WO2012029675A1

WO2012029675A1 - Method for producing polymer compound

Info

Publication number: WO2012029675A1
Application number: PCT/JP2011/069363
Authority: WO
Inventors: 上谷　保則; 吉村　研; 淳藤原
Original assignee: 住友化学株式会社
Priority date: 2010-09-03
Filing date: 2011-08-22
Publication date: 2012-03-08
Also published as: JP2012072398A

Abstract

Disclosed is a method for producing a polymer compound containing a repeating unit represented by formula (4), wherein a compound represented by formula (1) is caused to react with a compound represented by formula (2) or a compound represented by formula (3). A polymer compound that has high absorbance of light having a long wavelength can be produced by this method. (In formula (1), R represents a hydrogen atom, a fluorine atom, an alkyl group that may be substituted by a fluorine atom, an alkoxy group that may be substituted by a fluorine atom or an optionally substituted aryl group; and Q represents a dihydroxyboryl group or a boric acid ester residue.) (In formula (4), a represents 0 or 1; R is as defined above; and T represents a hydrogen atom, a fluorine atom, an alkyl group that may be substituted by a fluorine atom, an alkoxy group that may be substituted by a fluorine atom or an optionally substituted aryl group.)

Description

Method for producing polymer compound

The present invention relates to a method for producing a polymer compound.

Organic semiconductor materials are expected to be applied to organic photoelectric conversion elements (organic solar cells, optical sensors, etc.). In particular, when a polymer compound is used as the organic semiconductor material, the functional layer can be manufactured by an inexpensive coating method. In order to improve various characteristics of the organic photoelectric conversion element, use of organic semiconductor materials that are various polymer compounds for the organic photoelectric conversion element has been studied. As an organic semiconductor material, for example, 9,9-dioctylfluorene-2,7-diboronic acid ester and 5,5 ″ ″-dibromo-3 ″, 4 ″ -dihexyl-α-pentathiophene are polymerized. A polymer compound has been proposed (WO2005 / 092947).

However, the polymer compound has a problem that long-wavelength light is not sufficiently absorbed.
Accordingly, an object of the present invention is to provide a method for producing a polymer compound having a large absorbance for light having a long wavelength and a polymer compound having a large absorbance for light having a long wavelength.
That is, the present invention is first represented by the formula (4) in which the compound represented by the formula (1) is reacted with the compound represented by the formula (2) or the compound represented by the formula (3). The manufacturing method of the high molecular compound containing a repeating unit is provided.

(In the formula, R represents a hydrogen atom, a fluorine atom, an alkyl group optionally substituted with a fluorine atom, an alkoxy group optionally substituted with a fluorine atom, or an aryl group optionally substituted. R may be the same or different, Q represents a dihydroxyboryl group or a borate residue, and two Q may be the same or different.)

(In Formula (2) and Formula (3), T represents a hydrogen atom, a fluorine atom, an alkyl group optionally substituted with a fluorine atom, an alkoxy group optionally substituted with a fluorine atom, or an optionally substituted group. A plurality of T's may be the same or different, A represents a bromine atom, a chlorine atom or an iodine atom, and two A's may be the same or different. )

(In the formula, a represents 0 or 1. R and T represent the same meaning as described above.)
Moreover, this invention provides the high molecular compound containing the repeating unit represented by Formula (5).

(In the formula, R and T have the same meaning as described above.)
Furthermore, the present invention provides an organic photoelectric conversion device having a pair of electrodes and a functional layer provided between the electrodes, wherein the functional layer includes an electron-accepting compound and the polymer compound.

FIG. 1 is a graph showing an absorption spectrum of polymer compound A. FIG. 2 is a graph showing an absorption spectrum of the polymer compound B. FIG. 3 is a view showing an absorption spectrum of the polymer compound C.

Hereinafter, the present invention will be described in detail.
This invention contains the repeating unit represented by Formula (4) with which the compound represented by Formula (1), the compound represented by Formula (2), or the compound represented by Formula (3) is made to react. This is a method for producing a polymer compound.

(In the formula, R and Q have the same meaning as described above.)

(In Formula (2) and Formula (3), T and A represent the same meaning as described above.)

