TW201245262A - Production method for aromatic polymer - Google Patents

Abstract

A production method for aromatic polymer is characterized by including the step of mixing an aromatic monomer represented by the following formula (A) and an aromatic monomer represented by the following formula (B) in the presence of a base, a palladium compound, a phosphine represented by the following formula (C) and an aprotic organic solvent. The formula (A) represents X1-Ar1-X1 (A). ( In the formula, X1 each independently indicate a group represented by formula (1), (2), (3), (4), (5) or (6); Ar1 indicates a C6-C36 bivalent aromatic hydrocarbon group, wherein the carbon atoms contained therein may be substituted with heteroatom or carbonyl groups, and the hydrogen atoms contained therein may be substituted with fluorine atoms, etc.). The formula (B) represents X2-Ar2-X2 (B). (In the formula, X2 each independently indicate a chlorine atom, etc.; Ar2 indicates a C6-C36 bivalent aromatic hydrocarbon group, wherein the carbon atoms contained therein may be substituted with heteroatoms or carbonyl groups, and the hydrogen atoms contained therein may be substituted with fluorine atoms, etc.). The formula (C) represents: (In formula, R1, R2, R3, R4, and R5, each independently indicate a hydrogen atom, etc.; and A indicates a C1-C20 alkyl group).

Description

201245262 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing an aromatic polymer. [Prior Art] An aromatic polymer having 2 or more aromatic rings in a π-conjugated structure is useful, for example, in organic electronic materials. As a method for producing an aromatic polymer, a method of producing an aromatic monomer by a Suzuki coupling reaction is known. A method disclosed in the presence of palladium acetate, ginseng (2-methoxyphenyl)phosphine, aqueous tetraethylammonium hydroxide solution and toluene is disclosed in Japanese Laid-Open Patent Publication No. 2007-126652. An ester formed from 9,9-di-η-octylindole-2,7-diboronic acid and hydrazine (tetrapropylene glycol) with bis(4-bromophenyl)[4-(2-butyl)phenyl The amine is polymerized to produce a corresponding aromatic polymer having a molecular weight (Mw) of 3.0 x 105. SUMMARY OF THE INVENTION The present invention provides the following inventions [1] to [5]. [1] A method for producing an aromatic polymer, which comprises an aromatic monomer represented by the following formula (A) and an aromatic monomer represented by the following formula (B) in a base or a palladium compound. a step of mixing in the presence of a phosphine and an aprotic organic solvent represented by the following formula (C): Formula (A): X1 - Ar1-X1 (A) 201245262 In the formula, X1 is independently shown as a formula ( 1), (2), (3), (4 (5) or (6), H0\ HV°x 1 /- ---0 R- ¥ person / h3c (1) (2) ( 3) · 0 Factory 0, —— ( B—— τ>- · H3c (4) (5) (6)

The aryl group contained in Ar1 has a group of a group, (the formula is contained, and the aryl group is a divalent aromatic hydrocarbon group having a carbon number of 6 to 36, and some of the carbon atoms of the aromatic hydrocarbon group may pass through a hetero atom or Substituted by a carbonyl group, the aromatic hydrocarbon group may have a hydrogen atom via a fluorine atom, an alkyl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an aralkylthio group, an aralkenyl group, an aralkynyl group, a heterocyclic group which may be a substituent, an amine group which may have a substituent, a substituted fluorenyl group, a fluorenyl group, a quinone imine group partially having a carbon atom-nitrogen double bond, an alkoxycarbonyl group, a carboxyl group, and an atmosphere Substituted by a nitro group or a nitro group. In the formula (B): X2-Ar2-X2 (B), each of X2 is independently represented by a chlorine atom, a bromine atom or an iodine atom, and a divalent aromatic hydrocarbon group having an Ar2 carbon number of 6 to 36. The carbon atom contained in the aromatic hydrocarbon group may be substituted by a hetero atom or a carbonyl group, and the hydrogen atom in the aromatic hydrocarbon group may be a fluorine atom, an alkyl group, an alkoxy group, an alkylthio group, an aryloxy group or an arylthio group. An aralkylthio 'arylene group, an aralkynyl group, a heterocyclic group which may have a group, an amine group which may have a substituent, may have a substitution基基-6- 201245262 Mercapto, fluorenyl, partially structured as a radical having a carbon atom-nitrogen double bond, substituted with a quinone imine group, an alkoxycarbonyl group, a carboxyl group, a cyano group or a nitro group), ): R5 r3—-p*fA)2 (c) 〆R1 (wherein R1, R2, R3' R4 and R5 are each independently represented as a hydrogen atom, a fluoroalkyl group having a carbon number of 1 to 20 or a carbon number of 1~ 20 dialkylamino group, a is shown as a carbon number of 丨 20 alkyl). [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] a phosphine represented by the following formula (D), formula (D)

