JP2013234265A - POLYMER HAVING π BACKBONE PLANARITY AND APPLICATION THEREOF - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer that has a high degree of π backbone planarity and is excellent in absorption characteristics of light in the visible to near-infrared wavelength region.SOLUTION: A polymer includes a structural unit represented by general formula (1). [In formula (1), X represents an oxygen atom, a sulfur atom or a selenium atom; Y represents CRR, SiRR, GeRR, NR, an oxygen atom, a sulfur atom or a selenium atom wherein R, Rand Reach independently represent a hydrogen atom or a 1-20C alkyl group which may have a substituent and R, R, Rand Reach independently represent a 1-20C alkyl group which may have a substituent; and Z represents any one selected from (i) a divalent aromatic ring which may have a substituent, (ii) a divalent polynuclear aromatic ring having 2 to 7 aromatic rings which may have a substituent and (iii) a divalent polyarylene group having an aromatic ring selected from (i) and/or (ii) linked up to a maximum of 3].

Description

  The present invention relates to a polymer having high π skeleton planarity, a precursor thereof, and a use thereof.

Since a copolymer obtained by polymerizing an organic donor compound and an organic acceptor compound is suitable as a constituent material of an organic semiconductor device such as an organic thin film transistor or an organic thin film solar cell, research has been actively conducted in recent years. It is known that the performance of the organic semiconductor element mentioned above can be controlled by changing the combination of the organic donor compound and the organic acceptor compound of these copolymers. Among the copolymers of organic donors and organic acceptors that have been reported so far, copolymers using substituted or unsubstituted fluorene, carbazole, dibenzosilol, or dibenzogermole as organic donor compounds show good performance. It is known as a material for providing the element.
For example, poly [(9,9-dialkylfluorene-2,7-diyl) -alt- [bis (3-alkylthiophen-5-yl) -2,1,3-benzothiadiazole] (Non-patent Document 1), Or p-type such as poly [(N-alkylcarbazole-2,7-diyl) -alt- [bis (3-alkylthiophen-5-yl) -2,1,3-benzothiadiazole] (Non-patent Document 2) By using a material in which a polymer to be a semiconductor and phenyl C ₆₁ butyric acid methyl ester or phenyl C ₇₁ butyric acid methyl ester are mixed, an organic photoelectric conversion element having a high open-circuit voltage can be produced. Derivatives have been reported. From these absorption characteristics and structural analysis by X-ray diffraction, it is considered that the main chain skeleton of the polymer is twisted.

It is known that when the polymer main chain skeleton is on the same plane, the energy difference between the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) is reduced. When used as a constituent material of an organic photoelectric conversion element, if the energy difference between HOMO and LUMO is smaller, it can have the ability to absorb light having a longer wavelength. Therefore, it is generally known that in organic conjugated polymers, one of the conditions is that the main chain skeleton has high planarity in order for the polymer to have the ability to absorb long-wavelength light. Conversely, it is known that the twist of the main chain skeleton causes a significant decrease in the light absorption characteristics of these lights.
The photoelectric conversion efficiency of organic photoelectric conversion elements correlates with the light absorption characteristics of the polymers used therefor, so the main chain skeleton has high planarity and absorbs light of longer wavelengths than these previously reported polymers. It would be desirable to provide polymers with the ability to

Mei-Hsin Chen, Jianhui Hou, Ziruo Hong, Guiwen Yang, Srinivas Sista, Li-Min Chen and Yang Yang, Efficient Polymer Solar Cells with Thin Active Layers Based on Alternating Polyfluorene Copolymer / Fullerene Bulk Heterojunctions, Advanced Materials, 21, Issue 42 , p4238-4242 (2009) J. Li, A. C. Grimsdale, Carbazole-based polymers for organic photovoltaic devices, Chemical Society Reviews, 39, Issue 7, p2399-2410 (2010)

  The present invention has been made in order to solve the above problems, and has a polymer main chain skeleton having a high π skeleton planarity and a polymer excellent in light absorption characteristics in the visible to near-infrared wavelength region. The purpose is to provide.

[(１)式中、Ｒ^１及びＲ^２はそれぞれ独立して置換基を有してもよい炭素数１〜２０のアルキル基を表し、Ｘは酸素原子、硫黄原子又はセレン原子を表し、ＹはＣＲ^３Ｒ^４、ＳｉＲ^５Ｒ^６、ＧｅＲ^７Ｒ^８、ＮＲ^９、酸素原子、硫黄原子又はセレン原子を表す。ここで、Ｒ^３、Ｒ^４、及びＲ^９はそれぞれ独立して水素原子又は置換基を有してもよい炭素数１〜２０のアルキル基を表し、Ｒ^５、Ｒ^６、Ｒ^７、及びＲ^８はそれぞれ独立して置換基を有してもよい炭素数１〜２０のアルキル基を表す。
Ｚは（i）置換基を有してもよい２価の芳香環、（ii）置換基を有してもよい芳香環数２〜７の２価の多核芳香環、又は(iii)前記の(i)及び/若しくは(ii)から選ばれる芳香環を最大で３つまで連結させた２価のポリアリーレン基、から選択される何れか１つを表す。ｎは２以上の数でありｍは０又は１である。] That is, the present invention is a polymer represented by the following general formula (1).

[In the formula (1), R ¹ and R ² each independently represents an optionally substituted alkyl group having 1 to 20 carbon atoms, X represents an oxygen atom, a sulfur atom or a selenium atom, Y Represents CR ³ R ⁴ , SiR ⁵ R ⁶ , GeR ⁷ R ⁸ , NR ⁹ , an oxygen atom, a sulfur atom or a selenium atom. Here, R ³ , R ⁴ , and R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms that may have a substituent, and R ⁵ , R ⁶ , R ⁷ , and R 9 ⁸ represents a C1-C20 alkyl group which may have a substituent each independently.
Z is (i) a divalent aromatic ring which may have a substituent, (ii) a divalent polynuclear aromatic ring having 2 to 7 aromatic rings which may have a substituent, or (iii) the above-mentioned It represents any one selected from divalent polyarylene groups in which up to three aromatic rings selected from (i) and / or (ii) are linked. n is a number of 2 or more, and m is 0 or 1. ]

[(２)式中、Ｒ^１、Ｒ^２、Ｘ及びＹは前記（１）式と同義である。Ｗは、ハロゲン原子、−Ｓｎ（Ｒ^１０）_３、ボロン酸及びボロン酸エステル基からなる群から選択される１種を表す。ここで、Ｒ^１０は、置換基を有してもよい炭素数１〜１０のアルキル基又はアリール基を表す。] Moreover, this invention is a compound shown by following General formula (2).

[In the formula (2), R ¹ , R ² , X and Y are as defined in the formula (1). W represents one selected from the group consisting of a halogen atom, —Sn (R ¹⁰ ) ₃ , a boronic acid and a boronic ester group. Wherein, R ¹⁰ represents an alkyl group or an aryl group of good C1-10 substituted. ]

  Furthermore, this invention is the organic-semiconductor device produced using said polymer. The organic semiconductor device is suitable as an organic photoelectric conversion element.

  According to the present invention, a polymer having high π skeleton planarity can be provided. The polymer thus obtained is suitable as an organic semiconductor device material because it has excellent absorption characteristics of light in the visible to near-infrared wavelength region.

2 is an absorption spectrum of the polymers obtained in Examples 1 to 3 and Comparative Example 1. 3 is an absorption spectrum of the polymers obtained in Example 4 and Comparative Example 2.

[(１)式中、Ｒ^１及びＲ^２はそれぞれ独立して置換基を有してもよい炭素数１〜２０のアルキル基を表し、Ｘは酸素原子、硫黄原子又はセレン原子を表し、ＹはＣＲ^３Ｒ^４、ＳｉＲ^５Ｒ^６、ＧｅＲ^７Ｒ^８、ＮＲ^９、酸素原子、硫黄原子又はセレン原子を表す。ここで、Ｒ^３、Ｒ^４、及びＲ^９はそれぞれ独立して水素原子又は置換基を有してもよい炭素数１〜２０のアルキル基を表し、Ｒ^５、Ｒ^６、Ｒ^７、及びＲ^８はそれぞれ独立して置換基を有してもよい炭素数１〜２０のアルキル基を表す。
Ｚは
（ｉ）置換基を有してもよい２価の芳香環、
（ii）置換基を有してもよい芳香環数２〜７の２価の多核芳香環、又は
（iii）前記の(i)及び/若しくは(ii)から選ばれる芳香環を最大で３つまで連結させた２価のポリアリーレン基、から選択される何れか１つを表す。
ｎは２以上の数であり、ｍは０又は１である。]
本発明の重合体は、Ｒ^１及びＲ^２が酸素原子を介してポリマー主鎖骨格に結合していること、すなわちアルコキシ基がポリマー主鎖骨格に結合していることにより、高いπ骨格平面性を有し、優れた光電変換効率を発現する。 According to the present invention, a polymer represented by the following general formula (1) can be provided. Details will be described below.

[In the formula (1), R ¹ and R ² each independently represents an optionally substituted alkyl group having 1 to 20 carbon atoms, X represents an oxygen atom, a sulfur atom or a selenium atom, Y Represents CR ³ R ⁴ , SiR ⁵ R ⁶ , GeR ⁷ R ⁸ , NR ⁹ , an oxygen atom, a sulfur atom or a selenium atom. Here, R ³ , R ⁴ , and R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms that may have a substituent, and R ⁵ , R ⁶ , R ⁷ , and R 9 ⁸ represents a C1-C20 alkyl group which may have a substituent each independently.
Z is (i) a divalent aromatic ring optionally having a substituent,
(Ii) a divalent polynuclear aromatic ring having 2 to 7 aromatic rings which may have a substituent, or (iii) a maximum of three aromatic rings selected from the above (i) and / or (ii) Any one selected from divalent polyarylene groups linked to
n is a number of 2 or more, and m is 0 or 1. ]
The polymer of the present invention has high π skeleton planarity because R ¹ and R ² are bonded to the polymer main chain skeleton via an oxygen atom, that is, the alkoxy group is bonded to the polymer main chain skeleton. And exhibits excellent photoelectric conversion efficiency.

(1) Among R ^{1 to} R ⁹ in the formula, the alkyl group having 1 to 20 carbon atoms which may have a substituent may be, for example, a linear or branched alkyl group, or cyclic. May be a cycloalkyl group. For example, methyl group, ethyl group, n-propyl group, n-butyl, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl Linear of n group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group Alkyl group, 1-methylethyl group, 1,1-dimethylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-methylpentyl group, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2,3-dimethylbutyl, 2-ethylbutyl, 1-methylhexyl, 2-methyl Ruhexyl group, 3-methylhexyl group, 4-methylhexyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3-ethylpentyl group, 2,3,3-trimethylbutyl group, 1-methyl Heptyl group, 2-methylheptyl group, 6-methylheptyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 2,5-dimethylhexyl group, 1-methyloctyl group, 2-methyloctyl group, 4-methyloctyl group, 6-methyloctyl group, 3,5,5-trimethylhexyl group, 1-methylnonyl group, 2-methylnonyl group, 3,7-dimethyloctyl group, 2,3,3,4-tetra Branched alkyl groups such as methylpentyl, 1-methyldecyl, 2-methyldecyl, 5-methyldecyl, 4-methyldodecyl; Black group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptanyl group, cyclooctanyl group, cyclononanyl group, cyclodecanyl group, a cycloalkyl undecanyloxy group, a cycloalkyl group such as a cyclododecanyl group.
The alkyl group may have a substituent. Examples of the substituent include an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, and an arylalkylthio group. , Arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, Examples include a carboxyl group, a substituted carboxyl group, a nitro group, a cyano group, and a hydroxyl group. The hydrogen atom contained in these substituents may be replaced with a fluorine atom.

