JP2014028912A - Polymer compound and organic photoelectric conversion element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic photoelectric conversion element capable of giving a high open-circuit voltage.SOLUTION: A polymer compound contains a repeating unit represented by formula (A) and a repeating unit containing a specific thiophene derivative. [In the formula (A), a plurality of R's are each a hydrogen atom, a fluorine atom, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, or a specific ester-containing group.]

Description

  The present invention relates to a polymer compound and an organic photoelectric conversion device using the same.

  In recent years, organic photoelectric conversion elements (organic solar cells, optical sensors, etc.) have been actively developed. An organic semiconductor material is used for the active layer of the organic photoelectric conversion element. If a composition containing a polymer compound is used as the organic semiconductor material, the active layer can be formed by a coating method. If the active layer can be formed by a coating method, the cost of the device can be reduced. Therefore, various compositions applicable to the active layer have been studied. For example, an organic solar cell including an active layer in which a composition containing poly-3-hexylthiophene as a conjugated polymer compound and C60PCBM as a fullerene derivative is formed by a coating method has been proposed (for example, see Non-Patent Document 1). ).

Advanced Functional Materials, 2003, Vol. 13, p. 85

  However, the organic photoelectric conversion element has a problem that an open circuit voltage (Voc) is not always sufficient.

  Then, an object of this invention is to provide the organic photoelectric conversion element which can provide a high open end voltage.

〔式（Ａ）、式（Ｂ１）〜（Ｂ６）中、複数個あるＲは、それぞれ、水素原子、フッ素原子、アルキル基、アルコキシ基、アリール基、ヘテロアリール基又は式（２）で表される基を表す。これらの基に含まれる水素原子はフッ素原子で置換されていてもよい。複数個あるＲは、同一でも相異なっていてもよい。

（２）
（式（２）中、ｍ１は、０〜６の整数を表し、ｍ２は、０〜６の整数を表す。Ｒ’は、アルキル基、アリール基又はヘテロアリール基を表す。）〕 That is, the present invention firstly provides a polymer compound comprising a repeating unit represented by the following formula (A) and at least one repeating unit of the repeating units represented by the following formulas (B1) to (B6). I will provide a.

[In Formula (A) and Formula (B1) to (B6), a plurality of R's are each represented by a hydrogen atom, a fluorine atom, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, or Formula (2). Represents a group. The hydrogen atom contained in these groups may be substituted with a fluorine atom. A plurality of R may be the same or different.

(2)
(In formula (2), m1 represents an integer of 0 to 6, m2 represents an integer of 0 to 6. R ′ represents an alkyl group, an aryl group, or a heteroaryl group.)]

〔式（１ａ）〜（１ｆ）中、複数個あるＲは、それぞれ、水素原子、フッ素原子、アルキル基、アルコキシ基、アリール基、ヘテロアリール基又は式（２）で表される基を表す。これらの基に含まれる水素原子はフッ素原子で置換されていてもよい。複数個あるＲは、同一でも相異なっていてもよい。

（２）
（式（２）中、ｍ１は、０〜６の整数を表し、ｍ２は、０〜６の整数を表す。Ｒ’は、アルキル基、アリール基又はヘテロアリール基を表す。）〕 The high molecular compound containing the at least 1 repeating unit of the repeating units represented by following formula (1a)-(1f).

[In formulas (1a) to (1f), a plurality of Rs each represent a hydrogen atom, a fluorine atom, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, or a group represented by formula (2). The hydrogen atom contained in these groups may be substituted with a fluorine atom. A plurality of R may be the same or different.

(2)
(In formula (2), m1 represents an integer of 0 to 6, m2 represents an integer of 0 to 6. R ′ represents an alkyl group, an aryl group, or a heteroaryl group.)]

  Thirdly, the present invention provides an organic photoelectric conversion element 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.

  The polymer compound of the present invention is extremely useful because it exhibits deep HOMO energy and a high open-circuit voltage (Voc).

  Hereinafter, the present invention will be described in detail.

〔式（Ａ）、式（Ｂ１）〜（Ｂ６）中、複数個あるＲは、それぞれ、水素原子、フッ素原子、アルキル基、アルコキシ基、アリール基、ヘテロアリール基又は式（２）で表される基を表す。これらの基に含まれる水素原子はフッ素原子で置換されていてもよい。複数個あるＲは、同一でも相異なっていてもよい。

（２）
（式（２）中、ｍ１は、０〜６の整数を表し、ｍ２は、０〜６の整数を表す。Ｒ’は、アルキル基、アリール基又はヘテロアリール基を表す。）〕 <Polymer compound>
The polymer compound of the present invention includes a repeating unit represented by the following formula (A) and at least one repeating unit of repeating units represented by the following formulas (B1) to (B6).

[In Formula (A) and Formula (B1) to (B6), a plurality of R's are each represented by a hydrogen atom, a fluorine atom, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, or Formula (2). Represents a group. The hydrogen atom contained in these groups may be substituted with a fluorine atom. A plurality of R may be the same or different.

(2)
(In formula (2), m1 represents an integer of 0 to 6, m2 represents an integer of 0 to 6. R ′ represents an alkyl group, an aryl group, or a heteroaryl group.)]

  Examples of the alkyl group represented by R include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n- Examples include a pentyl group, n-hexyl group, n-octyl group, iso-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, and n-octadecyl group. A hydrogen atom in the alkyl group may be substituted with a fluorine atom. Examples of the alkyl group in which a hydrogen atom is substituted with a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.

  Examples of the alkoxy group represented by R include methoxy group, ethoxy group, propoxy group, iso-propoxy group, butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy Group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group. A hydrogen atom in the alkoxy group may be substituted with a fluorine atom. Examples of the alkoxy group in which a hydrogen atom is substituted with a fluorine atom include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyl group, and a perfluorooctyl group.

  The aryl group represented by R is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. The aryl group includes a group containing a benzene ring, a group containing a condensed ring having aromaticity, a group having a structure in which two or more benzene rings or a condensed ring having aromaticity are directly bonded, and two or more benzenes Examples include a group in which a ring or an aromatic condensed ring is bonded via a group such as vinylene. The aryl group preferably has 6 to 60 carbon atoms, more preferably 6 to 30 carbon atoms. A hydrogen atom in the aryl group may be substituted with a fluorine atom. The aryl group may have a substituent. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Examples of the substituent that the aryl group may have include a halogen atom, an alkyl group, and an alkoxy group.

  Examples of the heteroaryl group represented by R include a chenyl group, a pyrrolyl group, a furyl group, a pyridyl group, a quinolyl group, and an isoquinolyl group. The heteroaryl group may have a substituent. Examples of the substituent that the heteroaryl group may have include a halogen atom, an alkyl group, and an alkoxy group. For example, the hydrogen atom in the heteroaryl group may be substituted with a fluorine atom.

  In the group represented by the formula (2), m1 represents an integer of 0 to 6, and m2 represents an integer of 0 to 6. R 'represents an alkyl group, an aryl group or a heteroaryl group. The definition of the alkyl group, aryl group and heteroaryl group represented by R ′, and specific examples thereof are the same as the definition of the alkyl group, aryl group and heteroaryl group represented by R, and specific examples thereof. The hydrogen atom in the group represented by the formula (2) may be substituted with a fluorine atom.

  When R is an alkyl group or an alkoxy group, from the viewpoint of solubility of the polymer compound in a solvent, the alkyl group or alkoxy group preferably has 1 to 20 carbon atoms, and preferably 2 to 18 carbon atoms. Is more preferable, and it is further more preferable that it is 3-12.

Examples of the repeating unit represented by the formula (A) include the following repeating units.

Examples of the repeating unit represented by the formula (B1) include the following repeating units.

Examples of the compound represented by the formula (B2) include the following compounds.

Examples of the compound represented by the formula (B3) include the following compounds.

Examples of the compound represented by the formula (B4) include the following compounds.

Examples of the compound represented by the formula (B5) include the following compounds.

Examples of the compound represented by the formula (B6) include the following compounds.

  The total amount of the repeating unit represented by the formula (A) and the repeating unit represented by the formulas (B1) to (B6) contained in the polymer compound of the present invention is the functional layer containing the polymer compound. From the viewpoint of increasing the photoelectric conversion efficiency of the organic photoelectric conversion element, it is preferably 20 to 100 mol%, preferably 30 to 100 mol%, based on the total amount of repeating units contained in the polymer compound. Is more preferable.

〔式（１ａ）〜（１ｆ）中、Ｒは、前述と同じ意味を表す。〕 Another embodiment of the polymer compound of the present invention is a polymer compound containing at least one repeating unit among the repeating units represented by formulas (1a) to (1f).

[In formulas (1a) to (1f), R represents the same meaning as described above. ]

Examples of the repeating unit represented by the formula (1a) include the following repeating units.

Examples of the repeating unit represented by the formula (1b) include the following repeating units.

Examples of the repeating unit represented by the formula (1c) include the following repeating units.

Examples of the repeating unit represented by the formula (1d) include the following repeating units.

Examples of the repeating unit represented by the formula (1e) include the following repeating units.

Examples of the repeating unit represented by the formula (1f) include the following repeating units.

  The amount of the repeating unit represented by the formulas (1a) to (1f) contained in the polymer compound of the present invention is from the viewpoint of increasing the photoelectric conversion efficiency of the organic photoelectric conversion device having a functional layer containing the polymer compound. The amount of the repeating unit contained in the polymer compound is preferably 20 to 100 mol%, more preferably 30 to 100 mol%.

The weight average molecular weight in terms of polystyrene of the polymer compound of the present invention is preferably 10 ³ to 10 ⁸ , more preferably 10 ³ to 10 ⁷ , and still more preferably 10 ³ to 10 ⁶ .

  The polymer compound of the present invention is preferably a conjugated polymer compound. Here, the conjugated polymer compound means a compound in which atoms constituting the main chain of the polymer compound are substantially conjugated.

  The polymer compound of the present invention includes a repeating unit represented by the formula (A), a repeating unit represented by the formulas (B1) to (B6), and a repeating unit represented by the formulas (1a) to (1f). These repeating units may be included as a third repeating unit. 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 furandyl group, a pyrrole diyl group, a pyridinediyl group, a repeating unit represented by the formula (D-1) to the formula (D-11), and the like.

