dimer to pentamer of thiophene, or a dimer to pentamer of a thiophene derivative.
  • a polymer compound having a structure and a polymer compound having thiophene as a partial skeleton are preferable, and polythiophene and derivatives thereof are more preferable.
  • the polythiophene derivative is a polymer compound having a thiophenediyl group having a substituent.
  • the polythiophene and its derivatives are preferably homopolymers.
  • a homopolymer is a polymer formed by bonding only a plurality of groups selected from the group consisting of a thiophenediyl group and a substituted thiophenediyl group.
  • the thiophene diyl group is preferably a thiophene-2,5-diyl group, and the thiophene diyl group having a substituent is preferably an alkylthiophene-2, 5-diyl group.
  • homopolymer polythiophene and derivatives thereof include poly (3-hexylthiophene-2,5-diyl) (P3HT), poly (3-octylthiophene-2,5-diyl), poly (3-dodecyl) Thiophene-2,5-diyl) and poly (3-octadecylthiophene-2,5-diyl).
  • P3HT poly (3-hexylthiophene-2,5-diyl)
  • poly3HT poly (3-octylthiophene-2,5-diyl)
  • poly (3-dodecyl) Thiophene-2,5-diyl) and poly (3-octadecylthiophene-2,5-diyl
  • polythiophenes and derivatives thereof which are homopolymers polythiophene homopolymers comprising thiophene diyl groups substituted with alkyl groups having 6
  • Examples of the polymer compound having thiophene as a partial skeleton include a polymer compound represented by the following formula (2).
  • n represents the number of repetitions.
  • R 71 and R 72 each independently represent a hydrogen atom or a substituent.
  • Two R 71 may be the same or different.
  • Six R ⁇ 72> may be the same or may be different from each other.
  • an alkoxy group having 1 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms are preferable.
  • the polymer compound represented by the formula (2) is preferably a polymer compound in which R 71 is an alkyl group and R 72 is a hydrogen atom.
  • Specific examples of the polymer compound represented by the formula (2) include a polymer compound represented by the following formula (2-1).
  • Electrode-accepting compound examples include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, Diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, polyfluorene and its derivatives, C 60 fullerene (C 60 is the number of carbon atoms The number attached to the subscript means the number of carbon atoms.
  • the electron accepting compound is preferably a compound containing a benzothiadiazole structure, a polymer compound containing a benzothiadiazole structure in a repeating unit, a compound containing a quinoxaline structure, a polymer compound containing a quinoxaline structure in a repeating unit, titanium oxide, carbon Nanotubes, fullerenes, fullerene derivatives, more preferably fullerenes, fullerene derivatives, compounds containing a benzothiadiazole structure, polymer compounds containing a benzothiadiazole structure in a repeating unit, compounds containing a quinoxaline structure, and a quinoxaline structure in a repeating unit More preferably, it is a compound containing a benzothiadiazole structure, a polymer compound containing
  • Examples of the polymer compound containing a benzothiadiazole structure in the repeating unit include a polymer compound represented by the following formula (2).
  • n represents the number of repetitions.
  • R 71 and R 72 each independently represent a hydrogen atom or a substituent.
  • Two R 71 may be the same or different.
  • Six R ⁇ 72> may be the same or may be different from each other.
  • an alkoxy group having 1 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms are preferable.
  • the polymer compound represented by the formula (2) is preferably a polymer compound in which R 71 is an alkyl group and R 72 is a hydrogen atom.
  • Specific examples of the polymer compound represented by the formula (2) include a polymer compound represented by the following formula (2-1).
  • fullerene, C 60 fullerene, C 70 fullerene, C 76 fullerene, C 78 fullerene include C 84 fullerene.
  • fullerene derivatives include C 60 fullerene derivatives, C 70 fullerene derivatives, C 76 fullerene derivatives, C 78 fullerene derivatives, and C 84 fullerene derivatives.
  • C 60 fullerene derivative examples include the following compounds.
  • C 70 fullerene derivative examples include the following compounds.
  • fullerene derivatives include [6,6] phenyl-C 61 butyric acid methyl ester (C60PCBM, [6,6] -Phenyl C 61 butyric acid methyl ester), and [6,6] phenyl-C 71 butyric acid methyl ester.