(In the formula, a represents 0 or 1. T and R represent the same meaning as described above.)
In the formulas (1) and (4), the alkyl group represented by R may be linear or cyclic. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group Tert-butyl group, pentyl group, hexyl group, octyl group, isooctyl group, decyl group, dodecyl group, pentadecyl group and octadecyl group. A hydrogen atom in the alkyl group may be substituted with a fluorine atom. Examples of the alkyl group substituted with a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.
The alkyl part in the alkoxy group represented by R may be linear or cyclic. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, Examples include tert-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, and 3,7-dimethyloctyloxy group. A hydrogen atom in the alkoxy group may be substituted with a fluorine atom. Examples of the alkoxy group substituted with a fluorine atom include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, and a perfluorooctyloxy group.
When R is an alkyl group or an alkoxy group, from the viewpoint of solubility of the polymer compound in a solvent, the carbon number is preferably 1-20, more preferably 2-18, and more preferably 3-12. More preferably.
The aryl group represented by R is an atomic group obtained by removing one hydrogen atom from an unsubstituted aromatic hydrocarbon, having a benzene ring, having a condensed ring, an independent benzene ring or condensed ring 2 Those in which at least two are bonded directly or via a group such as vinylene are also included. The number of carbon atoms of the aryl group is preferably 6 to 60, and more preferably 6 to 30. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. The aryl group may have a substituent, and examples of the substituent that the aryl group may have include a halogen atom, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms. Etc.
In formulas (1) to (4), the definitions and specific examples of the alkyl group, alkoxy group and aryl group represented by T are the definitions and specific examples of the alkyl group, alkoxy group and aryl group represented by R. The same.
In the formula (1), Q is a dihydroxyboryl group represented by the following formula

Or represents a boric acid ester residue.
The boric acid ester residue means a group obtained by removing a hydroxy group from a boric acid diester, and specific examples thereof include a group represented by the following formula.

(In the formula, Me represents a methyl group, and Et represents an ethyl group.)
From the viewpoint of solubility of the compound represented by formula (1) in an organic solvent, Q is preferably a boric acid ester residue.
In formula (2) and formula (3), A represents a bromine atom, a chlorine atom or an iodine atom. From the viewpoint of reactivity, a bromine atom is preferable.
Examples of the compound represented by the formula (1) in which two Qs are dihydroxyboryl groups include the following compounds.

Examples of the compound represented by the formula (1) in which two Qs are boric acid ester residues include the following compounds.

The compound represented by the formula (1) in which two Qs are boric acid ester residues is obtained by, for example, dehydrating and condensing the compound represented by the formula (6) with an alcohol or diol in an organic solvent. Can be manufactured.

(In the formula, R represents the same meaning as described above.)
In the reaction, the slurry-like compound represented by formula (6) disappears, and the reaction solution becomes a uniform solution, so that two Qs are represented by formula (1), which is a borate ester residue. Production of the compound can be confirmed. After the reaction, the reaction solution is concentrated using an evaporator, the residue is washed with a hydrocarbon solvent having a relatively low boiling point, such as hexane, and then filtered, and the two formulas in which Q is a borate ester residue (1 ) Can be obtained.
Examples of the alcohol that can be used for the reaction include methanol, ethanol, propanol, 2-propanol, and butanol.
Examples of the diol that can be used in the reaction include pinacol, catechol, ethylene glycol, and 1,3-propanediol.
In the reaction, a dehydrating agent such as anhydrous magnesium sulfate or anhydrous sodium sulfate may be added.
The compound represented by the formula (6) is obtained by lithiating the compound represented by the formula (7) with an organolithium compound such as butyllithium (n-BuLi), and then the lithiated compound and trimethyl borate (trimethoxy). A compound represented by the formula (8) is produced by reacting with a boric acid ester such as borane), and the compound represented by the formula (8) can be produced by acid treatment with an acid such as dilute hydrochloric acid. .

(In the formula, R represents the same meaning as described above.)
The lithiation reaction is usually performed in an anhydrous ether solvent such as anhydrous tetrahydrofuran or anhydrous diethyl ether. The reaction temperature is usually −80 ° C. to 25 ° C., although it depends on the kind of the compound represented by the formula (7) as the reaction substrate. Moreover, hydrochloric acid, a sulfuric acid, an acetic acid etc. are mentioned as an acid used for the said acid treatment.
As a compound represented by Formula (2), the following compound is mentioned, for example.