In formula (D-1) to formula (D-11), X represents a sulfur atom, an oxygen atom or a selenium atom. When there are a plurality of Xs, the plurality of Xs may be the same or different.

  In formula (D-1) to formula (D-11), R represents the same one as described above. When there are a plurality of Rs, the plurality of Rs may be the same or different.

<Method for producing polymer compound>
The polymer compound of the present invention may be produced by any method. For example, after synthesizing a monomer having a functional group suitable for the polymerization reaction to be used, the monomer is dissolved in an organic solvent, if necessary, , And can be synthesized by polymerization using a known aryl coupling reaction using a catalyst, a ligand and the like. The synthesis of the monomer can be performed, for example, with reference to the methods disclosed in JP-A Nos. 2006-182920 and 2006-335933.

  Examples of the polymerization by the aryl coupling reaction include polymerization by Stille coupling reaction, polymerization by Suzuki coupling reaction, polymerization by Yamamoto coupling reaction, and polymerization by Kumada-Tamao coupling reaction.

  Polymerization by Stille coupling reaction is necessary using palladium complexes such as palladium [tetrakis (triphenylphosphine)], [tris (dibenzylideneacetone)] dipalladium, palladium acetate, bis (triphenylphosphine) palladium dichloride as catalysts. Depending on the ligand, ligands such as triphenylphosphine, tri (2-methylphenyl) phosphine, tri (2-methoxyphenyl) phosphine, diphenylphosphinopropane, tri (cyclohexyl) phosphine, tri (tert-butyl) phosphine A monomer having an organotin residue and a monomer having a halogen atom such as a bromine atom, an iodine atom or a chlorine atom, or a sulfonate group such as a trifluoromethanesulfonate group or a p-toluenesulfonate group. This is a polymerization in which the monomer is reacted. The details of the polymerization by the Stille coupling reaction are described in, for example, Angewante Chemie International Edition, 2005, Vol. 44, p. 4442-4489.

  Polymerization by Suzuki coupling reaction uses a palladium complex or nickel complex as a catalyst in the presence of an inorganic base or an organic base, and adds a ligand as necessary to have a boronic acid residue or a boronic acid ester residue. This is a polymerization in which a monomer is reacted with a monomer having a halogen atom such as a bromine atom, an iodine atom or a chlorine atom, or a monomer having a sulfonate group such as a trifluoromethanesulfonate group or a p-toluenesulfonate group.

  Examples of the inorganic base include sodium carbonate, potassium carbonate, cesium carbonate, tripotassium phosphate, and potassium fluoride. Examples of the organic base include tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, and tetraethylammonium hydroxide. Examples of the palladium complex include palladium [tetrakis (triphenylphosphine)], [tris (dibenzylideneacetone)] dipalladium, palladium acetate, and bis (triphenylphosphine) palladium dichloride. Examples of the nickel complex include bis (cyclooctadiene) nickel. Examples of the ligand include triphenylphosphine, tri (2-methylphenyl) phosphine, tri (2-methoxyphenyl) phosphine, diphenylphosphinopropane, tri (cyclohexyl) phosphine, and tri (tert-butyl) phosphine. It is done.

  Details of the polymerization by the Suzuki coupling reaction are described in, for example, Journal of Polymer Science: Part A: Polymer Chemistry (Part A: Polymer Chemistry), 2001, Vol. 39, p. 1533-1556.

  Polymerization by Yamamoto coupling reaction uses a catalyst and a reducing agent to react monomers having halogen atoms, monomers having sulfonate groups such as trifluoromethanesulfonate groups, or monomers having halogen atoms and monomers having sulfonate groups. Polymerization.

  Catalysts include nickel zero-valent complexes such as bis (cyclooctadiene) nickel and ligands such as bipyridyl, [bis (diphenylphosphino) ethane] nickel dichloride, [bis (diphenylphosphino) propane] nickel. A catalyst comprising a nickel complex other than a nickel zero-valent complex such as dichloride and a ligand such as triphenylphosphine, diphenylphosphinopropane, tri (cyclohexyl) phosphine, tri (tert-butyl) phosphine, if necessary. . Examples of the reducing agent include zinc and magnesium. Polymerization by the Yamamoto coupling reaction may be performed using a dehydrated solvent in the reaction, may be performed in an inert atmosphere, or may be performed by adding a dehydrating agent to the reaction system.

  Details of the polymerization by Yamamoto coupling are described in, for example, Macromolecules, 1992, Vol. 25, p. 1214-1223.

  Polymerization by Kumada-Tamao coupling reaction uses a nickel catalyst such as [bis (diphenylphosphino) ethane] nickel dichloride, [bis (diphenylphosphino) propane] nickel dichloride, and a compound having a magnesium halide group and a halogen atom. Polymerization to react with the compound having For the reaction, a dehydrated solvent may be used for the reaction, the reaction may be performed in an inert atmosphere, or a dehydrating agent may be added to the reaction system.

  In the polymerization by the aryl coupling reaction, a solvent is usually used. The 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 Examples thereof include a solvent having two phases of a phase and an aqueous phase. The solvent used in the Stille coupling reaction is preferably an organic solvent such as tetrahydrofuran, toluene, N, N-dimethylformamide, a mixed solvent obtained by mixing two or more of these solvents, or a solvent having two phases of an organic solvent phase and an aqueous phase. The solvent used for the Stille coupling reaction is preferably deoxygenated before the reaction in order to suppress side reactions. 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 and a solvent having two phases of an organic solvent phase and an aqueous phase are preferred. The solvent used for the Suzuki coupling reaction is preferably deoxygenated before the reaction in order to suppress side reactions. The solvent used for the Yamamoto coupling reaction is an organic solvent such as tetrahydrofuran, toluene, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, or a mixed solvent in which two or more of these solvents are mixed. A solvent is preferred. The solvent used for the Yamamoto coupling reaction is preferably deoxygenated before the reaction in order to suppress side reactions.

  Among the polymerizations by the aryl coupling reaction, from the viewpoint of reactivity, a method of polymerizing by a Stille coupling reaction, a method of polymerizing by a Suzuki coupling reaction, a method of polymerizing by a Yamamoto coupling reaction are preferable, and a Stille coupling reaction More preferred are a method of polymerizing, a method of polymerizing by a Suzuki coupling reaction, and a method of polymerizing by a Yamamoto coupling reaction using a nickel zero-valent complex.

  The lower limit of the reaction temperature of the aryl coupling reaction 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.

  In the polymerization by the aryl coupling reaction, a known method can be used as a method for removing the polymer compound of the present invention from the reaction solution after completion of the reaction. For example, the polymer compound of the present invention can be obtained by adding a reaction solution to a lower alcohol such as methanol, filtering the deposited precipitate, and drying the filtrate. When the purity of the obtained polymer compound is low, it can be purified by recrystallization, continuous extraction with a Soxhlet extractor, column chromatography, or the like.

  When the polymer compound of the present invention is used for the production of an organic photoelectric conversion element, if a polymerization active group remains at the terminal of the polymer compound, characteristics such as durability of the 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. Examples of the arylamino group include a phenylamino group and a diphenylamino group.
Examples of the monovalent heterocyclic group include thienyl group, pyrrolyl group, furyl group, pyridyl group, quinolyl group, and isoquinolyl group. Further, the polymerization active group remaining at the terminal of the polymer compound may be replaced with a hydrogen atom instead of a stable group. From the viewpoint of enhancing hole transportability, it is preferable that the stable group for protecting the terminal is a group imparting electron donating properties such as an arylamino group. When the polymer compound is a conjugated polymer compound, the end of a group having a conjugated bond in which the conjugated structure of the main chain of the polymer compound and the conjugated structure of a stable group protecting the end are continuous is also protected. It can preferably be used as a stable group. Examples of the group include an aryl group and a monovalent heterocyclic group having aromaticity.

  In the present invention, the HOMO energy and the excitation energy from the ground state to the lowest excited singlet state of the polymer compound composed of the repeating units represented by the formulas (1a) to (1f) are calculated as follows. As a calculation model structure, a calculation model structure in which the number n of repeating units represented by the formulas (1a) to (1f) is one, two connected calculation model structures, and three connected calculation model structures are created. Hydrogen atoms are bonded to the linking groups at both ends of each calculation model structure. Next, a structure optimization calculation is performed on each calculation model structure by a density functional method to obtain a stable structure. The B3LYP method is used for the functional and 3-21G * is used for the basis function. Further, the excitation energy from the ground state to the lowest excited singlet state is calculated by the time-dependent density functional method for the structure obtained by the structure optimization calculation. At that time, B3LYP is used as the functional and 3-21G * is used as the basis function. The calculation program uses Gaussian09 (manufactured by Gaussian Inc.), but other programs may be used as long as they are equivalent methods. The HOMO energy of each calculation model structure is plotted with the reciprocal 1 / n of each calculation model structure as the horizontal axis and the HOMO energy as the vertical axis. A straight line is drawn between the three plotted points by the least square method, the straight line is extrapolated, and the value when 1 / n is 0 is defined as the HOMO energy of the polymer compound. Similarly, the excitation energy from the ground state of each calculation model structure to the lowest singlet state is plotted with the reciprocal 1 / n of each calculation model structure as the horizontal axis and the excitation energy as the vertical axis. A straight line is drawn between the three plotted points by the least square method, the line is extrapolated, and the value when 1 / n is 0 is the excitation energy from the ground state of the polymer compound to the lowest excited singlet state. And

For example, when the polymer compound is composed of a repeating unit represented by the formula (C), the HOMO energy of the compound represented by the formula (C-1), the HOMO energy of the compound represented by the formula (C-2), And the HOMO energy of the compound represented by Formula (C-3) is calculated. Next, the horizontal axis is a value represented by 1 / n, the vertical axis is HOMO energy, and the coordinate of the horizontal axis is represented by 1 / n of the compound represented by the formula (C-1). 1st point which is a value and the coordinate of a vertical axis | shaft is the HOMO energy of the compound represented by Formula (C-1), and the coordinate of a horizontal axis is 1 / n of the compound represented by Formula (C-2) A second point that is the HOMO energy of the compound represented by the formula (C-2), and the coordinate of the horizontal axis is represented by the formula (C-3). The third point is a value represented by 1 / n of the compound and the coordinate of the vertical axis is the HOMO energy of the compound represented by the formula (C-3). And an approximate straight line connecting the third point and the third point are calculated by the method of least squares. In the table, the coordinate of the vertical axis of the intersection of the straight line having a value of 1 / n of 0 and the approximate straight line is the HOMO energy of the polymer compound containing the repeating unit represented by the formula (C).
-Ar ³ - ^{H-Ar 3} -H
(C) (C-1)
^{H-Ar 3 -Ar 3 -H H} -Ar 3 -Ar 3 -Ar 3 -H
(C-2) (C-3)
Wherein, Ar ³ represents a divalent organic group containing a structural unit represented by the formula (1a) ~ (1f). H represents a hydrogen atom. ]

（４）

（５）
（式（４）、（５）中、Ｒは、前述と同じ意味を表す。Ｚは、ボロン酸、ボロン酸エステル残基を表す。２個あるＺは、同一でも相異なっていてもよい。） In the polymer compound of the present invention, the polymer compound containing the repeating unit represented by the formula (1a) is obtained by polymerizing, for example, a compound represented by the formula (4) and a compound represented by the formula (5). Can be manufactured. Examples of the polymerization reaction include a Suzuki coupling reaction.

