JP2007023252A - Manufacturing method of conjugated polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a conjugated polymer by causing an aromatic monomer bearing a boron-containing functional group to react with an aromatic monomer bearing a reactive functional group or by causing an aromatic monomer bearing the reactive functional group and the boron-containing functional group in the same molecule to react. <P>SOLUTION: The manufacturing method of the conjugated polymer comprises causing (A) an aromatic monomer bearing at least two boron-containing functional groups to polymerize with an aromatic monomer bearing at least two reactive functional groups or (B) an aromatic monomer bearing at least one reactive functional group and at least one boron-containing functional group in the same molecule to polymerize, in the presence of an organic solvent using a catalytic amount of a palladium complex, where at least one selected from the group consisting of alkali metal hydroxides, alkali metal alkoxides, alkaline earth metal hydroxides and alkali earth metal alkoxides, and an alkylphosphine ligand is used. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a conjugated polymer. More specifically, the present invention reacts an aromatic monomer having a boron-containing functional group with an aromatic monomer having a reactive functional group, or at least one reactive functional group and one boron-containing functional group are the same. The present invention relates to a method for producing a conjugated polymer in which an aromatic monomer contained in a molecule is reacted.

Polymerization reaction was carried out in the presence of only an organic solvent using an alkali metal hydroxide, an alkali metal alkoxide, an alkaline earth metal hydroxide or an alkaline earth metal alkoxide, and a triarylphosphine ligand. In this case, alkali metal hydroxide, alkali metal alkoxide, alkaline earth metal hydroxide, or alkaline earth metal alkoxide does not sufficiently dissolve in an organic solvent, so that the molecular weight extension is generally slow or the extent Often low. Therefore, as a polymerization method, a method in which an additive functioning as a phase transfer catalyst for improving the mixed state is added to a two-phase system of an organic solvent and water and reacted is developed.

For example, Patent Document 1 discloses a method for producing a conjugated polymer using an inorganic base and a palladium catalyst in the presence of a phase transfer catalyst in a two-phase system of an organic solvent and water. Patent Document 2 discloses a method for synthesizing a conjugated polymer using a palladium catalyst in the presence of an aqueous solution such as tetraethylammonium hydroxide or bis (tetraethylammonium) carbonate.
However, since these methods use a phase transfer catalyst or a base that plays a role, there is a problem that it takes time to separate the organic layer and the aqueous layer after the reaction is completed. Also, depending on the substrate, hydrolysis has been a problem due to hydrolysis.

Further, Patent Document 3 discloses a synthesis method in which an inorganic salt is organically dissolved by a reaction in a ternary mixed solvent system comprising an organic solvent miscible with water, an organic solvent immiscible with water, and water. Has been. However, the degree of polymerization and yield largely depend on the solubility of the substrate, so that there is a problem that the versatility is poor and the reproducibility of data is low.
Furthermore, when the reactive halogen-containing functional group of the substrate is a chloro group, a conventional high molecular weight polymer cannot be obtained by the conventional technique, and the selection of the substrate is limited.
From the above, it has been desired to develop a method capable of obtaining a polymer having excellent operability and high versatility.
Special table 2001-520289 Japanese Patent No. 3310658 US2004 / 0260090

The present invention reacts an aromatic monomer having a boron-containing functional group with an aromatic monomer having a reactive functional group, or an aromatic monomer having a reactive functional group and a boron-containing functional group in the same molecule. An object of the present invention is to provide a method for producing a conjugated polymer to be reacted.

That is, the present invention
A) an aromatic monomer having at least two boron-containing functional groups and an aromatic monomer having at least two reactive functional groups,
Or
B) Method for producing a conjugated polymer in which an aromatic monomer having at least one reactive functional group and a boron-containing functional group in the same molecule is subjected to a polymerization reaction using a catalytic amount of a palladium complex in the presence of an organic solvent. Using at least one selected from the group consisting of alkali metal hydroxides, alkali metal alkoxides, alkaline earth metal hydroxides, alkaline earth metal alkoxides, and alkylphosphine ligands. A characteristic manufacturing method is provided.

“Conjugated polymer” refers to a polymer in which a part or all of the conjugated aromatic monomer is polymerized, and is a completely conjugated polymer, in other words, conjugated over the entire length of the polymer chain. Either a polymer or a partially conjugated polymer, in other words, a polymer including both a conjugated portion and a non-conjugated portion may be used.

The catalytic amount of the palladium complex used in the method according to the present invention includes a palladium (0) complex or a palladium (II) salt, and more preferably a palladium (0) complex. Specific examples of suitable palladium complexes include, but are not limited to, tetrakis (triphenylphosphine) palladium (0), tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium. (0) Chloroform adduct, bis (1,2-bis (diphenylphosphinoethane)) palladium (0), bis (tricyclohexylphosphine) palladium (0), bis (tri-tert-butylphosphine) palladium (0) , Palladium (II) acetate, palladium (II) trifluoroacetate, palladium (II) chloride, palladium (II) bromide, palladium (II) iodide, palladium (II) cyanide, allyl palladium (II) chloride dimer, chloride Tyl palladium (II) chloride dimer, 2-methyla Rylpalladium (II) chloride dimer, palladium (II) acetylacetonate, dichloro (1,5-cyclooctadiene) palladium (II), dichlorobis (acetonitrile) palladium (II), dichlorobis (benzonitrile) palladium (II), Dichlorobis (triphenylphosphine) palladium (II), dichlorobis (tri-ortho-tolylphosphine) palladium (II), dichlorobis (tricyclohexylphosphine) palladium (II), or dichloro (1,2-bis (diphenylphosphino) ethane ) Palladium (II), more preferably tris (dibenzylideneacetone) dipalladium (0).

The usage-amount of a catalyst is 0.01-10 mol% normally, More preferably, it is 0.1-1 mol%. These numerical values are calculated based on the total number of moles of monomers used.