As a compound represented by Formula (3), the following compound is mentioned, for example.

Examples of the repeating unit possessed by the polymer compound obtained by reacting the compound represented by the formula (1) with the compound represented by the formula (2) include the following repeating units.

Examples of the repeating unit possessed by the polymer compound obtained by reacting the compound represented by the formula (1) with the compound represented by the formula (3) include the following repeating units.

One preferable aspect of the repeating unit represented by Formula (4) is a repeating unit represented by Formula (5).

(In the formula, R and T have the same meaning as described above.)
From the viewpoint of increasing the photoelectric conversion efficiency of the organic photoelectric conversion element having an organic layer containing the polymer compound, the polymer compound containing the repeating unit represented by the formula (4) produced by the production method of the present invention is: The amount of the repeating unit represented by the formula (4) is preferably 20 to 100 mol%, more preferably 30 to 100 mol% with respect to the total of all repeating units in the polymer compound. preferable.
The polymer compound having a repeating unit represented by the formula (4) preferably has a polystyrene equivalent weight average molecular weight of 10 ³ to 10 ⁸ , more preferably 10 ³ to 10 ⁷ , and still more preferably 10 ³ to 10 ⁶ .
The polymer compound represented by the formula (4) is preferably a conjugated polymer compound. Here, the conjugated polymer compound means a compound in which the main chains of molecules constituting the compound are conjugated.
The high molecular compound which has a repeating unit represented by Formula (4) may have repeating units other than the repeating unit represented by Formula (4). Examples of the repeating unit include an arylene group and a heteroarylene group. Examples of the arylene group include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a pyrenediyl group, and a fluorenediyl group. Examples of the heteroarylene group include a flangyl group, a pyrrole diyl group, a pyridinediyl group, and the like.
The production method of the present invention is a repetition represented by the formula (4) in which the compound represented by the formula (1) is reacted with the compound represented by the formula (2) or the compound represented by the formula (3). It is a manufacturing method of the high molecular compound containing a unit. Examples of the reaction include a Suzuki coupling reaction.
Polymerization by Suzuki coupling reaction can be carried out by using inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, tripotassium phosphate, potassium fluoride, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, water Palladium [tetrakis (triphenylphosphine)], [tris (dibenzylideneacetone)] dipalladium, palladium acetate, bis (triphenylphosphine) palladium dichloride, bis (cyclooctadiene) in the presence of an organic base such as tetraethylammonium oxide Using a palladium complex such as nickel or a nickel complex as a catalyst, triphenylphosphine, tri (2-methylphenyl) phosphine, tri (2-methoxyphenyl) phosphine, Add a ligand such as nylphosphinopropane, tri (cyclohexyl) phosphine, tri (tert-butyl) phosphine, a monomer having boronic acid residue or boric acid ester residue, bromine atom, iodine atom, chlorine atom Polymerization in which a monomer having a halogen atom or the like is reacted. Details of the polymerization by the Suzuki coupling reaction are described in, for example, Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 39, 1533-1556 (2001).
In the production method of the present invention, a solvent is usually used. This solvent may be selected in consideration of the polymerization reaction used, the solubility of the monomer and polymer, and the like. Specifically, tetrahydrofuran, toluene, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, an organic solvent such as a mixed solvent obtained by mixing two or more of these solvents, an organic solvent A mixed solvent having two phases of a phase and an aqueous phase can be mentioned. Solvents used in the Suzuki coupling reaction are organic solvents such as tetrahydrofuran, toluene, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, and mixed solvents in which two or more of these solvents are mixed. A solvent, a mixed solvent having two phases of an organic solvent phase and an aqueous phase is preferable. The reaction solvent is preferably subjected to deoxygenation before the reaction in order to suppress side reactions.
The lower limit of the reaction temperature of the production method of the present invention is preferably −100 ° C., more preferably −20 ° C., and particularly preferably 0 ° C. from the viewpoint of reactivity. The upper limit of the reaction temperature is preferably 200 ° C., more preferably 150 ° C., and particularly preferably 120 ° C. from the viewpoint of the stability of the monomer and the polymer compound.
In the production method of the present invention, a known method may be used as a method for taking out the polymer compound having the repeating unit represented by the formula (4) from the reaction solution after completion of the reaction. For example, a polymer solution having a repeating unit represented by the formula (4) can be obtained by adding a reaction solution to a lower alcohol such as methanol and filtering and drying the deposited precipitate. When the purity of the obtained polymer compound is low, it can be purified by ordinary methods such as recrystallization, continuous extraction with a Soxhlet extractor, column chromatography and the like.
When the polymer compound having a repeating unit represented by the formula (4) is used for the production of an organic photoelectric conversion element, the polymerization active group represented by A or Q as an end group remains in the polymer compound. Since the properties such as durability of the obtained organic photoelectric conversion element may be deteriorated, it is preferable to protect the terminal of the polymer compound with a stable group.