  • Esters C 70 PCBM, [6,6] -Phenyl C 71 butyric acid methyl ester), [6,6] Phenyl-C 85 butyric acid methyl ester (C 84 PCBM, [6,6] -Phenyl C 85 butyric acid methyl ester) ester), [6,6] thienyl -C 61 butyric acid methyl ester ([6,6] -Thienyl C 61 butyric acid methyl ester) and the like.
  • the ratio of the electron-accepting compound to the electron-donating compound is preferably 10 to 1000 parts by weight, preferably 20 to 500 parts by weight with respect to 100 parts by weight of the electron-donating compound. More preferably.
  • the thickness of the active layer is usually preferably 1 nm to 100 ⁇ m, more preferably 2 nm to 1000 nm, still more preferably 5 nm to 500 nm, and particularly preferably 20 nm to 200 nm.
  • a preferred embodiment of the photoelectric conversion element of the present invention is a photoelectric conversion element containing a fullerene derivative in the active layer.
  • the photoelectric conversion device of the present invention is a photoelectric conversion device in which both the electron donating compound and the electron accepting compound are polymer compounds.
  • the electron donating compound may be polythiophene which may have a substituent.
  • the electron-accepting compound may be a polymer compound having a benzothiadiazole structure or a quinoxaline structure.
  • the active layer may contain other components as necessary in order to express various functions.
  • Other components that the active layer may contain include, for example, ultraviolet absorbers, antioxidants, sensitizers for sensitizing the function of generating charge by absorbed light, and stability from ultraviolet rays. And a light stabilizer for increasing the amount.
  • Components other than the electron donating compound and the electron accepting compound constituting the active layer are each 5 parts by weight or less, particularly 0.01 parts by weight with respect to 100 parts by weight of the total amount of the electron donating compound and the electron accepting compound. It is effective to add in a proportion of 3 parts by weight.
  • the active layer may contain a polymer compound other than the electron donating compound and the electron accepting compound as a polymer binder in order to enhance mechanical properties.
  • a polymer binder those that do not inhibit the electron transport property or hole transport property are preferable, and those that do not strongly absorb visible light are preferably used.
  • polymer binder examples include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, poly Examples include carbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.
  • the active layer of the photoelectric conversion element is formed by coating and forming a solution containing the electron donating compound, the electron accepting compound, and other components blended as necessary. be able to.
  • the active layer can be formed, for example, by applying the solution on an anode or a cathode. Then, another electrode can be formed on an active layer and a photoelectric conversion element can be manufactured.
  • the solvent used for film formation from a solution is not particularly limited as long as it dissolves the above-described electron-donating compound and electron-accepting compound.
  • a plurality of types of solvents may be mixed and used.
  • examples of such a solvent include unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, Halogenated saturated hydrocarbon solvents such as dichloropropane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, halogenated unsaturated hydrocarbon solvents such as chlorobenzene,
  • spin coating method for film formation, 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, gravure printing method, Application methods such as flexographic printing method, offset printing method, ink jet printing method, dispenser printing method, nozzle coating method, capillary coating method can be used, spin coating method, flexographic printing method, gravure printing method, ink jet printing method, dispenser A printing method is preferred.
  • the photoelectric conversion element can be operated as an organic thin film solar cell by generating a photovoltaic force between the electrodes by making light such as sunlight enter from a transparent or translucent electrode. It can also be used as an organic thin film solar cell module by integrating a plurality of organic thin film solar cells.
  • 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 organic thin film solar cell can basically have the same module structure as a conventional solar cell module.
  • a solar cell module generally has a structure in which cells are formed on a support substrate made of metal, ceramic, etc., which is covered with a filling resin, protective glass, etc., and light is incident from the opposite side of the support substrate.
  • a transparent material such as tempered glass can be used for the support substrate, and a cell can be formed thereon so that light can enter from the transparent support substrate side.
  • a module structure called a super straight type, a substrate type, or a potting type, a substrate integrated module structure used in an amorphous silicon solar cell, or the like is known.
  • these module structures can be appropriately selected depending on the purpose of use, the place of use, and the environment.
  • a typical super straight type or substrate type module cells are arranged at regular intervals between support substrates that are transparent on one or both sides and subjected to antireflection treatment, and adjacent cells are connected by metal leads or flexible wiring. It is connected, and the collector electrode is arrange
  • plastic materials such as ethylene vinyl acetate (EVA) may be used between the substrate and the cell in the form of a film or a filling resin depending on the purpose in order to protect the cell and improve the current collection efficiency.