The “alkyl phosphine ligand” is a phosphine having at least one alkyl group, and the alkyl group has 1 to 30 carbon atoms and may be substituted. Specific examples include, for example, tricyclohexylphosphine, tri-n-butylphosphine, tri-tert-butylphosphine, triisopropylphosphine, triethylphosphine, trimethylphosphine, n-butyldiadamantylphosphine, adamantyldi-n-butylphosphine, cyclohexyldiisopropyl. Phosphine, isopropyl dicyclohexylphosphine, tert-butyldicyclohexylphosphine, cyclohexyldi-tert-butylphosphine, tert-butyldimethylphosphine, di-tert-butylmethylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, diphenylphosphinomethane, ethyldiphenylphosphine , Diethylphenylphosphine, diphenylpropylphosphine , Dipropylphenylphosphine, n-butyldiphenylphosphine, di-n-butylphenylphosphine, cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine, tert-butyldiphenylphosphine, di-tert-butylphenylphosphine, 1,2-diphenylphosphino Ethane, 1,3-diphenylphosphinopropane, 1,4-diphenylphosphinobutane, 1,2-dicyclohexylphosphinoethane, 1,3-dicyclohexylphosphinopropane, 1,4-dicyclohexylphosphinobutane, 1,2 -Dimethylphosphinoethane, 1,3-dimethylphosphinopropane, 1,4-dimethylphosphinobutane, 1,2-diethylphosphinoethane, 1,3-diethylphosphinopropane, 1 4-diethylphosphinobutane, 1,2-diisopropylphosphinoethane, 1,3-diisopropylphosphinopropane, 1,4-diisopropylphosphinobutane, 2,3-bis (diphenylphosphino) butane, 2,4- Bis (diphenylphosphino) pentane, 1,2-bis (dipentafluorophenylphosphino) ethane, 1,3-bis (dipentafluorophenylphosphino) propane, 1,4-bis (dipentafluorophenylphosphino) ) Butane. Specific examples of suitable ligands include, but are not limited to, tricyclohexylphosphine and 1,2-diphenylphosphinoethane.

Although the usage-amount of an alkylphosphine ligand is not specifically limited, Usually, it is about 0.01-0.5 mol times with respect to a monomer.

“Alkali metal hydroxide”, “alkali metal alkoxide”, “alkaline earth metal hydroxide” and “alkaline earth metal alkoxide” are represented by MXn · xH 2 O, where M is an alkali metal or Represents an alkaline earth metal, and X represents OH or OR. R is an alkyl group having 1 to 8 carbon atoms and may be substituted. n is 1 or 2, x is 0 to 8, and is arbitrarily selected independently of each other.

The type and amount of the alkali metal hydroxide, alkali metal alkoxide, alkaline earth metal hydroxide or alkaline earth metal alkoxide are appropriately selected according to the type and amount of the monomer or solvent used. The amount used is usually about 0.1 to 20 mol times the monomer.

Alkali metal hydroxides, alkali metal alkoxides, alkaline earth metal hydroxides or alkaline earth metal alkoxides may be single or different types of alkali metal hydroxides, It may be a mixture of an alkali metal alkoxide, an alkaline earth metal hydroxide, or an alkaline earth metal alkoxide.

In the alkali metal alkoxide or alkaline earth metal alkoxide, examples of the alkoxide include methoxide, ethoxide, and tert-butoxide, and preferably methoxide. Specific examples of suitable alkali metal hydroxides, alkali metal alkoxides, alkaline earth metal hydroxides or alkaline earth metal alkoxides include, but are not limited to, lithium methoxy Sodium methoxide, sodium ethoxide, potassium tert-butoxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, barium hydroxide, more preferably lithium methoxide, hydroxide Mention may be made of barium octahydrate or cesium hydroxide monohydrate.

The type and amount of organic solvent depend on the type and amount of monomer used, alkali metal hydroxide, alkali metal alkoxide, alkaline earth metal hydroxide, alkaline earth metal alkoxide, and polymer produced. The amount used is usually about 1 to 50 times the weight of the monomer.

Examples of the organic solvent include nonpolar aromatic solvents, polar oxygen-containing solvents, polar nitrogen-containing solvents, and polar sulfur-containing solvents. Specifically, although not particularly limited, for example, benzene, toluene, xylene, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, N- Examples thereof include methyl-2-pyrrolidinone and dimethyl sulfoxide, and if necessary, they may be used as a mixture, more preferably toluene and dimethyl sulfoxide, toluene and N-methyl-2-pyrrolidinone, toluene and ethylene glycol dimethyl ether, A combination of tetrahydrofuran and N-methyl-2-pyrrolidinone is exemplified.

The “boron-containing functional group” is a boronic acid group represented by —B (OH) ₂ , a boronic acid ester group exemplified by —B (OR ²⁶ ) (OR ²⁷ ), —B (OR ²⁸ O), or ^-BR 29 ^{R 30} can be mentioned borane group exemplified. Here, R ²⁶ is an alkyl group having 1 to 6 carbon atoms and may be substituted. R ²⁷ is an alkyl group having 1 to 6 carbon atoms and may be substituted. R ²⁸ is an ester ring in which a divalent hydrocarbon radical finally becomes a 5-membered or 6-membered ring. The divalent hydrocarbon radical may be substituted. Suitable functional groups as R ²⁸ include alkylene groups having 2 or 3 carbon atoms, ortho- or meta-phenylene groups. In addition, these alkylene groups and meta-phenylene groups may be substituted. ^Then, R ^{29, R 30} are each independently an alkyl group having 1 to 6 carbon atoms, may be substituted.

Examples of the boronic acid ester group include alcohols having 1 to 6 carbon atoms, ethanediol such as pinacol, propanediol, 2,2-dimethyl-1,3-propanediol, or 1,2-dihydroxybenzene. And the product of esterification of an ortho aromatic diol with the corresponding boronic acid.