X is an oxygen atom, a sulfur atom or a selenium atom, and the 5-membered rings each having X are a furan ring, a thiophene ring and a selenophene ring. Of these, X is preferably a sulfur atom.
Y is CR ³ R ⁴ , SiR ⁵ R ⁶ , GeR ⁷ R ⁸ , NR ⁹ , an oxygen atom, a sulfur atom or a selenium atom, and among them, it is directly bonded to two benzene rings to form a central 5-membered ring. It is preferable that the atom is a carbon atom or a nitrogen atom, that is, the condensed ring constituting the polymer main chain skeleton is a fluorene ring or a carbazole ring.

(1) In the formula, among (i) to (iii) representing Z, (i) a divalent aromatic ring optionally having a substituent is, for example, (A1) to (A10) shown below. Can be mentioned.

Moreover, in formula (1), among (i) to (iii), (ii) a divalent polynuclear aromatic ring having 2 to 7 aromatic rings which may have a substituent is, for example, ( A11)-(A51).

R ^{11 to} R ¹⁴ in the above (A1) to (A51) are each independently an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, or an arylalkylthio group. , Arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, Examples include a carboxyl group, a substituted carboxyl group, a nitro group, a cyano group, and a hydroxyl group. The hydrogen atom contained in these substituents may be replaced with a fluorine atom. These substituents are exemplified in the same manner as described above.

  Among (i) to (iii) representing Z, (iii) as a divalent polyarylene group in which up to three aromatic rings selected from the above (i) and / or (ii) are linked, Examples thereof include bithiophene and terthiophene.

  Among the above (A1)-(A51), from the viewpoint of improving the light absorption characteristic light in the visible to near-infrared wavelength region, Z is a polynuclear heteroaromatic ring containing O, N and S atoms in the aromatic ring. Are preferred, and the aromatic rings represented by (A22), (A25) and (A27) are more preferred.

In addition to the structural unit represented by the general formula (1), the polymer of the present invention may have a structural unit composed of another π skeleton monomer or the like as long as the effects of the invention are not impaired. The copolymerization form of the other structural unit may be any of random copolymerization, alternating copolymerization, block copolymerization, and graft copolymerization.
The number average degree of polymerization n of the polymer of the present invention is a number of 2 or more, preferably 5 to 1000.

[(２)式中、Ｒ^１及びＲ^２はそれぞれ独立して置換基を有してもよい炭素数１〜２０のアルキル基を表し、Ｘは酸素原子、硫黄原子又はセレン原子を表し、ＹはＣＲ^３Ｒ^４、ＳｉＲ^５Ｒ^６、ＧｅＲ^７Ｒ^８、ＮＲ^９、酸素原子、硫黄原子又はセレン原子を表す。ここで、Ｒ^３、Ｒ^４、及びＲ^９はそれぞれ独立して水素原子又は置換基を有してもよい炭素数１〜２０のアルキル基を表し、Ｒ^５、Ｒ^６、Ｒ^７、及びＲ^８はそれぞれ独立して置換基を有してもよい炭素数１〜２０のアルキル基を表す。Ｗは、ハロゲン原子、−Ｓｎ（Ｒ^１０）_３、ボロン酸及びボロン酸エステル基からなる群から選択される１種を表す。ここで、Ｒ^１０は炭素数１〜６の炭化水素を表す。]
Ｒ^１０の表す炭素数１〜６の炭化水素とは、例えば、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、シクロヘキシル基が挙げられる。 The polymer represented by the general formula (1) can be obtained by using a compound represented by the following general formula (2) as a precursor.

[In the formula (2), R ¹ and R ² each independently represents an optionally substituted alkyl group having 1 to 20 carbon atoms, X represents an oxygen atom, a sulfur atom or a selenium atom, Y Represents CR ³ R ⁴ , SiR ⁵ R ⁶ , GeR ⁷ R ⁸ , NR ⁹ , an oxygen atom, a sulfur atom or a selenium atom. Here, R ³ , R ⁴ , and R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms that may have a substituent, and R ⁵ , R ⁶ , R ⁷ , and R 9 ⁸ represents a C1-C20 alkyl group which may have a substituent each independently. W represents one selected from the group consisting of a halogen atom, —Sn (R ¹⁰ ) ₃ , a boronic acid and a boronic ester group. ^{Wherein, R 10} represents a hydrocarbon having 1 to 6 carbon atoms. ]
Examples of the hydrocarbon having 1 to 6 carbon atoms represented by R ¹⁰ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and a cyclohexyl group.

(About the synthesis method)
In the present invention, a method for producing the polymer represented by the general formula (1) will be described.
In the present invention, among the polymers represented by the general formula (1), the polymer represented by m is 0 among the compounds represented by the general formula (2) as shown in the chemical reaction formula (I) below. , W can be obtained by polymerizing the compound (2a) in which a hydrogen atom is represented.

Although it does not specifically limit as a polymerization reaction of the said process (I), A suitable polymerization reaction is chemical oxidation polymerization or electrolytic polymerization.
As chemical oxidative polymerization, a method in which a polymer is obtained by dehydrogenation from a monomer compound using an oxidizing agent is suitably employed. Although it does not specifically limit as an oxidizing agent used by chemical oxidative polymerization, It is preferable that it is a transition metal salt. Examples of the transition metal salt include ferric chloride (FeCl 3), ferric sulfate (Fe 2 (SO 4) 3), iron alkoxybenzene sulfonate having 1 to 16 carbon atoms, and iron iron alkylbenzene sulfonate having 1 to 16 carbon atoms. , Iron naphthalene sulfonate, iron phenol sulfonate, iron disulfoisophthalate dialkyl ester, iron alkyl sulfonate, iron naphthalene sulfonate, iron alkoxy naphthalene sulfonate, iron tetralin sulfonate, iron tetralin sulfonate having 1 to 12 carbon atoms, etc. Ferric salts of the above, or cerium (IV) salts, copper (II) salts, manganese (VII) salts, ruthenium (III) salts, etc. in place of the iron (III) salts of these compounds Can do. Among these, iron (III) salts are preferably used.

In the above step (I), when polymerizing by electrolytic polymerization, an electrolytic solution in which a monomer as a polymerization raw material is dissolved is prepared, and an anodized heavy metal is applied by applying a voltage between the electrodes through the electrolytic solution. A method in which the coalescence is obtained on the anode is preferably employed. Examples of the solvent used for the electrolyte include nitromethane, acetonitrile, propylene carbonate, nitrobenzene, cyanobenzene, o-dichlorobenzene, dimethyl sulfoxide, γ-butyrolactone, and methylene chloride. The supporting electrolyte used in the electrolytic solution is a cation such as lithium ion, potassium ion, sodium ion or other alkali metal ions or quaternary ammonium ion, perchlorate ion, boron tetrafluoride ion, phosphorus hexafluoride ion, halogen atom ion, It is preferable to add a supporting salt made of a combination of anions such as arsenic hexafluoride ion, antimony hexafluoride ion, sulfate ion and hydrogen sulfate ion. As the electrolytic solution, an ionic liquid such as an alkyl imidazolium salt or an alkyl pyridinium salt can also be used. Platinum, gold, nickel, ITO or the like can be used as the electrode material.
The product obtained by chemical oxidative polymerization or electrolytic polymerization has an anion derived from an oxidant, Y- functions as a dopant, and an oxidized polymer is obtained. A polymer represented by the general formula (1) can be obtained. As the reducing agent, a reducing agent such as ammonia or hydrazine is preferably used.

Next, in the present invention, among the polymers represented by the general formula (1), a polymer in which m is 1 can be obtained by any of the following methods (a) or (b). it can.
(A) In the general formula (2), W is a halogen atom, and V in the general formula (3) described in the following reaction formula (II) is -Sn (R ¹⁰ ) ₃ (R ¹⁰ is the number of carbon atoms. 1 to 6 hydrocarbons), a compound represented by any one of boronic acid or boronic ester groups.
(A) In the general formula (2), W is represented by any one of -Sn (R ¹⁰ ) ₃ (R ¹⁰ represents a hydrocarbon having 1 to 6 carbon atoms), boronic acid or boronic ester group. A method in which a compound and a compound in which V in the general formula (3) described in the following reaction formula (II) is a halogen atom are cross-coupled.

［(II)式中、Ｒ^１、Ｒ^２、Ｘ、Ｙ及びＺは、前記一般式（１）及び（２）と同義である。Ｗ及びＶは上記（ア）若しくは（イ）の記載と同義である。］
上記反応式(II)におけるクロスカップリング反応としては、例えば、Ｓｔｉｌｌｅカップリング反応、Ｓｕｚｕｋｉカップリング反応が好適に採用される。

[In the formula (II), R ¹ , R ² , X, Y and Z have the same meanings as in the general formulas (1) and (2). W and V are as defined above in (a) or (b). ]
As the cross-coupling reaction in the above reaction formula (II), for example, Stille coupling reaction and Suzuki coupling reaction are preferably employed.

［(III)式中、Ｒ^１、Ｒ^２、Ｘ、Ｙ及びＺは、前記一般式（１）及び（２）と同義である。］
上記反応(III)の好適な実施態様としては、例えば、窒素、アルゴンなどの不活性ガス雰囲気下で、溶媒および金属錯体の存在下でクロスカップリング反応させる方法が挙げられる。上記反応（III）で用いられる金属錯体としては、例えば、ニッケルやパラジウム等の金属錯体が挙げられ、特にＰｄ（ＰＰｈ_３）_４、ＰｄＣｌ_２（ｄｐｐf）、又はＮｉＣｌ_２（ｄｐｐｐ）等のようにホスフィン類が配位している金属錯体を用いることが好ましい。 Hereinafter, the reaction formula (II) will be described in detail with specific examples, but the scope of the present invention is not limited to the following specific examples. For example, as shown in the following reaction formula (III), the polymer represented by the general formula (1) is a compound in which W is a bromine atom in the general formula (2) and V in the general formula (3). Can be obtained by polymerizing a compound represented by 4,4,5,5-tetramethyl-1,3,2-dioxaborolane by a Suzuki coupling reaction.

[In the formula (III), R ¹ , R ² , X, Y and Z have the same meanings as in the general formulas (1) and (2). ]
A preferred embodiment of the reaction (III) includes, for example, a method in which a cross-coupling reaction is performed in the presence of a solvent and a metal complex in an inert gas atmosphere such as nitrogen or argon. Examples of the metal complex used in the reaction (III) include metal complexes such as nickel and palladium, and in particular, Pd (PPh ₃ ) ₄ , PdCl ₂ (dppf), NiCl ₂ (dppp) and the like. It is preferable to use a metal complex in which phosphines are coordinated.

