WO2012133875A1

WO2012133875A1 - Production method for aromatic polymer

Info

Publication number: WO2012133875A1
Application number: PCT/JP2012/058783
Authority: WO
Inventors: 精二小田; 神川　卓
Original assignee: 住友化学株式会社
Priority date: 2011-03-29
Filing date: 2012-03-27
Publication date: 2012-10-04
Also published as: JP2012214704A; TW201307425A

Abstract

A production method for an aromatic polymer, characterized by including a step in which an aromatic monomer is mixed in the presence of a base, a paladium compound, a phosphine indicated by formula (C) (in the formula, R¹, R², R³, R⁴, and R⁵ each independently indicate a hydrogen atom, etc., and A indicates a C1-20 alkyl group), and an aprotic organic solvent.

Description

Method for producing aromatic polymer

The present invention relates to a method for producing an aromatic polymer.

An aromatic polymer having a structure in which two or more aromatic rings are π-conjugated is useful, for example, for an organic electronic material. As a method for producing an aromatic polymer, a method for producing an aromatic monomer by a Suzuki coupling reaction is known.
Specifically, JP-A-2007-126652 discloses 9,9-di-n-octylfluorene-2 in the presence of palladium acetate, tris (2-methoxyphenyl) phosphine, aqueous tetraethylammonium hydroxide and toluene. By polymerizing an ester formed from 7-diboronic acid and pinacol (tetramethylethylene glycol) and bis (4-bromophenyl) [4- (2-butyl) phenyl] amine, the corresponding aromatic polymer Is described with a molecular weight (Mw) of 3.0 × 10 ⁵ .

The present invention
[1] Formula (A):

(In the formula, each X ¹ independently represents the formula (1), (2), (3), (4), (5) or (6)

Ar ¹ represents a divalent aromatic hydrocarbon group having 6 to 36 carbon atoms. The carbon atom contained in the aromatic hydrocarbon group may be replaced with a hetero atom or a carbonyl group, and the hydrogen atom contained in the aromatic hydrocarbon group is a fluorine atom, an alkyl group, an alkoxy group, an alkylthio group, An aryl group, an aryloxy group, an arylthio group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, a heterocyclic group that may have a substituent, an amino group that may have a substituent, and a substituent It may be substituted with a silyl group, an acyl group, a group having a carbon atom-nitrogen atom double bond as a partial structure, an acid imide group, an alkoxycarbonyl group, a carboxyl group, a cyano group or a nitro group. )
An aromatic monomer represented by
Formula (B):

(In the formula, each X ² independently represents a chlorine atom, a bromine atom or an iodine atom, and Ar ² represents a divalent aromatic hydrocarbon group having 6 to 36 carbon atoms. The aromatic hydrocarbon group The carbon atom contained in may be replaced with a hetero atom or a carbonyl group, and the hydrogen atom contained in the aromatic hydrocarbon group may be a fluorine atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group. , Arylthio group, arylalkylthio group, arylalkenyl group, arylalkynyl group, heterocyclic group which may have a substituent, amino group which may have a substituent, silyl group which may have a substituent, Acyl group, group having carbon-nitrogen double bond as a partial structure, acid imide group, alkoxycarbonyl group, carboxyl group, cyano group or nitro group It may be substituted.)
An aromatic monomer represented by
Base, palladium compound, formula (C):

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a fluorine atom, a fluoroalkyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, carbon An acyl group having 2 to 20 carbon atoms, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a dialkylamino group having 1 to 20 carbon atoms And A represents an alkyl group having 1 to 20 carbon atoms.)
A process for producing an aromatic polymer, comprising the step of mixing in the presence of a phosphine and an aprotic organic solvent represented by:
[2] The production method according to [1], wherein the aprotic organic solvent is at least one selected from the group consisting of an ether solvent, an aromatic hydrocarbon solvent, and an aliphatic hydrocarbon solvent;
[3] The production method according to [1] or [2], wherein the palladium compound is a palladium (0) complex or a palladium (II) complex;
[4] Formula (D):

(Wherein R ⁶ represents an alkoxy group having 1 to 20 carbon atoms, and R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 20 carbon atoms. , An alkoxycarbonyl group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 6 to 20 carbon atoms Represents an aryl group or a dialkylamino group having 1 to 20 carbon atoms.)
A phosphine represented by
[5] Formula (E):

(Wherein R ¹¹ represents an alkoxy group having 1 to 20 carbon atoms, and R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 20 carbon atoms. , An alkoxycarbonyl group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 6 to 20 carbon atoms Represents an aryl group or a dialkylamino group having 1 to 20 carbon atoms, provided that R ¹² to R ¹⁵ are not all hydrogen atoms.)
A phosphine represented by
[6] A transition metal complex obtained by bringing the phosphine according to [4] into contact with a Group 10 transition metal compound;
[7] A transition metal complex obtained by bringing the phosphine according to [5] into contact with a Group 10 transition metal compound;

The aromatic monomer used in the production method of the present invention has the formula (A):

An aromatic monomer (hereinafter, sometimes referred to as an aromatic monomer (A)), and a formula (B):