  • EVA ethylene vinyl acetate
  • the surface protection layer is made of a transparent plastic film, or the protective function is achieved by curing the filling resin It is possible to eliminate the supporting substrate on one side.
  • the periphery of the support substrate is fixed in a sandwich shape with a metal frame in order to ensure internal sealing and module rigidity, and the support substrate and the frame are hermetically sealed with a sealing material.
  • a flexible material is used for the cell itself, the support substrate, the filling material, and the sealing material, a solar cell can be formed on the curved surface.
  • a solar cell using a flexible support such as a polymer film
  • cells are sequentially formed while feeding out a roll-shaped support, cut to a desired size, and then the periphery is sealed with a flexible and moisture-proof material.
  • a solar cell body can be produced.
  • SCAF module structure described in Solar Energy Materials and Solar Cells, 48, p383-391.
  • a solar cell using a flexible support can be used by being bonded and fixed to a curved glass or the like.
  • Synthesis example 1 Polymer Compound P1 (Synthesis of poly (3-hexyl-thienyleneethynylene))
  • the synthesis of the monomer 2-bromo-5-ethynyl-3-hexylthiophene was performed by H. Higuchi, T. Ishikura, K. Mori, Y. Takayama, K. Yamamoto, K. Tani, K. Miyabayashi, M. Miyake. Bull. Chem. Soc. Jpn., 2001, 74, p. 889.
  • the synthesis of the polymer compound using the Sonogashira reaction and the addition reaction of the acceptor molecule to the polymer compound are shown below.
  • a 50 mL pear-shaped flask was charged with 0.53 g (2.0 mmol) of 2-bromo-5-ethynyl-3-hexylthiophene and mixed by mixing 1: 1 (volume ratio) of diisopropylamine and tetrahydrofuran (THF). Dissolved in 24 mL of solution. After degassing with argon gas for 30 minutes in the flask, 30 mg (0.026 mmol) of tetrakis (triphenylphosphine) palladium and 4.9 mg (0.0026 mmol) of copper (I) iodide were placed in the flask under an inert atmosphere. Added to. The reaction solution was heated to 70 ° C.
  • the reaction solution was cooled to room temperature (25 ° C.) and poured into cooled methanol to cause precipitation, thereby obtaining 0.25 g of polymer compound P1.
  • the yield of the polymer compound P1 was 47%.
  • the number average molecular weight (Mn) in terms of polystyrene was 2000, and the weight average molecular weight (Mw) / Mn in terms of polystyrene, that is, the molecular weight distribution was 1.6.
  • Example 1 Synthesis of polymer compound P2
  • polymer compound P1 the amount of the repeating unit is 0.091 mmol
  • 11.6 mg (0.0910 mmol) of tetracyanoethylene (TCNE) are added, and 3 mL of 1,2-dichlorobenzene is added. Dissolved. Then, it was made to react at 100 degreeC for 4 hours, irradiating 33W microwave using the microwave synthesizer (brand name Discover, manufactured by Astec Co., Ltd.). After completion of the reaction, the solvent and unreacted TCNE were removed under reduced pressure to obtain 24 mg of polymer compound P2.
  • the yield of the polymer compound P2 was 35%. Mn was 2000 and Mw / Mn was 1.7.
  • Example 2 Synthesis of polymer compound P3
  • TCNQ tetracyanoquinodimethane
  • Example 3 (Production and evaluation of organic thin-film solar cells) A glass substrate on which an ITO film having a thickness of 150 nm was formed by a sputtering method was subjected to surface treatment by ozone UV treatment. Poly (3,4-ethylenedioxythiophene) (Poly (3,4-ethylenedioxythiophene)) and poly (4-styrenesulfonate) (PEDOT: PSS) (manufactured by HCStarck, AI4093) was applied on the ITO film by spin coating so as to have a thickness of about 60 nm, and heated on a hot plate at 200 ° C. for 10 minutes in the air to form a PEDOT: PSS layer. .
  • Poly (3,4-ethylenedioxythiophene) Poly (3,4-ethylenedioxythiophene)
  • PEDOT: PSS poly (4-styrenesulfonate
  • an orthodichlorobenzene solution containing the polymer compound P2 was applied onto the PEDOT: PSS layer by spin coating to form an active layer.
  • the thickness of the active layer was about 20 nm.