In the reaction (III), an organic solvent or a solvent such as water is usually used, and an organic solvent is preferably used. Examples of the organic solvent used include alcohols such as methanol and ethanol; aprotic polar solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide and acetonitrile; diethyl ether; Ethers such as diisopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 1,4-dioxane and tetrahydrofuran; aromatic compounds such as benzene, toluene, xylene, chlorobenzene and o-dichlorobenzene: aliphatic hydrocarbons such as hexane and heptane Among them, aromatic compounds or ethers are preferably used. Such solvents may be used alone or in combination of two or more. Moreover, it is preferable that it is 1-200 mass parts with respect to 1 mass part of compounds shown by General formula (3), and, as for the usage-amount of this organic solvent, it is more preferable that it is 5-100 mass parts.
The reaction temperature in the cross coupling reaction of the reaction (III) is not particularly limited, and is preferably in the range of −50 to 200 ° C. When reaction temperature is less than -50 degreeC, there exists a possibility that reaction rate may become very slow, and it is more preferable that it is -20 degreeC or more. On the other hand, when reaction temperature exceeds 200 degreeC, there exists a possibility of promoting decomposition | disassembly of the metal complex which is a product or a catalyst, and it is more preferable that it is 170 degrees C or less. The reaction time is preferably 1 minute to 100 hours, and more preferably 0.5 to 80 hours. The reaction pressure is preferably 0 to 3 MPa (gauge pressure).

Subsequently, in the present invention, a method for producing a compound represented by the general formula (2) which is a precursor of the polymer represented by the general formula (1) will be described.
In the present invention, among the compounds represented by the general formula (2), a compound in which W is a hydrogen atom can be obtained by any of the following methods (c) or (d).
(C) In the following reaction formula (IV), in the general formula (3), W ¹ is a halogen atom, and in the general formulas (4a) and (4b), W ² is -Sn (R ¹⁰ ) ₃ (R ¹⁰ represents a hydrocarbon having 1 to 6 carbon atoms), a method of cross-coupling with a compound represented by any one of boronic acid or boronic ester groups.
(D) In the following reaction formula (IV), in general formula (3), W ¹ is —Sn (R ¹⁰ ) ₃ (R ¹⁰ represents a hydrocarbon having 1 to 6 carbon atoms), boronic acid or boronic acid ester A method in which a compound represented by any one of the groups and a compound in which W ^{2 in} the general formulas (4a) and (4b) is represented by a halogen atom are cross-coupled.

［(IV)式中、Ｒ^１、Ｒ^２、Ｘ、Ｙ及びＺは、前記一般式（１）及び（２）と同義である。Ｗ^１及びＷ^２は上記（ウ）及び（エ）の記載と同義である。］
上記反応式(IV)におけるクロスカップリング反応としては、例えば、Ｓｔｉｌｌｅカップリング反応、Ｓｕｚｕｋｉカップリング反応が好適に採用される。

[In the formula (IV), R ¹ , R ² , X, Y and Z are as defined in the general formulas (1) and (2). W ¹ and W ² have the same meanings as described in the above (c) and (d). ]
As the cross coupling reaction in the above reaction formula (IV), for example, Stille coupling reaction and Suzuki coupling reaction are preferably employed.

［(Ｖ)式中、Ｒ^１、Ｒ^２、Ｘ、Ｙ及びＺは、前記一般式（１）及び（２）と同義である。］
上記反応(Ｖ)の好適な実施態様は、前記反応式（III）と同様である。 Hereinafter, the reaction formula (IV) will be described in detail with specific examples, but the scope of the present invention is not limited to the following specific examples. For example, as shown in the following reaction formula (3), the compound represented by the general formula (2) is a compound in which W is a bromine atom in the general formula (2) and V in the general formula (3) is Suzuki coupling can be achieved with a compound represented by a boronic ester group.

[In the formula (V), R ¹ , R ² , X, Y and Z have the same meanings as in the general formulas (1) and (2). ]
A preferred embodiment of the reaction (V) is the same as the reaction formula (III).

［(VI)式中、Ｒ^１、Ｒ^２、Ｘ及びＹは前記一般式（１）と同義である。Ｖ^１はハロゲン原子を表す。］
上記反応（VI）において、ハロゲン原子を導入する好適な実施態様としては、例えば、窒素、アルゴンなどの不活性ガス雰囲気下で、溶媒の存在下にハロゲン化剤を反応させる方法が挙げられる。
上記反応（VI）で用いられる溶媒としては、例えば、ベンゼン、トルエン、キシレン、クメン、ヘキサン、ヘプタン、オクタンなどの炭化水素；ジクロロメタン、クロロホルム、四塩化炭素、１，２−ジクロロエタン、１，１，２，２−テトラクロロエタン、クロロベンゼンなどのハロゲン化炭化水素；ジエチルエーテル、ジイソプロピルエーテル、ジブチルエーテル、テトラヒドロフラン、ジオキサン、ジメトキシエタンなどのエーテル；酢酸エチル、酢酸ブチルなどのエステル；アセトニトリル、プロピオニトリルなどのニトリル；ジメチルホルムアミド、Ｎ−メチルピロリドンなどのアミド等が挙げられる。溶媒は、単独で使用してもよいし、２種以上を併用してもよい。かかる溶媒の使用量は、一般式（２ａ）で示される化合物１質量部に対して、１〜１００質量部であることが好ましく、１〜５０質量部であることがより好ましい。 Subsequently, among the compounds represented by the general formula (2), a compound in which W is a halogen atom represented by the following general formula (2b) is represented by the general formula (2a) as in the chemical reaction formula (VI) below. It can obtain by introduce | transducing a halogen atom into the compound shown by these.

[In the formula (VI), R ¹ , R ² , X and Y are as defined in the general formula (1). V ¹ represents a halogen atom. ]
In the above reaction (VI), a preferred embodiment for introducing a halogen atom includes, for example, a method of reacting a halogenating agent in the presence of a solvent in an inert gas atmosphere such as nitrogen or argon.
Examples of the solvent used in the above reaction (VI) include hydrocarbons such as benzene, toluene, xylene, cumene, hexane, heptane, and octane; dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1, Halogenated hydrocarbons such as 2,2-tetrachloroethane and chlorobenzene; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane and dimethoxyethane; esters such as ethyl acetate and butyl acetate; acetonitrile and propionitrile Nitriles; Amides such as dimethylformamide, N-methylpyrrolidone and the like. A solvent may be used independently and may use 2 or more types together. The amount of the solvent used is preferably 1 to 100 parts by mass and more preferably 1 to 50 parts by mass with respect to 1 part by mass of the compound represented by the general formula (2a).

Examples of the halogenating agent used in the reaction (VI) include N-chlorosuccinimide, N-chlorophthalimide, chlorine, phosphorus pentachloride, thionyl chloride, 1,2-dichloro-1,1,2, Chlorating agents such as 2-tetrafluoroethane; N-bromosuccinimide, N-bromophthalimide, N-bromoditrifluoromethylamine, bromine, boron tribromide, copper bromide, silver bromide, bromide-t- Bromination agents such as butyl, bromine oxide, 1,2-dibromo-1,1,2,2-tetrafluoroethane; iodinating agents such as iodine, iodotrichloride, N-iodophthalimide, N-iodosuccinimide, etc. Is mentioned. Among these, it is preferable to use a brominating agent or an iodinating agent, and it is more preferable to use a brominating agent. The amount of the halogenating agent used in the reaction 2 is not particularly limited, and is preferably 0.5 to 5 mol with respect to 1 mol of the compound represented by the general formula (2a). When the usage-amount of a halogenating agent exceeds 5 mol, there exists a possibility that the removal operation | work of an unreacted halogenating agent may become complicated, and it is more preferable that it is 4 mol or less. On the other hand, when the amount of the halogenating agent used is less than 0.5 mol, the separation and purification work with the unreacted compound represented by the general formula (2a) as a raw material may be complicated, More preferably.
The reaction temperature in the halogenation of the reaction (VI) is not particularly limited and is preferably in the range of −50 to 200 ° C. When reaction temperature is less than -50 degreeC, there exists a possibility that reaction rate may become very slow, and it is more preferable that it is -20 degreeC or more. On the other hand, when reaction temperature exceeds 200 degreeC, there exists a possibility of promoting decomposition | disassembly of the metal complex which is a product or a catalyst, and it is more preferable that it is 170 degrees C or less. The reaction time is preferably 1 minute to 100 hours, and more preferably 0.5 to 80 hours. The reaction pressure is preferably 0 to 3 MPa (gauge pressure).

［(VII)式中、Ｒ^１、Ｒ^２、Ｘ及びＹは前記一般式（１）と同義である。Ｖ^１は−Ｓｎ（Ｒ^１０）_３、ボロン酸若しくはボロン酸エステル基を表す。ここで、Ｒ^１０は炭素数１〜６の炭化水素を表す。］
上記反応（VII）は、一般式（２ｂ）で示される化合物を塩基とともに、Ｓｎ（Ｒ^１０）_３Ｃｌ、ボロン酸及びボロン酸エステルから選択される少なくとも１種と反応させることにより、一般式（２ｃ）で示される化合物を得る反応である。 Subsequently, among the compounds represented by the general formula (2), a compound in which W is represented by —Sn (R ¹⁰ ) ₃ , a boronic acid or a boronic ester group is represented by the following chemical reaction formula (VII). The compound represented by the general formula (2b) can be obtained by reacting with at least one selected from the group consisting of Sn (R ¹⁰ ) ₃ Cl, boronic acid and boronic acid ester. ^{Wherein, R 10} represents a hydrocarbon having 1 to 6 carbon atoms.

[In the formula (VII), R ¹ , R ² , X and Y are as defined in the general formula (1). V ¹ represents —Sn (R ¹⁰ ) ₃ , a boronic acid or a boronic ester group. ^{Wherein, R 10} represents a hydrocarbon having 1 to 6 carbon atoms. ]
In the reaction (VII), the compound represented by the general formula (2b) is reacted with at least one selected from Sn (R ¹⁰ ) ₃ Cl, boronic acid and boronic acid ester together with a base, This is a reaction for obtaining a compound represented by 2c).

  It does not specifically limit as a base used by the said reaction (III), An organolithium compound is used suitably. Examples of the organic lithium compound include alkyllithium compounds such as methyllithium, n-butyllithium, sec-butyllithium, and tert-butyllithium; aryllithium compounds such as phenyllithium; alkenyllithium compounds such as vinyllithium; lithium diisopropylamide Lithium amide compounds such as lithium bistrimethylsilylamide are used. Among these, it is preferable to use an alkyl lithium compound. The amount of the organic lithium compound used is not particularly limited and is preferably 0.5 to 5 mol with respect to 1 mol of the compound represented by the general formula (3). When the usage-amount of an organolithium compound exceeds 5 mol, there exists a possibility of promoting a side reaction or decomposition | disassembly of a product, and it is more preferable that it is 4 mol or less. The amount of the organic lithium compound used is more preferably 1 mol or more.

  The polymer represented by the general formula (1) described above can be suitably used as a new organic semiconductor device material. Especially, it uses suitably as a material of an organic thin-film transistor element and an organic photoelectric conversion element, and is used more suitably as an organic photoelectric conversion element. An organic photoelectric conversion element can be implemented using the method of a nonpatent literature 1, for example.

Hereinafter, the present invention will be specifically described based on examples.
^<1 H-NMR spectrum>
The ¹ H-NMR spectrum in this example was measured using JNM-GSX270 manufactured by JEOL Ltd. All measurements were performed on dilute solution obtained by dissolving the compound in CDCl _3.
<Weight average molecular weight (Mw) / Number average molecular weight (Mn)>
The number average molecular weight and the weight average molecular weight are both determined in terms of polystyrene based on measurement by gel permeation chromatography (GPC). Here, HLC-8020 (product number) manufactured by Tosoh Corporation was used as the GPC apparatus, and two TSKgel Multipore HZs manufactured by Tosoh Corporation were connected in series as the column.
<UV-visible absorption spectrum>
The ultraviolet-visible absorption spectrum in this example was measured using Solid Spec 3700 manufactured by Shimadzu Corporation. For all measurements, the compound was dissolved in a chloroform solution (manufactured by Wako Pure Chemical Industries, Ltd., mass fraction 99.0 +%), and the resulting solution having a concentration of 5.0 × 10 ⁻⁴ M was placed in a quartz cell (optical path length 1 cm). It was. All the results (absorption spectrum, optical property data) in this example were obtained by subtracting the light absorption of the quartz cell containing the same amount of chloroform (manufactured by Wako Pure Chemical Industries, Ltd., mass fraction 99.0 +%), And the value which excluded the influence of the light absorption of a quartz cell is shown. All measurements were performed at room temperature, and the measurement wavelength region was 300 nm to 1200 nm, the slit width was 5 nm, and the direct light receiving method was used.