It is an aromatic monomer (Hereinafter, it may be described as an aromatic monomer (B).).
Ar ¹ And Ar ² Each independently represents a divalent aromatic hydrocarbon group having 6 to 36 carbon atoms. The divalent aromatic hydrocarbon group is a divalent monocyclic aromatic hydrocarbon group, a divalent condensed aromatic hydrocarbon group or two or more monocyclic aromatic hydrocarbon groups, a single bond, a heteroatom ( An oxygen atom, a nitrogen atom, a sulfur atom, etc.) or a divalent group formed by linking with a carbonyl group (—CO—). Specifically, bivalent monocyclic aromatic hydrocarbon group such as phenylene group, divalent condensed aromatic hydrocarbon group such as naphthalenediyl group, anthracenediyl group, fluorenediyl group, biphenylene group, etc. Examples thereof include a divalent group formed by connecting the above monocyclic aromatic hydrocarbon group with a single bond, a hetero atom (oxygen atom, nitrogen atom, sulfur atom, etc.) or a carbonyl group. The carbon atom contained in the aromatic hydrocarbon group may be substituted with a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom or a carbonyl group.
The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include a fluorine atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, and a heterocyclic group which may have a substituent. , An amino group which may have a substituent, a silyl group which may have a substituent, an acyl group, a group having a carbon atom-nitrogen atom double bond as a partial structure, an acid imide group, an alkoxycarbonyl group, a carboxyl Group (—COOH), cyano group (—CN) and nitro group (—NO) ₂ ). The hydrogen atom contained in the substituent is a fluorine atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, or It may be substituted with a cyano group.
Examples of the “alkyl group” include an alkyl group having 1 to 20 carbon atoms, which may be linear, branched, or cyclic. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2,2-dimethylpropyl group, Cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, 2-methylpentyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group Group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n-icosyl group.
Examples of the “alkoxy group” include an alkoxy group having 1 to 20 carbon atoms, which may be linear, branched, or cyclic. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, 2,2-dimethylpropoxy group, n -Hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group N-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group and n-icosyloxy group.
Examples of the “alkylthio group” include alkylthio groups having 1 to 20 carbon atoms, which may be linear, branched, or cyclic. Specifically, methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, n-pentylthio group, n-hexylthio group, cyclohexyl Examples include thio group, n-heptylthio group, n-octylthio group, 2-ethylhexylthio group, n-nonylthio group, n-decylthio group, 3,7-dimethyloctylthio group, n-dodecylthio group and trifluoromethylthio group. .
Examples of the “aryl group” include aryl groups having 6 to 20 carbon atoms. Specific examples include a phenyl group, a 4-methylphenyl group, a 2-methylphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 3-phenanthryl group, and a 2-anthryl group.
Examples of the “aryloxy group” include groups formed by bonding an oxygen atom to the aryl group having 6 to 20 carbon atoms. Specific examples include a phenoxy group, a naphthyloxy group, a phenanthryloxy group, and an anthryloxy group.
Examples of the “arylthio group” include a group formed by bonding a sulfur atom to the aryl group having 6 to 20 carbon atoms. Specific examples include a phenylthio group and a naphthylthio group.
Examples of the “arylalkylthio group” include a group formed by bonding a sulfur atom to the alkyl group having 1 to 20 carbon atoms substituted with the aryl group having 6 to 20 carbon atoms. Specific examples include a phenylmethylthio group and a naphthylmethylthio group.
Examples of the “arylalkenyl group” include a phenylalkenyl group and a naphthylalkenyl group. As the “alkenyl group”, vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-hexenyl group, Examples thereof include alkenyl groups having 2 to 8 carbon atoms such as 1-octenyl group.
Examples of the “arylalkynyl group” include phenylalkynyl group and naphthylalkynyl group. Examples of the “alkynyl group” include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 1-pentynyl group, 2-pentynyl group, 1-hexynyl group, 2-hexynyl group, Examples include alkynyl groups having 2 to 8 carbon atoms such as 1-octynyl group.
“A heterocyclic group which may have a substituent” means a group in which one hydrogen atom in a heterocyclic compound which may have a substituent becomes a bond. Examples of the heterocyclic group include thienyl group, alkylthienyl group, pyrrolyl group, furyl group, pyridyl group, alkylpyridyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, triazinyl group, pyrrolidyl group, piperidyl group, quinolyl group and isoquinolyl group. Can be mentioned. Examples of the substituent that the heterocyclic group has include an alkyl group, specifically, an alkyl group having 1 to 20 carbon atoms.
“Amino group optionally having substituent (s)” means —N (R ′) ₂ And two R ′ each independently represents a substituent. Examples of R ′ include a hydrocarbon group having 1 to 20 carbon atoms such as an alkyl group and an aryl group, a heterocyclic group which may have a substituent, and a hydrogen atom. Preferably, it is an amino group having a substituent, that is, an amino group in which at least one R ′ is a substituent other than a hydrogen atom. Specific examples of the “amino group optionally having a substituent” include a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, an n-propylamino group, a di-n-propylamino group, and an isopropylamino group. , Diisopropylamino group, n-butylamino group, isobutylamino group, sec-butylamino group, tert-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group 2-ethylhexylamino group, n-nonylamino group, n-decylamino group, 3,7-dimethyloctylamino group, n-dodecylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, bis (Trifluoromethyl) amino group, phenylamino group Diphenylamino group, naphthylamino group, pyridylamino group, pyridazinylamino group, pyrimidinyl group, include pyrazinylamino group and triazinylamino group.
“A silyl group optionally having substituent (s)” means —Si (R ′) ₃ In the formula, each of the three R's independently represents a substituent. Examples of R ′ include a hydrocarbon group having 1 to 20 carbon atoms such as an alkyl group and an aryl group, a heterocyclic group which may have a substituent, and a hydrogen atom. Preferably, it is a silyl group having a substituent, that is, a silyl group in which at least one R ′ is a substituent other than a hydrogen atom. Specific examples of “optionally substituted silyl group” include trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, dimethylisopropylsilyl group, diethylisopropylsilyl group, tert- Butylsilyldimethylsilyl group, n-pentyldimethylsilyl group, n-hexyldimethylsilyl group, n-heptyldimethylsilyl group, n-octyldimethylsilyl group, 2-ethylhexyldimethylsilyl group, n-nonyldimethylsilyl group, n- Decyldimethylsilyl group, 3,7-dimethyloctyldimethylsilyl group, n-dodecyldimethylsilyl group, phenylalkylsilyl group, alkoxyphenylalkylsilyl group, alkylphenylalkylsilyl group, naphthylalkylsilyl group, phenylallyldi Chirushiriru group, triphenylsilyl group, tri -p- Kishirirushiriru group, tribenzylsilyl group, diphenylmethylsilyl group, and a tert- butyldiphenylsilyl group and dimethylphenylsilyl group.
Examples of the “acyl group” include aliphatic acyl groups such as acetyl group, propionyl group, butyryl group and isobutyryl group, and aromatic acyl groups such as benzoyl group and naphthoyl group.
The “group having a carbon atom-nitrogen atom double bond as a partial structure” refers to a moiety from an imine compound having a partial structure represented by at least one of the formula: H—N═C <and the formula: —N═CH—. This means a group formed by removing a hydrogen atom in the structure (hereinafter sometimes referred to as an imine residue) and does not form a ring based on the aforementioned “carbon atom-nitrogen atom double bond”. Things can be mentioned. Examples of the “imine compound” include a compound in which a hydrogen atom bonded to a nitrogen atom in aldimine, ketimine and aldimine is substituted with a substituent such as an alkyl group, aryl group, arylalkyl group, arylalkenyl group, arylalkynyl group or the like. It is done. The carbon number of the imine residue is usually 2 to 20, preferably 2 to 18, and more preferably 2 to 16.
As the “imine residue”, the formula: —CR ″ = N—R ′ ″ and the formula: —N═C (R ″ ′) ₂ Wherein R ″ represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkenyl group or an arylalkynyl group, and R ′ ″ independently represents an alkyl group, an aryl group, an arylalkyl group. Represents an arylalkenyl group or arylalkynyl group, provided that when two R ′ ″ are present, the two R ′ ″ are bonded to each other to form a divalent group such as an ethylene group or trimethylene. Group, a tetramethylene group, a pentamethylene group, a hexamethylene group or the like, and a group having 2 to 18 carbon atoms are formed.
Specific examples of the “imine residue” include the following groups.

“Acid imide group” means a residue in which a hydrogen atom bonded to a nitrogen atom contained in an acid imide is a bond. The number of carbon atoms in the acid imide group is preferably 4-20, more preferably 4-18, and still more preferably 4-16. Specific examples of the “acid imide group” include the following groups.

Examples of the “alkoxycarbonyl group” include a group formed by bonding a carbonyl group to the alkoxy group. Specifically, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentyl Oxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group 3,7-dimethyloctyloxycarbonyl group, n-dodecyloxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, Over-fluoro-hexyloxy group, perfluorooctyl group, phenoxycarbonyl group, and a naphthoxycarbonyl group and pyridyloxycarbonyl group.
Examples of the aromatic hydrocarbon group include divalent groups represented by the formulas (a) to (e).

(In the formula, R represents a substituent, and n represents an integer of 0 to 4.)
As the substituent, Ar ¹ And Ar ² And the same groups as those exemplified as the substituents of.
Examples of the aromatic hydrocarbon group in which the carbon atom contained in the aromatic hydrocarbon group is substituted with a hetero atom or a carbonyl group include divalent groups represented by formulas (f) to (z).

(In the formula, R represents a substituent, n represents an integer of 0 to 2, and Y represents N, S, C = O.)
As the substituent, Ar ¹ And Ar ² And the same groups as those exemplified as the substituents of.
Examples of the divalent group formed by connecting two or more monocyclic aromatic hydrocarbon groups with a single bond, heteroatom or carbonyl group include divalent groups represented by the formulas (aa) to (ae). Groups.

(In the formula, R represents a substituent, and n represents an integer of 0 to 4.)
As the substituent, Ar ¹ And Ar ² And the same groups as those exemplified as the substituents of.
Ar in the aromatic monomer (A) ¹ And Ar in the aromatic monomer (B) ² May be the same or different from each other.
Preferred Ar ¹ And Ar ² Is represented by the formula (a), (b), (c), (d), (e), (m) (Y in (m) is preferably S), (y) or (aa) It is a group.
X of aromatic monomer (A) ¹ Are each independently the formula (1), (2), (3), (4), (5) or (6)