(4)

(5)
(In formulas (4) and (5), R represents the same meaning as described above. Z represents a boronic acid or boronic ester residue. The two Zs may be the same or different. )

（式中、Ｍｅはメチル基を表し、Ｅｔはエチル基を表す。） In formula (4), the boronic ester residue represented by Z represents a group in which one hydrogen atom has been removed from the boronic ester, and specific examples thereof include groups represented by the following formula.

(In the formula, Me represents a methyl group, and Et represents an ethyl group.)

As a compound represented by Formula (4), the following compounds are mentioned, for example.

（６）
（式（６）中、Ｒは、前述と同じ意味を表す。） The compound represented by the formula (4) can be produced by reacting the compound represented by the formula (6) with diboronic acid or diboronic acid ester in an organic solvent.

(6)
(In formula (6), R represents the same meaning as described above.)

The diboronic acid or diboronic acid ester to be reacted with the compound represented by the formula (6) is preferably a diboronic acid ester from the viewpoint of reactivity. Examples of the diboronic acid ester include the following structures (D-1) to (D-6).

  The diboronic acid ester is preferably (D-1) or (D-3), and particularly preferably (D-3). The amount of diboronic acid or diboronic acid ester used is usually 2 molar equivalents (hereinafter, the molar equivalents are simply referred to as equivalents) to 10 equivalents relative to the compound represented by formula (6), preferably 2 to 4 equivalents, more preferably 2 to 3 equivalents.

  The reaction of the compound represented by the formula (6) with diboronic acid or diboronic acid ester is usually carried out in an organic solvent. Examples of the organic solvent include aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ether solvents, Examples thereof include halogen-based solvents and aprotic polar solvents. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, cumene and the like. Examples of the aliphatic hydrocarbon solvent include hexane, octane, decane and the like. Examples of ether solvents include diethyl ether, dibutyl ether, dimethoxyethane, tetrahydrofuran, 1,4-dioxane and the like. Examples of the halogen solvent include dichloromethane, chloroform, chlorobenzene, dichlorobenzene and the like. Examples of the aprotic polar solvent include N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and the like. The solvent is preferably an aromatic hydrocarbon solvent or an ether solvent, and more preferably an ether solvent. Of the ether solvents, tetrahydrofuran and 1,4-dioxane are preferable, and 1,4-dioxane is more preferable.

  The reaction between the compound represented by formula (6) and diboronic acid or diboronic acid ester is preferably performed in the presence of a catalyst. Examples of the catalyst include a palladium catalyst, a rhodium catalyst, a ruthenium catalyst, and a platinum catalyst, and among them, a palladium catalyst is preferable. Examples of the palladium catalyst include a Pd (0) catalyst and a Pd (II) catalyst. Specifically, palladium [tetrakis (triphenylphosphine)], palladium acetates, dichlorobis (triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium, dichlorobis (diphenyl) Phosphinoferrocene) palladium, and dichlorobis (diphenylphosphinoferrocene) palladium is preferred from the viewpoint of ease of reaction operation and reaction rate. The addition amount of the palladium catalyst is not particularly limited as long as it is an effective amount as a catalyst, but is usually 0.0001 mol to 0.5 mol, preferably 0.0003 mol, relative to 1 mol of the compound represented by the formula (6). ~ 0.2 mol. In the reaction, a ligand can be used as necessary. Examples of the ligand include triphenylphosphine, tri (o-tolyl) phosphine, tri (o-methoxyphenyl) phosphine, tris (2-furyl) phosphine, 1,1′-bis (diphenylphosphino) ferrocene, and the like. And arsenic compounds such as triphenylarsine and triphenoxyarsine. The ligand is preferably 1,1'-bis (diphenylphosphino) ferrocene. When using a ligand, the addition amount of the ligand is usually 0.5 mol to 100 mol, preferably 0.9 mol to 20 mol, more preferably 1 mol to 10 mol, relative to 1 mol of the palladium catalyst. is there.

  The temperature at which the compound represented by formula (6) is reacted with diboronic acid or diboronic acid ester is usually about 50 to 160 ° C, preferably 60 to 120 ° C, although it depends on the solvent. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed. The time for performing the reaction (reaction time) is usually about 0.1 to 200 hours, although it may be analyzed by high performance liquid chromatography or the like and the target conversion rate may be reached as an end point. About 1 to 30 hours is efficient and preferable.

  The compound represented by formula (6) is, for example, Macromolecules, 2009, Vol. 42, No. 17, p. It can be synthesized using the method described in 6564-6571 (Macromolecules, 42 (17), 6564 (2009)).

  The compound represented by Formula (5) is compoundable using the method of publication patent publication 2010-5001030, for example.

（式（７）、（８）、式（９）、式（１０）、式（１１）中、Ｒは前述と同じ意味を表す。複数あるＲは、同一でも相異なっていてもよい。） Similarly, polymer compounds containing repeating units represented by formulas (1b), (1c), (1d), (1e), and (1f) are represented by formulas (7), (8), and (9), respectively. The compound represented by Formula (10) and Formula (11) and the compound represented by Formula (5) can be polymerized and produced. Examples of the polymerization reaction include a Suzuki coupling reaction.

(In formulas (7), (8), (9), (10), and (11), R represents the same meaning as described above. Multiple Rs may be the same or different.)

<Organic photoelectric conversion element>
The polymer compound of the present invention has a deep HOMO and can provide a large open-circuit voltage. Moreover, since the absorption wavelength is a long wavelength, a high short-circuit current density can be obtained.

The organic photoelectric conversion device of the present invention has a pair of electrodes and a functional layer between the electrodes, and the functional layer contains the electron-accepting compound and the polymer compound of the present invention. As the electron-accepting compound, fullerenes and fullerene derivatives are preferable. As a specific example of 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 the polymer compound of the present invention;
2. An organic photoelectric conversion element comprising a pair of electrodes and a functional layer between the electrodes, the functional layer containing an electron-accepting compound and the polymer compound of the present invention, wherein the electron-accepting compound is a fullerene An organic photoelectric conversion element which is a derivative;
Is mentioned. In general, at least one of the pair of electrodes is transparent or translucent. Hereinafter, this case will be described as an example.

  1 above. In the organic photoelectric conversion element, the amount 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. Is preferable, and it is more preferable that it is 20-500 weight part. In addition, 2. In the organic photoelectric conversion element, the amount of the fullerene derivative in the functional layer containing the fullerene derivative and the polymer compound is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the polymer. More preferably, it is 500 parts by weight. From the viewpoint of increasing the photoelectric conversion efficiency, the amount of the fullerene derivative in the functional layer is preferably 20 to 400 parts by weight and more preferably 40 to 250 parts by weight with respect to 100 parts by weight of the polymer. Preferably, it is 80 to 120 parts by weight. From the viewpoint of increasing the short-circuit current density, the amount of the fullerene derivative in the functional layer is preferably 20 to 250 parts by weight and more preferably 40 to 120 parts by weight with respect to 100 parts by weight of the polymer. preferable.

  In order for the organic photoelectric conversion element to have high photoelectric conversion efficiency, the electron-accepting compound and the polymer compound of the present invention have an absorption region that can efficiently absorb the spectrum of desired incident light. It is important that the heterojunction interface includes many heterojunction interfaces in order to efficiently separate excitons, and that the heterojunction interface has a charge transporting property for quickly transporting charges generated by the heterojunction interface to the electrode.

  From such a viewpoint, as the organic photoelectric conversion element, the above 1. , 2. From the standpoint of including a large number of heterojunction interfaces, the organic photoelectric conversion element is preferable. The organic photoelectric conversion element is more preferable. Further, in the organic photoelectric conversion element of the present invention, an additional layer may be provided between at least one electrode and the functional layer in the element. Examples of the additional layer include a charge transport layer that transports holes or electrons, and a buffer layer.

  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.

  As a material for the pair of electrodes, a metal, a conductive polymer, or the like can be used. The material of one of the pair of electrodes is preferably a material having a low work function. For example, 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 of two or more of these metals, or one or more of those metals and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin An alloy with metal, graphite, a graphite intercalation compound, or the like is used. Examples of 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.

  Examples of 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. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode material.

  As 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. In addition, fine particles of an inorganic semiconductor such as titanium oxide can be used.

<Organic thin film>
Examples of the functional layer in the organic photoelectric conversion device of the present invention include at least one repeating unit selected from the repeating unit represented by the formula (A) and the repeating units represented by the formulas (B1) to (B6). The organic thin film containing the high molecular compound which has these, and an electron-accepting compound can be used.

  The organic thin film has a thickness of usually 1 nm to 100 μm, 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 polymer compound alone or in combination of two or more. Moreover, in order to improve the hole transport property of the organic thin film, a low molecular compound and / or a high molecular compound other than the high molecular compound can be mixed and used as the electron donating compound in the organic thin film.

  An electron that the organic thin film may contain in addition to the polymer compound having the repeating unit represented by the formula (A) and at least one repeating unit of the repeating units represented by the formulas (B1) to (B6) Examples of the donor 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. And polysiloxane derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, and polythienylene vinylene and derivatives thereof.