<Example 1>
Hereinafter, a method for producing poly [(fluorene-2,7-diyl) -alt- [bis (4-dodecyloxythiophen-5-yl) -2,1,3-benzothiadiazole] will be described in detail.

窒素雰囲気下、２００ｍＬ三口フラスコに３−ドデシロキシチオフェン（１．７ｇ，６．３ｍｍｏｌ）、ＴＨＦ（６８ｍＬ）を加え、氷浴を用いて０℃まで冷却した。Ｎ−ブロモスクシンイミド（１．１ｇ，６．３ｍｍｏｌ）を反応溶液が０℃を保つようにゆっくりと加え、０℃で１時間攪拌した。反応終了後、水（３０ｍＬ）を加え、ヘキサン（１００ｍＬ×２）で抽出を行い、水（１００ｍＬ×２）で洗浄を行い、硫酸ナトリウムを用いて乾燥した。減圧下で溶媒を留去することで白色固体として化学式（３）で示される２−ブロモ−３−ドデシロキシチオフェンを得た（２．１７ｇ，９９％）。^１Ｈ−ＮＭＲ（２７０ＭＨｚ）：σ＝７．１７（ｄ，１Ｈ）、６．７３（ｄ，１Ｈ）、４．０２（ｄ，２Ｈ）、１．８２−１．５９（ｍ，２Ｈ）、１．５２−１．２０（ｍ，１８Ｈ）０．８８（ｔ，６．４８，３Ｈ）。 Synthesis Example 1 2-Bromo-3-dodecyloxythiophene

Under a nitrogen atmosphere, 3-dodecyloxythiophene (1.7 g, 6.3 mmol) and THF (68 mL) were added to a 200 mL three-necked flask and cooled to 0 ° C. using an ice bath. N-bromosuccinimide (1.1 g, 6.3 mmol) was slowly added so that the reaction solution maintained at 0 ° C., and the mixture was stirred at 0 ° C. for 1 hour. After completion of the reaction, water (30 mL) was added, extracted with hexane (100 mL × 2), washed with water (100 mL × 2), and dried over sodium sulfate. The solvent was distilled off under reduced pressure to obtain 2-bromo-3-dodecyloxythiophene represented by the chemical formula (3) as a white solid (2.17 g, 99%). ¹ H-NMR (270 MHz): σ = 7.17 (d, 1H), 6.73 (d, 1H), 4.02 (d, 2H), 1.82-1.59 (m, 2H), 1.52-1.20 (m, 18H) 0.88 (t, 6.48, 3H).

窒素雰囲気下、２０ｍＬナスフラスコに２，７−ジブロモフルオレン（１．０ｇ，ｍｍｏｌ）、酢酸カリウム（１．８２ｇ，ｍｍｏｌ）、ＰｄＣｌ_２（ｄｐｐｆ）（４５ｍｇ，ｍｍｏｌ）、ビス（ピナコラート）ジボロン（１．８８ｇ，ｍｍｏｌ）、ジオキサン（５ｍＬ）を加え、９０℃で１８時間攪拌した。反応溶液を室温まで冷却し、酢酸エチル（５０ｍＬ×２）で抽出し、水（５０ｍＬ×２）で洗浄し、硫酸ナトリウムを用いて乾燥を行った。減圧下で溶媒を留去することにより淡黄色固体として粗生成物を得た。粗生成物を酢酸エチル：ヘキサン混合溶媒を展開溶媒とするシリカゲルカラムクロマトグラフィーで精製することにより、白色固体として化学式（４）で示される化合物を得た（１．２８ｇ，９９％）。^１Ｈ−ＮＭＲ（２７０ＭＨｚ）：σ＝８．００（ｓ，２Ｈ）、７．８３（ｓ，４Ｈ）、３．８９（ｓ，２Ｈ）、１．３７（ｓ，２４Ｈ）。 Synthesis Example 2 3,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -fluorene

In a 20 mL eggplant flask under a nitrogen atmosphere, 2,7-dibromofluorene (1.0 g, mmol), potassium acetate (1.82 g, mmol), PdCl ₂ (dppf) (45 mg, mmol), bis (pinacolato) diboron (1 .88 g, mmol) and dioxane (5 mL) were added, and the mixture was stirred at 90 ° C. for 18 hours. The reaction solution was cooled to room temperature, extracted with ethyl acetate (50 mL × 2), washed with water (50 mL × 2), and dried using sodium sulfate. The solvent was distilled off under reduced pressure to obtain a crude product as a pale yellow solid. The crude product was purified by silica gel column chromatography using an ethyl acetate: hexane mixed solvent as a developing solvent to obtain a compound represented by the chemical formula (4) as a white solid (1.28 g, 99%). ¹ H-NMR (270 MHz): σ = 8.00 (s, 2H), 7.83 (s, 4H), 3.89 (s, 2H), 1.37 (s, 24H).

窒素雰囲気下、１００ｍＬ三口フラスコに２−ブロモ−３−ドデシロキシチオフェン（２．２６ｇ，６．５０ｍｍｏｌ）、ピナコールジボランフルオレン（１．２５ｇ，２．９９ｍｍｏｌ）、テトラキストリフェニルホスフィンパラジウム（０．２１ｇ，０．１８ｍｍｏｌ）、２Ｍ炭酸カリウム水溶液（１０ｍＬ，２０ｍｍｏｌ）、トルエン（２０ｍＬ）、Ａｌｉｑｕａｔ３３６（３０ｍｇ）を加え、環流下で２４時間攪拌した。反応終了後室温まで冷却し、有機層を水（３０ｍＬ×３）で洗浄し、水層をトルエン（３０ｍＬ×３）で抽出した後に、硫酸ナトリウムを用いて乾燥した。減圧下で溶媒を留去することにより黒色の固体として粗生成物を得た。粗生成物を、ヘキサンを展開溶媒とするシリカゲルカラムクロマトグラフィーを用いて精製することにより、黄白色の固体として化学式（５）で示される化合物を得た（１．４２ｇ，６８％）。^１Ｈ−ＮＭＲ（２７０ＭＨｚ）：σ＝７．９９（ｓ，２Ｈ）、７．９７（ｄ，２Ｈ）、７．６１（ｄ，２Ｈ）、７．１３（ｓ，２Ｈ）、６．９２（ｄ、２Ｈ）、４．０９（ｔ，４Ｈ）、１．８２（ｍ，４Ｈ）、１．１〜１．７（ｂｒ、３６Ｈ）、０．８６（ｔ，６Ｈ）。 Synthesis Example 3 2,7-bis (3-dodecyloxythiophen-2-yl) fluorene

Under a nitrogen atmosphere, a 100 mL three-necked flask was charged with 2-bromo-3-dodecyloxythiophene (2.26 g, 6.50 mmol), pinacol diboranefluorene (1.25 g, 2.99 mmol), tetrakistriphenylphosphine palladium (0.21 g). , 0.18 mmol), 2M aqueous potassium carbonate solution (10 mL, 20 mmol), toluene (20 mL) and Aliquat 336 (30 mg) were added, and the mixture was stirred under reflux for 24 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, the organic layer was washed with water (30 mL × 3), the aqueous layer was extracted with toluene (30 mL × 3), and then dried using sodium sulfate. The crude product was obtained as a black solid by distilling off the solvent under reduced pressure. The crude product was purified using silica gel column chromatography using hexane as a developing solvent to obtain a compound represented by the chemical formula (5) as a pale yellow solid (1.42 g, 68%). ¹ H-NMR (270 MHz): σ = 7.99 (s, 2H), 7.97 (d, 2H), 7.61 (d, 2H), 7.13 (s, 2H), 6.92 ( d, 2H), 4.09 (t, 4H), 1.82 (m, 4H), 1.1-1.7 (br, 36H), 0.86 (t, 6H).

窒素雰囲気下、５０ｍＬ三口フラスコに２，７−ビス（３−ドデシロキシチオフェン−２−イル）−フルオレン（０．９７ｇ，１．３８ｍｍｏｌ）とクロロホルム（２０ｍＬ）を加え、氷浴を用いて０℃まで冷却した。Ｎ−ブロモスクシンイミド（０．４９ｇ，２．７７ｍｍｏｌ）を，０℃を保持するようにゆっくりと加えた後に、室温まで昇温して１時間攪拌した。反応終了後、水（２０ｍＬ）を加え、１５分間攪拌した。有機層を水（３０ｍＬ×３）で洗浄し、水層をクロロホルム（２０ｍＬ×２）で抽出したのちに、硫酸ナトリウムにて乾燥した。減圧下で溶媒を留去することにより黄色固体として粗生成物を得た。粗生成物を、ヘキサンを展開溶媒とするシリカゲルカラムクロマトグラフィーで精製することにより、黄白色固体として化学式（６）で示される化合物を得た（１．０６ｇ，７７％）。^１Ｈ−ＮＭＲ（２７０ＭＨｚ）：σ＝７．８２（ｓ，２Ｈ）、７．６９（ｄ，４Ｈ）、６．９１（ｓ，２Ｈ）、４．０３（ｔ，４Ｈ）、１．７９（ｍ，４Ｈ）、１．１〜１．７（ｂｒ、３６Ｈ）、０．８７（ｔ，６Ｈ）。 Synthesis Example 4 2,7-Bis (5-bromo-3-dodecyloxythiophen-2-yl) fluorene

Under a nitrogen atmosphere, 2,7-bis (3-dodecyloxythiophen-2-yl) -fluorene (0.97 g, 1.38 mmol) and chloroform (20 mL) were added to a 50 mL three-necked flask, and 0 ° C was added using an ice bath. Cooled to ° C. N-bromosuccinimide (0.49 g, 2.77 mmol) was slowly added so as to maintain 0 ° C., and then the mixture was warmed to room temperature and stirred for 1 hour. After completion of the reaction, water (20 mL) was added and stirred for 15 minutes. The organic layer was washed with water (30 mL × 3), the aqueous layer was extracted with chloroform (20 mL × 2), and then dried over sodium sulfate. The crude product was obtained as a yellow solid by distilling off the solvent under reduced pressure. The crude product was purified by silica gel column chromatography using hexane as a developing solvent to obtain a compound represented by the chemical formula (6) as a yellowish white solid (1.06 g, 77%). ¹ H-NMR (270 MHz): σ = 7.82 (s, 2H), 7.69 (d, 4H), 6.91 (s, 2H), 4.03 (t, 4H), 1.79 ( m, 4H), 1.1-1.7 (br, 36H), 0.87 (t, 6H).