Examples of the stable group for protecting the terminal include an alkyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkoxy group, an aryl group, an arylamino group, and a monovalent heterocyclic group. Moreover, it replaces with stable group and the hydrogen atom may be located in the terminal. From the viewpoint of enhancing the hole transport property by the terminal group, a group imparting electron donating properties such as an arylamino group is preferable. As the terminal group, a group having a conjugated bond continuous with the conjugated structure of the main chain can also be preferably used. Examples of the group include a group bonded to an aryl group or a monovalent heterocyclic group through a carbon-carbon bond. Examples of the arylamino group include a phenylamino group and a diphenylamino group. Examples of the monovalent heterocyclic group include a chenyl group, a pyrrolyl group, a furyl group, a pyridyl group, a quinolyl group, and an isoquinolyl group.
The polymer compound having a repeating unit represented by the formula (4) has a high absorbance of light having a long wavelength such as 600 nm light, and is produced using the polymer compound in order to efficiently absorb sunlight. The organic photoelectric conversion element has a large short-circuit current density.
The organic photoelectric conversion element of the present invention includes a pair of electrodes, a functional layer between the electrodes, and the functional layer containing a polymer compound containing an electron-accepting compound and a repeating unit represented by the formula (4) To do. As an electron-accepting compound, fullerene and a fullerene derivative are preferable. Moreover, among the high molecular compounds containing the repeating unit represented by Formula (4), the high molecular compound containing the repeating unit represented by Formula (5) is 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 a polymer compound containing a repeating unit represented by the formula (4);
2. An organic photoelectric conversion element having a pair of electrodes and a functional layer between the electrodes, the functional layer containing an electron-accepting compound and a polymer compound containing a repeating unit represented by formula (4) An organic photoelectric conversion element in which the electron-accepting compound is a fullerene 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 ratio of the electron-accepting compound in the functional layer containing the electron-accepting compound and the polymer compound is 10 to 1000 parts by weight with respect to 100 parts by weight of the polymer compound. It is preferably 20 to 500 parts by weight. In addition, 2. In the organic photoelectric conversion element, from the viewpoint of increasing the photoelectric conversion efficiency, the ratio of the fullerene derivative in the functional layer is preferably 20 to 400 parts by weight with respect to 100 parts by weight of the polymer compound. The amount is more preferably 250 parts by weight, and further preferably 80 to 120 parts by weight. From the viewpoint of increasing the short-circuit current density, the ratio of the fullerene derivative in the functional layer is preferably 20 to 250 parts by weight, more preferably 40 to 120 parts by weight with respect to 100 parts by weight of the polymer. preferable.
In order for the organic photoelectric conversion element to have high photoelectric conversion efficiency, the electron-accepting compound and the polymer compound having the repeating unit represented by the formula (4) can efficiently absorb the spectrum of desired incident light. It has an absorption region that can be formed, the heterojunction interface includes many heterojunction interfaces in order to efficiently separate excitons, and has a charge transport property that quickly transports the charges generated by the heterojunction interface to the electrode. This is very important.
From such a viewpoint, as the organic photoelectric conversion element, the above 1. , 2. 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.
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 of the pair of electrodes, a metal, a conductive polymer, or the like can be used. Preferably, 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.
As said functional layer in the organic photoelectric conversion element of this invention, the organic thin film containing the high molecular compound which has a repeating unit represented by Formula (4) can be used, for example.
The thickness of the organic thin film is usually 1 nm to 100 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 high molecular compound which has a repeating unit represented by Formula (4) individually by 1 type, or may contain it in combination of 2 or more types. Moreover, in order to improve the hole transport property of an organic thin film, another high molecular compound or a low molecular compound can also be mixed and used as an electron-donating compound in an organic thin film.
Examples of the electron-donating compound that the organic thin film may contain in addition to the polymer compound having the repeating unit represented by the formula (4) include, for example, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligos. Thiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof Derivatives, polythienylene vinylene and its derivatives.
Examples of the electron accepting compound include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, and fluorenone derivatives. , diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, 8-hydroxyquinoline and metal complexes of derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and its derivatives, polyfluorene and its derivatives, fullerene and derivatives thereof such as C _60, carbon nanotube And phenanthroline derivatives such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, and fullerene and derivatives thereof are particularly preferable.
The electron-donating compound and the electron-accepting compound are relatively determined from the energy levels of these compounds.
Fullerenes and derivatives thereof include C ₆₀ , C ₇₀ , C ₈₄ and derivatives thereof. A fullerene derivative represents a compound in which at least a part of fullerene is modified.
Examples of the fullerene derivative include a compound represented by the formula (I), a compound represented by the formula (II), a compound represented by the formula (III), and a compound represented by the formula (IV).