Examples of the electron-accepting compound include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinones 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.

Examples of fullerenes include C ₆₀ , C ₇₀ , and C ₈₄ , and examples of fullerene derivatives include derivatives such as C ₆₀ , C ₇₀ , and C ₈₄ . The fullerene derivative represents a compound in which at least a part of fullerenes is modified.

（Ｉ） （ＩＩ） （ＩＩＩ） （ＩＶ）
（式（Ｉ）〜（ＩＶ）中、Ｒ^ａは、アルキル基、アリール基、ヘテロアリール基又はエステル構造を有する基である。複数個あるＲ^ａは、同一であっても相異なってもよい。Ｒ^ｂはアルキル基又はアリール基を表す。複数個あるＲ^ｂは、同一であっても相異なってもよい。） Examples of the derivatives of fullerenes include compounds represented by formula (I), compounds represented by formula (II), compounds represented by formula (III), and compounds represented by formula (IV). It is done.

(I) (II) (III) (IV)
(In formulas (I) to (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, aryl group and heteroaryl group represented by R ^a and R ^b are the same as the definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R.

（Ｖ）
（式（Ｖ）中、ｕ１は、１〜６の整数を表す、ｕ２は、０〜６の整数を表す、Ｒ^ｃは、アルキル基、アリール基又はヘテロアリール基を表す。） Examples of the group having an ester structure represented by ^Ra include a group represented by the formula (V).

(V)
(In formula (V), u1 represents an integer of 1 to 6, u2 represents an integer of 0 to 6, and 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.

Specific examples of the C ₆₀ derivative include the following.

Specific examples of the C ₇₀ derivative include the following.

<Method for producing organic thin film>
The organic thin film may be produced by any method. For example, the organic thin film may be produced by a film formation method from a solution containing the polymer compound of the present invention, or an organic thin film may be formed by a vacuum deposition method. Good. 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 of the present invention. Examples of the solvent include unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane. Halogenated saturated hydrocarbon solvents such as dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, and halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene Examples of the solvent include ether solvents such as tetrahydrofuran and tetrahydropyran. The polymer compound of the present invention can usually be dissolved in the solvent in an amount of 0.1% by weight or more.

  For film formation from solution, 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.

<Application of device>
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.

  Hereinafter, calculation examples will be shown to explain the present invention in more detail. By calculation, the HOMO energy of the polymer compound and the excitation energy from the ground state to the lowest excited singlet state were determined.

高分子化合物１ 最小の繰り返し単位 Calculation example 1
The polymer compound 1 has a minimum repeating unit represented by the following formula. As a calculation model structure, a calculation model structure having one repeating unit, two connected calculation model structures, and three connected calculation model structures were prepared. Hydrogen atoms were bonded to the linking groups at both ends of each calculation model structure. Next, the structure optimization calculation by the density functional method was performed on each calculation model structure to obtain a stable structure. B3LYP was used for the functional and 3-21G * was used for the basis function. Furthermore, the excitation energy from the ground state to the lowest excited singlet state was calculated for the structure obtained by the structure optimization calculation by the time-dependent density functional method. At that time, B3LYP was used as the functional, and 3-21G * was used as the basis function. As a calculation program, Gaussian09 (manufactured by Gaussian Inc.) was used. The reciprocal number of the repeating unit n of each calculation model structure, that is, 1 / n is plotted on the horizontal axis, and the HOMO energy is plotted on the vertical axis. A straight line was drawn between the three plotted points by the least square method, and the straight line was extrapolated. For the excitation energy from the ground state to the lowest excited singlet state, the excitation energy from the ground state to the lowest excited singlet state of each calculation model structure is plotted with 1 / n as the horizontal axis and the excitation energy as the vertical axis. . A straight line is drawn between the three plotted points by the least square method, the line is extrapolated, and the energy when 1 / n is 0 is expressed as the excitation energy from the ground state of polymer A to the lowest excited singlet state. It was. The HOMO energy of the polymer compound 1 was −4.91 (eV), and the excitation energy from the ground state to the lowest excited singlet state was 1.54 (eV).

Polymer compound 1 The smallest repeating unit

高分子化合物２ 最小の繰り返し単位 Calculation example 2
The polymer compound 2 has a minimum repeating unit represented by the following formula. In the same manner as in Calculation Example 1, the HOMO energy of the polymer compound 2 and the excitation energy from the ground state to the lowest excited singlet state were 1.76 (eV). Was calculated. The HOMO energy of the polymer compound 2 was 1.76 (eV) from the −5.07 (eV) ground state to the lowest excited singlet state.

Polymer 2 Minimum repeat unit

高分子化合物３ 最小の繰り返し単位 Calculation example 3
The polymer compound 3 has a minimum repeating unit represented by the following formula. In the same manner as in Calculation Example 1, the HOMO energy of the polymer compound 3 and the excitation energy from the ground state to the lowest excited singlet state were calculated. The HOMO energy of the polymer compound 3 was −4.70 (eV), and the excitation energy from the ground state to the lowest excited singlet state was 1.90 (eV).

Polymer 3 Minimum repeat unit

最小の繰り返し単位 Calculation example 4
The polymer compound 4 has a minimum repeating unit represented by the following formula. In the same manner as in Calculation Example 1, the HOMO energy of the polymer compound 4 and the excitation energy from the ground state to the lowest excited singlet state were calculated. The HOMO energy of the polymer compound 4 was −4.77 (eV), and the excitation energy from the ground state to the lowest excited singlet state was 1.61 (eV).

Smallest repeating unit

最小の繰り返し単位 Calculation example 5
The polymer compound 5 has the minimum repeating unit represented by the following formula. In the same manner as in Calculation Example 1, the HOMO energy of the polymer compound 5 and the excitation energy from the ground state to the lowest excited singlet state were calculated. The HOMO energy of the polymer compound 5 was −4.90 (eV), and the excitation energy from the ground state to the lowest excited singlet state was 1.76 (eV). Met.

Smallest repeating unit

最小の繰り返し単位 Calculation example 6
The polymer compound 6 has a minimum repeating unit represented by the following formula. In the same manner as in Calculation Example 1, the HOMO energy and the excitation energy from the ground state to the lowest excited singlet state of the polymer compound 6 were calculated. The HOMO energy of the polymer compound 6 was −4.55 (eV), and the excitation energy from the ground state to the lowest excited singlet state was 2.01 (eV). Met.

Smallest repeating unit

As shown in Calculation Examples 1 to 3, the polymer compound including the repeating unit represented by the formula (A) and the repeating unit represented by any one of the formulas (B1), (B2), and (B3) is The HOMO energy is deeper and higher open-circuit voltage (Voc) can be obtained as compared with other polymer compounds shown in calculation examples 4 to 6.

  Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.

  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 mm I.d. x 15 cm); Detector: RI (SHIMADZU RID-10A); Mobile phase: Tetrahydrofuran (THF)

化合物１ 化合物２

攪拌装置を備えた２Lの４つ口フラスコに９８％硫酸を２８００ｇ、化合物１を８０．０ｇ（０．３８４M）入れ、室温、 アルゴン雰囲気下で撹拌した。続いて撹拌下でＮ−ブロモコハク酸イミド（以下、ＮＢＳと呼称することもある） ２３．９ｇ（０．１３４Ｍ）を加えて３０分間室温で攪拌した。その後、ＮＢＳ ２３．９ｇ（０．１３４Ｍ）を加えて３０分間室温で攪拌する操作を５回行った。ＮＢＳの添加量は合計で１４３．４ｇであった。その後、さらにＮＢＳ ２０．４g（０．１１５M）を投入し、２時間室温で攪拌した。得られたスラリーを氷 ７ Kgに加え、３０分間撹拌した後、析出した結晶（オレンジ色）を濾過、水洗した。得られた固体を６０℃、真空で乾燥して、粗結晶 を得た。得られた粗結晶 にクロロホルム １４３０ｍｌを注入し、２時間の加熱、還流を行い、スラリー状態とした。冷却後、ろ過、乾燥して 化合物２を９５．１ｇ得た。 Synthesis example 1
(Synthesis of Compound 2)

Compound 1 Compound 2

2800 g of 98% sulfuric acid and 80.0 g (0.384 M) of Compound 1 were placed in a 2 L four-necked flask equipped with a stirrer, and stirred at room temperature under an argon atmosphere. Subsequently, 23.9 g (0.134M) of N-bromosuccinimide (hereinafter also referred to as NBS) was added with stirring, and the mixture was stirred at room temperature for 30 minutes. Then, 23.9g (0.134M) of NBS was added and the operation which stirs at room temperature for 30 minutes was performed 5 times. The total amount of NBS added was 143.4 g. Thereafter, 20.4 g (0.115 M) of NBS was further added and stirred at room temperature for 2 hours. The obtained slurry was added to 7 Kg of ice and stirred for 30 minutes, and then the precipitated crystals (orange) were filtered and washed with water. The obtained solid was dried at 60 ° C. in vacuo to obtain crude crystals. Chloroform 1430 ml was poured into the obtained crude crystals, heated for 2 hours and refluxed to form a slurry. After cooling, it was filtered and dried to obtain 95.1 g of Compound 2.