窒素雰囲気下、１０ｍＬ三口フラスコに２，７−ビス（５−ブロモ−３−ドデシロキシチオフェン−２−イル）フルオレン化合物（６００ｍｇ、０．７０ｍｍｏｌ）、４，７−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゾチアジアゾール（２７２ｍｇ、０．７０ｍｍｏｌ）、２Ｍ炭酸カリウム水溶液（４ｍＬ，８．００ｍｍｏｌ）テトラキストリフェニルホスフィンパラジウム（１６．１８ｍｇ，０．０１４ｍｍｏｌ）、トルエン（４ｍＬ）を加え、８５℃で３時間加熱攪拌した。反応終了後、室温まで冷却し、クロロベンゼン（１０ｍＬ）を加えて析出した固体を溶解させた。その後、反応溶液をメタノール（３０ｍＬ）に注ぎ、析出した固体を濾取し真空下で乾燥を行うことで黒紫色の固体として化学式（７）で示される化合物を得た（１２９ｍｇ、２２．２％）。ＧＰＣ（ＣＨＣｌ_３）：Ｍｎ＝１２７００ｇ／ｍｏｌ、Ｍｗ＝２１６００ｇ／ｍｏｌ、ＰＤＩ（Ｍｗ／Ｍｎ）＝１．７。 Synthesis Example 5 Poly [(fluorene-2,7-diyl) -alt- [bis (4-dodecyloxythiophen-5-yl) -2,1,3-benzothiadiazole]

In a 10 mL three-necked flask under a nitrogen atmosphere, 2,7-bis (5-bromo-3-dodecyloxythiophen-2-yl) fluorene compound (600 mg, 0.70 mmol), 4,7-bis (4,4,5 , 5-Tetramethyl-1,3,2-dioxaborolan-2-yl) benzothiadiazole (272 mg, 0.70 mmol), 2M aqueous potassium carbonate (4 mL, 8.00 mmol) tetrakistriphenylphosphine palladium (16.18 mg, 0 .014 mmol) and toluene (4 mL) were added, and the mixture was heated and stirred at 85 ° C. for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and chlorobenzene (10 mL) was added to dissolve the precipitated solid. Thereafter, the reaction solution was poured into methanol (30 mL), and the precipitated solid was collected by filtration and dried under vacuum to obtain a compound represented by the chemical formula (7) as a black purple solid (129 mg, 22.2%) ). GPC (CHCl ₃ ): Mn = 12,700 g / mol, Mw = 21600 g / mol, PDI (Mw / Mn) = 1.7.

<Example 2>
Hereinafter, a method for producing poly [(fluorene-2,7-diyl) -alt- [bis (4- (2-ethylhexyloxythiophene) -5-yl) -2,1,3-benzothiadiazole] will be described in detail. Describe.

窒素雰囲気下、２００ｍＬ三口フラスコに３−メトキシチオフェン（５．００ｇ，４３．８ｍｍｏｌ）、キシレン（１００ｍＬ）、硫酸水素ナトリウム（０．４７ｇ，３．９０ｍｍｏｌ）、２−エチルヘキサノール（６．８４ｇ，５２．６ｍｍｏｌ）を加え、１７０℃まで加熱し、ディーンシュターク脱水装置を用いて反応中に発生する水を系外に除去しながら３時間攪拌した。反応終了後、水（５０ｍＬ）を加え、ヘキサン（５０ｍＬ×２）で抽出を行い、水（５０ｍＬ）で洗浄を行い、硫酸ナトリウムを用いて乾燥した。減圧下で溶媒を留去することにより緑色の液体として粗生成物を得た。粗生成物を、ヘキサンを展開溶媒とするシリカゲルカラムクロマトグラフィーを用いて精製することにより、黄色液体として化学式（８）で示される化合物を得た（１０．４ｇ，９３％）。^１Ｈ−ＮＭＲ（２７０ＭＨｚ）：σ＝７．１５（ｄｄ，１Ｈ）、６．７５（ｄｄ，１Ｈ）、６．２１（ｄｄ，１Ｈ）、３．８２（ｄ，２Ｈ）、１．８３−１．６２（ｍ，１Ｈ）、１．５２−１．２７（ｍ，８Ｈ）、１．０４−０．８５（ｍ，６Ｈ）。 Synthesis Example 6 Synthesis of 3- (2-ethylhexyloxy) thiophene

Under a nitrogen atmosphere, in a 200 mL three-necked flask, 3-methoxythiophene (5.00 g, 43.8 mmol), xylene (100 mL), sodium hydrogen sulfate (0.47 g, 3.90 mmol), 2-ethylhexanol (6.84 g, 52 6 mmol), heated to 170 ° C., and stirred for 3 hours while removing water generated during the reaction out of the system using a Dean-Stark dehydrator. After completion of the reaction, water (50 mL) was added, extracted with hexane (50 mL × 2), washed with water (50 mL), and dried over sodium sulfate. The crude product was obtained as a green liquid by distilling off the solvent under reduced pressure. The crude product was purified using silica gel column chromatography using hexane as a developing solvent to obtain a compound represented by the chemical formula (8) as a yellow liquid (10.4 g, 93%). ¹ H-NMR (270 MHz): σ = 7.15 (dd, 1H), 6.75 (dd, 1H), 6.21 (dd, 1H), 3.82 (d, 2H), 1.83 1.62 (m, 1H), 1.52-1.27 (m, 8H), 1.04-0.85 (m, 6H).

窒素雰囲気下、２００ｍＬ三口フラスコに３−（２−エチルヘキシロキシ）チオフェン（３．００ｇ，１４．１３ｍｍｏｌ）、ＴＨＦ（１００ｍＬ）を加え、氷浴を用いて０℃まで冷却した。Ｎ−ブロモスクシンイミド（２．２６ｇ，１２．７１ｍｍｏｌ）を反応溶液が０℃を保つようにゆっくりと加え、０℃で１時間攪拌した。反応終了後、亜硫酸ナトリウム水溶液（５０ｍＬ）を加え、ヘキサン（５０ｍＬ×２）で抽出を行い、水（５０ｍＬ）で洗浄を行い、硫酸ナトリウムを用いて乾燥した。減圧下で溶媒を留去することで淡茶色液体として化学式（９）で示される化合物を得た（４．１５ｇ，１０１％）。^１Ｈ−ＮＭＲ（２７０ＭＨｚ）：σ＝７．１７（ｄ，１Ｈ）、６．７３（ｄ，１Ｈ）、３．９１（ｄ，２Ｈ）、１．５７−１．２６（ｍ，９Ｈ）、１．０６−０．８８（ｍ，６Ｈ）。 Synthesis Example 7 Synthesis of 2-bromo-3- (2-ethylhexyloxy) thiophene

Under a nitrogen atmosphere, 3- (2-ethylhexyloxy) thiophene (3.00 g, 14.13 mmol) and THF (100 mL) were added to a 200 mL three-necked flask and cooled to 0 ° C. using an ice bath. N-bromosuccinimide (2.26 g, 12.71 mmol) was slowly added so that the reaction solution maintained at 0 ° C., and the mixture was stirred at 0 ° C. for 1 hour. After completion of the reaction, an aqueous sodium sulfite solution (50 mL) was added, extracted with hexane (50 mL × 2), washed with water (50 mL), and dried over sodium sulfate. The solvent was distilled off under reduced pressure to obtain a compound represented by the chemical formula (9) as a light brown liquid (4.15 g, 101%). ¹ H-NMR (270 MHz): σ = 7.17 (d, 1H), 6.73 (d, 1H), 3.91 (d, 2H), 1.57-1.26 (m, 9H), 1.06-0.88 (m, 6H).

窒素雰囲気下、１００ ｍＬ三口フラスコに２−ブロモ−３−（２−エチルヘキシロキシ）チオフェン（３．６２ ｇ，１２．４４ ｍｍｏｌ）、２，７−ビス（１，３，２−ジオキサボロラン−２−イル）フルオレン（２．００ｇ，４．７８ ｍｍｏｌ）、テトラキストリフェニルホスフィンパラジウム（０．３３ｇ，０．２８７ｍｍｏｌ）、２Ｍ炭酸カリウム水溶液（１６ｍＬ，３２ｍｍｏｌ）、トルエン（３２ｍＬ）、を加え、環流下で時間攪拌した。反応終了後室温まで冷却し、有機層を水（１５ｍＬ×３）で洗浄し、水層をトルエン（５０ｍＬ）で抽出した後に、硫酸ナトリウムを用いて乾燥した。減圧下で溶媒を留去することにより黒色の固体として粗生成物を得た。粗生成物を、ヘキサンを展開溶媒とするシリカゲルカラムクロマトグラフィーを用いて精製することにより、橙色液体として化学式（１０）で示される化合物を得た（０．９７ｇ，３４．６％）。^１Ｈ−ＮＭＲ（２７０ＭＨｚ）：σ＝７．９９（ｓ，２Ｈ）、７．８４（ｍ，２Ｈ）、７．８０（ｍ，２Ｈ）、７．１５（ｍ，１Ｈ）、６．９４（ｍ，１Ｈ）、４．０１（ｍ，２Ｈ）、１．７２−１．２８（ｍ，１８Ｈ）、１．０８−０．８８（ｍ，１２Ｈ）。 (Synthesis Example 8) 2,7-bis (3- (2-ethylhexyloxy) thiophen-2-yl) fluorene

2-Bromo-3- (2-ethylhexyloxy) thiophene (3.62 g, 12.44 mmol), 2,7-bis (1,3,2-dioxaborolane-2) in a 100 mL three-necked flask under a nitrogen atmosphere -Yl) fluorene (2.00 g, 4.78 mmol), tetrakistriphenylphosphine palladium (0.33 g, 0.287 mmol), 2M aqueous potassium carbonate solution (16 mL, 32 mmol), toluene (32 mL) were added and refluxed For an hour. After completion of the reaction, the reaction mixture was cooled to room temperature, the organic layer was washed with water (15 mL × 3), the aqueous layer was extracted with toluene (50 mL), and then dried using sodium sulfate. The crude product was obtained as a black solid by distilling off the solvent under reduced pressure. The crude product was purified using silica gel column chromatography using hexane as a developing solvent to obtain a compound represented by the chemical formula (10) as an orange liquid (0.97 g, 34.6%). ¹ H-NMR (270 MHz): σ = 7.99 (s, 2H), 7.84 (m, 2H), 7.80 (m, 2H), 7.15 (m, 1H), 6.94 ( m, 1H), 4.01 (m, 2H), 1.72-1.28 (m, 18H), 1.08-0.88 (m, 12H).