(In the 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 and aryl group represented by R ^a and R ^b are the same as the definitions and specific examples of the alkyl group and aryl group represented by R.
The heteroaryl group represented by ^Ra usually has 3 to 60 carbon atoms, and examples thereof include a chenyl group, a pyrrolyl group, a furyl group, a pyridyl group, a quinolyl group, and an isoquinolyl group.
Examples of the group having an ester structure represented by ^Ra include a group represented by the formula (V).

(In the formula, 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 ^a .
Specific examples of the C ₆₀ derivative include the following.

Specific examples of the C ₇₀ derivative include the following.

The organic thin film may be produced by any method, for example, a method by film formation from a solution containing a polymer compound having a repeating unit represented by formula (4), or vacuum deposition. An organic thin film may be formed by a method. Examples of the method for producing an organic thin film by film formation from a solution include a method of producing an organic thin film by applying the solution on one electrode and then evaporating the solvent.
The solvent used for film formation from a solution is not particularly limited as long as it dissolves the polymer compound. Examples of the solvent include hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, Examples thereof include halogenated hydrocarbon solvents such as bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, chlorobenzene, dichlorobenzene, and trichlorobenzene, and ether solvents such as tetrahydrofuran and tetrahydropyran. The polymer compound 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.
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.

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 ml.d. × 15 cm); Detector: RI (SHIMADZU RID-10A); Mobile phase: Tetrahydrofuran (THF)
Synthesis Example 1 Synthesis of Compound (2)

In a 100 ml three-necked flask equipped with a Dimroth condenser in a nitrogen atmosphere, Adv. Funct. Mater. 2007, Vol. 17, pages 3836-3842, 3.1 g (4.5 mmol) of compound (1) synthesized by the method described in pages 3836-3842 and 50 ml of anhydrous tetrahydrofuran (THF) were added and stirred at -78 ° C. While maintaining the temperature in the flask at −70 ° C. or lower, 5.9 ml (9.3 mmol) of a 1.57 M n-butyllithium hexane solution was added dropwise and stirred for 1 hour. Thereafter, 1.0 g (9.6 mmol) of trimethoxyborane was dropped into the flask, stirred for 30 minutes, then warmed to room temperature (25 ° C.) and stirred for 5 hours. Thereafter, 50 ml of water was added, and extraction with 100 ml of diethyl ether was performed twice. After concentrating the obtained organic layer with an evaporator, 50 ml of chloroform and 50 ml of 6N-hydrochloric acid were added to the concentrated solution, and the mixture was stirred at room temperature (25 ° C.) for 5 hours. After standing for 1 hour, the solid obtained by filtration was dried under reduced pressure (30 mmHg, 80 ° C.) for 5 hours to obtain 0.74 g of Compound (2). The compound (2) was used for the next reaction without purification. The yield of compound (2) was 26%.
Synthesis Example 2 Synthesis of Compound (3)