Represents a group represented by
Two X in the aromatic monomer (A) ¹ May be the same or different from each other, but in terms of easy preparation of the aromatic monomer (A), the two X ¹ Are preferably the same. Preferred X ¹ Is a group represented by formula (3).
As the aromatic monomer (A), 2,2 ′-(9,9-dihexyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborolane), 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-dioxaborolane), 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-dioxaborolane), 2,2 ′-(9,9 -Dioctyl-9H-fluorene-2,7-diyl) bis (1, , 2-dioxaborinane), 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane), 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-dioxaborolane), 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 (4,4,5,5-tetramethyl-1,3,2-dioxaborolane), 2 , 2 '-(9,9-didodecyl-9H-fluorene 2,7-diyl) bis (5,5-dimethyl-1,3,2-dioxaborinane), 2,2 '-(3,5-dimethoxy-9,9-dihexyl-9H-fluorene-2,7-diyl ) Bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane), 2,2 ′-(9-octyl-9H-carbazole-3,6-diyl) bis (1,3,2) -Dioxaborolane), 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-dioxaborolane), 2,2 ′-(2-methyl-5-octyl-1,4-phenylene) bis (4,4,5,5-tetramethyl-1,3,2) -Dioxaborolane), 2,2 '-(2,5-dibutyl-1,4-phenyle) ) Bis (5,5-dimethyl-1,3,2-dioxaborinane), 2,2 ′-[2,5-bis (hexyloxy) -1,4-phenylene] bis (5,5-dimethyl-1) , 3,2-dioxaborinane), 2,5-bis (1,3,2-dioxaborolan-2-yl) thiophene, 2,5-bis (4,4,5,5-tetramethyl-1,3,2) -Dioxaborolan-2-yl) thiophene, 2,5-bis (1,3,2-dioxaborinan-2-yl) thiophene, 2,5-bis (5,5-dimethyl-1,3,2-dioxaborinane-2 -Yl) thiophene, 1,1'-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4,4'-biphenyl, 1,1'-bis ( 1,3,2-dioxaborolan-2-yl) -4,4′-bi 1,1′-bis (1,3,2-dioxaborin-2-yl) -4,4′-biphenyl, 1,1′-bis (5,5-dimethyl-1,3,2-dioxaborinane- 2-yl) -4,4′-biphenyl and 5,5′-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -2,2′- Bithiophene is mentioned. Preferably, 2,2 ′-(9,9-dihexyl-9H-fluorene-2,7-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane), 2,2 '-(9,9-Dioctyl-9H-fluorene-2,7-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane), 2,2'-(9,9 -Didodecyl-9H-fluorene-2,7-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane), 2,2 '-(3,5-dimethoxy-9,9 -Dihexyl-9H-fluorene-2,7-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane), 2,2 '-(2-methyl-5-octyl-1) , 4-Phenylene) bis (4,4,5,5-tetramethyl-1,3,2 Dioxaborolane), 2,5-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiophene, 1,1′-bis (4,4,5,5-tetra Methyl-1,3,2-dioxaborolan-2-yl) -4,4′-biphenyl and 5,5′-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane- 2-yl) -2,2′-bithiophene.
In the production method of the present invention, two or more aromatic monomers (A) may be used in combination.
X of aromatic monomer (B) ² Each independently represents a chlorine atom, a bromine atom or an iodine atom.
Two X in the aromatic monomer (B) ² May be the same or different from each other, but the same X in that the aromatic polymer (B) can be easily prepared. ² It is preferable that Preferred X ² Is a bromine atom.
As the aromatic monomer (B), 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, 1,3-dibromobenzene, 1,4-dibromo-2-ethylbenzene, 1,4-dibromo-2-me Xibenzene, dimethyl 2,5-dibromoterephthalate, 1,4-dibromonaphthalene, 3,5-dibromopyridine, 1,1′-dibromo-4,4′-biphenyl, 2,5-dibromopyridine, 1,4-dibromo -2,5-dihexyloxybenzene, 1-bromo-4-chlorobenzene, 1-bromo-4-chlorotoluene, 1-bromo-4-chloro-2-propylbenzene, 2,5-dibromo-4'-phenoxybenzophenone 2,5-dibromo-3-hexylthiophene, 2,5-dibromo-3, 2,5-dibromo-3-octylthiophene-dodecylthiophene, 2,5-dichloro-3-hexylthiophene, 5,5′- Dibromo-2,2′-bithiophene, 5,5′-dibromo-3,3′-dihexyl-2,2′-bithiophene, bis 4-bromophenyl) -4- (4-tert-butyl) benzenamine, bis (4-bromophenyl) -4- (1-methylpropyl) benzeneamine, bis (4-bromophenyl) -4-benzeneamine, N, N′-bis (4-bromophenyl) -N, N′-bis (4-n-butylphenyl) -1,4-benzenediamine, N, N′-bis (4-bromophenyl) -bicyclo [ 4.2.0] Octa-1,3,5-trien-3-amine, N, N′-bis (4-bromophenyl) -N, N′-bis (4-butylphenyl) -1,4- Benzenediamine, N, N′-bis (4-bromophenyl) -N, N′-bis [4- (1,1-dimethylethyl) -2,6-dimethylphenyl] -1,4-benzenediamine, 4 , 7-Dibromo-2,1,3-benzothia Azole, 4,7-dibromo-2,1,3-benzoselenadiazole, 4,7-bis (5-bromo-2-thienyl) -2,1,3-benzothiadiazole, 4,7-bis (5 -Bromo-4-methyl-2-thienyl) -2,1,3-benzothiadiazole, 4,7-bis (5-bromo-3-methyl-2-thienyl) -2,1,3-benzothiadiazole, 3 , 7-dibromo-10- (4-n-butylphenyl) -10H-phenothiazine, 3,7-dibromo-10- (4-n-butylphenyl) -10H-phenoxyazine, 3,3 ′-[1, 1′-biphenyl-4,4′-diylbis [(4-bromophenyl) imino]] bisbenzoic acid diethyl ester and 4,4′-bis [(4-bromophenyl) phenylamino] biphenyl And the like. Preferably, 2,7-dibromo-9,9-dihexyl-9H-fluorene, 2,7-dibromo-9,9-dioctyl-9H-fluorene, 2,7-dibromo-9,9-didodecyl-9H-fluorene 1,4-dibromobenzene, 1,3-dibromobenzene, 2,5-dibromo-3-hexylthiophene, and bis (4-bromophenyl) -4-benzeneamine.
Two or more aromatic monomers (B) may be used in the production method of the present invention.
The amount of the aromatic monomer (B) used in the production method of the present invention is usually in the range of 0.8 mol to 1.2 mol, preferably 0.9 mol, relative to 1 mol of the aromatic monomer (A). The range is from mol to 1.1 mol.
<Base>
Examples of the base include inorganic bases and organic bases.
Inorganic bases include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carboxylates, alkaline earth metal carboxylates, alkali metal carbonates, alkaline earth metal carbonates, alkali metal bicarbonates , Alkaline earth metal hydrogencarbonate, alkali metal phosphate, and alkaline earth metal phosphate, and alkali metal carbonate and alkali metal phosphate are preferable.
Specific examples of the inorganic base include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, barium hydroxide, sodium formate, potassium formate, calcium formate, sodium acetate, potassium acetate, sodium carbonate, Examples thereof include potassium carbonate, cesium carbonate, calcium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate and potassium phosphate. Sodium carbonate, potassium carbonate, cesium carbonate, sodium phosphate and potassium phosphate are preferred.
Examples of the organic base include alkylammonium hydroxide, alkylammonium carbonate, alkylammonium bicarbonate, alkylammonium boronate, 1,5-diazabicyclo [4.3.0] non-5-ene (DBN), 1 , 8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,4-diazabicyclo [2.2.2] octane (DABCO), dimethylaminopyridine (DMAP), pyridine, trialkylamine, And alkylammonium fluorides such as tetraalkylammonium fluoride. Preferred are tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetra-n-propylammonium hydroxide.
The amount of the base used is usually 0.5 to 20 equivalents (here, the equivalent is X contained in the aromatic monomer (B)). ² X contained in the aromatic monomer (B) in the theoretical amount of base necessary to neutralize hydrogen ions equal to the total amount of ² Represents a ratio to the total amount of substances), and a range of 0.5 equivalents to 6 equivalents is preferable.
<Correlation transfer catalyst>
In the production method of the present invention, when an inorganic base is used as the base, a phase transfer catalyst may be used in combination. Examples of the phase transfer catalyst include tetraalkyl ammonium halide, tetraalkyl ammonium hydrogen sulfate, and tetraalkyl ammonium hydroxide. Preferred is a tetraalkylammonium halide such as tricaprylylmethyl ammonium chloride (available as Aliquat® 336 from Sigma-Aldrich).
The amount of the phase transfer catalyst used is usually from 0.001 equivalent to 1 equivalent (here, the equivalent is X contained in the aromatic monomer (B)). ² X contained in the aromatic monomer (B) in the theoretical amount of base necessary to neutralize hydrogen ions equal to the total amount of ² Represents the ratio of to the total amount of material. In the range of 0.01 equivalent to 0.5 equivalent.
<Aprotic organic solvent>
The “aprotic organic solvent” does not have a group having an active hydrogen such as a hydroxyl group, an amino group, or a carboxyl group in the molecule, and dissolves the aromatic monomer (A) and the aromatic monomer (B). Mean organic solvent to be obtained.
Examples of the aprotic organic solvent include ether solvents such as acyclic ether solvents and cyclic ether solvents, aprotic polar solvents, aromatic hydrocarbon solvents and aliphatic hydrocarbon solvents. Aprotic polar solvents include N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide and acetonitrile. Acyclic ether solvents include diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether. Cyclic ether solvents include 1,4-dioxane and tetrahydrofuran. Aromatic hydrocarbon solvents include benzene, toluene, xylene and mesitylene. Aliphatic hydrocarbon solvents include hexane, heptane and cyclohexane.
From the viewpoint of the solubility of the aromatic monomer (A) and the aromatic monomer (B), toluene, xylene, mesitylene, diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 1,4-dioxane and tetrahydrofuran are preferred.
If necessary, two or more kinds of aprotic organic solvents may be mixed and used. Specific examples include a mixed solvent of tetrahydrofuran and toluene and a mixed solvent of ethylene glycol dimethyl ether and toluene.
<Palladium compound>
Examples of palladium compounds include palladium (0) complexes and palladium (II) complexes.
Examples of the palladium (0) complex include a complex in which dibenzylideneacetone is coordinated to zerovalent palladium, a so-called dibenzylideneacetone-palladium (0) complex. Specific examples include tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) chloroform adduct and bis (dibenzylideneacetone) palladium (0).
Examples of the palladium (II) complex include palladium carboxylates such as palladium (II) acetate, palladium (II) trifluoroacetate, palladium (II) acetylacetonate, palladium (II) chloride, palladium (II) bromide, iodine Palladium halides such as palladium (II) halide, and allyl palladium (II) chloride dimer, bis (2-methylallyl) palladium (II) chloride dimer, dichloro (1,5-cyclooctadiene) palladium (II), dichlorobis Examples thereof include palladium halide complexes such as (acetonitrile) palladium (II) and dichlorobis (benzonitrile) palladium (II). Of these, tris (dibenzylideneacetone) dipalladium (0), bis (dibenzylideneacetone) palladium (0), palladium (II) chloride, palladium (II) bromide and palladium (II) acetate are preferred.
The amount of the palladium compound used is usually in the range of 0.0001 mol to 0.8 mol, preferably in the range of 0.001 mol to 0.2 mol, per 1 mol of the aromatic monomer (B).
<Phosphine represented by formula (C)>
The phosphine represented by the formula (C) is represented by the formula (C):