窒素雰囲気下、５０ｍＬ三口フラスコに２，７−ビス｛３−（２−エチルヘキシロキシ）チオフェン−２−イル｝−フルオレン（０．６７ｇ，１．１４ｍｍｏｌ）とクロロホルム（２０ｍＬ）を加え、氷浴を用いて０℃まで冷却した。Ｎ−ブロモスクシンイミド（０．４３ｇ，２．４０ｍｍｏｌ）を，０℃を保持するようにゆっくりと加えた後、１時間攪拌した。反応終了後、亜硫酸ナトリウム水溶液（２０ｍＬ）を加え、１５分間攪拌した。有機層を水（２０ｍＬ）で洗浄し、水層をクロロホルム（２０ｍＬ）で抽出したのちに、硫酸ナトリウムにて乾燥した。減圧下で溶媒を留去することにより黄色固体として粗生成物を得た。粗生成物を、ヘキサン−酢酸エチル混合溶媒を展開溶媒とするシリカゲルカラムクロマトグラフィーで精製することにより、茶色固体として化学式（１１）で示される化合物を得た（０．６５ｇ，７６％）。^１Ｈ−ＮＭＲ（２７０ＭＨｚ）：σ＝７．８０（ｓ，２Ｈ）、７．６０（ｄ，４Ｈ）、６．９１（ｓ，２Ｈ）、４．０３（ｔ，４Ｈ）、１．７２−１．２８（ｍ，１８Ｈ）、１．０８−０．８８（ｍ，１２Ｈ）。 Synthesis Example 9 2,7-bis (5-bromo-3- (2-ethylhexyloxy) thiophen-2-yl) fluorene

Under a nitrogen atmosphere, 2,7-bis {3- (2-ethylhexyloxy) thiophen-2-yl} -fluorene (0.67 g, 1.14 mmol) and chloroform (20 mL) were added to a 50 mL three-necked flask, and an ice bath was added. And cooled to 0 ° C. N-bromosuccinimide (0.43 g, 2.40 mmol) was slowly added so as to maintain 0 ° C., followed by stirring for 1 hour. After completion of the reaction, an aqueous sodium sulfite solution (20 mL) was added and stirred for 15 minutes. The organic layer was washed with water (20 mL), and the aqueous layer was extracted with chloroform (20 mL) and then dried over sodium sulfate. The crude product was obtained as a yellow solid by distilling off the solvent under reduced pressure. The crude product was purified by silica gel column chromatography using a mixed solvent of hexane-ethyl acetate as a developing solvent to obtain a compound represented by the chemical formula (11) as a brown solid (0.65 g, 76%). ¹ H-NMR (270 MHz): σ = 7.80 (s, 2H), 7.60 (d, 4H), 6.91 (s, 2H), 4.03 (t, 4H), 1.72- 1.28 (m, 18H), 1.08-0.88 (m, 12H).

窒素雰囲気下、２５ｍＬ三口フラスコに２，７−ビス｛５−ブロモ−３−（２−エチルヘキシロキシ）チオフェン−２−イル｝フルオレン化合物（０．２０ｇ、０．２７ｍｍｏｌ）、４，７−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゾチアジアゾール（０．１０ｇ、０．２７ｍｍｏｌ）、２Ｍ炭酸カリウム水溶液（１．８ｍＬ，３．６ｍｍｏｌ）テトラキストリフェニルホスフィンパラジウム（６．２ｍｇ，５．４μｍｏｌ）、トルエン（１．８ｍＬ）を加え、８５℃で３時間加熱攪拌した。反応終了後、室温まで冷却し、クロロベンゼン（１０ｍＬ）を加えて析出した固体を溶解させた。その後、反応溶液をメタノール（１５０ｍＬ）に注ぎ、析出した固体を濾取し真空下で乾燥を行うことで黒紫色の固体として化学式（１２）で示される化合物を得た（０．２３ｇ、１１９％）。ＧＰＣ（ＣＨＣｌ_３）：Ｍｎ＝３０００ｇ／ｍｏｌ、Ｍｗ＝６０００ｇ／ｍｏｌ、ＰＤＩ＝２．３。 Synthesis Example 10 Poly [(fluorene-2,7-diyl) -alt- [bis (4- (2-ethylhexyloxy) thiophen-5-yl) -2,1,3-benzothiadiazole]

In a 25 mL three-necked flask under a nitrogen atmosphere, 2,7-bis {5-bromo-3- (2-ethylhexyloxy) thiophen-2-yl} fluorene compound (0.20 g, 0.27 mmol), 4,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzothiadiazole (0.10 g, 0.27 mmol), 2M aqueous potassium carbonate (1.8 mL, 3.6 mmol) tetrakis Triphenylphosphine palladium (6.2 mg, 5.4 μmol) and toluene (1.8 mL) were added, and the mixture was heated with stirring at 85 ° C. for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and chlorobenzene (10 mL) was added to dissolve the precipitated solid. Thereafter, the reaction solution was poured into methanol (150 mL), and the precipitated solid was collected by filtration and dried under vacuum to obtain a compound represented by the chemical formula (12) as a black purple solid (0.23 g, 119%). ). GPC (CHCl ₃ ): Mn = 3000 g / mol, Mw = 6000 g / mol, PDI = 2.3.

<Example 3>
The production method of poly [(fluorene-2,7-diyl) -alt- [bis (4- (3,7-dimethyloctyloxy) -5-yl) -2,1,3-benzothiadiazole] is described below. Detailed description.

窒素雰囲気下、２００ｍＬ三口フラスコに３−メトキシチオフェン（５．００ｇ，４３．８ｍｍｏｌ）、キシレン（１００ｍＬ）、硫酸水素ナトリウム（０．４７ｇ，３．９０ｍｍｏｌ）、３，７−ジメチルオクタノール（６．９３ｇ，４３．８ｍｍｏｌ）を加え、１７０℃まで加熱し、ディーンシュターク脱水装置を用いて反応中に発生する水を系外に除去しながら２時間攪拌した。反応終了後、水（５０ｍＬ）を加え、ヘキサン（５０ｍＬ）で抽出を行い、水（５０ｍＬ）で洗浄を行い、硫酸ナトリウムを用いて乾燥した。減圧下で溶媒を留去することにより緑色の液体として粗生成物を得た。粗生成物を、ヘキサンを展開溶媒とするシリカゲルカラムクロマトグラフィーを用いて精製することにより、淡橙色液体として化学式（１３）で示される化合物を得た（９．７７ｇ，１０５％）。^１Ｈ−ＮＭＲ（２７０ＭＨｚ）：σ＝７．１６（ｄｄ，１Ｈ）、６．７４（ｄｄ，１Ｈ）、６．２２（ｄｄ，１Ｈ）、３．９９（ｍ，２Ｈ）、１．９５−１．７５（ｍ，１Ｈ）、１．７８−１．５０（ｍ，３Ｈ）、１．４２−１．０９（ｍ，６Ｈ）、０．９５−０．９１（ｍ，３Ｈ）、０．８９−０．８５（ｍ，６Ｈ）。 Synthesis Example 11 Synthesis of 3- (3,7-dimethyloctyloxy) thiophene

Under a nitrogen atmosphere, in a 200 mL three-necked flask, 3-methoxythiophene (5.00 g, 43.8 mmol), xylene (100 mL), sodium hydrogensulfate (0.47 g, 3.90 mmol), 3,7-dimethyloctanol (6.93 g). , 43.8 mmol), was heated to 170 ° C., and stirred for 2 hours while removing water generated during the reaction out of the system using a Dean-Stark dehydrator. After completion of the reaction, water (50 mL) was added, extracted with hexane (50 mL), washed with water (50 mL), and dried using sodium sulfate. The crude product was obtained as a green liquid by distilling off the solvent under reduced pressure. The crude product was purified by silica gel column chromatography using hexane as a developing solvent to obtain a compound represented by the chemical formula (13) as a pale orange liquid (9.77 g, 105%). ¹ H-NMR (270 MHz): σ = 7.16 (dd, 1H), 6.74 (dd, 1H), 6.22 (dd, 1H), 3.99 (m, 2H), 1.95− 1.75 (m, 1H), 1.78-1.50 (m, 3H), 1.42-1.09 (m, 6H), 0.95-0.91 (m, 3H), 0.7. 89-0.85 (m, 6H).

窒素雰囲気下、１００ｍＬ三口フラスコに３−（３，７−ジメチルオクチロキシ）チオフェン（２．３０ｇ，９．５７ｍｍｏｌ）、ＴＨＦ（６０ｍＬ）を加え、氷浴を用いて０℃まで冷却した。Ｎ−ブロモスクシンイミド（１・６９ｇ，９．５０ｍｍｏｌ）を反応溶液が０℃を保つようにゆっくりと加え、０℃で１時間攪拌した。反応終了後、亜硫酸ナトリウム水溶液（３０ｍＬ）を加え、ヘキサン（５０ｍＬ×２）で抽出を行い、水（５０ｍＬ）で洗浄を行い、硫酸ナトリウムを用いて乾燥した。減圧下で溶媒を留去することで白色固体として化学式（１４）で示される化合物を得た（２．８１ｇ，９２％）。^１Ｈ−ＮＭＲ（２７０ＭＨｚ）：σ＝７．１８（ｄ，１Ｈ）、６．７３（ｄ，１Ｈ）、４．０７（ｔ，２Ｈ）、１．８０−１．５０（ｍ，４Ｈ）、１．３０−１．１（ｍ，６Ｈ）、０．９３（ｄ、３Ｈ），０．８６（ｄ、６Ｈ）。 Synthesis Example 12 Synthesis of 2-bromo-3- (3,7-dimethyloctyloxy) thiophene

Under a nitrogen atmosphere, 3- (3,7-dimethyloctyloxy) thiophene (2.30 g, 9.57 mmol) and THF (60 mL) were added to a 100 mL three-necked flask and cooled to 0 ° C. using an ice bath. N-bromosuccinimide (1.69 g, 9.50 mmol) was slowly added so that the reaction solution maintained at 0 ° C., and the mixture was stirred at 0 ° C. for 1 hour. After completion of the reaction, an aqueous sodium sulfite solution (30 mL) was added, extracted with hexane (50 mL × 2), washed with water (50 mL), and dried over sodium sulfate. The solvent was distilled off under reduced pressure to obtain a compound represented by the chemical formula (14) as a white solid (2.81 g, 92%). ¹ H-NMR (270 MHz): σ = 7.18 (d, 1H), 6.73 (d, 1H), 4.07 (t, 2H), 1.80-1.50 (m, 4H), 1.30-1.1 (m, 6H), 0.93 (d, 3H), 0.86 (d, 6H).

窒素雰囲気下、５０ｍＬ三口フラスコに２−ブロモ−３−（３，７−ジメチルオクチロキシ）チオフェン（２．１８ｇ，６．８４ｍｍｏｌ）、２，７−ビス（１，３，２−ジオキサボロラン−２−イル）フルオレン（１．１０ｇ，２．６３ｍｍｏｌ）、テトラキストリフェニルホスフィンパラジウム（０．１８ｇ，０．１６ｍｍｏｌ）、２Ｍ炭酸カリウム水溶液（９ｍＬ，１８．０ｍｍｏｌ）、トルエン（１５ｍＬ）、Ａｌｉｑｕａｔ３３６（２５ｍｇ）を加え、環流下で時間攪拌した。反応終了後室温まで冷却し、有機層を水（１０ｍＬ×２）で洗浄し、水層をトルエン（２５ｍＬ×２）で抽出した後に、硫酸ナトリウムを用いて乾燥した。減圧下で溶媒を留去することにより黒色の固体として粗生成物を得た。粗生成物を、ヘキサン−酢酸エチル混合溶媒を展開溶媒とするシリカゲルカラムクロマトグラフィーを用いて精製することにより、茶色の固体として化学式（１５）で示される化合物を得た（０．６５ｇ，３８．４％）。^１Ｈ−ＮＭＲ（２７０ＭＨｚ）：σ＝７．９２（ｓ，２Ｈ）、７．７９（ｄ，２Ｈ）、７．７２（ｄ，２Ｈ）、７．１３（ｄ、２Ｈ）、６．９２（ｄ、２Ｈ）、４．１２（ｔ、４Ｈ）、３．９４（ｓ、２Ｈ）、１．８０−１．５０（ｍ，４Ｈ）、１．３０−１．１（ｍ，６Ｈ）、０．９３（ｄ、３Ｈ）、０．８６（ｄ、６Ｈ）。 Synthesis Example 13 2,7-bis (3- (3,7-dimethyloctyloxy) thiophen-2-yl) fluorene

In a 50 mL three-necked flask under a nitrogen atmosphere, 2-bromo-3- (3,7-dimethyloctyloxy) thiophene (2.18 g, 6.84 mmol), 2,7-bis (1,3,2-dioxaborolane-2- Yl) fluorene (1.10 g, 2.63 mmol), tetrakistriphenylphosphine palladium (0.18 g, 0.16 mmol), 2M aqueous potassium carbonate solution (9 mL, 18.0 mmol), toluene (15 mL), Aliquat 336 (25 mg). In addition, the mixture was stirred for an hour under reflux. After completion of the reaction, the reaction mixture was cooled to room temperature, the organic layer was washed with water (10 mL × 2), the aqueous layer was extracted with toluene (25 mL × 2), and then dried using sodium sulfate. The crude product was obtained as a black solid by distilling off the solvent under reduced pressure. The crude product was purified by silica gel column chromatography using a mixed solvent of hexane-ethyl acetate as a developing solvent to obtain a compound represented by the chemical formula (15) as a brown solid (0.65 g, 38. 4%). ¹ H-NMR (270 MHz): σ = 7.92 (s, 2H), 7.79 (d, 2H), 7.72 (d, 2H), 7.13 (d, 2H), 6.92 ( d, 2H), 4.12 (t, 4H), 3.94 (s, 2H), 1.80-1.50 (m, 4H), 1.30-1.1 (m, 6H), 0 .93 (d, 3H), 0.86 (d, 6H).