The "reactive functional group", Cl, halogen atom such as Br or I, triflate _(CF 3 _SO 3 -), tosylate _{(CH 3 C 6 H 4 SO} 3 -) or mesylate _(CH 3 _SO 3 -) And sulfonic acid ester groups such as

（式中、ＺはＯ、Ｓ、ＮＲ^２１又はＣＲ^２２Ｒ^２３を表し、Ｘ及びＹは、それぞれＣｌ、Ｂｒ、Ｉ又はＢ（ＯＲ^２４）（ＯＲ^２５）を表す。Ｒ^１〜Ｒ^２５は、水素原子又は反応に関与しない基を表し、互いに独立に選択され、結合して環を形成することもできる。） Examples of the “aromatic monomer” include a monomer having a substituent that can be directly substituted with one or more aromatic rings. In the case of a monomer having one or more aromatic rings, the functional group can be substituted with either the same aromatic ring or a different aromatic ring. Suitable monomers include, but are not limited to, arylene, heterocyclic aromatic monomers, condensed aromatic systems such as biphenylene, naphthalene, and fluorene.
As an aromatic monomer, what is shown by following formula (1)-(4) is mentioned, for example.

(In the formula, Z represents O, S, NR ²¹ or CR ²² R ²³ , and X and Y represent Cl, Br, I or B (OR ²⁴ ) (OR ²⁵ ), respectively, R ^{1 to} R ^25. Represents a hydrogen atom or a group that does not participate in the reaction, and can be selected independently of each other and bonded to form a ring.)

The aromatic monomer having at least two boron-containing functional groups is not particularly limited. For example, 2,2 ′-(9,9-dihexyl-9H-fluorene-2,7-diyl) bis (1 , 3,2-dioxaborolene), 2,2 ′-(9,9-dihexyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborinane), 2,2 ′-(9,9 -Dihexyl-9H-fluorene-2,7-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolene), 2,2 '-(9,9-dihexyl-9H-fluorene -2,7-diyl) bis (5,5-dimethyl-1,3,2-dioxaborinane), 2,2 '-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1, 3,2-dioxaborolene), 2,2 '-(9,9-dioc) -9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborinane), 2,2 '-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (4,4 , 5,5-tetramethyl-1,3,2-dioxaborolene), 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (5,5-dimethyl-1,3) , 2-dioxaborinane), 2,2 ′-(9,9-didodecyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene), 2,2 ′-(9,9-didodecyl) -9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborinane), 2,2 '-(9,9-didodecyl-9H-fluorene-2,7-diyl) bis (4,4,4) 5,5-tetramethyl-1,3,2-dioxaborolene), 2,2 ′-(9, 9-didodecyl-9H-fluorene-2,7-diyl) bis (5,5-dimethyl-1,3,2-dioxaborinane), 2,2 ′-(1,4-phenylene) bis (1,3,2) -Dioxaborolene), 2,2 '-(1,4-phenylene) bis (1,3,2-dioxaborinane), 2,2'-(1,4-phenylene) bis (4,4,5,5-tetra Methyl-1,3,2-dioxaborolene), 2,2 ′-(1,4-phenylene) bis (5,5-dimethyl-1,3,2-dioxaborinane), 2,2 ′-(2,5- Dimethyl-1,4-phenylene) bis (1,3,2-dioxaborolene), 2,2 ′-(2-methyl-5-octyl-1,4-phenylene) bis (1,3,2-dioxaborolene), 2,2 '-(2,5-diethyl-1,4-phenylene) Bis (1,3,2-dioxaborinane), 2,2 ′-(2,5-dipropyl-1,4-phenylene) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolene) 2,2 ′-(2,5-diisopropyl-1,4-phenylene) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolene), 2,2 ′-(2,5 -Dibutyl-1,4-phenylene) bis (5,5-dimethyl-1,3,2-dioxaborinane), 2,2 '-(2-butyl-5-phenyl-1,4-phenylene) bis (5 5-dimethyl-1,3,2-dioxaborinane), 2,2 ′-(2,3-dicyclohexyl-1,4-phenylene) bis (5,5-dimethyl-1,3,2-dioxaborinane), 2, 2 '-(2,5-diphenyl-1,4-phenylene Bis (5,5-dimethyl-1,3,2-dioxaborinane), 2,2 ′-(2,3,5-trimethyl-1,4-phenylene) bis (5,5-dimethyl-1,3,2) -Dioxaborinane), 2,2 '-[2,5-bis (methoxy) -1,4-phenylene] bis (1,3,2-dioxaborolene), 2,2'-[2,5-bis (ethoxy) -1,4-phenylene] bis (1,3,2-dioxaborolene), 2,2 '-[2-ethoxy-5-butoxy-1,4-phenylene] bis (1,3,2-dioxaborolene), 2 , 2 '-[2-Ethoxy-3-phenoxy-1,4-phenylene] bis (1,3,2-dioxaborolene), 2,2'-[2,6-bis (hexyloxy) -1,4- Phenylene] bis (1,3,2-dioxaborinane), 2,2 ′-[2,5-biphenyl] (Methoxy) -1,4-phenylene] bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolene), 2,2 ′-[2,5-bis (butoxy) -1,4 -Phenylene] bis (5,5-dimethyl-1,3,2-dioxaborinane), 2,2 '-[2,5-bis (phenoxy) -1,4-phenylene] bis (5,5-dimethyl-1 , 3,2-dioxaborinane) and the like.

