JP2007023253A - Manufacturing method of conjugated polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a conjugated polymer that comprises causing an aromatic monomer bearing a boron-containing functional group to react with an aromatic monomer bearing a reactive functional group or causing an aromatic monomer bearing the reactive functional group and the boron-containing functional group in the same molecule to react and has an excellent feature that it permits acquisition of a high-molecular weight polymer. <P>SOLUTION: The manufacturing method of the conjugated polymer comprises causing (A) an aromatic monomer bearing at least two boron-containing functional groups to react with an aromatic monomer bearing at least two reactive functional groups or (B) an aromatic monomer bearing a reactive functional group (preferably, the reactive functional group is a halogen atom or a sulfonate ester group) and a boron-containing functional group in the same molecule to react, in the presence of an organic solvent, a palladium complex and a tetraalkylammonium halide. <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 has a reactive functional group and a boron-containing functional group in the same molecule. The present invention relates to a method for producing a conjugated polymer in which an aromatic monomer is reacted.

  A reaction in which a corresponding biphenyl is formed by a reaction between an aromatic boronic acid derivative and an aromatic halide in the presence of a palladium catalyst is called a Suzuki-Miyaura coupling reaction (see Non-Patent Document 1). In general, this reaction is carried out in the presence of a zero-valent or divalent palladium compound, a phosphorus ligand and an inorganic base such as an alkali carbonate or phosphate.

Patent Document 1 discloses a method for synthesizing a conjugated polymer using a palladium catalyst in the presence of an organic base such as tetraalkylammonium hydroxide or tetraalkylammonium carbonate. In Patent Document 1, when the boron derivative functional group is a boronic ester group or a borane group, the reaction mixture contains a sufficient amount for hydrolyzing the boronic ester group or borane group to the corresponding boronic acid group. It is stated that it is necessary to contain water.
However, it has been clarified that this method has the following problems. First, since the organic base described in Patent Document 1 has an effect of mixing the organic layer and the aqueous layer, it takes time to separate the organic layer and the aqueous layer in the purification process, and the operability is deteriorated. To do. Secondly, depending on the monomer used, it is hydrolyzed and the yield and degree of polymerization of the resulting polymer are reduced. Third, the palladium catalyst tends to be deactivated, and the degree of polymerization of the resulting polymer is reduced.
Japanese Patent No. 3310658 Synthetic Communications 11 (7), 513, 1981

In such a situation, the problem to be solved by the present invention is to react an aromatic monomer having a boron-containing functional group and an aromatic monomer having a reactive functional group, or a reactive functional group and a boron-containing functional group. Is a method for producing a conjugated polymer having an excellent characteristic that a polymer having a high molecular weight can be obtained. is there.

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) an aromatic monomer having a reactive functional group and a boron-containing functional group in the same molecule,
Is produced in the presence of a catalytic amount of a palladium complex and a tetraalkylammonium halide in the presence of an organic solvent in which the polymer can be dissolved.

According to the present invention, a high molecular weight conjugated polymer can be obtained.

Hereinafter, the present invention will be described in detail.
“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 conjugated polymer herein preferably has a weight average molecular weight (Mw) of 50,000 to 500,000 g / mol relative to polystyrene standards, and a weight average molecular weight (Mw) / number average molecular weight (Mn). ) Is a conjugated polymer having a value of less than 3.

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, 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) di Palladium (0) chloroform adduct, palladium (II) acetate or palladium (II) chloride, (bicyclo [2.2.1] hepta-2,5-diene) dichloropalladium (II), (2,2′-bipyridyl) ) Dichloropalladium (II), bis (acetate) bis (triphenylphosphine) palladium (II), bis (acetonitrile) chloronitropalladium (II), bis (benzonitrile) dichloropalladium (II), bis (acetonitrile) dichloropalladium (II), bis [1,2-bis (diphenylphosphino) Tan] palladium (0), [1,2-bis (diphenylphosphino) ethane] dichloropalladium (II), trans-dibromobis (triphenylphosphine) palladium (II), dichloro (1,5-cyclooctadiene) palladium (II), dichloro (ethylenediamine) palladium (II), dichloro (N, N, N ′, N′-tetramethylenediamine) palladium (II), dichloro (1,10-phenanthroline) palladium (II), cis-dichlorobis (Dimethylphenylphosphine) palladium (II), dichlorobis (methyldiphenylphosphine) palladium (II), dichlorobis (tricyclohexylphosphine) palladium (II), dichlorobis (triethylphosphine) palladium (II), dichlorobis (triphenylphosphine) Pd (II), dichlorobis (tri-o-toluylphosphine) palladium (II), palladium (II) acetylacetonate, palladium (II) bromide, palladium (II) hexafluoroacetylacetonate, palladium (II) iodide , Palladium (II) nitrate, palladium sulfate, palladium (II) trifluoroacetate, palladium (IV) potassium chloride, palladium (II) potassium bromide, palladium (II) potassium chloride, palladium (II) sodium chloride, palladium tetraammine nitrate (II), tetrakis (acetonitrile) palladium (II) tetrafluoroborate, tetrakis (methyldiphenylphosphine) palladium (0), and the like, more preferably tris (dibenzylideneacetone) dipalladium (0).