Each of them is independently represented by a hydrogen atom or a carbon (wherein R6, R7, R8, R9 and R1 are a fluoroalkyl group having 1 to 20 carbon atoms or a dialkylamino group having 1 to 20 carbon atoms, but R6 to R115 are not In the case where all numbers are hydrogen atoms). [5] A transition metal complex' obtained by contacting a phosphine of [4] with a 201245262 oxime transition metal compound. [Best Mode for Carrying Out the Invention] The aromatic monomer used in the production method of the present invention is an aromatic monomer represented by the formula (a): X1 - Ar1 - X1 (A) In the case of the aromatic monomer (A), and the formula (B): a square aromatic monomer represented by X2 Ar2 X2 (B) (hereinafter, also referred to as an aromatic monomer (B)) .

Ar1 and Ar2 are each independently shown as a divalent aromatic hydrocarbon group having 6 to 36 carbon atoms. The monovalent aromatic aromatic hydrocarbon group, which comprises a divalent monocyclic aromatic hydrocarbon group, a divalent condensed aromatic hydrocarbon group, and 2 or more monocyclic aromatic hydrocarbon groups by a single bond, a hetero atom (oxygen atom, nitrogen atom, A divalent group formed by linking a sulfur atom or the like or a carbonyl group (-C 0 ·). Specific examples thereof include a divalent monocyclic aromatic hydrocarbon group such as a phenyl group; a divalent condensed aromatic hydrocarbon group such as a naphthalenediyl group, a fluorenyldiyl group or a fluorenyldiyl group; and a monocyclic ring of 2 or more groups such as a biphenyl group. The aromatic hydrocarbon group is a divalent group formed by a single bond, a hetero atom (an oxygen atom, a nitrogen atom, a sulfur atom or the like) 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. -8- 201245262 A hydrogen atom contained in an aromatic hydrocarbon group may be substituted with a substituent. As the substituent, for example, a fluorine atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aralkylthio group, an aralkenyl group, or an aralkynyl group may have a substituent. a cyclic group, an amine group which may have a substituent, a fluorenyl group which may have a substituent, a fluorenyl group, a moiety partially constituted by a carbon atom-nitrogen atom double bond, a quinone imine group, an alkoxycarbonyl group, a carboxyl group (-COOH) ), cyano (-CN) and nitro (-N02). The hydrogen atom contained in the substituent may be a fluorine atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 2 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a carbon number of 2 to 20 Substituted by thiol or cyano. The "alkyl group" may, for example, be an alkyl group having 1 to 20 carbon atoms, which may be a linear chain, a branched chain or a cyclic chain. Specific examples are, for example, methyl, ethyl, n-propyl, isopropyl, η-butyl, isobutyl, sec-butyl, tert-butyl, η-pentyl, 2,2-dimethylpropane Base, cyclopentyl, η·hexyl, cyclohexyl, η·heptyl, 2-methylpentyl, η-octyl '2-ethylhexyl, η-fluorenyl, η-fluorenyl, η-~\ - alkyl, η-dodecyl, η-tridecyl, η.14, η-pentadecyl, η-hexadecyl, η-heptadecyl, η-ten Octaalkyl, η-nine-yard and η-thenyl. The "alkoxy group" may, for example, be a linear or branched chain or a cyclic alkoxy group having a carbon number of 1 to 20%. Specific examples are 'methoxy, ethoxy, η-propoxy, isopropoxy, η-butoxy' sec-butoxy, tert • butoxy, η-pentyloxy, 2, 2 - dimethylpropoxy, η hexyloxy, cyclohexyloxy, η-heptyloxy, η-octyloxy, η-methoxy, η-methoxy, η-undecyloxy , η·dodecyloxy, η-tridecyloxy, η-tetradecyloxy′ η-pentadecanyloxy, η-hexadecyloxy, η-heptadecanyloxy, η - octadecane-9- 201245262 oxy, η-nine-yard oxy and η·20-thyloxy. The "alkylthio group" is, for example, a linear sulfur group having a carbon number of 1 to 20, a branched chain, or a cyclic group. Specifically, for example, methylthio, η-propylthio, isopropylthio, η·butylthio, isobutylthio, yl, tert-butylthio, η-pentylthio, η-hexylthio, Cyclohexylthio group, η-octylthio group, 2-ethylhexylthio group, η·壬thio group, η-| , 7-dimethyloctylthio group, η-dodecylthio group and trifluoromethyl As the "aryl group", the thio group is, for example, an aryl group having 6 to 20 carbon atoms. For example, phenyl, 4-methylphenyl, 2-methylphenyl, 1-naphthyl, 3-phenanthryl and 2-indenyl. As the "aryloxy group", a group formed by an aryl group bonded to the first to 20 Å by an oxygen atom is exemplified. Specifically, for example, a phenoxy group, a phenanthryloxy group, and an anthyloxy group as an "arylthio group" are exemplified by a group formed by a sulfur atom bonded to an aryl group of the first to -20. Specifically, for example, phenylthio hydrazine as the "aralkylthio group" is exemplified by the above-mentioned alkyl group having 1 to 20 carbon atoms which is substituted by an aryl group having 6 to 20 carbon atoms. Specifically, for example, a benzylthio group and a naphthylthio group. Examples of the "aromatic alkenyl group" include a phenyl alkenyl group and a naphthyl alkene "alkenyl group", and examples thereof include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-butenyl group, and a 1-pentenyl group. An alkenyl group having 2 to 8 carbon atoms such as 2-pentenyl group, 1-hexenyl group or 1-octenyl group. The "aryl alkynyl group", for example, a phenylalkynyl group and a naphthyl alkynyl group, may be an ethylthio group, a sec-butylthio group, a η-heptanylthio group, or a triphenyl group, specifically a 2-naphthyl group, and a carbon number. 6. A naphthyloxy group having 6 carbon atoms and a naphthylthio group formed by the aforementioned carbon. As 1, 1-butene and 2-hexene. As -10- 201245262 "alkynyl", for example, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 1-pentynyl, 2-pentynyl An alkynyl group having 2 to 8 carbon atoms such as a 1-hexynyl group, a 2-hexynyl group or a 1-octynyl group. The "heterocyclic group which may have a substituent" means that one of the heterocyclic compounds which may have a substituent becomes a group of a bond. As the heterocyclic group, for example, a thienyl group, an alkylthiophenyl group, a pyrrolyl group, a furyl group, a pyridyl group, an alkylpyridyl group, a fluorenyl group, a pyrimidinyl group, a pyridyl group, a tri-nral group, a pyrrolidyl group. , piperidinyl, quinolyl and isoquinolyl. The substituent of the heterocyclic group as described above may be an alkyl group, and specific examples thereof include the alkyl group having 1 to 20 carbon atoms. The "amino group which may have a substituent" means a group represented by -N (R ') 2 , and each of two R' is independently represented as a substituent. Examples of R' include a hydrocarbon group having 1 to 20 carbon atoms such as an alkyl group or an aryl group, a heterocyclic group which may have a substituent, and a hydrogen atom. An amine group having a substituent, that is, an amine group having at least one substituent other than a hydrogen atom, is preferred. Specific examples of the "amino group which may have a substituent" include, for example, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a η-propylamino group, a