The aromatic monomer having at least two reactive functional groups is not particularly limited, and examples thereof include 2,7-dibromo-9,9-dihexyl-9H-fluorene, 2,7-dibromo-9,9. -Dioctyl-9H-fluorene, 2,7-dibromo-9,9-didodecyl-9H-fluorene, 2,7-dichloro-9,9-dihexyl-9H-fluorene, 2,7-dichloro-9,9-dioctyl -9H-fluorene, 2,7-dichloro-9,9-didodecyl-9H-fluorene, 2-bromo-7-chloro-9,9-dihexyl-9H-fluorene, 2-bromo-7-chloro-9,9 -Dioctyl-9H-fluorene, 2-bromo-7-chloro-9,9-didodecyl-9H-fluorene, 1,4-dibromobenzene, 1,4-dibromotoluene, 1 4-dibromo-2-ethylbenzene, 1,4-dibromo-2-ethoxybenzene, 1,4-dibromo-2,5-dihexylbenzene, 1,4-dibromo-2,6-dihexylbenzene, 1,4-di Chlorobenzene, 1,4-dichlorotoluene, 1,4-dichloro-2-propylbenzene, 1,4-dichloro-2-ethyl-3-propylbenzene, 1,4-dichloro-2-decyl-5-propylbenzene, 1,4-dichloro-2-decyl-6-propylbenzene, 1,4-dichloro-2-ethoxy-3-propylbenzene, 1-bromo-4-chlorobenzene, 1-bromo-4-chlorotoluene, 1-bromo -4-chloro-5-propylbenzene, 1-bromo-2-butyl-4-chlorobenzene, 1-bromo-4-chloro-5-methoxybenzene, 1-bromo-4-chloro-6-hexylbenzene, 2,5-dibromo-4'-phenoxybenzophenone, 2,5-dibromo-3-methyl-4'-phenoxybenzophenone, 2,5-dichloro-4 ' -Phenoxybenzophenone, 2,5-dichloro-3-hexyl-4'-phenoxybenzophenone, 2-bromo-5-chloro-4'-phenoxybenzophenone, 2-bromo-3-butyl-5-chloro-4'-phenoxy Benzophenone, 2-bromo-4-butyl-5-chloro-4'-phenoxybenzophenone, 2-bromo-5-chloro-6-ethyl-4'-phenoxybenzophenone, 2,5-dibromo-3-hexylthiophene, 2 , 5-Dibromo-3-hexyl-4-pentylthiophene, 2,5-dibromo-3-octylthiophene 2,5-dibromo-3-octyl-4-phenoxythiophene, 2,5-dibromo-3-dodecylthiophene, 2,5-dibromo-3-dodecyl-4-ethoxythiophene, 2,5-dichloro-3 -Hexylthiophene, 2,5-dichloro-3,4-dihexylthiophene, 2,5-dichloro-3-octylthiophene, 2,5-dichloro-3-octyl-4-propylthiophene, 2,5-dichloro-3 -Dodecylthiophene, 2,5-dichloro-3-dodecyl-4-methoxythiophene, 2-bromo-3-butyl-5-chlorothiophene, 2-bromo-4-butyl-5-chlorothiophene, N, N'- Bis (4-bromophenyl) -N, N′-bis [4- (1,1-dimethylethyl) -2,6-dimethylphenyl] -1,4-benzenediamy N, N′-bis (4-chlorophenyl) -N, N′-bis [4- (1,1-dimethylethyl) -2,6-dimethylphenyl] -1,4-benzenediamine, 4,7- Dibromobenzothiadiazole, 4,7-dibromo-5-methylbenzothiadiazole, 4,7-dibromo-5-phenoxybenzothiadiazole, 4,7-dichlorobenzothiadiazole, 4,7-dichloro-5,6-diethylbenzothiadiazole, 4,7-dichloro-5-ethyl-6-methoxybenzothiadiazole, 4-bromo-7-chlorobenzothiadiazole, 4-bromo-5-butyl-7-chlorobenzothiadiazole, 4-bromo-6-butyl-7- And chlorobenzothiadiazole.