化合物２ 化合物３
攪拌装置を備えた５００ｍＬ４つ口フラスコにマグネシウム１２．０ｇ（４９２ｍM）を入れてフラスコ内の気体をアルゴン置換した。この中へ、ｎ―ドデシルブロマイド １２２．８ｇ（４９２ｍM）を無水THF １５０ｍＬに溶解させた溶液を４５分間かけて滴下した。滴下後、フラスコを８５℃のオイルバスに浸して、１．５時間攪拌した。その後、無水THF ２５０ｍｌを加えて希釈し、２５℃に冷却した。この操作で得られた溶液を溶液１と呼称する。
攪拌装置を備えた上記とは別の１Lの4 つ口フラスコに 化合物２を ３０．０ｇ（８２ｍM）、無水THF１１３ｍｌを仕込み、撹拌させた。このフラスコを氷水で冷却しながら、上記の溶液２を１時間かけて滴下した。滴下後、さらに１２時間撹拌した。氷水で冷却しながら、飽和塩化アンモニウム水溶液 ４００ｍｌを１時間かけて滴下し、３０分間撹拌後、酢酸エチル ５００ｍｌで抽出した。得られた有機層を飽和塩化アンモニウム水溶液で2 回洗浄し、硫酸マグネシウムで脱水、脱溶剤し、粗オイルを得た。さらに析出した赤色結晶をろ過して回収した。得られた赤色結晶を５ｍｍＨｇに減圧し、１１８℃まで加温することで揮発成分を留去し、粗精製物 ５５．３ｇを得た。さらにシリカゲルカラムクロマトグラフィーで精製（溶出溶剤 ヘキサン／酢酸エチル＝２０／１（ｖｏｌ／ｖｏｌ））することによって ２６．０ｇの化合物３の結晶を得た。 Synthesis example 2
(Synthesis of Compound 3)

Compound 2 Compound 3
Magnesium 12.0 g (492 mM) was placed in a 500 mL four-necked flask equipped with a stirrer, and the gas in the flask was purged with argon. To this, a solution prepared by dissolving 122.8 g (492 mM) of n-dodecyl bromide in 150 mL of anhydrous THF was added dropwise over 45 minutes. After dropping, the flask was immersed in an oil bath at 85 ° C. and stirred for 1.5 hours. Thereafter, 250 ml of anhydrous THF was added for dilution, and the mixture was cooled to 25 ° C. The solution obtained by this operation is referred to as Solution 1.
Into a 1 L four-neck flask equipped with a stirrer, 30.0 g (82 mM) of Compound 2 and 113 ml of anhydrous THF were added and stirred. The solution 2 was added dropwise over 1 hour while cooling the flask with ice water. After dropping, the mixture was further stirred for 12 hours. While cooling with ice water, 400 ml of saturated aqueous ammonium chloride solution was added dropwise over 1 hour, stirred for 30 minutes, and extracted with 500 ml of ethyl acetate. The obtained organic layer was washed twice with a saturated aqueous ammonium chloride solution, dehydrated with magnesium sulfate, and desolvated to obtain a crude oil. Further, the precipitated red crystals were collected by filtration. The obtained red crystals were depressurized to 5 mmHg and heated to 118 ° C. to distill away volatile components, thereby obtaining 55.3 g of a crude product. Further, the residue was purified by silica gel column chromatography (elution solvent hexane / ethyl acetate = 20/1 (vol / vol)) to obtain 26.0 g of compound 3 crystals.

化合物３ 化合物４
攪拌装置を備えた２００ｍLの4 つ口フラスコに 化合物３を２６．０ｇ（３６．８ｍM）、トリフルオロ酢酸 １４０ｍｌ、氷酢酸 ７９ｍｌ、塩化亜鉛 ６．８ｇを仕込み、室温、アルゴン置換、撹拌下、８２℃に昇温し、３時間攪拌した。続いてフラスコを徐々に減圧してトリフルオロ酢酸および酢酸を除去した。このフラスコに水を加えて、酢酸エチルで抽出し、飽和炭酸水素ナトリウム水溶液で洗浄して、硫酸マグネシウムで乾燥した。エバポレーターで溶媒を留去して粗生成物 ２４．６ｇを得た。その後、シリカゲルカラムクロマトグラフィー（溶出溶媒：ヘキサン）で精製して化合物４を１６．６ｇ得た。 Synthesis example 3
(Synthesis of Compound 4)

Compound 3 Compound 4
A 200 mL four-necked flask equipped with a stirrer was charged with 26.0 g (36.8 mM) of Compound 3, 140 ml of trifluoroacetic acid, 79 ml of glacial acetic acid, and 6.8 g of zinc chloride. The temperature was raised to ° C. and stirred for 3 hours. Subsequently, the flask was gradually decompressed to remove trifluoroacetic acid and acetic acid. Water was added to the flask, and the mixture was extracted with ethyl acetate, washed with a saturated aqueous sodium hydrogen carbonate solution, and dried over magnesium sulfate. The solvent was distilled off with an evaporator to obtain 24.6 g of a crude product. Then, it refine | purified by silica gel column chromatography (elution solvent: hexane), and 16.6g of compounds 4 were obtained.

化合物２ 化合物５
攪拌装置を備えた５００ｍL４つ口フラスコにマグネシウムを１２．０ｇ（４９２ｍM）入れてフラスコ内部の気体をアルゴンで置換した。このフラスコに、ｎ−へキシルブロミド ８１．２ｇ（４９２ｍM）の無水THF （１５０ｍｌ）溶液を４５分間かけて滴下した。滴下後、さらに８５℃に昇温し、１．５時間の還流反応を行った。その後、無水THF （２５０ｍｌ）を加えて希釈し、２５℃に冷却した。得られた溶液を溶液２と呼称する。
攪拌装置を備えた上記とは異なる１Lの4 つ口フラスコに 化合物２を３０．０ｇ（８２ｍM）、無水THF １１４ｍｌを入れて溶液とした。得られた溶液を氷冷下で攪拌しながら、上記の溶液２を１時間かけて滴下した。滴下後、さらに１２時間撹拌した。その後、飽和塩化アンモニウム水溶液４００ｍｌを１時間かけて滴下し、３０分間撹拌後、酢酸エチル ５００ｍｌで抽出した。得られた有機層を飽和塩化アンモニウム水溶液で2 回洗浄し、硫酸マグネシウムで脱水した。エバポレーターで溶媒を留去し、粗生成物を得た。得られた粗生成物をヘキサンで洗浄して１９．６ｇの粗生成物を得た。得られた粗生成物をシリカゲルカラムクロマトグラフィ（溶出溶液 ヘキサン／酢エチ＝２０／１（ｖｏｌ／ｖｏｌ）） １３．９ｇの化合物５を得た。 Synthesis example 4
(Synthesis of Compound 5)

Compound 2 Compound 5
12.0 g (492 mM) of magnesium was placed in a 500 mL four-necked flask equipped with a stirrer, and the gas inside the flask was replaced with argon. To this flask, a solution of 81.2 g (492 mM) of n-hexyl bromide in anhydrous THF (150 ml) was added dropwise over 45 minutes. After the dropwise addition, the temperature was further raised to 85 ° C., and a reflux reaction was performed for 1.5 hours. Thereafter, anhydrous THF (250 ml) was added for dilution, and the mixture was cooled to 25 ° C. The resulting solution is referred to as Solution 2.
30.0 g (82 mM) of Compound 2 and 114 ml of anhydrous THF were added to a 1 L four-necked flask equipped with a stirrer and different from the above to prepare a solution. While stirring the resulting solution under ice-cooling, the above solution 2 was added dropwise over 1 hour. After dropping, the mixture was further stirred for 12 hours. Thereafter, 400 ml of a saturated aqueous ammonium chloride solution was added dropwise over 1 hour, stirred for 30 minutes, and extracted with 500 ml of ethyl acetate. The obtained organic layer was washed twice with a saturated aqueous ammonium chloride solution and dehydrated with magnesium sulfate. The solvent was distilled off with an evaporator to obtain a crude product. The obtained crude product was washed with hexane to obtain 19.6 g of a crude product. The obtained crude product was subjected to silica gel column chromatography (elution solution hexane / ethyl acetate = 20/1 (vol / vol)) to obtain 13.9 g of compound 5.

化合物５ 化合物６
攪拌装置を備えた２００ｍｌの4 つ口フラスコに 化合物５を１３．９ｇ（２５．８ｍM）、トリフルオロ酢酸 ７９ｍｌ、氷酢酸 ４２ｍｌ、塩化亜鉛 ３．６ｇを仕込み、アルゴン雰囲気下、８２℃度で３時間攪拌した。続いてフラスコを減圧してトリフルオロ酢酸と酢酸を留去した。その後、水を加えて酢酸エチルで抽出し、有機層を飽和炭酸水素ナトリウム水溶液で洗浄し、硫酸マグネシウムで脱水した。その後、エバポレーターで溶媒を留去して粗生成物 １２．６ｇを得た。その後、シリカゲルカラムクロマトグラフィー（溶出溶液 ヘキサン）で精製して目的の化合物６を６．４９ｇを得た。 Synthesis example 5
(Synthesis of Compound 6)

Compound 5 Compound 6
A 200 ml four-necked flask equipped with a stirrer was charged with 13.9 g (25.8 mM) of compound 5, 79 ml of trifluoroacetic acid, 42 ml of glacial acetic acid, and 3.6 g of zinc chloride. Stir for hours. Subsequently, the flask was decompressed to distill off trifluoroacetic acid and acetic acid. Thereafter, water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and dehydrated with magnesium sulfate. Thereafter, the solvent was distilled off with an evaporator to obtain 12.6 g of a crude product. Then, it refine | purified by silica gel column chromatography (elution solution hexane), and 6.49g of the target compounds 6 were obtained.

化合物７ 化合物８
窒素気流雰囲気下ジムロートを取付けた100ml３口フラスコに化合物７（Luminescence Technology社より購入、3.70ｇ、5.4mmol）、bis(pinacolato)diboron（3.00g、11.8mmol）、酢酸カリウム（2.59g、26.4mmol）、PdCl₂(dppf)（0.09g、0.1mmol）、dppf（0.06g、0.1mmol）、無水1,4-ジオキサン300mlを室温下にて仕込み、１５時間加熱還流下攪拌した。攪拌後反応液をセライトろ過し、セライトケーキをクロロホルム２００mｌを用い、５回洗浄した。ろ液をエバポレータにて濃縮し、得られた残渣にクロロホルム２００mｌを加え８０℃にて加熱攪拌し、そこへアセトニトリル４００ｍｌ加え、攪拌を続けながら、室温まで放冷後さらに１時間攪拌した。得られたスラリーをろ取、アセトニトリル１００ｍｌを用い２回洗浄した後減圧乾燥（50mmHg、70℃、3hr）することで、化合物８を２．２５g（0.24mmol、収率53.4%）得た。 Synthesis Example 6
(Synthesis of Compound 8)

Compound 7 Compound 8
Compound 7 (purchased from Luminescence Technology, 3.70 g, 5.4 mmol), bis (pinacolato) diboron (3.00 g, 11.8 mmol), potassium acetate (2.59 g, 26.4 mmol) in a 100 ml three-necked flask equipped with a Dimroth in a nitrogen atmosphere , PdCl ₂ (dppf) (0.09 g, 0.1 mmol), dppf (0.06 g, 0.1 mmol), and 300 ml of anhydrous 1,4-dioxane were charged at room temperature and stirred for 15 hours while heating under reflux. After stirring, the reaction solution was filtered through Celite, and the Celite cake was washed 5 times with 200 ml of chloroform. The filtrate was concentrated with an evaporator, 200 ml of chloroform was added to the obtained residue, and the mixture was heated and stirred at 80 ° C., 400 ml of acetonitrile was added thereto, and the mixture was allowed to cool to room temperature and further stirred for 1 hour. The obtained slurry was collected by filtration, washed twice with 100 ml of acetonitrile, and then dried under reduced pressure (50 mmHg, 70 ° C., 3 hr) to obtain 2.25 g (0.24 mmol, yield 53.4%) of Compound 8.