The general usage amount of the catalyst in the reaction mixture is 0.01 to 10 mol%, more preferably 0.1 to 1 mol%. These numerical values are calculated based on the total number of moles of monomers used.

When the phosphine is not included in the palladium complex, it is preferable to add the following ligands.
Examples of the ligand include an phosphine compound having an alkyl group, an aryl group, or both an alkyl group and an aryl group. Specific examples of suitable ligands include, but are not limited to, triphenylphosphine, tri-ortho-tolylphosphine, tri-meta-tolylphosphine, tri-para-tolylphosphine, tris (pentafluoro Phenyl) phosphine, tris (para-fluorophenyl) phosphine, tris (ortho-methoxyphenyl) phosphine, tris (meta-methoxyphenyl) phosphine, tris (para-methoxyphenyl) phosphine, tris (2,4,6-trimethoxy Phenyl) phosphine, tri (meta-chlorophenyl) phosphine, tri (para-chlorophenyl) phosphine, tricyclohexylphosphine, tri-tert-butylphosphine, tri-n-butylphosphine, tri-2-furylphosphine, 2- (disicyl) Hexylphosphino) biphenyl, 2- (di-tert-butylphosphino) biphenyl, 2-di-tert-butylphosphino-2′-methylbiphenyl, 2- (dicyclohexylphosphino-2 ′, 6′-dimethoxy-) 1,1′-biphenyl, 2- (dicyclohexylphosphino) -2 ′-(N, N-dimethylamino) biphenyl, 2-dicyclohexylphosphino-2′-methyl-biphenyl, 2- (dicyclohexylphosphino) -2 ', 4', 6'-tri-isopropyl-1,1'-biphenyl, and the like, more preferably triphenylphosphine, although the amount of the ligand used is not particularly limited, Usually, it is about 0.01-0.5 mol times with respect to a monomer.

The type and amount of the tetraalkylammonium halide are appropriately selected according to the type and amount of the monomer and solvent to be used, but the usage amount is usually about 0.1 to 20 mol times with respect to the monomer.

The tetraalkylammonium halide may be a single one or a mixture of different types of tetraalkylammonium halides.

In the tetraalkylammonium halide, the alkyl group includes methyl, ethyl, isopropyl, n-propyl, tert-butyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, or An n-octyl group is mentioned, Preferably a methyl group or n-butyl group is mentioned. Examples of the halide include fluorine, chlorine, bromine, and iodine, and more preferably fluorine. Specific examples of suitable tetraalkylammonium halides include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetra-n-butylammonium fluoride, and tetra-tert-butyl fluoride. Ammonium, tetramethylammonium chloride, tetraethylammonium chloride, tetra-n-butylammonium chloride, tetra-tert-butylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetra-n-butylammonium bromide, tetrabromide -Tert-butylammonium iodide, tetramethylammonium iodide, tetraethylammonium iodide, tetra-n-butylammonium iodide, tetra-tert-butylammonium iodide, teto -N-pentylammonium fluoride, tetra-n-pentylammonium chloride, tetra-n-pentylammonium bromide, tetra-n-pentylammonium iodide, tetra-n-hexylammonium fluoride, tetra-n-hexylammonium chloride Tetra-n-hexylammonium bromide, tetra-n-hexylammonium iodide, tetra-n-heptylammonium fluoride, tetra-n-heptylammonium chloride, tetra-n-heptylammonium bromide, tetra-n iodide -Heptylammonium, tetra-n-octylammonium fluoride, tetra-n-octylammonium chloride, tetra-n-octylammonium bromide, tetra-n-octylammonium iodide, Preferable examples thereof include tetramethylammonium or tetrabutylammonium fluoride fluoride.

The organic solvent for dissolving the polymer is appropriately selected depending on the kind and amount of the polymer to be produced. The amount used is usually about 1 to 50 times the weight of the monomer.

For example, in the case of a conjugated polymer having a fluorene skeleton, suitable organic solvents include benzene, toluene, xylene, 1,4-dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether, more preferably toluene or tetrahydrofuran.

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, 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. R ²⁹ and R ³⁰ are each independently an alkyl group having 1 to 6 carbon atoms, and may be substituted.

Specific examples of suitable boronic acid ester groups include, but are not limited to, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, i-butyl alcohol, sec-butyl alcohol, tert -Butyl alcohol, n-pentyl alcohol, neopentyl alcohol, cyclopentyl alcohol, n-hexyl alcohol, cyclohexyl alcohol, ethylene glycol, pinacol, propanediol, 2,2-dimethyl-1,3-propanediol or 1,2-dihydroxy The product of esterification with alcohol, such as benzene, and a corresponding boronic acid is mentioned, More preferably, ethylene glycol, pinacol, propanediol, or 2,2-dimethyl-1,3-propanediene is mentioned. And Lumpur include product by esterification of the corresponding boronic acid.