The aromatic monomer having at least one reactive functional group and at least one boron-containing functional group in the same molecule is not particularly limited. For example, 2- (2-bromo-9,9-dihexyl-9H- Fluoren-7-yl) -1,3,2-dioxaborolene, 2- (2-bromo-9,9-dihexyl-9H-fluoren-7-yl) -1,3,2-dioxaborinane, 2- (2- Bromo-9,9-dihexyl-9H-fluoren-7-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolene, 2- (2-bromo-9,9-dihexyl-9H -Fluoren-7-yl) -5,5-dimethyl-1,3,2-dioxaborinane, 2- (2-bromo-9,9-dioctyl-9H-fluoren-7-yl) -1,3,2- Dioxaborolene, 2- (2 Bromo-9,9-dioctyl-9H-fluoren-7-yl) -1,3,2-dioxaborinane, 2- (2-bromo-9,9-dioctyl-9H-fluoren-7-yl) -4,4 , 5,5-tetramethyl-1,3,2-dioxaborolene, 2- (2-bromo-9,9-dioctyl-9H-fluoren-7-yl) -5,5-dimethyl-1,3,2- Dioxaborinane, 2- (2-bromo-9,9-didodecyl-9H-fluoren-7-yl) -1,3,2-dioxaborolene, 2- (2-bromo-9,9-didodecyl-9H-fluorene-7 -Yl) -1,3,2-dioxaborinane, 2- (2-bromo-9,9-didodecyl-9H-fluoren-7-yl) -4,4,5,5-tetramethyl-1,3,2 -Dioxaborolene, 2- (2-bromo- 9,9-didodecyl-9H-fluoren-7-yl) -5,5-dimethyl-1,3,2-dioxaborinane, 2- (2-chloro-9,9-dihexyl-9H-fluoren-7-yl) -1,3,2-dioxaborolene, 2- (2-chloro-9,9-dihexyl-9H-fluoren-7-yl) -1,3,2-dioxaborinane, 2- (2-chloro-9,9- Dihexyl-9H-fluoren-7-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolene, 2- (2-chloro-9,9-dihexyl-9H-fluoren-7-yl) ) -5,5-dimethyl-1,3,2-dioxaborinane, 2- (2-chloro-9,9-dioctyl-9H-fluoren-7-yl) -1,3,2-dioxaborolene, 2- (2 -Chloro-9,9-dioctyl-9 H-fluoren-7-yl) -1,3,2-dioxaborinane, 2- (2-chloro-9,9-dioctyl-9H-fluoren-7-yl) -4,4,5,5-tetramethyl- 1,3,2-dioxaborolene, 2- (2-chloro-9,9-dioctyl-9H-fluoren-7-yl) -5,5-dimethyl-1,3,2-dioxaborinane, 2- (2-chloro -9,9-didodecyl-9H-fluoren-7-yl) -1,3,2-dioxaborolene, 2- (2-chloro-9,9-didodecyl-9H-fluoren-7-yl) -1,3 2-dioxaborinane, 2- (2-chloro-9,9-didodecyl-9H-fluoren-7-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolene, 2- (2- Chloro-9,9-didodecyl-9H-full Len-7-yl) -5,5-dimethyl-1,3,2-dioxaborinane, 2- (4-bromophenyl) -1,3,2-dioxaborolene, 2- (4-bromophenyl) -1,3 , 2-dioxaborinane, 2- (4-bromophenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolene, 2- (4-bromophenyl) -5,5-dimethyl-1, 3,2-dioxaborinane, 2- (4-bromo-2-ethyl-3-methylphenyl) -1,3,2-dioxaborolene, 2- (4-bromo-2,5-dimethylphenyl) -1,3 2-dioxaborolene, 2- (4-bromo-2-ethoxy-5-isopropylphenyl) -1,3,2-dioxaborolene, 2- (4-bromo-3,6-diisopropylphenyl) -1,3,2- Dioqui Borolene, 2- (4-bromo-2-ethoxy-5-methoxyphenyl) -1,3,2-dioxaborinane, 2- (4-bromo-2-butylphenyl) -1,3,2-dioxaborinane, 2- (4-bromo-2,3-dipropylphenyl) -1,3,2-dioxaborinane, 2- (4-bromo-2,5-dibutylphenyl) -4,4,5,5-tetramethyl-1, 3,2-dioxaborolene, 2- (4-bromo-2,3,5-triethylphenyl) -5,5-dimethyl-1,3,2-dioxaborinane, 2- (4-chlorophenyl) -1,3,2 -Dioxaborolene, 2- (4-chlorophenyl) -1,3,2-dioxaborinane, 2- (4-chlorophenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolene, 2- (4 -Chloro Phenyl) -5,5-dimethyl-1,3,2-dioxaborinane, 2- (4-chloro-2,5-dimethylphenyl) -1,3,2-dioxaborolene, 2- (4-chloro-2,3 -Diisopropylphenyl) -1,3,2-dioxaborolene, 2- (3-butyl-4-chloro-5-ethoxyphenyl) -1,3,2-dioxaborinane, 2- (4-chloro-2-methyl-3) -Propylphenyl) -1,3,2-dioxaborinane, 2- (4-chloro-2-methoxyphenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolene, 2- (4- Chloro-2-ethoxy-3-methylphenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolene, 2- (4-chloro-2-butoxyphenyl) -5,5-dimethyl- 1, , 2-dioxaborinane, 2- (4-chloro-2,5-dibutoxyphenyl) -5,5-dimethyl-1,3,2-dioxaborinane, 2- [4′-bromo- (1,1′-biphenyl) )]-4-yl-1,3,2-dioxaborolene, 2- [4′-bromo- (1,1′-biphenyl)]-4-yl-1,3,2-dioxaborinane, 2- [4 ′ -Bromo- (1,1'-biphenyl)]-4-yl-4,4,5,5-tetramethyl-1,3,2-dioxaborolene, 2- [4'-bromo- (1,1'- Biphenyl)]-4-yl-5,5-dimethyl-1,3,2-dioxaborinane, 2- [4′-chloro- (1,1′-biphenyl)]-4-yl-1,3,2- Dioxaborolene, 2- [4′-chloro- (1,1′-biphenyl)]-4-yl-1,3,2-dio Savoryan, 2- [4′-chloro- (1,1′-biphenyl)]-4-yl-4,4,5,5-tetramethyl-1,3,2-dioxaborolene, 2- [4′-chloro -(1,1′-biphenyl)]-4-yl-5,5-dimethyl-1,3,2-dioxaborinane and the like.

The reaction temperature of the present invention is usually room temperature to 200 ° C, preferably 40 to 120 ° C.

The reaction time of the present invention is usually 1 to 96 hours, preferably 3 to 48 hours.

  The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.

  FIG. 1 shows 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) and 2,7-dibromo-9,9-didodecyl-9H. -The reaction formula with fluorene is shown.

Example 1 (Polymerization with LiOMe, PCy ₃ )
In a glass reaction vessel fitted with a cooling apparatus, 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) (111.4 mg,. 21 mmol), 2,7-dibromo-9,9-didodecyl-9H-fluorene (132.1 mg, 0.20 mmol), tris (dibenzylideneacetone) dipalladium (0) (4.6 mg, 5 μmol), Tricyclohexylphosphine (5.6 mg, 20 μmol), lithium methoxide (47.9 mg, 1.26 mmol), toluene (2 ml), and dimethyl sulfoxide (1 ml) were added. The reaction mixture was reacted at 100 ° C. for 8 hours under a nitrogen atmosphere. The reaction mixture was then cooled to room temperature. After the solvent was distilled off, THF was added and the molecular weight was measured.
The molecular weight measurement by gel permeation chromatography on the polystyrene standard of the polymer obtained by the above method showed 320,000 g / mol Mw and 210,000 g / mol Mn.

Example 2 (Polymerization with Ba (OH) ₂ .8H ₂ O, PCy ₃ )
In a glass reaction vessel fitted with a cooling apparatus, 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) (111.4 mg,. 21 mmol), 2,7-dibromo-9,9-didodecyl-9H-fluorene (132.1 mg, 0.20 mmol), tris (dibenzylideneacetone) dipalladium (0) (4.6 mg, 5 μmol), Tricyclohexylphosphine (5.6 mg, 20 μmol), barium hydroxide octahydrate (397.5 mg, 1.26 mmol), toluene (2 ml) and N-methyl-2-pyrrolidinone (1 ml) were added. The reaction mixture was reacted at 100 ° C. for 8 hours under a nitrogen atmosphere. The reaction mixture was then cooled to room temperature. After the solvent was distilled off, THF was added and the molecular weight was measured.
The molecular weight measurement by gel permeation chromatography on the polystyrene standard of the polymer obtained by the above method showed 122,000 g / mol Mw and 58,000 g / mol Mn.