¹ H-NMR (270 MHz / CDCl ₃ ):
δ8.93 (d, 2H), 7.72 (d, 2H), 4.07 (m, 4H), 1.85 (m, 2H), 1.37 (s, 24H), 1.50-1 .15 (m, 16H), 0.95-0.80 (d, 12H)

化合物８ 化合物４ 高分子化合物７
内部を窒素ガスで置換した１００ｍＬの四つ口フラスコに化合物４（１０６．３ｍｇ、０．１５４ｍｍｏｌ）、乾燥クロロベンゼン（５ｍＬ）を加えて３０分間アルゴンでバブリングして脱気した。脱気後にトリス(ジベンジリデンアセトン)ジパラジウム（７．０７ｍｇ，０．００７７２ｍｍｏｌ）、トリ-tert-ブチルホスホニウムテトラフルオロボラート（８．９６ｍｇ、０．０３０９ｍｍｏｌ）、３Ｍリン酸カリウム水溶液（２ｍＬ）を加え、８０℃に加熱した。このフラスコに、３０分間アルゴンでバブリングして脱気した化合物８（１２０ｍｇ，０．１５４ｍｍｏｌ）の乾燥ＴＨＦ（５ｍＬ）溶液を５分間かけて滴下し、８０℃で３時間加熱した。続いて、ジエチルジチオカルバミン酸ナトリウム二水和物（１．７４ｇ）とイオン交換水（１０ｍＬ）を加え、９０℃で２時間加熱した。得られた有機層をイオン交換水（２０ｍＬ）で２回、１０ｗｔ％酢酸水溶液（２０ｍＬ）で２回、イオン交換水（２０ｍＬ）で２回洗浄した後、メタノール（５０ｍＬ）に注いで固体を析出させた。得られた固体をｏ−ジクロロベンゼン８ｍＬに再溶解させて、カラムクロマトグラフィ（ＳｉＯ_２およびアルミナ）を通過させ、得られた溶液をメタノール（５０ｍＬ）に注いで固体を析出させた。析出した固体をろ過、乾燥を行うことにより、高分子化合物７を１１１ｍｇ得た。ＧＰＣで測定した高分子化合物７の分子量はＭｎ＝９６５００、Ｍｗ=７２９０００であった。 Example 1
(Synthesis of polymer compound 7)

Compound 8 Compound 4 Polymer compound 7
Compound 4 (106.3 mg, 0.154 mmol) and dry chlorobenzene (5 mL) were added to a 100 mL four-necked flask whose inside was replaced with nitrogen gas, and deaerated by bubbling with argon for 30 minutes. After degassing, tris (dibenzylideneacetone) dipalladium (7.07 mg, 0.00772 mmol), tri-tert-butylphosphonium tetrafluoroborate (8.96 mg, 0.0309 mmol), 3M aqueous potassium phosphate solution (2 mL) were added. In addition, it was heated to 80 ° C. To this flask, a dry THF (5 mL) solution of Compound 8 (120 mg, 0.154 mmol) deaerated by bubbling with argon for 30 minutes was dropped over 5 minutes and heated at 80 ° C. for 3 hours. Subsequently, sodium diethyldithiocarbamate dihydrate (1.74 g) and ion-exchanged water (10 mL) were added and heated at 90 ° C. for 2 hours. The obtained organic layer was washed twice with ion-exchanged water (20 mL), twice with 10 wt% aqueous acetic acid (20 mL) and twice with ion-exchanged water (20 mL), and then poured into methanol (50 mL) to precipitate a solid. I let you. The obtained solid was redissolved in 8 mL of o-dichlorobenzene, passed through column chromatography (SiO ₂ and alumina), and the obtained solution was poured into methanol (50 mL) to precipitate a solid. The precipitated solid was filtered and dried to obtain 111 mg of polymer compound 7. The molecular weight of the polymer compound 7 measured by GPC was Mn = 96500 and Mw = 729000.

化合物８ 化合物６ 高分子化合物８
内部を窒素ガスで置換した１００ｍＬの四つ口フラスコに化合物６（８０ｍｇ、０．１５４ｍｍｏｌ）、乾燥クロロベンゼン（５ｍＬ）を加えて３０分間アルゴンでバブリングして脱気した。脱気後にトリス(ジベンジリデンアセトン)ジパラジウム（７．０４ｍｇ，０．００７６９ｍｍｏｌ）、トリ-tert-ブチルホスホニウムテトラフルオロボラート（８．９２ｍｇ、０．０３０８ｍｍｏｌ）、３Ｍリン酸カリウム水溶液（２ｍＬ）を加え、８０℃に加熱した。このフラスコに、３０分間アルゴンでバブリングして脱気した化合物８（１２０ｍｇ，０．１５４ｍｍｏｌ）の乾燥ＴＨＦ（５ｍＬ）溶液を５分間かけて滴下し、８０℃で３時間加熱した。続いて、ジエチルジチオカルバミン酸ナトリウム二水和物（１．７４ｇ）とイオン交換水（１０ｍＬ）を加え、９０℃で２時間加熱した。得られた有機層をイオン交換水（２０ｍＬ）で２回、１０ｗｔ％酢酸水溶液（２０ｍＬ）で２回、イオン交換水（２０ｍＬ）で２回洗浄した後、メタノール（５０ｍＬ）に注いで固体を析出させた。得られた固体をｏ−ジクロロベンゼン７ｍＬに再溶解させて、カラムクロマトグラフィ（ＳｉＯ_２およびアルミナ）を通過させ、得られた溶液をメタノール（５０ｍＬ）に注いで固体を析出させた。析出した固体をろ過、乾燥を行うことにより、高分子化合物８を１０９ｍｇ得た。ＧＰＣで測定した高分子化合物８の分子量はＭｎ＝１４４０００、Ｍｗ＝８０００００であった。 Example 2
(Synthesis of polymer compound 8)

Compound 8 Compound 6 Polymer compound 8
Compound 6 (80 mg, 0.154 mmol) and dry chlorobenzene (5 mL) were added to a 100 mL four-necked flask whose inside was replaced with nitrogen gas, and deaerated by bubbling with argon for 30 minutes. After degassing, tris (dibenzylideneacetone) dipalladium (7.04 mg, 0.00769 mmol), tri-tert-butylphosphonium tetrafluoroborate (8.92 mg, 0.0308 mmol), 3M aqueous potassium phosphate solution (2 mL) were added. In addition, it was heated to 80 ° C. To this flask, a dry THF (5 mL) solution of Compound 8 (120 mg, 0.154 mmol) deaerated by bubbling with argon for 30 minutes was dropped over 5 minutes and heated at 80 ° C. for 3 hours. Subsequently, sodium diethyldithiocarbamate dihydrate (1.74 g) and ion-exchanged water (10 mL) were added and heated at 90 ° C. for 2 hours. The obtained organic layer was washed twice with ion-exchanged water (20 mL), twice with 10 wt% aqueous acetic acid (20 mL) and twice with ion-exchanged water (20 mL), and then poured into methanol (50 mL) to precipitate a solid. I let you. The obtained solid was redissolved in 7 mL of o-dichlorobenzene, passed through column chromatography (SiO ₂ and alumina), and the obtained solution was poured into methanol (50 mL) to precipitate a solid. 109 mg of polymer compound 8 was obtained by filtering and drying the depositing solid. The molecular weight of the polymer compound 8 measured by GPC was Mn = 144000 and Mw = 800,000.

化合物９ 化合物６ 高分子化合物９
フラスコ内の気体をアルゴンで置換した１００ｍＬフラスコに、特開２０１１−２４９７５７号公報に記載の化合物９を３０３．０ｍｇ（０．２８８ｍｍｏｌ）、化合物６を１５０ｍｇ（０．２８８ｍｍｏｌ）、トリス(２−トリル)ホスフィンを７．９０ｍｇ（０．０２５９ｍｍｏｌ）、脱水トルエン１２ｍｌを入れて均一溶液とした。得られたトルエン溶液を、アルゴンで３０分バブリングした。その後、トルエン溶液に、トリス（ジベンジリデンアセトン）ジパラジウムを３．９６ｍｇ（０．００４３２ｍｍｏｌ）加え、１０５℃で４時間攪拌した。その後、フラスコを室温までに冷却し、反応液をメタノール２００ｍＬと濃塩酸２０ｍＬの混合溶液に注いだ。析出したポリマーをろ過して回収し、得られたポリマーを、円筒ろ紙に入れ、ソックスレー抽出器を用いて、メタノールおよびアセトンでそれぞれ３時間洗浄した。円筒ろ紙内に残ったポリマーを、ｏ−ジクロロベンゼン１２ｍＬに溶解させ、ジエチルジチオカルバミン酸ナトリウム０．２４ｇと水２．０ｍＬを加え、９０℃で３時間攪拌を行った。水層を除去後、有機層を水５０ｍｌで２回洗浄し、次いで、３ｗｔ%の酢酸水溶液５０ｍＬで２回洗浄し、次いで、水５０ｍＬで２回洗浄し、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーをろ過後、乾燥し、得られたポリマーをｏ−ジクロロベンゼン２４ｍＬに再度溶解し、アルミナ／シリカゲルカラムを通した。得られた溶液をメタノールに注いでポリマーを析出させ、ポリマーをろ過後、乾燥し、精製された高分子化合物９を１６６ｍｇを得た。ＧＰＣで測定した高分子化合物９の分子量はＭｎ＝７３０００、Ｍｗ＝１９３０００であった。 Example 3
(Synthesis of polymer compound 9)