In a 100 ml three-necked flask, 0.74 g (1.2 mmol) of compound (2), 0.29 g (2.5 mmol) of pinacol, and 30 ml of chloroform were added at room temperature (25 ° C.) to form a slurry reaction. The mixture was stirred while heating to reflux until the solution became a homogeneous solution. Thereafter, 1.0 g of anhydrous magnesium sulfate was added to the reaction solution, and the mixture was further stirred while heating under reflux for 4 hours. After stirring, the mixture was filtered, and the filtrate was concentrated with an evaporator. After concentration, the residue was washed with 20 ml of hexane, and the resulting crystals were collected by filtration and dried under reduced pressure (50 mmHg, 30 ° C.) for 3 hours to obtain 0.57 g (0.73 mmol) of Compound (3). The yield of compound (3) was 62%.
¹ H-NMR (270 MHz / CDCl ₃ ):
δ 7.9 (s, 2H), 7.39 (brs, 2H), 7.15 (m, 4H), 6.87 (m, 2H), 3.88 (t, 4H), 1.77-1 .66 (m, 4H), 1.47 (s, 24H), 1.50-1.20 (m, 24H), 0.89 (t, 6H)
Example 1 Synthesis of Polymer Compound A In an argon atmosphere, 150 mg (0.190 mmol) of compound (3), 46 mg (0.190 mmol) of 2,5-dibromothiophene (manufactured by Tokyo Chemical Industry), trioctylmethyl in a reaction vessel 49 mg of ammonium chloride (trade name Aliquat 336 (registered trademark), manufactured by Sigma-Aldrich Co.) and 10 mL of toluene were added, and the resulting solution was bubbled with argon and sufficiently deaerated. Further, 0.64 mg (0.00285 mmol) of palladium acetate, 3.50 mg (0.00993 mmol) of tris (methoxyphenyl) phosphine, and 1.0 mL of degassed 16.7 wt (wt)% aqueous sodium carbonate solution were added, The reaction was refluxed for 4 hours. Next, 10.0 mg of phenylboric acid was added to the reaction solution, followed by refluxing for 2 hours. Thereafter, 10 ml of a 9.1 wt% sodium diethyldithiocarbamate aqueous solution was added to the reaction solution, and the mixture was refluxed for 5 hours. After completion of the reflux, the reaction solution was cooled to room temperature (25 ° C.). Thereafter, the reaction solution was allowed to stand, and a separated toluene layer was obtained. The toluene layer was washed twice with 10 mL of water, twice with 10 mL of 3 wt% aqueous acetic acid and twice with 10 mL of water, and the obtained toluene layer was poured into methanol to obtain a deposited precipitate. This precipitate was dried under reduced pressure and then dissolved in toluene. Next, the obtained toluene solution was filtered to remove insoluble matters, and then passed through an alumina / silica gel column for purification. The obtained toluene solution was concentrated under reduced pressure and then poured into methanol to obtain a generated precipitate. The precipitate was washed with methanol and dried under reduced pressure to obtain 65 mg of polymer compound A.
The high molecular compound A contains only the repeating unit represented by the following formula.