Example 3 [(Polymerization with CsOH · H ₂ O, dppe)
In a glass reaction vessel fitted with a cooling apparatus, 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) (111.4 mg,. 21 mmol), 2,7-dibromo-9,9-didodecyl-9H-fluorene (132.1 mg, 0.20 mmol), tris (dibenzylideneacetone) dipalladium (0) (4.6 mg, 5 μmol), 1,2-diphenylphosphinoethane (4.0 mg, 10 μmol), cesium hydroxide monohydrate (211.6 mg, 1.26 mmol), toluene (2 ml) and ethylene glycol dimethyl ether (1 ml) were added. . The reaction mixture was reacted at 100 ° C. for 8 hours under a nitrogen atmosphere. The reaction mixture was then cooled to room temperature. After the solvent was distilled off, THF was added and the molecular weight was measured.
The molecular weight measurement by gel permeation chromatography on the polystyrene standard of the polymer obtained by the above method showed Mw of 95,000 g / mol and Mn of 46,000 g / mol.

  FIG. 2 shows a reaction formula of 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) and 1,4-dichlorotoluene.

[Example _{4] (Ba (OH)} polymerization in _{2 · 8H 2 O, PCy 3} )
In a glass reaction vessel fitted with a cooling apparatus, 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) (111.4 mg,. 21 mmol), 1,4-dichlorotoluene (32.2 mg, 0.20 mmol), tris (dibenzylideneacetone) dipalladium (0) (4.6 mg, 5 μmol), and tricyclohexylphosphine (5.6 mg, 20 μmol). ), Barium hydroxide octahydrate (397.5 mg, 1.26 mmol), toluene (2 ml), and N-methyl-2-pyrrolidinone (1 ml) were added. The reaction mixture was reacted at 100 ° C. for 8 hours under a nitrogen atmosphere. The reaction mixture was then cooled to room temperature. After the solvent was distilled off, THF was added and the molecular weight was measured.
The molecular weight measurement by gel permeation chromatography on the polystyrene standard of the polymer obtained by the above method showed 29,000 g / mol Mw and 13,000 g / mol Mn.

  FIG. 3 shows 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) and 2,5-dichloro-4′-phenoxybenzophenone. The reaction formula is shown.

Example 5 (Polymerization with Ba (OH) ₂ .8H ₂ O, PCy ₃ )
In a glass reaction vessel fitted with a cooling apparatus, 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) (111.4 mg,. 21 mmol), 2,5-dichloro-4′-phenoxybenzophenone (68.6 mg, 0.20 mmol), tris (dibenzylideneacetone) dipalladium (0) (4.6 mg, 5 μmol), tricyclohexylphosphine ( 5.6 mg, 20 μmol), barium hydroxide octahydrate (397.5 mg, 1.26 mmol), toluene (2 ml) and N-methyl-2-pyrrolidinone (1 ml) were added. The reaction mixture was reacted at 100 ° C. for 8 hours under a nitrogen atmosphere. The reaction mixture was then cooled to room temperature. After the solvent was distilled off, THF was added and the molecular weight was measured.
The molecular weight measurement by gel permeation chromatography on the polystyrene standard of the polymer obtained by the above method showed Mw of 64,000 g / mol and Mn of 37,000 g / mol.

Comparative Example 1 (Polymerization with Na ₂ CO ₃ aq., Aliquat 336, Pd (PPh ₃ ) ₄ )
In a glass reaction vessel fitted with a cooling apparatus, 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) (106.1 mg, 0. 1). 20 mmol), 2,5-dichloro-4′-phenoxybenzophenone (68.6 mg, 0.20 mmol), toluene (1.63 ml), and Aliquat 336 (0.0102 g, 0.025 mmol) in a tetrakis (Triphenylphosphine) palladium (11.6 mg, 10 μmol) and 2M aqueous sodium carbonate (0.34 ml, 0.68 mmol) were added. The reaction mixture was reacted under reflux for 8 hours under a nitrogen atmosphere. The reaction mixture was then cooled to room temperature. After the solvent was distilled off, THF was added and the molecular weight was measured.
The molecular weight measurement by gel permeation chromatography on the polystyrene standard of the polymer obtained by the above method showed Mw of 5,900 g / mol and Mn of 5,300 g / mol. This indicates that the degree of polymerization is extremely low.

[Comparative Example 2] (Polymerization with Et ₄ NOH aq., Pd (PPh ₃ ) ₄ )
In a glass reaction vessel fitted with a cooling apparatus, 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) (106.1 mg, 0. 1). 20 mmol), 2,5-dichloro-4′-phenoxybenzophenone (68.6 mg, 0.20 mmol), and tetrakis (triphenylphosphine) palladium (11.6 mg, 10 μmol) were added with toluene (2 ml). . The solution was stirred for 10 minutes at room temperature under a nitrogen atmosphere. Tetraethylammonium hydroxide (0.67 ml, 20 wt / vol%) was added to the stirred mixture. Under a nitrogen atmosphere, the reaction mixture was reacted under reflux for an additional 8 hours. The reaction mixture was then cooled to room temperature. After the solvent was distilled off, THF was added and the molecular weight was measured.
Molecular weight measurement by gel permeation chromatography on the polystyrene standard of the polymer obtained by the above method showed Mw of 2,300 g / mol and Mn of 2,300 g / mol. This indicates that the degree of polymerization is extremely low.

  FIG. 4 shows the reaction of 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) with 2,5-dibromo-3-dodecylthiophene. An expression is shown.

Example 6 (Polymerization with LiOMe, PCy ₃ )
In a glass reaction vessel fitted with a cooling apparatus, 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) (111.4 mg,. 21 mmol), 2,5-dibromo-3-dodecylthiophene (82.1 mg, 0.20 mmol), tris (dibenzylideneacetone) dipalladium (0) (4.6 mg, 5 μmol), and tricyclohexylphosphine (5 .6 mg, 20 μmol), lithium methoxide (47.9 mg, 1.26 mmol), toluene (2 ml) and dimethyl sulfoxide (1 ml) were added. The reaction mixture was reacted at 100 ° C. for 8 hours under a nitrogen atmosphere. The reaction mixture was then cooled to room temperature. After the solvent was distilled off, THF was added and the molecular weight was measured.
The molecular weight measurement by gel permeation chromatography on the polystyrene standard of the polymer obtained by the above method showed 11,000 g / mol of Mw and 5,300 g / mol of Mn.