  • C 60 fullerene is vapor-deposited on the active layer with a thickness of 20 nm using a vacuum vapor deposition machine, then lithium fluoride is vapor-deposited with a thickness of 4 nm, and aluminum (Al) is further deposited with a thickness of 100 nm.
  • the organic thin film solar cell was produced by vapor deposition.
  • the shape of the obtained organic thin film solar cell was a square of 2 mm ⁇ 2 mm.
  • the obtained organic thin-film solar cell is irradiated with light having a wavelength of 300 to 1200 nm using an IPCE measuring device (trade name: CEP-2000 type spectral sensitivity measuring device manufactured by Spectrometer Co., Ltd.), and the spectral sensitivity for each wavelength is measured. did.
  • IPCE measuring device trade name: CEP-2000 type spectral sensitivity measuring device manufactured by Spectrometer Co., Ltd.
  • the absorbance of the active layer was 0.024 at a wavelength of 750 nm.
  • Measurement example 1 (Production and evaluation of thin films) A thin film of polymer compound P2 is formed on a glass substrate, and the absorption spectrum of the thin film of polymer compound P2 is measured using an ultraviolet-visible near-infrared spectrophotometer (JASCO Corporation, trade name: Jasco V-670). It was measured. As a result, the absorption spectrum of the thin film of the polymer compound P2 showed the maximum value on the lowest energy side at a wavelength of 490 nm.
  • JASCO Corporation ultraviolet-visible near-infrared spectrophotometer
  • Example 4 (Production and evaluation of organic thin-film solar cells) An organic thin film solar cell was prepared and evaluated in the same manner as in Example 3 except that the polymer compound P3 was used instead of the polymer compound P2. As a result, it was confirmed that when the light having a wavelength of 750 nm was irradiated, the spectral sensitivity was recognized and the power generation was performed. The absorbance of the active layer was 0.023 at a wavelength of 750 nm.
  • Measurement example 2 (Production and evaluation of thin films) A thin film of the polymer compound P3 is formed on a glass substrate, and the absorption spectrum of the thin film of the polymer compound P3 is measured using an ultraviolet-visible-near infrared spectrophotometer (JASCO Corporation, trade name: Jasco V-670). It was measured. As a result, the absorption spectrum of the thin film of the polymer compound P3 showed the maximum value on the lowest energy side at a wavelength of 745 nm.
  • JASCO Corporation ultraviolet-visible-near infrared spectrophotometer
  • Comparative Example 3 (Production and evaluation of organic thin-film solar cells) An organic thin film solar cell was prepared and evaluated in the same manner as in Example 3 except that the polymer compound P1 was used instead of the polymer compound P2. As a result, no spectral sensitivity was observed when light having a wavelength of 750 nm was irradiated. The absorbance of the active layer was 0.014 at a wavelength of 750 nm.
  • Measurement example 3 (Production and evaluation of thin films) A thin film of the polymer compound P1 is formed on a glass substrate, and the absorption spectrum of the thin film of the polymer compound P1 is measured using an ultraviolet-visible near-infrared spectrophotometer (JASCO Corporation, trade name: Jasco V-670). It was measured. As a result, the absorption spectrum of the thin film of the polymer compound P1 showed the maximum value on the lowest energy side at a wavelength of 385 nm.
  • JASCO Corporation ultraviolet-visible near-infrared spectrophotometer
  • Example 5 (Production and evaluation of organic thin-film solar cells) A glass substrate on which an ITO film having a thickness of 150 nm was formed by a sputtering method was subjected to surface treatment by ozone UV treatment. Poly (3,4-ethylenedioxythiophene) (Poly (3,4-ethylenedioxythiophene)) and poly (4-styrenesulfonate) (PEDOT: PSS) (manufactured by HCStarck, AI4093) was applied and formed on the ITO film by spin coating so as to have a thickness of about 60 nm, and heated in the air on a hot plate at 200 ° C. for 10 minutes to form a PEDOT: PSS layer.
  • PEDOT poly (4-styrenesulfonate
  • an orthodichlorobenzene solution containing the polymer compound P2 and [6,6] phenyl-C 61 butyric acid methyl ester (C 60 PCBM) (phenyl C 61 -butyric acid methyl ester, manufactured by Frontier Carbon Co.) which is a fullerene derivative was prepared.
  • the weight ratio of the polymer compound P2 to C 60 PCBM was 1/3.