Example 2 Synthesis of polymer compound B

Monomer synthesized by a method described in 312 mg (0.395 mmol) of Compound (3) in a reaction vessel in an argon atmosphere, Journal of Materials Chemistry, 2002, No. 12, pages 2887-2892 200 mg (0.436 mmol) of A, 128 mg of trioctylmethylammonium chloride (trade name Aliquat 336 (registered trademark), manufactured by Sigma-Aldrich Co.) and 26 mL of toluene were added, and the solution obtained using argon was sufficiently bubbled. Deaerated. Further, 1.47 mg (0.00655 mmol) of palladium acetate, 8.10 mg (0.0230 mmol) of tris (methoxyphenyl) phosphine, and 2.6 mL of degassed 16.7 wt% aqueous sodium carbonate solution were added, and the reaction solution was added to 1 Reflux for hours. Next, 60.0 mg of phenylboric acid was added to the reaction solution, followed by refluxing for 2 hours. Thereafter, the reaction solution was poured into methanol, and the precipitated polymer was filtered and obtained. The obtained polymer was washed twice with 50 mL of pure water and twice with 50 mL of methanol and dried to obtain 230 mg of a polymer.
The polymer obtained above was dissolved in 30 mL of orthodichlorobenzene, 10 ml of a 9.1 wt% sodium diethyldithiocarbamate aqueous solution was added, and the reaction solution was refluxed for 5 hours. After completion of the reflux, the reaction solution was cooled to around room temperature (25 ° C.). Thereafter, the reaction solution was allowed to stand to obtain a separated orthodichlorobenzene layer. The orthodichlorobenzene layer was washed twice with 10 mL of water, twice with 10 mL of 3 wt% acetic acid water, and further twice with 10 mL of water, and the resulting orthodichlorobenzene layer was poured into methanol to obtain a deposited precipitate. did. The precipitate was dried under reduced pressure and then dissolved in orthodichlorobenzene. Next, the obtained orthodichlorobenzene solution was filtered to remove insolubles, and then the filtrate was passed through an alumina / silica gel column for purification. The obtained orthodichlorobenzene solution was concentrated under reduced pressure, poured into methanol, and the resulting precipitate was recovered. This precipitate was washed with methanol and then dried under reduced pressure to obtain 170 mg of polymer compound B.
The high molecular compound B contains only the repeating unit represented by the following formula.

Synthesis Example 3 Synthesis of Polymer Compound C

In a 2 L four-necked flask in which the gas in the flask was replaced with argon, 7.928 g (16.72 mmol) of compound (C), 13.00 g (17.60 mmol) of compound (F), trioctylmethylammonium chloride ( 4.979 g of trade name Aliquat 336 (registered trademark), manufactured by Sigma-Aldrich, CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ Cl, density 0.884 g / ml, 25 ° C.), and 405 ml of toluene were added and stirred. Then, argon was bubbled through the reaction system for 30 minutes. 0.02 g of dichlorobis (triphenylphosphine) palladium (II) was added to the flask, the temperature was raised to 105 ° C., and 42.2 ml of a 2 mol / L sodium carbonate aqueous solution was added dropwise with stirring. After completion of the dropwise addition, the reaction was allowed to proceed for 5 hours, and then 2.6 g of phenylboronic acid and 1.8 ml of toluene were added, followed by stirring at 105 ° C. for 16 hours. Thereafter, 700 ml of toluene and 200 ml of a 7.5 wt% sodium diethyldithiocarbamate trihydrate aqueous solution were added to the reaction solution, followed by stirring at 85 ° C. for 3 hours. After removing the aqueous layer of the reaction solution, the organic layer was washed twice with 300 ml of ion exchange water at 60 ° C., once with 300 ml of 3 wt% acetic acid at 60 ° C., and further three times with 300 ml of ion exchange water at 60 ° C. The organic layer was passed through a column filled with celite, alumina and silica to obtain a filtrate. Thereafter, the column was washed with 800 ml of hot toluene, and the washed toluene solution was added to the filtrate. After the obtained solution was concentrated to 700 ml, the concentrated solution was added to 2 L of methanol to reprecipitate the polymer. The polymer was obtained by filtration, and the polymer was washed with 500 ml of methanol, 500 ml of acetone, and 500 ml of methanol. The polymer was vacuum-dried at 50 ° C. overnight to obtain 12.21 g of a pentathienyl-fluorene copolymer (polymer compound C). The weight average molecular weight in terms of polystyrene of the polymer compound C was 1.1 × 10 ⁵ .
Measurement Example 1 Measurement of absorbance of organic thin film Polymer compound A was dissolved in o-dichlorobenzene at a concentration of 0.5% by weight to prepare a coating solution. The obtained coating solution was applied onto a glass substrate by spin coating. The coating operation was performed at 23 ° C. Then, it baked for 5 minutes on 120 degreeC conditions in air | 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). The measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm and 700 nm.
Measurement Example 2 Measurement of Absorbance of Organic Thin Film An organic thin film was prepared in the same manner as in Measurement Example 1 except that polymer compound B was used instead of polymer compound A, and the absorption spectrum of the organic thin film was measured. The measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm and 700 nm.
Comparative Example 1 Measurement of Absorbance of Organic Thin Film An organic thin film was prepared in the same manner as in Measurement Example 1 except that the polymer compound C was used in place of the polymer compound A, and the absorption spectrum of the organic thin film was measured. The measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm and 700 nm.