Indicated by
In formula (C), R ¹ , R ² , R ³ , R ⁴ And R ⁵ Each independently represents a hydrogen atom, a fluorine atom, a fluoroalkyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, a cyano group, a nitro group, or 1 to Represents an alkyl group having 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a dialkylamino group having 1 to 20 carbon atoms, and A represents an alkyl group having 1 to 20 carbon atoms.
Examples of the fluoroalkyl group having 1 to 20 carbon atoms include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, and A perfluoroisopropyl group is mentioned, and a fluoroalkyl group having 1 to 4 carbon atoms is preferred.
The alkoxycarbonyl group having 1 to 20 carbon atoms is a group formed by bonding an alkoxy group having 1 to 20 carbon atoms and a carbonyl group, and specifically includes a methoxycarbonyl group, an ethoxycarbonyl group, and n-propoxy group. Carbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, n-dodecyloxy group Cicarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perfluorooctyloxycarbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group and pyridyloxycarbonyl group An alkoxycarbonyl group having 1 to 8 carbon atoms is preferable, and an alkoxycarbonyl group having 1 to 4 carbon atoms is more preferable.
Examples of the acyl group having 2 to 20 carbon atoms include aliphatic acyl groups such as acetyl group, propionyl group, butyryl group and isobutyryl group, and aromatic acyl groups such as benzoyl group and naphthoyl group.
The alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2,2-dimethylpropyl group, Cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, 2-methylpentyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group Group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n-icosyl group. Are preferred, and alkyl groups having 1 to 4 carbon atoms are more preferred.
The alkoxy group having 1 to 20 carbon atoms may be linear, branched, or cyclic. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, 2,2-dimethylpropoxy group, n -Hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group , N-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group and n-icosyloxy group. An alkoxy group having 1 to 8 carbon atoms is preferable, and an alkoxy group having 1 to 4 carbon atoms is more preferable.
Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 4-methylphenyl group, 2-methylphenyl group, 1-naphthyl group, 2-naphthyl group, 3-phenanthryl group and 2-anthryl group.
The dialkylamino group having 1 to 20 carbon atoms is an amino group substituted with two alkyl groups having 1 to 20 carbon atoms, specifically, a dimethylamino group, a diethylamino group, a di-n-propylamino group, Examples include diisopropylamino group, di-n-butylamino group, di-sec-butylamino group and di-tert-butylamino group, preferably a dialkylamino group having 1 to 8 carbon atoms, and a dialkyl having 1 to 4 carbon atoms. An amino group is more preferable.
The alkyl group having 1 to 20 carbon atoms represented by A may be linear, branched, or cyclic. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2,2-dimethylpropyl group, Cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, 2-methylpentyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, 1-adamantyl group, n-undecyl 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 and n-icosyl group, An alkyl group having 1 to 8 carbon atoms is preferable, and a tert-butyl group and a cyclohexyl group are more preferable.
As the phosphine represented by the formula (C),
A phosphine represented by the formula (C), wherein A is an alkyl group having 1 to 8 carbon atoms;
A phosphine of formula (C) wherein A is a tert-butyl group,
A phosphine of formula (C) wherein A is a cyclohexyl group;
R ¹ , R ² , R ³ , R ⁴ And R ⁵ A phosphine of the formula (C) in which is a hydrogen atom,
A is an alkyl group having 1 to 8 carbon atoms, and R ¹ , R ² , R ³ , R ⁴ And R ⁵ A phosphine of the formula (C) in which is a hydrogen atom,
A is a tert-butyl group and R ¹ , R ² , R ³ , R ⁴ And R ⁵ A phosphine of the formula (C) in which is a hydrogen atom,
A is a cyclohexyl group, R ¹ , R ² , R ³ , R ⁴ And R ⁵ A phosphine of the formula (C) in which is a hydrogen atom,
R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ A phosphine represented by the formula (C) in which is a fluorine atom,
R ² , R ³ , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ A phosphine represented by the formula (C) in which is a fluorine atom,
A is an alkyl group having 1 to 8 carbon atoms, and R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ A phosphine represented by the formula (C) in which is a fluorine atom,
A is a tert-butyl group and R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ A phosphine represented by the formula (C) in which is a fluorine atom,
A is a cyclohexyl group, R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ A phosphine represented by the formula (C) in which is a fluorine atom,
A is an alkyl group having 1 to 8 carbon atoms, and R ² , R ³ , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ A phosphine represented by the formula (C) in which is a fluorine atom,
A is a tert-butyl group and R ² , R ³ , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ A phosphine represented by the formula (C) in which is a fluorine atom,
A is a cyclohexyl group, R ² , R ³ , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ A phosphine represented by the formula (C) in which is a fluorine atom,
R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ Phosphine represented by the formula (C), wherein is a fluoroalkyl group having 1 to 4 carbon atoms,
R ² , R ³ , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ Phosphine represented by the formula (C), wherein is a fluoroalkyl group having 1 to 4 carbon atoms,
A is an alkyl group having 1 to 8 carbon atoms, and R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ Phosphine represented by the formula (C), wherein is a fluoroalkyl group having 1 to 4 carbon atoms,
A is a tert-butyl group and R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ Phosphine represented by the formula (C), wherein is a fluoroalkyl group having 1 to 4 carbon atoms,
A is a cyclohexyl group, R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ Phosphine represented by the formula (C), wherein is a fluoroalkyl group having 1 to 4 carbon atoms,
A is an alkyl group having 1 to 8 carbon atoms, and R ² , R ³ , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ Phosphine represented by the formula (C), wherein is a fluoroalkyl group having 1 to 4 carbon atoms,
A is a tert-butyl group and R ² , R ³ , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ Phosphine represented by the formula (C), wherein is a fluoroalkyl group having 1 to 4 carbon atoms,
A is a cyclohexyl group, R ² , R ³ , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ Phosphine represented by the formula (C), wherein is a fluoroalkyl group having 1 to 4 carbon atoms,
R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ Phosphine represented by the formula (C), wherein is an alkoxy group having 1 to 4 carbon atoms,
R ² , R ³ , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ Phosphine represented by the formula (C), wherein is an alkoxy group having 1 to 4 carbon atoms,
A is an alkyl group having 1 to 8 carbon atoms, and R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ Phosphine represented by the formula (C), wherein is an alkoxy group having 1 to 4 carbon atoms,
A is a tert-butyl group and R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ Phosphine represented by the formula (C), wherein is an alkoxy group having 1 to 4 carbon atoms,
A is a cyclohexyl group, R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ Phosphine represented by the formula (C), wherein is an alkoxy group having 1 to 4 carbon atoms,
A is an alkyl group having 1 to 8 carbon atoms, and R ² , R ³ , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ Phosphine represented by the formula (C), wherein is an alkoxy group having 1 to 4 carbon atoms,
A is a tert-butyl group and R ² , R ³ , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ Phosphine represented by the formula (C), wherein is an alkoxy group having 1 to 4 carbon atoms,
A is a cyclohexyl group, R ² , R ³ , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ Phosphine represented by the formula (C), wherein is an alkoxy group having 1 to 4 carbon atoms,
R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ And R ³ Phosphine represented by the formula (C), wherein is an alkoxy group having 1 to 4 carbon atoms,
A is an alkyl group having 1 to 8 carbon atoms, and R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ And R ³ Phosphine represented by the formula (C), wherein is an alkoxy group having 1 to 4 carbon atoms,
A is a tert-butyl group and R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ And R ³ Phosphine represented by the formula (C), wherein is an alkoxy group having 1 to 4 carbon atoms,
A is a cyclohexyl group, R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ And R ³ Phosphine represented by the formula (C), wherein is an alkoxy group having 1 to 4 carbon atoms,
A is an alkyl group having 1 to 8 carbon atoms, and R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ Phosphine represented by the formula (C), wherein is a C 1-4 alkyl group,
A is a tert-butyl group and R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ Phosphine represented by the formula (C), wherein is a C 1-4 alkyl group,
A is a cyclohexyl group, R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ Phosphine represented by the formula (C), wherein is a C 1-4 alkyl group,
A is an alkyl group having 1 to 8 carbon atoms, and R ² , R ³ , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ Phosphine represented by the formula (C), wherein is a C 1-4 alkyl group,
A is a tert-butyl group and R ² , R ³ , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ Phosphine represented by the formula (C), wherein is a C 1-4 alkyl group,
A is a cyclohexyl group, R ² , R ³ , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ Phosphine represented by the formula (C), wherein is a C 1-4 alkyl group,
A is an alkyl group having 1 to 8 carbon atoms, and R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ Is an alkoxy group having 1 to 4 carbon atoms and R ³ Phosphine represented by the formula (C), wherein is a C 1-4 alkyl group,
A is a tert-butyl group and R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ Is an alkoxy group having 1 to 4 carbon atoms and R ³ Phosphine represented by the formula (C), wherein is a C 1-4 alkyl group,
A is a cyclohexyl group, R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ Is an alkoxy group having 1 to 4 carbon atoms and R ³ Phosphine represented by the formula (C), wherein is a C 1-4 alkyl group,
A is an alkyl group having 1 to 8 carbon atoms, and R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ Is an alkoxy group having 1 to 4 carbon atoms and R ³ A phosphine represented by the formula (C) in which is a fluorine atom,
A is a tert-butyl group and R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ Is an alkoxy group having 1 to 4 carbon atoms and R ³ A phosphine represented by the formula (C) in which is a fluorine atom,
A is a cyclohexyl group, R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ¹ Is an alkoxy group having 1 to 4 carbon atoms and R ³ A phosphine represented by the formula (C) in which is a fluorine atom,
A is an alkyl group having 1 to 8 carbon atoms, and R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ A phosphine represented by the formula (C) in which is a cyano group,
A is a tert-butyl group and R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ A phosphine represented by the formula (C) in which is a cyano group,
A is a cyclohexyl group, R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ A phosphine represented by the formula (C) in which is a cyano group,
A is an alkyl group having 1 to 8 carbon atoms, and R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ A phosphine of the formula (C) in which is a nitro group,
A is a tert-butyl group and R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ A phosphine of the formula (C) in which is a nitro group,
A is a cyclohexyl group, R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ A phosphine of the formula (C) in which is a nitro group,
A is an alkyl group having 1 to 8 carbon atoms, and R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ Is a phosphine represented by the formula (C), which is an aliphatic acyl group having 1 to 20 carbon atoms,
A is a tert-butyl group and R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ Is a phosphine represented by the formula (C), which is an aliphatic acyl group having 1 to 20 carbon atoms, and
A is a cyclohexyl group, R ¹ , R ² , R ⁴ And R ⁵ Is a hydrogen atom and R ³ Is a phosphine represented by the formula (C) in which is an aliphatic acyl group having 1 to 20 carbon atoms.
Specific examples of the phosphine represented by the formula (C) include tert-butyldiphenylphosphine, tert-butylbis (4-fluorophenyl) phosphine, tert-butylbis (2-fluorophenyl) phosphine, tert-butylbis (4-trifluoro). Methylphenyl) phosphine, tert-butylbis (2-trifluoromethylphenyl) phosphine, tert-butylbis (4-methoxyphenyl) phosphine, tert-butylbis (2-methoxyphenyl) phosphine, tert-butylbis (2,4-dimethoxyphenyl) ) Phosphine, tert-butylbis (2-methoxy-4-methylphenyl) phosphine, tert-butylbis (2-methoxy-4-fluorophenyl) phosphine, tert-butylbis (2- Toxi-4-trifluoromethylphenyl) phosphine, tert-butylbis (3,5-dimethyl-4-methoxyphenyl) phosphine, tert-butylbis (4-acetylphenyl) phosphine, tert-butylbis (4-methoxycarbonylphenyl) phosphine , Tert-butylbis (4-cyanophenyl) phosphine, tert-butylbis (4-nitrophenyl) phosphine, tert-butylbis [(1,1′-biphenyl) -2-yl] phosphine, tert-butylbis [4- (N , N-dimethylamino) phenyl] phosphine, tert-butylbis [2- (N, N-dimethylamino) phenyl] phosphine, tert-butylbis (4-methylphenyl) phosphine, tert-butylbis (2-methylpheny ) Phosphine, cyclohexyldiphenylphosphine, cyclohexylbis (4-fluorophenyl) phosphine, cyclohexylbis (2-fluorophenyl) phosphine, cyclohexylbis (4-trifluoromethylphenyl) phosphine, cyclohexylbis (2-trifluoromethylphenyl) phosphine , Cyclohexylbis (4-methoxyphenyl) phosphine, cyclohexylbis (2-methoxyphenyl) phosphine, cyclohexylbis (2,4-dimethoxyphenyl) phosphine, cyclohexylbis (2-methoxy-4-methylphenyl) phosphine, cyclohexylbis ( 2-methoxy-4-fluorophenyl) phosphine, cyclohexylbis (2-methoxy-4-trifluoromethylphenyl) phosphine Cyclohexylbis (2,5-dimethyl-4-methoxyphenyl) phosphine, cyclohexylbis (4-acetylphenyl) phosphine, cyclohexylbis (4-methoxycarbonylphenyl) phosphine, cyclohexylbis (4-cyanophenyl) phosphine, cyclohexylbis ( 4-nitrophenyl) phosphine, cyclohexylbis [(1,1′-biphenyl) -2-yl] phosphine, cyclohexylbis [4- (N, N-dimethylamino) phenyl] phosphine, cyclohexylbis [2- (N, N-dimethylamino) phenyl] phosphine, cyclohexylbis (4-methylphenyl) phosphine and cyclohexylbis (2-methylphenyl) phosphine.
<Phosphine represented by formula (D)>
The phosphine represented by formula (D) is represented by formula (D):