窒素雰囲気下、２５ｍＬ三口フラスコに２，７−ビス｛３−（３，７−ジメチルオクチロキシ）チオフェン−２−イル｝−フルオレン（０．３５ｇ，０．５４ｍｍｏｌ）とクロロホルム（１０ｍＬ）を加え、氷浴を用いて０℃まで冷却した。Ｎ−ブロモスクシンイミド（０．２０ｇ，１．１４ｍｍｏｌ）を，０℃を保持するようにゆっくりと加えた後、１時間攪拌した。反応終了後、亜硫酸ナトリウム水溶液（１０ｍＬ）を加え、１５分間攪拌した。有機層を水（１０ｍＬ×２）で洗浄し、水層をクロロホルム（１０ｍＬ）で抽出したのちに、硫酸ナトリウムにて乾燥した。減圧下で溶媒を留去することにより黄色固体として粗生成物を得た。粗生成物を、ヘキサン−酢酸エチル混合溶媒を展開溶媒とするシリカゲルカラムクロマトグラフィーで精製することにより、茶色固体として化学式（１６）で示される化合物を得た（０．３７ｇ，８５％）。^１Ｈ−ＮＭＲ（２７０ＭＨｚ）：σ＝７．８０（ｓ，２Ｈ）、７．６０（ｄ，４Ｈ）、６．９１（ｓ，２Ｈ）、４．０３（ｔ，４Ｈ）、１．７２−１．２８（ｍ，１８Ｈ）、１．０８−０．８８（ｍ，１２Ｈ）。 Synthesis Example 14 3,7-Bis (5-bromo-3- (3,7-dimethyloctyloxy) thiophen-2-yl) fluorene

Under a nitrogen atmosphere, 2,7-bis {3- (3,7-dimethyloctyloxy) thiophen-2-yl} -fluorene (0.35 g, 0.54 mmol) and chloroform (10 mL) were added to a 25 mL three-necked flask, Cooled to 0 ° C. using an ice bath. N-bromosuccinimide (0.20 g, 1.14 mmol) was slowly added so as to maintain 0 ° C., followed by stirring for 1 hour. After completion of the reaction, an aqueous sodium sulfite solution (10 mL) was added and stirred for 15 minutes. The organic layer was washed with water (10 mL × 2), the aqueous layer was extracted with chloroform (10 mL), and dried over sodium sulfate. The crude product was obtained as a yellow solid by distilling off the solvent under reduced pressure. The crude product was purified by silica gel column chromatography using a mixed solvent of hexane-ethyl acetate as a developing solvent to obtain a compound represented by the chemical formula (16) as a brown solid (0.37 g, 85%). ¹ H-NMR (270 MHz): σ = 7.80 (s, 2H), 7.60 (d, 4H), 6.91 (s, 2H), 4.03 (t, 4H), 1.72- 1.28 (m, 18H), 1.08-0.88 (m, 12H).

窒素雰囲気下、１０ｍＬ三口フラスコに２，７−ビス｛５−ブロモ−３−（３，７−ジメチルオクチロキシ）チオフェン−２−イル｝フルオレン化合物（０．１５ｇ、０．１９ｍｍｏｌ）、４，７−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゾチアジアゾール（０．０７ｇ、０．１９ｍｍｏｌ）、２Ｍ炭酸カリウム水溶液（１．２ｍＬ，２．４ｍｍｏｌ）テトラキストリフェニルホスフィンパラジウム（４．３ｍｇ，３．８μｍｏｌ）、トルエン（１．２ｍＬ）を加え、８５℃で３時間加熱攪拌した。反応終了後、室温まで冷却し、クロロベンゼン（１０ｍＬ）を加えて析出した固体を溶解させた。その後、反応溶液をメタノール（１５０ｍＬ）に注ぎ、析出した固体を濾取し真空下で乾燥を行うことで黒紫色の固体として化学式（１７）で示される化合物を得た（０．２４ｇ、２４２％）。ＧＰＣ（ＣＨＣｌ_３）：Ｍｎ＝４０００ｇ／ｍｏｌ、Ｍｗ＝１００００ｇ／ｍｏｌ、ＰＤＩ＝２．５。 Synthesis Example 15 Poly [(fluorene-2,7-diyl) -alt- [bis (4- (3,7-dimethyloctyloxy) thiophen-5-yl) -2,1,3-benzothiadiazole]

2,7-bis {5-bromo-3- (3,7-dimethyloctyloxy) thiophen-2-yl} fluorene compound (0.15 g, 0.19 mmol), 4,7 in a 10 mL three-necked flask under nitrogen atmosphere -Bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzothiadiazole (0.07 g, 0.19 mmol), 2M aqueous potassium carbonate solution (1.2 mL, 2.4 mmol) ) Tetrakistriphenylphosphine palladium (4.3 mg, 3.8 μmol) and toluene (1.2 mL) were added, and the mixture was heated with stirring at 85 ° C. for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and chlorobenzene (10 mL) was added to dissolve the precipitated solid. Thereafter, the reaction solution was poured into methanol (150 mL), and the precipitated solid was collected by filtration and dried under vacuum to obtain a compound represented by the chemical formula (17) as a black purple solid (0.24 g, 242%). ). GPC (CHCl ₃ ): Mn = 4000 g / mol, Mw = 10000 g / mol, PDI = 2.5.

<Example 4>
Hereinafter, the production method of poly [(carbazole-2,7-diyl) -alt- [bis (4- (2-ethylhexyloxythiophene) -5-yl) -2,1,3-benzothiadiazole] will be described in detail. Describe.

窒素雰囲気下、２０ｍＬナスフラスコに２，７−ジブロモカルバゾール（１ｇ，３．０８ｍｍｏｌ）、酢酸カリウム（１．８２ｇ，１８．４６ｍｍｏｌ）、ＰｄＣｌ_２（ｄｐｐｆ）（４５ｍｇ，０．０６２ｍｍｏｌ）、ビス（ピナコラート）ジボロン（１．８６ｇ，７．３８ｍｍｏｌ）、ジオキサン（５ｍＬ）を加え、９０℃で１８時間攪拌した。反応溶液を室温まで冷却し、酢酸エチル（２０ｍＬ×２）で抽出し、水（５０ｍＬ×２）で洗浄し、硫酸ナトリウムを用いて乾燥を行った。減圧下で溶媒を留去することにより淡黄色固体として粗生成物を得た。粗生成物を酢酸エチル：ヘキサン混合溶媒を展開溶媒とするシリカゲルカラムクロマトグラフィーで精製することにより、白色固体として化学式（１８）で示される化合物を得た（１．２８ｇ，９９％）。^１Ｈ−ＮＭＲ（２７０ＭＨｚ）：σ＝８．０９（ｄ，４Ｈ）、８．０２（ｓ，１Ｈ）、７．９２（ｓ，２Ｈ）、７．６７（ｄ，２Ｈ）、１．３８（ｓ，２４Ｈ）。 (Synthesis Example 16) 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) carbazole

In a 20 mL eggplant flask under nitrogen atmosphere, 2,7-dibromocarbazole (1 g, 3.08 mmol), potassium acetate (1.82 g, 18.46 mmol), PdCl ₂ (dppf) (45 mg, 0.062 mmol), bis (pinacolato) ) Diboron (1.86 g, 7.38 mmol) and dioxane (5 mL) were added and stirred at 90 ° C. for 18 hours. The reaction solution was cooled to room temperature, extracted with ethyl acetate (20 mL × 2), washed with water (50 mL × 2), and dried using sodium sulfate. The solvent was distilled off under reduced pressure to obtain a crude product as a pale yellow solid. The crude product was purified by silica gel column chromatography using an ethyl acetate: hexane mixed solvent as a developing solvent to obtain a compound represented by the chemical formula (18) as a white solid (1.28 g, 99%). ¹ H-NMR (270 MHz): σ = 8.09 (d, 4H), 8.02 (s, 1H), 7.92 (s, 2H), 7.67 (d, 2H), 1.38 ( s, 24H).

窒素雰囲気下、２０ｍＬ三口フラスコに２−ブロモ−３−ドデシロキシチオフェン（２．２ｇ，６．３３ｍｍｏｌ）、２，７−ビス（１，３，２−ジオキサボロラン−２−イル）カルバゾール（１．１１ｇ，２．６５ｍｍｏｌ）、テトラキストリフェニルホスフィンパラジウム（０．１８４ｇ，０．１５９ｍｍｏｌ）、２Ｍ炭酸カリウム水溶液（１０ｍＬ，２０．０ｍｍｏｌ）、トルエン（２０ｍＬ）、Ａｌｉｑｕａｔ３３６（２５ｍｇ）を加え、環流下で時間攪拌した。反応終了後室温まで冷却し、有機層を水（５０ｍＬ×３）で洗浄し、水層をトルエン（５０ｍＬ×３）で抽出した後に、硫酸ナトリウムを用いて乾燥した。減圧下で溶媒を留去することにより黒色の固体として粗生成物を得た。粗生成物を、ヘキサンを展開溶媒とするシリカゲルカラムクロマトグラフィーを用いて精製することにより、黄白色の固体として化学式（１９）で示される化合物を得た（１．５４ｇ，３５％）。^１Ｈ−ＮＭＲ（２７０ＭＨｚ）：σ＝７．９７（ｄ，２Ｈ）、７．８７（Ｓ，２Ｈ）、７．６１（ｄ，２Ｈ）、７．１３（ｄ，２Ｈ）、６．９２（ｄ，２Ｈ）、４．０９（ｔ，４Ｈ）、１．８３（ｍ、４Ｈ）、１．７−１．１（ｍ，３６Ｈ）、０．８７（ｔ，６Ｈ）。 (Synthesis Example 17) 2,7-bis (3-dodecyloxythiophen-2-yl) carbazole

Under a nitrogen atmosphere, 2-bromo-3-dodecyloxythiophene (2.2 g, 6.33 mmol), 2,7-bis (1,3,2-dioxaborolan-2-yl) carbazole (1. 11 g, 2.65 mmol), tetrakistriphenylphosphine palladium (0.184 g, 0.159 mmol), 2M aqueous potassium carbonate solution (10 mL, 20.0 mmol), toluene (20 mL), Aliquat 336 (25 mg) were added, and the mixture was refluxed for hours. Stir. After completion of the reaction, the reaction mixture was cooled to room temperature, the organic layer was washed with water (50 mL × 3), the aqueous layer was extracted with toluene (50 mL × 3), and then dried using sodium sulfate. The crude product was obtained as a black solid by distilling off the solvent under reduced pressure. The crude product was purified using silica gel column chromatography using hexane as a developing solvent to obtain a compound represented by the chemical formula (19) as a pale yellow solid (1.54 g, 35%). ¹ H-NMR (270 MHz): σ = 7.97 (d, 2H), 7.87 (S, 2H), 7.61 (d, 2H), 7.13 (d, 2H), 6.92 ( d, 2H), 4.09 (t, 4H), 1.83 (m, 4H), 1.7-1.1 (m, 36H), 0.87 (t, 6H).