di-η-propylamino group, an isopropylamine group, Diisopropylamino, η-butylamino, isobutylamino, sec-butylamino, tert-butylamino, η-pentylamino, η-hexylamino, η-heptylamino, n-octylamine , 2-ethylhexylamino, η-nonylamino ' η-nonylamino, 3,7-dimethyloctylamino, η-dodecylamino, cyclopentylamino, dicyclopentylamine , cyclohexylamine, dicyclohexylamino, bis(trifluoromethyl)amino, anilino, diphenylamine, naphthylamino, pyridinyl, hydrazine, pyrimidinyl, pyridin And triterpenoid. The "thiol group which may have a substituent" means a group represented by -S i ( R ′) 3 -11 - 201245262, and each of 3 R' is independently represented as a substituent. Examples of R· are, for example, a hydrocarbon group having 1 to 20 carbon atoms such as an alkyl group or an aryl group, a heterocyclic group which may have a substituent, and a hydrogen atom. Preferred is a fluorenyl group having a substituent, that is, at least one thiol group having a substituent other than a hydrogen atom. Specific examples of the "thiol group which may have a substituent" include, for example, a trimethylsulfonyl group, a triethylsulfonyl group, a tri-n-propylsulfonyl group, a triisopropylsulfonyl group, and a dimethylisopropyl group. Mercapto, diethyl isopropyl fluorenyl, tert-butyl decyl dimethyl fluorenyl, η-pentyl dimethyl sand, η-hexyl dimethyl sand, η-heptyl dimethyl Sand base, η-octyl dimethyl fluorenyl, 2-ethylhexyl dimethyl fluorenyl, η-fluorenyl dimethyl fluorenyl, η-fluorenyl dimethyl fluorenyl, 3,7-dimethyl Benzyl dimethyl fluorenyl, η-dodecyl dimethyl fluorenyl, phenylalkyl fluorenyl, alkoxyphenylalkyl fluorenyl, polyphenyl phenyl group, naphthyl Base sand, phenyl propyl dimethyl decyl 'triphenyl fluorenyl, tri- fluorenyl dimethyl fluorenyl, tribenzyl fluorenyl, diphenylmethyl fluorenyl, tert-butyl Phenyl fluorenyl and dimethylphenyl fluorenyl hydrazine are used as "mercapto group". For example, an aliphatic fluorenyl group such as an ethyl group, a propyl group, a butyl group or an isobutyl group, a benzamidine group, a naphthyl group, etc. Aromatic sulfhydryl. "Partially constructed as a group having a carbon atom-a nitrogen atom double bond" means an imine compound having a structure represented by at least one of the formula: HN = C< and the formula: -N = CH·, by The group formed by removing the hydrogen atom in the partial structure (hereinafter also referred to as an imine residue) may be exemplified by the above-mentioned "carbon atom-nitrogen atom double bond" without forming a ring. As an "imine compound", for example, a hydrogen atom bonded to a nitrogen atom in an aldimine, a ketimine, and a -12-201245262 aldimine, an alkyl group, an aryl group, an arylalkyl group, an aralkenyl group a compound substituted with a substituent such as an aralkynyl group. The carbon number of the imine residue is usually 2 to 20, preferably 2 to 18, more preferably 2 to 16. As the "imine residue", for example, -CRm = N-R&quot;', and: -N = C(R&quot;') 2 (wherein R" is represented by a hydrogen atom, an alkyl group, or an aryl group. , arylalkyl, aralkenyl or aralkynyl, R'&quot; are each independently shown as alkyl, aryl, arylalkyl, aralkenyl or aralkynyl. However, if there are 2 R'&quot When two R'·· are bonded to each other to form a divalent group, specifically, a carbon number of 2 to 18 such as an ethyl group, a trimethylene group, a tetramethylene group, a pentamethylene group or a hexamethylene group. A group represented by an alkyl group. As a specific example of the "imine residue", for example, the group shown below is used.