Reference Example 1 Preparation and Evaluation of Organic Thin Film Solar Cell Fullerene derivative C70PCBM (Phenyl C71-butylic acid methyl ester, trade name: ADS71BFA), which is an electron-accepting compound, and a polymer which is an electron-donating compound Compound A was mixed at a weight ratio of 2: 1 and dissolved in o-dichlorobenzene so that the concentration of the mixture was 2% by weight. The obtained solution was filtered through a Teflon (registered trademark) filter having a pore size of 1.0 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 HC Starck Co., Ltd.) is applied onto the ITO film by spin coating, and heated at 120 ° C. for 10 minutes in the atmosphere to thereby form a hole injection layer having a thickness of 50 nm. It was created. 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 resulting organic thin-film solar cell is measured by irradiating with constant light using a solar simulator (trade name OTENTO-SUN II: AM1.5G filter, irradiance 100 mW / cm ² , manufactured by Spectrometer Co., Ltd.), and a generated current And the voltage was measured to obtain the photoelectric conversion efficiency. The photoelectric conversion efficiency was 3.87%, the short-circuit current density was 8.5 mA / cm ² , the open-circuit voltage was 0.91 V, and the fill factor (FF) was 0.50.
Reference Example 2 Production and Evaluation of Organic Thin Film Solar Cell Instead of C70PCBM, C60PCBM (phenyl C61-butyric acid methyl ester, product name: E100) was used instead of polymer compound A instead of C70PCBM. An organic thin film solar cell was prepared and evaluated in the same manner as in Reference Example 1 except that the polymer compound B was used and C60PCBM and the polymer compound B were mixed at a weight ratio of 3: 1. The photoelectric conversion efficiency was 1.6%, the short-circuit current density was 5.6 mA / cm ² , the open-circuit voltage was 0.54 V, and FF was 0.53.

The method for producing a polymer compound of the present invention is useful for producing a polymer compound having a large absorbance of light having a long wavelength.

Claims

A polymer compound comprising a repeating unit represented by formula (4), wherein a compound represented by formula (1) and a compound represented by formula (2) or a compound represented by formula (3) are reacted. Production method.

In the formula, R represents a hydrogen atom, a fluorine atom, an alkyl group which may be substituted with a fluorine atom, an alkoxy group which may be substituted with a fluorine atom, or an aryl group which may be substituted. Two R may be the same or different. Q represents a dihydroxyboryl group or a borate ester residue. Two Qs may be the same or different.

In Formula (2) and Formula (3), T is a hydrogen atom, a fluorine atom, an alkyl group which may be substituted with a fluorine atom, an alkoxy group which may be substituted with a fluorine atom, or an optionally substituted group. Represents an aryl group. A plurality of T may be the same or different. A represents a bromine atom, a chlorine atom or an iodine atom. Two A may be the same or different.

In the formula, a represents 0 or 1. T and R represent the same meaning as described above.
The high molecular compound containing the repeating unit represented by Formula (5).

In the formula, R represents a hydrogen atom, a fluorine atom, an alkyl group which may be substituted with a fluorine atom, an alkoxy group which may be substituted with a fluorine atom, or an aryl group which may be substituted. Two R may be the same or different. T represents a hydrogen atom, a fluorine atom, an alkyl group which may be substituted with a fluorine atom, an alkoxy group which may be substituted with a fluorine atom, or an aryl group which may be substituted. A plurality of T may be the same or different.
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 2.
The organic photoelectric conversion device 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 element according to claim 3, wherein the electron-accepting compound is a fullerene derivative.
The organic photoelectric conversion element according to claim 4, wherein the electron-accepting compound is a fullerene derivative.