Compound 9 Compound 6 Polymer compound 9
In a 100 mL flask in which the gas in the flask was replaced with argon, 303.0 mg (0.288 mmol) of compound 9 described in JP 2011-249757 A, 150 mg (0.288 mmol) of compound 6, tris (2-tolyl) ) 7.90 mg (0.0259 mmol) of phosphine and 12 ml of dehydrated toluene were added to obtain a uniform solution. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 3.96 mg (0.00432 mmol) of tris (dibenzylideneacetone) dipalladium was added to the toluene solution, and the mixture was stirred at 105 ° C. for 4 hours. Thereafter, the flask was cooled to room temperature, and the reaction solution was poured into a mixed solution of 200 mL of methanol and 20 mL of concentrated hydrochloric acid. The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol and acetone for 3 hours using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 12 mL of o-dichlorobenzene, 0.24 g of sodium diethyldithiocarbamate and 2.0 mL of water were added, and the mixture was stirred at 90 ° C. for 3 hours. After removing the aqueous layer, the organic layer was washed twice with 50 ml of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was poured into methanol. A polymer was precipitated. The polymer was filtered and dried, and the resulting polymer was dissolved again in 24 mL of o-dichlorobenzene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 166 mg of purified polymer compound 9. The molecular weight of the polymer compound 9 measured by GPC was Mn = 73000 and Mw = 193000.

化合物１０ 化合物１１
フラスコ内の気体をアルゴンで置換した２００ｍＬフラスコに、国際公開第２０１１／０５２７０９号の記載に従って合成した化合物１０を２．００ｇ(３．７７ ｍｍｏｌ)、脱水テトラヒドロフランを１００ｍＬ入れて均一な溶液とした。該溶液を−７８℃に保ち、該溶液に１．６Ｍのｎ−ブチルリチウムのヘキサン溶液５．８９ｍＬ（９．４２ｍｍｏｌ）を１０分かけて滴下した。滴下後、反応液を−７８℃で３０分攪拌し、次いで、室温（２５℃）で２時間攪拌した。その後、フラスコを−７８℃に冷却し、反応液にトリブチルスズクロリドを３．３７ｇ（１０．４ｍｍｏｌ）加えた。添加後、反応液を−７８℃で３０分攪拌し、次いで、室温（２５℃）で３時間攪拌した。その後、反応液に水２００ｍｌを加えて反応を停止し、酢酸エチルを加えて反応生成物を含む有機層を抽出した。有機層を硫酸ナトリウムで乾燥させ、濾過後、濾液をエバポレーターで濃縮し、溶媒を留去した。得られたオイル状の物質を展開溶媒がヘキサンであるシリカゲルカラムで精製した。シリカゲルカラムのシリカゲルには、あらかじめ１０重量％のトリエチルアミンを含むヘキサンに５分間浸し、その後、ヘキサンで濯いだシリカゲルを用いた。精製後、化合物１１を３．５５ｇ（３．２０ｍｍｏｌ）得た。 Synthesis example 7
(Synthesis of Compound 11)

Compound 10 Compound 11
In a 200 mL flask in which the gas in the flask was replaced with argon, 2.00 g (3.77 mmol) of Compound 10 synthesized according to the description of WO 2011/052709 and 100 mL of dehydrated tetrahydrofuran were added to obtain a uniform solution. The solution was kept at −78 ° C., and 5.89 mL (9.42 mmol) of a 1.6M n-butyllithium hexane solution was added dropwise to the solution over 10 minutes. After the addition, the reaction solution was stirred at -78 ° C for 30 minutes, and then stirred at room temperature (25 ° C) for 2 hours. Thereafter, the flask was cooled to −78 ° C., and 3.37 g (10.4 mmol) of tributyltin chloride was added to the reaction solution. After the addition, the reaction solution was stirred at −78 ° C. for 30 minutes, and then stirred at room temperature (25 ° C.) for 3 hours. Thereafter, 200 ml of water was added to the reaction solution to stop the reaction, and ethyl acetate was added to extract an organic layer containing the reaction product. The organic layer was dried over sodium sulfate and filtered, and then the filtrate was concentrated with an evaporator and the solvent was distilled off. The obtained oily substance was purified by a silica gel column whose developing solvent was hexane. As the silica gel of the silica gel column, silica gel previously immersed in hexane containing 10% by weight of triethylamine for 5 minutes and then rinsed with hexane was used. After purification, 3.55 g (3.20 mmol) of Compound 11 was obtained.

化合物１１ 化合物６ 高分子化合物１０
フラスコ内の気体をアルゴンで置換した１００ｍＬフラスコに、化合物１１を２５５．５ｍｇ（０．２３０ｍｍｏｌ）、化合物６を１２０ｍｇ（０．２３１ｍｍｏｌ）、トリス(２−トリル)ホスフィンを６．３２ｍｇ（０．０２０８ｍｍｏｌ）、脱水トルエン１０ｍｌを入れて均一溶液とした。得られたトルエン溶液を、アルゴンで３０分バブリングした。その後、トルエン溶液に、トリス（ジベンジリデンアセトン）ジパラジウムを３．１７ｍｇ（０．００３４６ｍｍｏｌ）加え、１０５℃で５時間攪拌した。その後、フラスコを室温までに冷却し、反応液をメタノール２００ｍＬと濃塩酸２０ｍＬの混合溶液に注いだ。析出したポリマーをろ過して回収し、得られたポリマーを、円筒ろ紙に入れ、ソックスレー抽出器を用いて、メタノール、アセトン及びヘキサンでそれぞれ３時間洗浄した。円筒ろ紙内に残ったポリマーを、ｏ−ジクロロベンゼン７ｍＬに溶解させ、ジエチルジチオカルバミン酸ナトリウム０．１１ｇと水２．０ｍＬを加え、９０℃で３時間攪拌を行った。水層を除去後、有機層を水５０ｍｌで２回洗浄し、次いで、３ｗｔ%の酢酸水溶液５０ｍＬで２回洗浄し、次いで、水５０ｍＬで２回洗浄し、得られた溶液をメタノールに注いでポリマーを析出させた。ポリマーをろ過後、乾燥し、得られたポリマーをｏ−ジクロロベンゼン７ｍＬに再度溶解し、アルミナ／シリカゲルカラムを通した。得られた溶液をメタノールに注いでポリマーを析出させ、ポリマーをろ過後、乾燥し、精製された高分子化合物１０を１０８ｍｇ得た。ＧＰＣで測定した高分子化合物１０の分子量はＭｎ＝３６７００、Ｍｗ＝９００００であった。 Example 3
Synthesis of polymer compound 10

Compound 11 Compound 6 Polymer Compound 10
In a 100 mL flask in which the gas in the flask was replaced with argon, 255.5 mg (0.230 mmol) of compound 11, 120 mg (0.231 mmol) of compound 6, and 6.32 mg (0.0208 mmol) of tris (2-tolyl) phosphine. ), 10 ml of dehydrated toluene was added to obtain a uniform solution. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 3.17 mg (0.00346 mmol) of tris (dibenzylideneacetone) dipalladium was added to the toluene solution, and the mixture was stirred at 105 ° C. for 5 hours. Thereafter, the flask was cooled to room temperature, and the reaction solution was poured into a mixed solution of 200 mL of methanol and 20 mL of concentrated hydrochloric acid. The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol, acetone and hexane for 3 hours using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 7 mL of o-dichlorobenzene, 0.11 g of sodium diethyldithiocarbamate and 2.0 mL of water were added, and the mixture was stirred at 90 ° C. for 3 hours. After removing the aqueous layer, the organic layer was washed twice with 50 ml of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was poured into methanol. A polymer was precipitated. The polymer was filtered and dried, and the resulting polymer was dissolved again in 7 mL of o-dichlorobenzene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and then dried to obtain 108 mg of purified polymer compound 10. The molecular weight of the polymer compound 10 measured by GPC was Mn = 36700 and Mw = 90000.

化合物４ 化合物１２

窒素気流雰囲気下ジムロートを取付けた１００ｍｌ３口フラスコに化合物４（１．００g、１．４５mmol）、bis(pinacolato)diboron（０．７７５ｇ、３．０５ｍｍｏｌ）、酢酸カリウム（０．３７０g、３．７７ｍｍｏｌ）、PdCl₂(dppf)（５９．４ｍｇ、０．０７２７ｍｍｏｌ）、無水1,4-ジオキサン１００ｍｌを室温下にて仕込み、１００℃で５時間攪拌した。攪拌後反応液をセライトろ過し、ろ液をエバポレータで濃縮した。得られた粗精製物をシリカゲルカラムクロマトグラフィ（ヘキサン：酢酸エチル＝５：１（ｖｏｌ：ｖｏｌ））で精製して目的の化合物１２を０．９０ｇ得た。 Synthesis example 8
(Synthesis of Compound 12)

Compound 4 Compound 12

Compound 4 (1.00 g, 1.45 mmol), bis (pinacolato) diboron (0.775 g, 3.05 mmol), potassium acetate (0.370 g, 3.77 mmol) in a 100 ml three-necked flask equipped with a Dimroth in a nitrogen stream atmosphere , PdCl ₂ (dppf) (59.4 mg, 0.0727 mmol) and 100 ml of anhydrous 1,4-dioxane were charged at room temperature and stirred at 100 ° C. for 5 hours. After stirring, the reaction solution was filtered through Celite, and the filtrate was concentrated with an evaporator. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 5: 1 (vol: vol)) to obtain 0.90 g of the desired compound 12.