  • the total of the weight of C 60 PCBM and the weight of the polymer compound P2 was 2% by weight with respect to the weight of the orthodichlorobenzene solution.
  • An orthodichlorobenzene solution was applied onto the PEDOT: PSS layer by spin coating to form an active layer.
  • the thickness of the active layer was about 100 nm.
  • lithium fluoride was deposited on the active layer with a thickness of 4 nm by a vacuum deposition machine, and then Al was deposited with a thickness of 70 nm to produce an organic thin film solar cell.
  • the shape of the obtained organic thin film solar cell was a square of 2 mm ⁇ 2 mm.
  • the obtained organic thin-film solar cell was irradiated with a certain amount of light using a solar simulator (spectrometer Co., Ltd., trade name: CEP-2000 type spectral sensitivity measuring device, AM1.5G filter, irradiance 100 mW / cm 2 ). It was confirmed that it was generating electricity.
  • Example 6 (Production and evaluation of organic thin-film solar cells) An organic thin film solar cell was prepared and evaluated in the same manner as in Example 5 except that the polymer compound P3 was used instead of the polymer compound P2. When the obtained organic thin film solar cell was irradiated with a certain amount of light using a solar simulator (spectrometer Co., Ltd., trade name CEP-2000 type spectral sensitivity measuring device, AM1.5G filter, irradiance 100 mW / cm 2 ), It was confirmed that it was generating electricity.
  • a solar simulator spectrometer Co., Ltd., trade name CEP-2000 type spectral sensitivity measuring device, AM1.5G filter, irradiance 100 mW / cm 2

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Abstract

L'invention porte sur un procédé par lequel de composés de masse moléculaire élevée ayant des groupes cyano peuvent être produits avec des rendements de production accrus. Le procédé comprend la réaction d'un composé de masse moléculaire élevée ayant des motifs de structure représentés par la formule (I) avec un composé représenté par la formule (II) ou la formule générale (III)/[dans laquelle Ar3 représente un groupe organique tétravalent] sous irradiation par des micro-ondes pour former un composé de masse moléculaire élevée ayant des motifs de structure représentés par la formule (IV)/[dans laquelle A1 et A2/représentent chacun indépendamment =C(CN)2 ou un groupe représenté par la formule (V) [dans laquelle Ar3 représente un groupe organique tétravalent]].
PCT/JP2011/063595 2010-06-17 2011-06-14 Procédé pour la production de composés de masse moléculaire élevée Ceased WO2011158831A1 (fr)

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* Cited by examiner, † Cited by third party
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WO2012102061A1 (fr) * 2011-01-28 2012-08-02 国立大学法人東京工業大学 Procédé de synthèse d'un composé, d'un composé polymère et d'un composé cyclique

Families Citing this family (1)

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Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
BRUCE, M.I. ET AL.: "Synthesis and Some Reactions of the Heterometallic C7 Complex {Cp* (dppe)Ru}C=CC=CC=CC{Co3 (p-dppm) (CO) }", ORGANOMETALLICS, vol. 27, no. 14, 2008, pages 3352 - 3367 *
BUTLER, P. ET AL.: "The reactions of some o- alkynylnickel complexes with 7,7,8,8- tetracyanoquinodimethane", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 693, no. 3, 2008, pages 381 - 392 *
KIVALA, M. ET AL.: "Organic Super-Acceptors with Efficient Intramolecular Charge-Transfer Interactions by [2+2] Cycloadditions of TCNE, TCNQ, and F4-TCNQ to Donor-Substituted Cyanoalkynes", CHEMISTRY--A EUROPEAN JOURNAL, vol. 15, no. 16, 2009, pages 4111 - 4123, S4111/1- S4111/31 *
MICHINOBU, T. ET AL.: "One-Step Synthesis of Donor-Acceptor type Conjugated Polymers from Ferrocene-Containing Poly(aryleneethynylene)s", MACROMOLECULES, vol. 42, no. 16, 2009, pages 5903 - 5905 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012102061A1 (fr) * 2011-01-28 2012-08-02 国立大学法人東京工業大学 Procédé de synthèse d'un composé, d'un composé polymère et d'un composé cyclique
JP5411995B2 (ja) * 2011-01-28 2014-02-12 国立大学法人東京工業大学 化合物合成方法、高分子化合物および環状化合物

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