The “reactive functional group” is a halogen atom such as Cl, 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 monomers composed of one or more aromatic rings having at least one boron-containing functional group and one or more reactive functional groups, preferably 1 to 3 aromatic rings. In the case of a monomer having two or more aromatic rings, the functional group can be substituted with either the same aromatic ring or a different aromatic ring. Suitable types of monomers include heteroatom-containing aromatic monomers having a skeleton such as thiophene and condensed aromatic monomers having a skeleton such as biphenylene, naphthalene or fluorene, more preferably a condensed aromatic having a fluorene skeleton. Monomer.
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.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

  In FIG. 1, 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolene) and 2, The reaction formula with 7-dibromo-9,9-didodecyl-9H-fluorene is shown.

[Example 1]
To a glass reaction vessel equipped with a cooling device, 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (4,4,5,5-tetramethyl-1,3,3). 2-dioxaborolene) (128.5 mg, 0.20 mmol), 2,7-dibromo-9,9-didodecyl-9H-fluorene (132.1 mg, 0.20 mmol), tris (dibenzylideneacetone) dipalladium ( 0) (4.6 mg, 5 μmol), triphenylphosphine (5.3 mg, 20 μmol), tetra-n-butylammonium fluoride (397.6 mg, 1.26 mmol), and THF (3 ml) were added. The reaction mixture was refluxed for 8 hours under a nitrogen atmosphere.
The molecular weight measurement by gel permeation chromatography on the polystyrene standard of the polymer obtained by the above method showed Mw of 339,000 g / mol and Mn of 142,000 g / mol.

  FIG. 2 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 2]
In a glass reaction vessel equipped with a cooling device, 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) (2.33 g, 4. 4 mmol), 2,7-dibromo-9,9-didodecyl-9H-fluorene (2.77 g, 4.2 mmol), tris (dibenzylideneacetone) dipalladium (0) (11.6 mg, 13 μmol), Triphenylphosphine (13.3 mg, 51 μmol), tetra-n-butylammonium fluoride (8.33 g, 26.4 mmol) and THF (45 ml) were added. The reaction mixture was refluxed for 48 hours under a nitrogen atmosphere. Thereafter, the reaction mixture was cooled to room temperature, and methanol was added to precipitate a polymer.
The molecular weight measurement by gel permeation chromatography on the polystyrene standard of the polymer obtained by the above method showed 328,000 g / mol Mw and 164,000 g / mol Mn.

[Example 3]
The same procedure as in Example 2 was performed except that tri-para-tolylphosphine (15.5 mg, 51 μmol) was used instead of triphenylphosphine.
The molecular weight measurement by gel permeation chromatography on the polystyrene standard of the polymer obtained by the above method showed an Mp (peak molecular weight) of 410,000 g / mol.

[Comparative Example 1] (Polymerization using Et ₄ NOH as base)
In a glass reaction vessel equipped with a cooling device, 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolene) (2.33 g, 4. 4 mmol), 2,7-dibromo-9,9-didodecyl-9H-fluorene (2.77 g, 4.2 mmol), tris (dibenzylideneacetone) dipalladium (0) (11.6 mg, 13 μmol), Triphenylphosphine (13.3 mg, 51 μmol), 20 wt% tetraethylammonium hydroxide aqueous solution (2.88 g, 19.6 mmol as tetraethylammonium hydroxide), and THF (45 ml) were added. The reaction mixture was refluxed for 48 hours under a nitrogen atmosphere. Thereafter, the reaction mixture was cooled to room temperature, and methanol was added to precipitate a polymer.
The molecular weight measurement by gel permeation chromatography on the polystyrene standard of the polymer obtained by the above method showed 137,000 g / mol Mw and 57,000 g / mol Mn.

  FIG. 3 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 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) (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 triphenylphosphine (5 3 mg, 20 μmol), tetra-n-butylammonium fluoride (397.6 mg, 1.26 mmol) and THF (3 ml) were added. The reaction mixture was refluxed 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 10,000 g / mol and Mn of 7,500 g / mol.

[Example 5]:
In a glass reaction vessel equipped with a cooling device, 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), triphenylphosphine (5.3 mg, 20 μmol), tetra-n-butylammonium fluoride (397.6 mg, 1.26 mmol), and THF (3 ml) were added. It was. 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 88,000 g / mol and Mn of 30,000 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.

Claims (7)

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) A process for producing a conjugated polymer comprising reacting an aromatic monomer having a reactive functional group and a boron-containing functional group in the same molecule in the presence of an organic solvent, a palladium complex and a tetraalkylammonium halide. . The production method according to claim 1, wherein the halogen of the tetraalkylammonium halide is fluorine. The method according to claim 1 or 2, wherein the alkyl of the tetraalkylammonium halide is an alkyl having 1 to 8 carbon atoms which may be the same or different. The production method according to claim 1, wherein the tetraalkylammonium halide is tetramethylammonium fluoride or tetrabutylammonium fluoride. 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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