Me

The "nonimino group" means that a hydrogen atom bonded to a nitrogen atom contained in the quinone imine becomes a residue of a bonding portion. The carbon number of the quinone imine group is preferably 4 to 20, more preferably 4 to 18, still more preferably 4 to 16. Specific examples of the "indenine group" include the groups shown below. -13- 201245262

As the "alkoxycarbonyl group", a group formed by bonding a carbonyl group to the above group is exemplified. Specifically, for example, methoxycarbonyl, ethoxycarbonyl η-propoxycarbonyl, isopropoxycarbonyl, η-butoxycarbonyl, isobutylcarbonyl, sec-butoxycarbonyl, tert. butoxycarbonyl , η·pentyloxy, η-hexyloxycarbonyl 'cyclohexyloxycarbonyl, η-heptyloxycarbonyl, η-ylcarbonyl, 2-ethylhexyloxycarbonyl, η-decyloxycarbonyl, η- Alkoxy, 3,7-dimethyloctyloxycarbonyl, η-dodecyloxycarbonyl, trioxycarbonyl, pentafluoroethoxycarbonyl, perfluorobutoxycarbonyl, perfluorocarbonyl, all Fluorocyloxycarbonyl, phenoxycarbonyl, naphthyloxycarbonylpyridyloxycarbonyl. The aromatic hydrocarbon group is, for example, a group represented by the formulae (a) to (e). Alkoxy group, oxy γμι 甘 溺 S octyloxycarbonyl fluoromethyl hexyloxy and pyridyl

(e) (wherein R is a substituent and n is an integer of 0 to 4). -14-201245262 The above substituents are exemplified by the same substituents as those exemplified as A' and Ar. The carbon atom contained in the aromatic hydrocarbon group is an aromatic hydrocarbon group substituted with a hetero atom or a carbonyl group, and for example, a divalent group represented by the formulae (f) to (z)

(t) (h)

The substituent is exemplified as the same as those exemplified as the substituents of Ar1 and Ar2. -15-201245262 The monocyclic aromatic hydrocarbon group of 2 or more is a divalent group formed by a single bond, a hetero atom or a carbonyl group, and examples thereof include a divalent group represented by the formula (aa) to (ae).

(wherein 'R is shown as a substituent, and n is an integer of 〇~4). The substituent is exemplified as the same as those exemplified as the substituents of Ar 1 and Ar 2 . Ar1 in the aromatic monomer (A) and Ar2' in the aromatic monomer (B) may be the same or different from each other. Preferred Ar1 and Ar2 are those of the formulae (a), (b), (c), (d), (e), (m) (wherein γ is preferably S), (y) or (aa) The base shown. X1 of the aromatic monomer (A) is independently shown as a group represented by the formula (1), (2), (3), (4), (5) or (6). -16- 201245262