Example 7 (Polymerization with LiOMe, PCy ₃ )
In a glass reaction vessel fitted with a cooling apparatus, 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) (111.4 mg,. 21 mmol), 2,5-dibromo-3-dodecylthiophene (82.1 mg, 0.20 mmol), tris (dibenzylideneacetone) dipalladium (0) (4.6 mg, 5 μmol), and tricyclohexylphosphine (5 .6 mg, 20 μmol), lithium methoxide (47.9 mg, 1.26 mmol), THF (2 ml) and dimethyl sulfoxide (1 ml) were added. The reaction mixture was reacted at 100 ° C. for 8 hours under a nitrogen atmosphere. The reaction mixture was then cooled to room temperature. After the solvent was distilled off, THF was added and the molecular weight was measured.
The molecular weight measurement by gel permeation chromatography on the polystyrene standard of the polymer obtained by the above method showed Mw of 11,000 g / mol and Mn of 4,300 g / mol.

Example 8 (Polymerization with Ba (OH) ₂ .8H ₂ O, PCy ₃ )
In a glass reaction vessel fitted with a cooling apparatus, 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) (111.4 mg,. 21 mmol), 2,5-dibromo-3-dodecylthiophene (82.1 mg, 0.20 mmol), tris (dibenzylideneacetone) dipalladium (0) (4.6 mg, 5 μmol), and tricyclohexylphosphine (5 .6 mg, 20 μmol), barium hydroxide octahydrate (397.5 mg, 1.26 mmol), toluene (2 ml) and N-methyl-2-pyrrolidinone (1 ml) were added. The reaction mixture was reacted at 100 ° C. for 8 hours under a nitrogen atmosphere. The reaction mixture was then cooled to room temperature. After the solvent was distilled off, THF was added and the molecular weight was measured.
The molecular weight measurement by gel permeation chromatography on the polystyrene standard of the polymer obtained by the above method showed 31,000 g / mol Mw and 15,000 g / mol Mn.

Example 9 (Polymerization with Ba (OH) ₂ .8H ₂ O, PCy ₃ )
In a glass reaction vessel fitted with a cooling apparatus, 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) (111.4 mg,. 21 mmol), 2,5-dibromo-3-dodecylthiophene (82.1 mg, 0.20 mmol), tris (dibenzylideneacetone) dipalladium (0) (4.6 mg, 5 μmol), and tricyclohexylphosphine (5 .6 mg, 20 μmol), barium hydroxide octahydrate (397.5 mg, 1.26 mmol), THF (2 ml) and N-methyl-2-pyrrolidinone (1 ml) were added. The reaction mixture was reacted at 100 ° C. for 8 hours under a nitrogen atmosphere. The reaction mixture was then cooled to room temperature. After the solvent was distilled off, THF was added and the molecular weight was measured.
The molecular weight measurement by gel permeation chromatography on the polystyrene standard of the polymer obtained by the above method showed 106,000 g / mol Mw and 24,000 g / mol Mn.

[Example _{10] (CsOH · H 2 O} , polymerization in dppe)
In a glass reaction vessel fitted with a cooling apparatus, 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) (111.4 mg,. 21 mmol), 2,5-dibromo-3-dodecylthiophene (82.1 mg, 0.20 mmol), tris (dibenzylideneacetone) dipalladium (0) (4.6 mg, 5 μmol), 1,2-diphenyl Phosphinoethane (4.0 mg, 10 μmol), cesium hydroxide monohydrate (211.6 mg, 1.26 mmol), toluene (2 ml) and ethylene glycol dimethyl ether (1 ml) were added. The reaction mixture was reacted at 100 ° C. for 8 hours under a nitrogen atmosphere. The reaction mixture was then cooled to room temperature. After the solvent was distilled off, THF was added and the molecular weight was measured.
The molecular weight measurement by gel permeation chromatography on the polystyrene standard of the polymer obtained by the above method showed Mw of 26,000 g / mol and Mn of 15,000 g / mol.

Example 11 (Polymerization with LiOMe, PCy ₃ )
In a glass reaction vessel fitted with a cooling apparatus, 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) (111.4 mg,. 21 mmol), 2,7-dibromo-9,9-didodecyl-9H-fluorene (52.9 mg, 0.08 mmol), N, N′-bis (4-bromophenyl) -N, N′-bis [ 4- (1,1-dimethylethyl) -2,6-dimethylphenyl] -1,4-benzenediamine (88.6 mg, 0.12 mmol) and tris (dibenzylideneacetone) dipalladium (0) (4. 6 mg, 5 μmol), tricyclohexylphosphine (5.6 mg, 20 μmol), lithium methoxide (47.9 mg, 1.26 mmol), THF (2 ml), dimethylsulfo Sid (1ml) was added. The reaction mixture was reacted at 100 ° C. for 8 hours under a nitrogen atmosphere. The reaction mixture was then cooled to room temperature. After the solvent was distilled off, THF was added and the molecular weight was measured.
The molecular weight measurement by gel permeation chromatography with respect to the polystyrene standard of the polymer obtained by the above method showed Mw of 25,000 g / mol and Mn of 15,000 g / mol.

Example 12 (Polymerization with Ba (OH) ₂ .8H ₂ O, PCy ₃ )
In a glass reaction vessel fitted with a cooling apparatus, 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) (111.4 mg,. 21 mmol), 2,7-dibromo-9,9-didodecyl-9H-fluorene (52.9 mg, 0.08 mmol), N, N′-bis (4-bromophenyl) -N, N′-bis [ 4- (1,1-dimethylethyl) -2,6-dimethylphenyl] -1,4-benzenediamine (88.6 mg, 0.12 mmol) and tris (dibenzylideneacetone) dipalladium (0) (4. 6 mg, 5 μmol), tricyclohexylphosphine (5.6 mg, 20 μmol), barium hydroxide octahydrate (397.5 mg, 1.26 mmol), toluene (2 ml), N-methyl It was added-2-pyrrolidinone (1 ml). The reaction mixture was reacted at 100 ° C. for 8 hours under a nitrogen atmosphere. The reaction mixture was then cooled to room temperature. After the solvent was distilled off, THF was added and the molecular weight was measured.
The molecular weight measurement by gel permeation chromatography on the polystyrene standard of the polymer obtained by the above method showed Mw of 102,000 g / mol and Mn of 65,000 g / mol.