Indicated by
Formula (D), R ⁶ Represents an alkoxy group having 1 to 20 carbon atoms and R ⁷ , R ⁸ , R ⁹ And R ¹⁰ Each independently represents a hydrogen atom, a fluorine atom, a fluoroalkyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, a cyano group, a nitro group, or 1 to It represents a 20 alkyl group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a dialkylamino group having 1 to 20 carbon atoms.
R ⁶ The alkoxy group having 1 to 20 carbon atoms represented by the above formula may be linear, branched or cyclic. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, 2,2-dimethylpropoxy group, n -Hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group , N-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group and n-icosyloxy group. An alkoxy group having 1 to 8 carbon atoms is preferable, and an alkoxy group having 1 to 4 carbon atoms is more preferable.
Examples of the fluoroalkyl group having 1 to 20 carbon atoms include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, and A perfluoroisopropyl group is mentioned, and a fluoroalkyl group having 1 to 4 carbon atoms is preferred.
The alkoxycarbonyl group having 1 to 20 carbon atoms is a group formed by bonding an alkoxy group having 1 to 20 carbon atoms and a carbonyl group, and specifically includes a methoxycarbonyl group, an ethoxycarbonyl group, and n-propoxy group. Carbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, n-dodecyloxy group Cicarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perfluorooctyloxycarbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group and pyridyloxycarbonyl group An alkoxycarbonyl group having 1 to 8 carbon atoms is preferable, and an alkoxycarbonyl group having 1 to 4 carbon atoms is more preferable.
Examples of the acyl group having 2 to 20 carbon atoms include aliphatic acyl groups such as acetyl group, propionyl group, butyryl group and isobutyryl group, and aromatic acyl groups such as benzoyl group and naphthoyl group.
The alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2,2-dimethylpropyl group, Cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, 2-methylpentyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group Group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n-icosyl group. Are preferred, and alkyl groups having 1 to 4 carbon atoms are more preferred.
The alkoxy group having 1 to 20 carbon atoms may be linear, branched, or cyclic. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, 2,2-dimethylpropoxy group, n -Hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group , N-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group and n-icosyloxy group. An alkoxy group having 1 to 8 carbon atoms is preferable, and an alkoxy group having 1 to 4 carbon atoms is more preferable.
Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 4-methylphenyl group, 2-methylphenyl group, 1-naphthyl group, 2-naphthyl group, 3-phenanthryl group and 2-anthryl group.
The dialkylamino group having 1 to 20 carbon atoms is an amino group substituted with two alkyl groups having 1 to 20 carbon atoms, specifically, a dimethylamino group, a diethylamino group, a di-n-propylamino group, Examples include diisopropylamino group, di-n-butylamino group, di-sec-butylamino group and di-tert-butylamino group, preferably a dialkylamino group having 1 to 8 carbon atoms, and a dialkyl having 1 to 4 carbon atoms. An amino group is more preferable.
As the phosphine represented by the formula (D),
R ⁶ , R ⁷ , R ⁹ And R ¹⁰ Is a hydrogen atom and R ⁸ Phosphine represented by the formula (D), wherein is an alkoxy group having 1 to 4 carbon atoms,
R ⁷ , R ⁸ , R ⁹ And R ¹⁰ Is a hydrogen atom and R ⁶ Phosphine represented by the formula (D), wherein is an alkoxy group having 1 to 4 carbon atoms,
R ⁷ , R ⁹ And R ¹⁰ Is a hydrogen atom and R ⁶ And R ⁸ Phosphine represented by the formula (D), wherein is an alkoxy group having 1 to 4 carbon atoms,
R ⁷ , R ⁹ And R ¹⁰ Is a hydrogen atom and R ⁶ Is an alkoxy group having 1 to 4 carbon atoms and R ⁸ Phosphine represented by the formula (D), wherein is a C 1-4 alkyl group,
R ⁷ , R ⁹ And R ¹⁰ Is a hydrogen atom and R ⁶ Is an alkoxy group having 1 to 4 carbon atoms and R ⁸ A phosphine of formula (D) wherein is a fluorine atom, and
R ⁷ , R ⁹ And R ¹⁰ Is a hydrogen atom and R ⁶ Is an alkoxy group having 1 to 4 carbon atoms and R ⁸ Is a phosphine represented by the formula (D), wherein is a fluoroalkyl group having 1 to 4 carbon atoms.
Specific examples of the phosphine represented by the formula (D) include tert-butylbis (2-methoxyphenyl) phosphine, tert-butylbis (2,4-dimethoxyphenyl) phosphine, tert-butylbis (2-methoxy-4-methylphenyl). ) Phosphine, tert-butylbis (2-methoxy-4-fluorophenyl) phosphine and tert-butylbis (2-methoxy-4-trifluoromethylphenyl) phosphine.
<Phosphine represented by formula (E)>
The phosphine represented by formula (E) is represented by formula (E):