化合物１２ 化合物１３
内部を窒素ガスで置換した１００ｍＬの四つ口フラスコにEuropean Journal of Organic Chemistry, 2011年, Issue 25, pages 4841-4852に記載のある方法で合成した化合物１３（１００．０ｍｇ、０．１６０ｍｍｏｌ）、乾燥クロロベンゼン（４ｍＬ）を加えて３０分間アルゴンでバブリングして脱気した。脱気後にトリス(ジベンジリデンアセトン)ジパラジウム（７．３１ｍｇ，０．００８０ｍｍｏｌ）、トリ-tert-ブチルホスホニウムテトラフルオロボラート（９．２６ｍｇ、０．０３２ｍｍｏｌ）、３Ｍリン酸カリウム水溶液（１．６ｍＬ）を加え、８０℃に加熱した。このフラスコに、３０分間アルゴンでバブリングして脱気した化合物１２（１２４．８ｍｇ，０．１５９ｍｍｏｌ）の乾燥ＴＨＦ（５ｍＬ）溶液を５分間かけて滴下し、８０℃で３時間加熱した。続いて、ジエチルジチオカルバミン酸ナトリウム二水和物（１．８０ｇ）とイオン交換水（１０ｍＬ）を加え、９０℃で２時間加熱した。得られた有機層をイオン交換水（３０ｍＬ）で２回、１０ｗｔ％酢酸水溶液（３０ｍＬ）で２回、イオン交換水（３０ｍＬ）で２回洗浄した後、メタノール（１００ｍＬ）に注いで固体を析出させた。得られた固体をｏ−ジクロロベンゼン８ｍＬに再溶解させて、カラムクロマトグラフィ（ＳｉＯ_２およびアルミナ）を通過させ、得られた溶液をメタノール（５０ｍＬ）に注いで固体を析出させた。析出した固体をろ過、乾燥を行うことにより、下式で表される高分子化合物１１を８９ｍｇ得た。

Example 4
Synthesis of polymer compound 11

Compound 12 Compound 13
Compound 13 (100.0 mg, 0.160 mmol) synthesized in a method described in European Journal of Organic Chemistry, 2011, Issue 25, pages 4841-4852 in a 100 mL four-necked flask with the inside replaced with nitrogen gas, Dry chlorobenzene (4 mL) was added and degassed by bubbling with argon for 30 minutes. After degassing, tris (dibenzylideneacetone) dipalladium (7.31 mg, 0.0080 mmol), tri-tert-butylphosphonium tetrafluoroborate (9.26 mg, 0.032 mmol), 3M aqueous potassium phosphate (1.6 mL) ) And heated to 80 ° C. To this flask, a dry THF (5 mL) solution of Compound 12 (124.8 mg, 0.159 mmol) deaerated by bubbling with argon for 30 minutes was added dropwise over 5 minutes and heated at 80 ° C. for 3 hours. Subsequently, sodium diethyldithiocarbamate dihydrate (1.80 g) and ion-exchanged water (10 mL) were added and heated at 90 ° C. for 2 hours. The obtained organic layer was washed twice with ion-exchanged water (30 mL), twice with 10 wt% aqueous acetic acid (30 mL) and twice with ion-exchanged water (30 mL), and then poured into methanol (100 mL) to precipitate a solid. I let you. The obtained solid was redissolved in 8 mL of o-dichlorobenzene, passed through column chromatography (SiO ₂ and alumina), and the obtained solution was poured into methanol (50 mL) to precipitate a solid. The precipitated solid was filtered and dried to obtain 89 mg of polymer compound 11 represented by the following formula.

化合物１２ 化合物１４
内部を窒素ガスで置換した１００ｍＬの四つ口フラスコに国際公開特許公報ＷＯ２０１１０５２７１０Ａ１号公報に記載のある方法で合成した化合物１４（５０．０ｍｇ、０．０７３ｍｍｏｌ）、乾燥クロロベンゼン（４ｍＬ）を加えて３０分間アルゴンでバブリングして脱気した。脱気後にトリス(ジベンジリデンアセトン)ジパラジウム（３．３５ｍｇ，０．００３７ｍｍｏｌ）、トリ-tert-ブチルホスホニウムテトラフルオロボラート（４．２５ｍｇ、０．０１５ｍｍｏｌ）、３Ｍリン酸カリウム水溶液（０．８ｍＬ）を加え、８０℃に加熱した。このフラスコに、３０分間アルゴンでバブリングして脱気した化合物１２（５７．４ｍｇ，０．０７３ｍｍｏｌ）の乾燥ＴＨＦ（５ｍＬ）溶液を５分間かけて滴下し、８０℃で３時間加熱した。続いて、ジエチルジチオカルバミン酸ナトリウム二水和物（０．８３ｇ）とイオン交換水（８ｍＬ）を加え、９０℃で２時間加熱した。得られた有機層をイオン交換水（２０ｍＬ）で２回、１０ｗｔ％酢酸水溶液（２０ｍＬ）で２回、イオン交換水（２０ｍＬ）で２回洗浄した後、メタノール（５０ｍＬ）に注いで固体を析出させた。得られた固体をｏ−ジクロロベンゼン５ｍＬに再溶解させて、カラムクロマトグラフィ（ＳｉＯ_２およびアルミナ）を通過させ、得られた溶液をメタノール（５０ｍＬ）に注いで固体を析出させた。析出した固体をろ過、乾燥を行うことにより、下式で表される高分子化合物１２を４４ｍｇ得た。ＧＰＣで測定した高分子化合物１２の分子量はＭｎ＝２８０００、Ｍｗ＝２２９０００であった。

Example 5
Synthesis of polymer compound 12

Compound 12 Compound 14
Compound 14 (50.0 mg, 0.073 mmol) synthesized by a method described in International Publication No. WO201110552710A1 and dry chlorobenzene (4 mL) were added to a 100 mL four-necked flask whose inside was replaced with nitrogen gas, and 30 Degassed by bubbling with argon for min. After degassing, tris (dibenzylideneacetone) dipalladium (3.35 mg, 0.0037 mmol), tri-tert-butylphosphonium tetrafluoroborate (4.25 mg, 0.015 mmol), 3M aqueous potassium phosphate solution (0.8 mL) ) And heated to 80 ° C. To this flask, a dry THF (5 mL) solution of Compound 12 (57.4 mg, 0.073 mmol) deaerated by bubbling with argon for 30 minutes was added dropwise over 5 minutes and heated at 80 ° C. for 3 hours. Subsequently, sodium diethyldithiocarbamate dihydrate (0.83 g) and ion-exchanged water (8 mL) were added and heated at 90 ° C. for 2 hours. The obtained organic layer was washed twice with ion-exchanged water (20 mL), twice with 10 wt% aqueous acetic acid (20 mL) and twice with ion-exchanged water (20 mL), and then poured into methanol (50 mL) to precipitate a solid. I let you. The obtained solid was redissolved in 5 mL of o-dichlorobenzene, passed through column chromatography (SiO ₂ and alumina), and the obtained solution was poured into methanol (50 mL) to precipitate a solid. The precipitated solid was filtered and dried to obtain 44 mg of polymer compound 12 represented by the following formula. The molecular weight of the polymer compound 12 measured by GPC was Mn = 28000 and Mw = 229000.

Measurement example 1
(Measurement of absorbance of organic thin film)
Polymer compounds 7 to 12 were dissolved in o-dichlorobenzene at a concentration of 0.75% 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 | atmosphere, and obtained the organic thin film with a film thickness of about 100 nm. The absorption spectrum of the organic thin film was measured with a spectrophotometer (trade name: V-670, manufactured by JASCO Corporation). Table 7 shows the wavelengths at which the absorption obtained from the measured spectrum becomes maximum.

Measurement example 2
(Measurement of ionization potential of organic thin film)
With the organic thin film prepared in Measurement Example 1, the ionization potential was measured using an atmospheric photoelectron spectrometer (AC-2 manufactured by Riken Keiki Co., Ltd.). Table 7 shows the obtained ionization potential.

(Production and evaluation of organic thin-film solar cells)
Fullerene derivative C60PCBM (Phenyl C61-butyric acid methyl ester, manufactured by Frontier Carbon Co., trade name: E100 (lot number 11A0082-A)), which is an electron-accepting compound, and polymer compounds 7-12, which are electron-donating compounds, Were mixed in a weight ratio of 2: 1 each and dissolved in o-dichlorobenzene so that the concentration of the mixture was 2.25 wt%. The obtained solution was filtered through a Teflon (registered trademark) filter having a pore diameter of 0.5 μm to prepare a coating solution 1.

A glass substrate provided with an ITO film with a thickness of 150 nm by a sputtering method was subjected to surface treatment by ozone UV treatment. Next, a PEDOT: PSS solution (CleviosP VP AI4083 manufactured by Heraeus Co., Ltd.) was applied onto the ITO film by spin coating, and heated in the atmosphere at 120 ° C. for 10 minutes to form a hole injection layer having a thickness of 50 nm. Next, 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. Then, 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 obtained organic thin film solar cell is irradiated with a certain amount of light using a solar simulator (trade name: OTENTO-SUNII: AM1.5G filter, irradiance: 100 mW / cm ² ), and the generated current and voltage are measured. did. Table 7 shows the obtained Voc (open end voltage).

  As shown in Table 7, the polymer compounds of Examples have a deep ionization potential corresponding to the HOMO energy and can obtain a high open-circuit voltage (Voc).

Claims (5)

A polymer compound comprising a repeating unit represented by the following formula (A) and at least one repeating unit among the repeating units represented by the following formulas (B1) to (B6).

[In Formula (A) and Formula (B1) to (B6), a plurality of R's are each represented by a hydrogen atom, a fluorine atom, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, or Formula (2). Represents a group. A plurality of R may be the same or different.

(2)
(In formula (2), m1 represents an integer of 0 to 6, m2 represents an integer of 0 to 6. R ′ represents an alkyl group, an aryl group, or a heteroaryl group.)] The high molecular compound containing the at least 1 repeating unit of the repeating units represented by following formula (1a)-(1f).

[In formulas (1a) to (1f), a plurality of Rs each represent a hydrogen atom, a fluorine atom, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, or a group represented by formula (2). A plurality of R may be the same or different.

(2)
(In formula (2), m1 represents an integer of 0 to 6, m2 represents an integer of 0 to 6. R ′ represents an alkyl group, an aryl group, or a heteroaryl group.)]   An organic photoelectric conversion element 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 according to claim 1.   The organic photoelectric conversion element according to claim 3, wherein the amount of the electron-accepting compound contained in the functional layer is 10 to 1000 parts by weight with respect to 100 parts by weight of the polymer compound.   The organic photoelectric conversion device according to claim 3 or 4, wherein the electron-accepting compound is a fullerene derivative.