窒素雰囲気下、１００ｍＬ三口フラスコに２，７−ビス（３−ドデシロキシチオフェン−２−イル）カルバゾール化合物（１ｇ，１．４２ｍｍｏｌ）とクロロホルム（２０ｍＬ）を加え、氷浴を用いて０℃まで冷却した。Ｎ−ブロモスクシンイミド（０．５０８ｇ，２．８６ｍｍｏｌ）を，０℃を保持するようにゆっくりと加えた後に、室温まで昇温して１時間攪拌した。反応終了後、水（５０ｍＬ）を加え、１５分間攪拌した。有機層を水（５０ｍＬ×３）で洗浄し、水層をクロロホルム（２０ｍＬ×２）で抽出したのちに、硫酸ナトリウムにて乾燥した。減圧下で溶媒を留去することにより茶色固体として粗生成物を得た。粗生成物を、ヘキサン−酢酸エチル混合溶媒を展開溶媒とするシリカゲルカラムクロマトグラフィーで精製することにより、黄白色固体として化学式（２０）で示される化合物を得た（０．９０７ｇ，７４．１％）。^１Ｈ−ＮＭＲ（２７０ＭＨｚ）：σ＝７．８２（ｄ，２Ｈ）、７．６９（ｄｄ，４Ｈ）、６．９１（ｓ，２Ｈ）、４．０３（ｔ，４Ｈ）、１．７９（ｍ、６Ｈ）、１．６５−１．１５（ｍ，３６Ｈ）、０．８７（ｔ，６Ｈ）。 (Synthesis Example 18) 2,7-bis (5-bromo-3-dodecyloxythiophen-2-yl) carbazole

Under a nitrogen atmosphere, 2,7-bis (3-dodecyloxythiophen-2-yl) carbazole compound (1 g, 1.42 mmol) and chloroform (20 mL) were added to a 100 mL three-necked flask, and the mixture was heated to 0 ° C. using an ice bath. Cooled down. N-bromosuccinimide (0.508 g, 2.86 mmol) was slowly added so as to maintain 0 ° C., and then the mixture was warmed to room temperature and stirred for 1 hour. After completion of the reaction, water (50 mL) was added and stirred for 15 minutes. The organic layer was washed with water (50 mL × 3), the aqueous layer was extracted with chloroform (20 mL × 2), and then dried over sodium sulfate. The crude product was obtained as a brown solid by distilling off the solvent under reduced pressure. The crude product was purified by silica gel column chromatography using a mixed solvent of hexane-ethyl acetate as a developing solvent to obtain a compound represented by the chemical formula (20) as a yellowish white solid (0.907 g, 74.1%). ). ¹ H-NMR (270 MHz): σ = 7.82 (d, 2H), 7.69 (dd, 4H), 6.91 (s, 2H), 4.03 (t, 4H), 1.79 ( m, 6H), 1.65-1.15 (m, 36H), 0.87 (t, 6H).

窒素雰囲気下、１０ｍＬ三口フラスコに２，７−ビス（５−ブロモ−３−ドデシロキシチオフェン−２−イル）カルバゾール化合物（１５０ｍｇ、０．１７５ｍｍｏｌ）、４，７−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンゾチアジアゾール（６７．９ｍｇ、０．１７５ｍｍｏｌ）、２Ｍ炭酸カリウム水溶液（１．２ｍＬ，２．４ｍｍｏｌ）テトラキストリフェニルホスフィンパラジウム（４．３ｍｇ，３．８μｍｏｌ）、トルエン（１．２ｍＬ）を加え、８５℃で３時間加熱攪拌した。反応終了後、室温まで冷却し、クロロベンゼン（１０ｍＬ）を加えて析出した固体を溶解させた。その後、反応溶液をメタノール（１５０ｍＬ）に注ぎ、析出した固体を濾取し真空下で乾燥を行うことで黒紫色の固体として化学式（２１）で示される化合物を得た（１０２ｍｇ、４７．８％）。ＧＰＣ（ＣＨＣｌ_３）：Ｍｎ＝３４０００ｇ／ｍｏｌ、Ｍｗ＝２１８０００ｇ／ｍｏｌ、ＰＤＩ＝６．５。 Synthesis Example 19 Poly [(carbazole-2,7-diyl) -alt- [bis (4-dodecyloxythiophen-5-yl) -2,1,3-benzothiadiazole]

In a 10 mL three-necked flask under a nitrogen atmosphere, 2,7-bis (5-bromo-3-dodecyloxythiophen-2-yl) carbazole compound (150 mg, 0.175 mmol), 4,7-bis (4,4,5 , 5-Tetramethyl-1,3,2-dioxaborolan-2-yl) benzothiadiazole (67.9 mg, 0.175 mmol), 2M aqueous potassium carbonate (1.2 mL, 2.4 mmol) tetrakistriphenylphosphine palladium (4 .3 mg, 3.8 μmol) and toluene (1.2 mL) were added, and the mixture was stirred with heating at 85 ° C. for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and chlorobenzene (10 mL) was added to dissolve the precipitated solid. Thereafter, the reaction solution was poured into methanol (150 mL), and the precipitated solid was collected by filtration and dried under vacuum to obtain a compound represented by the chemical formula (21) as a black purple solid (102 mg, 47.8%). ). GPC (CHCl ₃ ): Mn = 34000 g / mol, Mw = 218000 g / mol, PDI = 6.5.

<Comparative Example 1>
Production of poly [(9,9-didecylfluorene-2,7-diyl) -alt- [bis (thiophen-5-yl) -2,1,3-benzothiadiazole] synthesized as a comparative example below The method will be described in detail.

非特許文献１に記載の方法に従い、（２２）式で表されるポリ[（フルオレン−２,７−ジイル）−アルト−[ビス（チオフェン−５−イル）−２,１,３−ベンゾチアジアゾール]を得た。 (Synthesis Example 20)
Synthesis of poly [(9,9-didecylfluorene-2,7-diyl) -alt- [bis (thiophen-5-yl) -2,1,3-benzothiadiazole]

According to the method described in Non-Patent Document 1, poly [(fluorene-2,7-diyl) -alt- [bis (thiophen-5-yl) -2,1,3-benzothiadiazole represented by the formula (22) ]

<Comparative example 2>
Hereinafter, poly [(9- (1-octylnonyl) -9H-carbazol-2,7-diyl) -alt- [bis (thiophen-5-yl) -2,1,3- The production method of benzothiadiazole] will be described in detail.

非特許文献１に記載の方法に従い、（２３）式で表されるポリ[（９−（１−オクチルノニル）−９Ｈ−カルバゾール−２,７−ジイル）−アルト−[ビス（チオフェン−５−イル）−２,１,３−ベンゾチアジアゾール]を得た。 (Synthesis Example 21) Poly [(9- (1-octylnonyl) -9H-carbazol-2,7-diyl) -alt- [bis (thiophen-5-yl) -2,1,3-benzothiadiazole] Composition

According to the method described in Non-Patent Document 1, poly [(9- (1-octylnonyl) -9H-carbazol-2,7-diyl) -alt- [bis (thiophen-5-5] represented by the formula (23) Yl) -2,1,3-benzothiadiazole].

<Light absorption characteristics>
FIG. 1 shows absorption spectra of the polymer compounds (7), (12), (17) and (22) in a dilute chloroform solution. The polymer compounds (7), (12) and (17) having the fluorene ring and the alkoxythiophene unit of Examples 1 to 3 are compared with the polymer compound (22) having no alkoxy group of Comparative Example 1. It can be seen that the light absorption characteristics in the long wavelength region are improved.
Similarly, FIG. 2 shows absorption spectra of the polymer compounds (21) and (23) in a dilute chloroform solution. From FIG. 2, the polymer compound (21) having a carbazole ring and an alkoxythiophene unit of Example 4 has a light absorption in a long wavelength region as compared with the polymer compound (23) having no alkoxy group of Comparative Example 2. It can be seen that the characteristics are improved.

<Production and evaluation of organic solar cells>
According to the method described in Non-Patent Document 1, the polymer represented by the chemical formulas (7), (12), (17), (21), (22), and (23) of the present invention was used as an organic semiconductor material. A photoelectric conversion element was produced.
Poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate) was laminated by spin coating on a glass substrate on which 300 nm of cleaned indium-tin oxide (ITO) was laminated. A mixture (1: 4, w) of each of the polymers represented by the chemical formulas (7), (12), (17), (21), (22), and (23) and phenyl C ₆₁ butyric acid methyl ester (PCBM). A photoactive layer was prepared by applying a solution of / w) dissolved in dichlorobenzene at 32 mg / mL by spin coating. At this time, the film thickness of the photoactive layer was 80 nm. Lithium fluoride (1 nm) and an Al pattern (80 nm) were vapor-deposited on the produced film using a mask.
Pseudo sunlight (AM1.5, 100 mW / cm < ² >) was irradiated using the produced photoelectric conversion element, and the photoelectric conversion efficiency was measured. The measurement results are shown in Table 1.

表１に示したとおり、本発明の化合物（７）、（１２）、（１７）、（２１）は既存のＬＢＧＰである化合物（２２）、（２３）と比較して、同等またはそれ以上の良好な性能を示すことが明らかになった。

As shown in Table 1, the compounds (7), (12), (17) and (21) of the present invention are equal to or higher than the compounds (22) and (23) which are existing LBGP. It became clear that it showed good performance.

Claims (4)

A polymer represented by the following general formula (1).

[In the formula (1), R ¹ and R ² each independently represents an optionally substituted alkyl group having 1 to 20 carbon atoms, X represents an oxygen atom, a sulfur atom or a selenium atom, Y Represents CR ³ R ⁴ , SiR ⁵ R ⁶ , GeR ⁷ R ⁸ , NR ⁹ , an oxygen atom, a sulfur atom or a selenium atom. Here, R ³ , R ⁴ , and R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms that may have a substituent, and R ⁵ , R ⁶ , R ⁷ , and R 9 ⁸ represents a C1-C20 alkyl group which may have a substituent each independently.
Z is (i) a divalent aromatic ring which may have a substituent, (ii) a divalent polynuclear aromatic ring having 2 to 7 aromatic rings which may have a substituent, or (iii) the above-mentioned It represents any one selected from divalent polyarylene groups in which up to three aromatic rings selected from (i) and / or (ii) are linked. n is a number of 2 or more, and m is 0 or 1. ] A compound represented by the following general formula (2).

[In the formula (2), R ¹ , R ² , X and Y are as defined in the formula (1). W represents one selected from the group consisting of a halogen atom, —Sn (R ¹⁰ ) ₃ , a boronic acid and a boronic ester group. Wherein, R ¹⁰ represents an alkyl group or an aryl group of good C1-10 substituted. ]   An organic semiconductor device produced using the polymer according to claim 1.   The organic semiconductor device according to claim 3, which is an organic photoelectric conversion element.

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