Indicated by
In formula (E), R ¹¹ Represents an alkoxy group having 1 to 20 carbon atoms and R ¹² , R ¹³ , R ¹⁴ And R ¹⁵ Each independently represents a hydrogen atom, a fluorine atom, a fluoroalkyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, a cyano group, a nitro group, or 1 to It represents a 20 alkyl group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a dialkylamino group having 1 to 20 carbon atoms. However, R ¹² ~ R ¹⁵ Are not all hydrogen atoms.
R ¹¹ The alkoxy group having 1 to 20 carbon atoms represented by the above formula may be linear, branched or cyclic. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, 2,2-dimethylpropoxy group, n -Hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group , N-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group and n-icosyloxy group. An alkoxy group having 1 to 8 carbon atoms is preferable, and an alkoxy group having 1 to 4 carbon atoms is more preferable.
Examples of the fluoroalkyl group having 1 to 20 carbon atoms include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, and A perfluoroisopropyl group is mentioned, and a fluoroalkyl group having 1 to 4 carbon atoms is preferred.
The alkoxycarbonyl group having 1 to 20 carbon atoms is a group formed by bonding an alkoxy group having 1 to 20 carbon atoms and a carbonyl group, and specifically includes a methoxycarbonyl group, an ethoxycarbonyl group, and n-propoxy group. Carbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, n-dodecyloxy group Cicarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perfluorooctyloxycarbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group and pyridyloxycarbonyl group An alkoxycarbonyl group having 1 to 8 carbon atoms is preferable, and an alkoxycarbonyl group having 1 to 4 carbon atoms is more preferable.
Examples of the acyl group having 2 to 20 carbon atoms include aliphatic acyl groups such as acetyl group, propionyl group, butyryl group and isobutyryl group, and aromatic acyl groups such as benzoyl group and naphthoyl group.
The alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2,2-dimethylpropyl group, Cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, 2-methylpentyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group Group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n-icosyl group. Are preferred, and alkyl groups having 1 to 4 carbon atoms are more preferred.
The alkoxy group having 1 to 20 carbon atoms may be linear, branched, or cyclic. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, 2,2-dimethylpropoxy group, n -Hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group , N-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group and n-icosyloxy group. An alkoxy group having 1 to 8 carbon atoms is preferable, and an alkoxy group having 1 to 4 carbon atoms is more preferable.
Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 4-methylphenyl group, 2-methylphenyl group, 1-naphthyl group, 2-naphthyl group, 3-phenanthryl group and 2-anthryl group.
The dialkylamino group having 1 to 20 carbon atoms is an amino group substituted with two alkyl groups having 1 to 20 carbon atoms, specifically, a dimethylamino group, a diethylamino group, a di-n-propylamino group, Examples include diisopropylamino group, di-n-butylamino group, di-sec-butylamino group and di-tert-butylamino group, preferably a dialkylamino group having 1 to 8 carbon atoms, and a dialkyl having 1 to 4 carbon atoms. An amino group is more preferable.
As the phosphine represented by the formula (E),
R ¹¹ , R ¹² , R ¹⁴ And R ¹⁵ Is a hydrogen atom and R ¹³ Phosphine represented by the formula (E), wherein is an alkoxy group having 1 to 4 carbon atoms,
R ¹² , R ¹³ , R ¹⁴ And R ¹⁵ Is a hydrogen atom and R ¹¹ Phosphine represented by the formula (E), wherein is an alkoxy group having 1 to 4 carbon atoms,
R ¹² , R ¹⁴ And R ¹⁵ Is a hydrogen atom and R ¹¹ And R ¹³ Phosphine represented by the formula (E), wherein is an alkoxy group having 1 to 4 carbon atoms,
R ¹² , R ¹⁴ And R ¹⁵ Is a hydrogen atom and R ¹¹ Is an alkoxy group having 1 to 4 carbon atoms and R ¹³ Phosphine represented by the formula (E), wherein is an alkyl group having 1 to 4 carbon atoms,
R ¹² , R ¹⁴ And R ¹⁵ Is a hydrogen atom and R ¹¹ Is an alkoxy group having 1 to 4 carbon atoms and R ¹³ A phosphine of formula (E) wherein is a fluorine atom, and
R ¹² , R ¹⁴ And R ¹⁵ Is a hydrogen atom and R ¹¹ Is an alkoxy group having 1 to 4 carbon atoms and R ¹³ Is a phosphine represented by the formula (E), wherein is a fluoroalkyl group having 1 to 4 carbon atoms.
Specific examples of the phosphine represented by the formula (E) include cyclohexylbis (2,4-dimethoxyphenyl) phosphine, cyclohexylbis (2-methoxy-4-methylphenyl) phosphine, and cyclohexylbis (2-methoxy-4-fluoro). Phenyl) phosphine and cyclohexylbis (2-methoxy-4-trifluoromethylphenyl) phosphine.
The phosphine represented by the formula (D) and the formula (E) can be used as a ligand of the Suzuki coupling reaction, for example, Metal-Catalyzed Cross-Coupling Reactions Second, Completely Revised and Enhancing Edition Volume 1, 2 (de Meijere Armin, edited by Dietrich Francois, 2004, issued by Wiley-VCH). Specific examples of the coupling reaction include Stille coupling, Heck coupling, Hiyama coupling, Sonogashira coupling, Kumada coupling, and Buchwald-Hartwig coupling.
The phosphine represented by the formula (C) is preferably a phosphine represented by the formula (D) or a phosphine represented by the formula (E).
The amount of the phosphine represented by the formula (C) used in the production method of the present invention is usually in the range of 0.1 mol to 10 mol, preferably 0.5 mol to 5 mol, relative to 1 mol of the palladium compound. It is a range.
The phosphine represented by the formula (C) is Journal of Molecular Catalysis A: Chemical 2003, 200, 81-94. It can synthesize | combine according to well-known methods, such as.
<Transition metal complex>
A transition metal complex can be prepared by contacting a phosphine represented by formula (C), a phosphine represented by formula (D) or a phosphine represented by formula (E) with a Group 10 transition metal compound. . Examples of Group 10 transition metal compounds include nickel compounds, palladium compounds, and platinum compounds, with palladium compounds being preferred. As a palladium compound, the palladium compound described in the column of the above <palladium compound> is mentioned.
The transition metal complex obtained by bringing the phosphine represented by the formula (C), the phosphine represented by the formula (D) or the phosphine represented by the formula (E) and the palladium compound into contact with each other is, for example, the 5th edition experimental chemistry It can be prepared according to a known method such as a course (edited by Chemical Society of Japan, published by Maruzen Co., Ltd.) 21 organic transition metal complex / supermolecular complex p308-327 (9.2 organic palladium complex).
<Polymerization process>
The polymerization step is a step of mixing the aromatic monomer (A) and the aromatic monomer (B) in the presence of a base, a palladium compound, a phosphine represented by the formula (C) and an aprotic organic solvent, Although the mixing order is not limited, for example, (i) palladium compound, phosphine represented by formula (C), base, aromatic monomer (A), aromatic monomer (B) and aprotic organic solvent are mixed together (Ii) after mixing the base, aromatic monomer (A), aromatic monomer (B) and aprotic organic solvent, the palladium compound and the phosphine represented by formula (C), or palladium A step of polymerizing a complex prepared in advance from a compound and a phosphine represented by the formula (C) and an aprotic organic solvent may be mentioned.
The polymerization temperature in the polymerization step is usually in the range of 0 ° C to 180 ° C, preferably in the range of 30 ° C to 100 ° C.
The polymerization time in the polymerization step is usually in the range of 1 hour to 96 hours, preferably in the range of 3 hours to 48 hours.
For example, the target aromatic polymer may be precipitated by a method of adding a poor solvent to the reaction mixture containing the aromatic polymer obtained by the polymerization step, and the aromatic polymer may be taken out by a normal separation means such as filtration. Good.
In order to remove impurities such as metals, the target aromatic polymer may be taken out by the above-mentioned method after the reaction mixture is washed with an acidic solution such as hydrochloric acid.
The obtained aromatic polymer may be subjected to purification treatment such as fractionation by chromatography.