Example 13 (Polymerization with Ba (OH) ₂ .8H ₂ O, PCy ₃ )
In a glass reaction vessel fitted with a cooling apparatus, 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) (111.4 mg,. 21 mmol), 2,7-dibromo-9,9-didodecyl-9H-fluorene (52.9 mg, 0.08 mmol), N, N′-bis (4-bromophenyl) -N, N′-bis [ 4- (1,1-dimethylethyl) -2,6-dimethylphenyl] -1,4-benzenediamine (88.6 mg, 0.12 mmol) and tris (dibenzylideneacetone) dipalladium (0) (4. 6 mg, 5 μmol), tricyclohexylphosphine (5.6 mg, 20 μmol), barium hydroxide octahydrate (397.5 mg, 1.26 mmol), THF (2 ml), N-methyl 2- pyrrolidinone (1 ml) was added. The reaction mixture was reacted at 100 ° C. for 8 hours under a nitrogen atmosphere. The reaction mixture was then cooled to room temperature. After the solvent was distilled off, THF was added and the molecular weight was measured.
The molecular weight measurement by gel permeation chromatography on the polystyrene standard of the polymer obtained by the above method showed Mw of 106,000 g / mol and Mn of 57,000 g / mol.

Example 14 (polymerization with CsOH.H ₂ O, dppe)
In a glass reaction vessel fitted with a cooling apparatus, 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) (111.4 mg,. 21 mmol), 2,7-dibromo-9,9-didodecyl-9H-fluorene (52.9 mg, 0.08 mmol), N, N′-bis (4-bromophenyl) -N, N′-bis [ 4- (1,1-dimethylethyl) -2,6-dimethylphenyl] -1,4-benzenediamine (88.6 mg, 0.12 mmol) and tris (dibenzylideneacetone) dipalladium (0) (4. 6 mg, 5 μmol), 1,2-diphenylphosphinoethane (4.0 mg, 10 μmol), cesium hydroxide monohydrate (211.6 mg, 1.26 mmol), toluene (2 ml), Chi glycol dimethyl ether (1 ml) was added. The reaction mixture was reacted at 100 ° C. for 8 hours under a nitrogen atmosphere. The reaction mixture was then cooled to room temperature. After the solvent was distilled off, THF was added and the molecular weight was measured.
The molecular weight measurement by gel permeation chromatography on the polystyrene standard of the polymer obtained by the above method showed Mw of 23,000 g / mol and Mn of 17,000 g / mol.

Example 15 (Polymerization with Ba (OH) ₂ .8H ₂ O, PCy ₃ )
In a glass reaction vessel fitted with a cooling apparatus, 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) (111.4 mg,. 21 mmol), 2,7-dibromo-9,9-didodecyl-9H-fluorene (52.9 mg, 0.08 mmol), 4,7-dibromobenzothiadiazole (35.3 mg, 0.12 mmol), tris ( Dibenzylideneacetone) dipalladium (0) (4.6 mg, 5 μmol), tricyclohexylphosphine (5.6 mg, 20 μmol), barium hydroxide octahydrate (397.5 mg, 1.26 mmol), toluene ( 2 ml) and N-methyl-2-pyrrolidinone (1 ml). The reaction mixture was reacted at 100 ° C. for 8 hours under a nitrogen atmosphere. The reaction mixture was then cooled to room temperature. After the solvent was distilled off, THF was added and the molecular weight was measured.
The molecular weight measurement by gel permeation chromatography on the polystyrene standard of the polymer obtained by the above method showed Mw of 30,000 g / mol and Mn of 13,000 g / mol.

It is a figure which shows one example of reaction which concerns on this invention. It is a figure which shows one example of reaction which concerns on this invention. It is a figure which shows one example of reaction which concerns on this invention. It is a figure which shows one example of reaction which concerns on this invention.

Claims (11)

A) an aromatic monomer having at least two boron-containing functional groups and an aromatic monomer having at least two reactive functional groups,
Or
B) Method for producing a conjugated polymer in which an aromatic monomer having at least one reactive functional group and a boron-containing functional group in the same molecule is subjected to a polymerization reaction using a catalytic amount of a palladium complex in the presence of an organic solvent. Using at least one selected from the group consisting of alkali metal hydroxides, alkali metal alkoxides, alkaline earth metal hydroxides, alkaline earth metal alkoxides, and alkylphosphine ligands. A featured manufacturing method. The production method according to claim 1, wherein the alkylphosphine is a trialkylphosphine. The production method according to claim 1, wherein the alkylphosphine is tricyclohexylphosphine. The method according to any one of claims 1 to 3, wherein the alkali metal is one or more alkali metals selected from lithium, sodium, potassium, rubidium, and cesium. The method according to any one of claims 1 to 3, wherein the alkaline earth metal is one or more alkaline earth metals selected from magnesium, calcium, strontium, and barium. The method according to claim 1, wherein the alkali metal alkoxide is lithium methoxide. The method according to any one of claims 1 to 3, wherein the alkali metal hydroxide is cesium hydroxide or a hydrate thereof. 4. The production method according to claim 1, wherein the alkaline earth metal hydroxide is barium hydroxide or a hydrate thereof. The manufacturing method of Claim 1 made to react on the conditions which do not add water. The production method according to claim 1, wherein the reactive functional group is a halogen atom or a sulfonate group. The manufacturing method according to claim 1, wherein the aromatic monomer is represented by any one of the following formulas (1) to (4).

(In the formula, Z represents O, S, NR ²¹ or CR ²² R ²³ , and X and Y represent Cl, Br, I or B (OR ²⁴ ) (OR ²⁵ ), respectively, R ^{1 to} R ^25. Represents a hydrogen atom or a group that does not participate in the reaction, and can be selected independently of each other and bonded to form a ring.)

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