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.
The molecular weight of the obtained aromatic polymer was subjected to gel permeation chromatography (hereinafter sometimes referred to as GPC), and the weight average molecular weight (Mw) in terms of polystyrene was calculated and evaluated from the analysis result. The GPC analysis conditions are as follows.
<GPC analysis conditions>
GPC measuring device: CTO-20A (Shimadzu Corporation column oven), SPD-20A (Shimadzu Corporation detector)
Column: PLgel 10 μm MIXED-B 300 × 7.5 mm (manufactured by Polymer Laboratories)
-Column temperature: 40 ° C
・ Mobile phase: Tetrahydrofuran ・ Flow rate: 2 mL / min ・ Detection: UV detection (wavelength: 228 nm)
Example 1
Boronate ester (6.0 mmol) formed from 9,9-di-n-octylfluorene-2,7-diboronic acid and pinacol in a glass reaction vessel equipped with a cooling device at room temperature under a nitrogen atmosphere. ), Bis (4-bromophenyl) [4- (methylpropyl) phenyl] amine (6.0 mmol), 20 wt% aqueous tetraethylammonium hydroxide (20 ml) and toluene (110 ml) were added. While stirring the resulting mixture, the temperature was raised (bath temperature 100 ° C.). After heating, bis [cyclohexylbis (2-methoxyphenyl) phosphine] dichloropalladium (II) (3 μmol) and toluene (12 ml) were added. While stirring the obtained mixture, polymerization was carried out at a bath temperature of 100 ° C. for 4 hours. After the polymerization, the molecular weight of the obtained aromatic polymer was analyzed by the GPC measurement. As a result, it was confirmed that the molecular weight (Mw) was 5.3 × 10 ⁵ .
Example 2
Example 1 except that bis [tert-butylbis (2-methoxyphenyl) phosphine] dichloropalladium (II) was used instead of bis [cyclohexylbis (2-methoxyphenyl) phosphine] dichloropalladium (II). Polymerization was carried out. As a result of analyzing the molecular weight of the obtained aromatic polymer by the GPC measurement, it was confirmed that the molecular weight (Mw) was 4.9 × 10 ⁵ .
Example 3
Example 1 except that bis [cyclohexylbis (2,4-dimethoxyphenyl) phosphine] dichloropalladium (II) was used instead of bis [cyclohexylbis (2-methoxyphenyl) phosphine] dichloropalladium (II). Polymerization was carried out in the same manner. As a result of analyzing the molecular weight of the obtained aromatic polymer by the above GPC measurement, it was confirmed that the molecular weight (Mw) was 4.7 × 10 ⁵ .
Example 4
Instead of bis (4-bromophenyl) [4- (methylpropyl) phenyl] amine (6.0 mmol), 9,9-di-n-octyl-2,7-dibromofluorene (5.9 mmol) was used. Polymerization was carried out in the same manner as in Example 1 except that. As a result of analyzing the molecular weight of the obtained aromatic polymer by the GPC measurement, it was confirmed that the molecular weight (Mw) was 3.6 × 10 ⁵ .
Example 5
Under a nitrogen atmosphere, 2.35 g of 1-bromo-2,4-dimethoxybenzene and 15 ml of diethyl ether were added to a reaction vessel equipped with a dropping funnel. After cooling the obtained solution to -10 degreeC, 6.6 ml of n-butyl lithium (1.62M / hexane solution) was dripped. The resulting mixture was stirred at the same temperature for 3 hours. Thereafter, a solution obtained by dissolving 1.00 g of dichlorocyclohexylphosphine in 13 ml of diethyl ether was added dropwise to the obtained mixture. The resulting mixture was stirred at −10 ° C. for 4 hours. The white solid that formed was removed by filtration. After concentrating the obtained filtrate, the obtained concentrate (crude product) was purified by silica gel column chromatography to obtain 0.48 g of cyclohexylbis (2,4-dimethoxyphenyl) phosphine as a transparent viscous liquid. It was.
¹ H-NMR (δ: ppm, CDCl ₃ solvent, TMS standard)
7.15-7.25 (m, 2H), 6.39-6.49 (m, 4H), 3.79 (s, 6H), 3.74 (s, 6H), 2.28 (m, 1H), 1.66-1.74 (m, 4H), 1.23-1, 29 (m, 6H)
³¹ P-NMR (δ: ppm, CDCl ₃ solvent) -32.5
Example 6
Under a nitrogen atmosphere, 0.43 g of cyclohexylbis (2,4-dimethoxyphenyl) phosphine synthesized in Example 5, 0.17 g of dichlorobis (acetonitrile) palladium (II) and 6 ml of ethanol were added to the reaction vessel. The resulting mixture was stirred at room temperature for 5 hours. After stirring, the precipitated solid was removed by filtration and washed 3 times with 6 ml of ethanol. The obtained solid was dried under reduced pressure at 60 ° C. for 3 hours to obtain 0.45 g of bis [cyclohexylbis (2,4-dimethoxyphenyl) phosphine] dichloropalladium (II) as a desired transition metal complex. Obtained as a solid.
¹ H-NMR (δ: ppm, CDCl ₃ solvent, TMS standard)
7.70-7.76 (m, 2H), 6.39-6.47 (m, 4H), 3.82 (s, 6H), 3.76 (s, 6H), 3.14 (m, 1H), 1.87 (m, 4H), 1.66-1, 27 (m, 6H)
³¹ P-NMR (δ: ppm, CDCl ₃ solvent) 18.0
Example 7
Under a nitrogen atmosphere, 2.35 g of 2-bromoanisole and 15 ml of diethyl ether were added to a reaction vessel equipped with a dropping funnel. After cooling the obtained solution to -10 degreeC, 7.6 ml of n-butyl lithium (1.62M / hexane solution) was dripped. The resulting mixture was stirred at the same temperature for 3 hours. Thereafter, a solution obtained by dissolving 1.00 g of tert-butyldichlorophosphine in 13 ml of diethyl ether was added dropwise to the obtained mixture. The resulting mixture was stirred at −10 ° C. for 4 hours. The white solid that formed was removed by filtration. By concentrating the obtained filtrate, 1.12 g (transparent viscous liquid) of tert-butylbis (2-methoxyphenyl) phosphine was obtained as a concentrate (crude product).
Example 8
Under a nitrogen atmosphere, 1.12 g of tert-butylbis (2-methoxyphenyl) phosphine synthesized in Example 7, 0.40 g of dichlorobis (acetonitrile) palladium (II) and 12 ml of ethanol were added to the reaction vessel. The resulting mixture was stirred at room temperature for 12 hours. After stirring, the precipitated solid was removed by filtration and washed 3 times with 12 ml of ethanol. The obtained solid was dried under reduced pressure at 50 ° C. for 3 hours to obtain 0.80 g of desired transition metal complex bis [tert-butylbis (2-methoxyphenyl) phosphine] dichloropalladium (II) as a pale yellow solid. Got as.
¹ H-NMR (δ: ppm, CDCl ₃ solvent, TMS standard)
8.20 (m, 2H), 7.38-7.44 (m, 2H), 6.88-6.97 (m, 4H), 3.95 (s, 6H), 1.51-1. 56 (m, 9H)
³¹ P-NMR (δ: ppm, CDCl ₃ solvent) 53.0
Example 9
Under a nitrogen atmosphere, 2.73 g of 1-bromo-2,4-dimethoxybenzene and 15 ml of diethyl ether were added to a reaction vessel equipped with a dropping funnel. After cooling the obtained solution to -10 degreeC, 7.6 ml of n-butyl lithium (1.62M / hexane solution) was dripped. The resulting mixture was stirred at the same temperature for 3 hours. Thereafter, a solution obtained by dissolving 1.00 g of tert-butyldichlorophosphine in 13 ml of diethyl ether was added dropwise to the obtained mixture. The resulting mixture was stirred at −10 ° C. for 1 hour. The white solid that formed was removed by filtration. By concentrating the obtained filtrate, 2.30 g (transparent viscous liquid) of tert-butyl (2,4-dimethoxyphenyl) phosphine was obtained as a concentrate (crude product).
Example 10
Under a nitrogen atmosphere, 2.30 g of tert-butyl (2,4-dimethoxyphenyl) phosphine synthesized in Example 9, 0.70 g of dichlorobis (acetonitrile) palladium (II) and 12 ml of ethanol were added to the reaction vessel. The resulting mixture was stirred at room temperature for 17 hours. After stirring, the precipitated solid was removed by filtration and washed 3 times with 12 ml of ethanol. The obtained solid was dried under reduced pressure at 50 ° C. for 4 hours to obtain 1.18 g of bis [tert-butylbis (2,4-dimethoxyphenyl) phosphine] dichloropalladium (II), which is a desired transition metal complex, as an ocher solid. Got as.
¹ H-NMR (δ: ppm, CDCl ₃ solvent, TMS standard)
7.95 (m, 2H), 6.39-6.48 (m, 4H), 3.80 (s, 12H), 1.43-1.51 (m, 9H)
³¹ P-NMR (δ: ppm, CDCl ₃ solvent) 50.0

According to the production method of the present invention, a high molecular weight aromatic polymer can be produced.

Claims

Formula (A):

(In the formula, each X 1 independently represents the formula (1), (2), (3), (4), (5) or (6)

Ar 1 represents a divalent aromatic hydrocarbon group having 6 to 36 carbon atoms. The carbon atom contained in the aromatic hydrocarbon group may be replaced with a hetero atom or a carbonyl group, and the hydrogen atom contained in the aromatic hydrocarbon group is a fluorine atom, an alkyl group, an alkoxy group, an alkylthio group, An aryl group, an aryloxy group, an arylthio group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, a heterocyclic group that may have a substituent, an amino group that may have a substituent, and a substituent It may be substituted with a silyl group, an acyl group, a group having a carbon atom-nitrogen atom double bond as a partial structure, an acid imide group, an alkoxycarbonyl group, a carboxyl group, a cyano group or a nitro group. )
An aromatic monomer represented by
Formula (B):

(In the formula, each X 2 independently represents a chlorine atom, a bromine atom or an iodine atom, and Ar 2 represents a divalent aromatic hydrocarbon group having 6 to 36 carbon atoms. The aromatic hydrocarbon group The carbon atom contained in may be replaced with a hetero atom or a carbonyl group, and the hydrogen atom contained in the aromatic hydrocarbon group may be a fluorine atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group. , Arylthio group, arylalkylthio group, arylalkenyl group, arylalkynyl group, heterocyclic group which may have a substituent, amino group which may have a substituent, silyl group which may have a substituent, Acyl group, group having carbon-nitrogen double bond as a partial structure, acid imide group, alkoxycarbonyl group, carboxyl group, cyano group or nitro group It may be substituted.)
An aromatic monomer represented by
Base, palladium compound, formula (C):

(Wherein R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom, a fluorine atom, a fluoroalkyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, carbon An acyl group having 2 to 20 carbon atoms, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a dialkylamino group having 1 to 20 carbon atoms And A represents an alkyl group having 1 to 20 carbon atoms.)
A process for producing an aromatic polymer comprising the step of mixing in the presence of a phosphine and an aprotic organic solvent.
The production method according to claim 1, wherein the aprotic organic solvent is at least one selected from the group consisting of an ether solvent, an aromatic hydrocarbon solvent, and an aliphatic hydrocarbon solvent.
The production method according to claim 1 or 2, wherein the palladium compound is a palladium (0) complex or a palladium (II) complex.
Formula (D):

(Wherein R 6 represents an alkoxy group having 1 to 20 carbon atoms, and R 7 , R 8 , R 9 and R 10 are each independently a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 20 carbon atoms. , An alkoxycarbonyl group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 6 to 20 carbon atoms Represents an aryl group or a dialkylamino group having 1 to 20 carbon atoms.)
A phosphine represented by
Formula (E):

(Wherein R 11 represents an alkoxy group having 1 to 20 carbon atoms, and R 12 , R 13 , R 14 and R 15 are each independently a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 20 carbon atoms. , An alkoxycarbonyl group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 6 to 20 carbon atoms Represents an aryl group or a dialkylamino group having 1 to 20 carbon atoms, provided that R 12 to R 15 are not all hydrogen atoms.)
A phosphine represented by
A transition metal complex obtained by contacting the phosphine according to claim 4 with a Group 10 transition metal compound.
A transition metal complex obtained by contacting the phosphine according to claim 5 with a Group 10 transition metal compound.