The two X1 in the aromatic monomer (A) may be the same or different from each other, and in terms of the ease of preparing the aromatic monomer (A), it is preferred that two X1 are the same. It is a group represented by the formula (3). As the aromatic monomer (A), for example, 2,2'-(9,9-dihexyl-9H-indole-2,7-diyl)bis(1,3,2-dioxaborolane) )[2,2'-( 9.9- dihexyl-9H-fluorene-2,7-diyl ) bis ( 1,3,2- dioxaborolane ) ], 2,2,- ( 9,9 -dihexyl-9 Η -芴-2,7-diyl) bis(1,3,2-dioxaborane)[2,2'-(9,9-£111^\丫1-911彳111〇"116- 2.7- Diyl)bis(l,3,2-dioxaborinane)], 2,2'-(9,9-:S-based-9H-indole-2,7-diyl) bis (4,4,5,5-tetra Methyl-1,3,2-dioxaborolane, 2,2'-(9,9-dihexyl-911-indole-2,7-diyl) bis(5,5-dimethyl 1,3,2-dioxaborane, 2,2'-(9,9-dioctyl-9H-indole-2.7-diyl)bis(1,3,2-dioxacyclo) Pentaborane, 2,2'-(9,9-dioctyl-9H-indole-2,7-diyl)bis(1,3,2-dioxaborane), 2,2'- (9.9-dioctyl-9H-indole-2,7-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane), 2,2 '-(9,9-Dioctyl-911-芴-2,7-diyl)bis(5,5-dimethyl-1,3,2-dioxaborane), 2,2,- (9,9-bis(dodecyl)-911-芴-2,7-diyl) bis(1,3,2-dioxy) Cyclopentane, 2,2'·(9,9-di(dodecyl)-911-芴-2,7-diyl)bis(1,3,2-dioxaboron-17- 201245262 ring), 2,2,-(9,9-di(dodecyl)·9Η·芴_2,7·diyl) bis (4.4.5.5-tetramethyl-1,3,2-di Oxacycloborane), 2,2'-(9,9-mono(dodecyl)-9H-indole-2,7-diyl)bis(5,5·dimethyl-1,3 , 2·-oxo boron heterocycle), 2,2,-( 3,5-dimethoxy·9,9·dihexyl_911_芴_2,7_diyl) bis (4,4,5, 5-tetramethyl-1,3,2-dioxolane), 2,2'-(9-octyl-9Η-sodium- 3,6-diyl) bis (1,3, 2 - dioxolane), 2,2'-(1,4-phenylene)bis(5,5-dimethyl-1,3,2.dioxaborane), 2, 2,-(2,5·Dimethyl-1,4·phenylene)bis(I,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·Extended phenyl)bis(5,5-dimethyl·1,3,2-dioxaborane), 2,2'-[2,5-bis(hexyloxy)-1, 4-phenylene]bis (5,5-di Base-1,3,2-dioxaborolane, 2,5-bis(1,3,2-dioxaborolan-2-yl)propenyl, 2,5-bis (4, 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene 2,5-bis(1,3,2-dioxaborolan-2 - Thiophene, 2.5-bis(5,5-dimethyl-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, 1,1'-bis(1,3,2-dioxaborolane -2-yl)-4,4'-biphenyl, 1,1'-bis(1,3,2-dioxaborolan-2-yl)-4,4'-biphenyl, 1,1' _Bis(5.5-dimethyl-1,3,2-dioxaborolan-2-yl)-4,4'-biphenyl, and 5,5'-bis (4,4,5,5- Tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2'-dithiophene. Preferably, 2,2'-(9,9-dihexyl-911-indole-2,7-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxo Heterocyclic pentaborane, 2,2'-(9,9-dioctyl-9Η-芴-2,7-diyl)bis(4,4,5,5-tetramethyl-1,3, 2-Dioxa-18- 201245262 cyclopentane), 2,2'- (9,9-di(dodecyl)-911-芴-2,7-diyl) bis (4,4, 5,5-tetramethyl-1,3,2-dioxaborolane, 2,2'-(3,5-dimethoxy-9,9-dihexyl-9H-indole-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, fluorene-bis(4,4,5,5-tetramethyl-1,3,2- Dioxaborolan-2-yl)-4,4'-biphenyl, and 5,5'-bis(4,4,5,5-tetramethyl-1,3,2-dioxa Cyclopentane-2-yl)-2,2'-bidithiophene. In the production method of the present invention, two or more kinds of aromatic monomers (A) may be used in combination. X2 of the aromatic monomer (B) is each independently represented by a chlorine atom, a bromine atom or an iodine atom. The two X2 in the aromatic monomer (B) may be the same or different from each other, and the point of the aromatic polymer (B) is preferably adjusted to be the same X2. Desirable X2 is a bromine atom. As the aromatic monomer (B), for example, 2,7-dibromo-9,9-dihexyl-9H-indole, 2,7-dibromo-9,9-dioctyl-9H-indole, 2, 7-Dibromo-9,9-di(dodecyl)-9H-indole, 2,7-dichloro-9,9-dihexyl-9H-indole, 2,7-dichloro-9,9- Dioctyl-9H-indole, 2,7-dichloro-9,9-di(dodecyl)-9H-indole, 2-bromo-7-chloro-9,9-dihexyl-9H-indole, 2-bromo-7-chloro-9,9-dioctyl-91^-indole, 2-bromo-7-chloro-9,9-di(dodecyl)-9H-indole, 1,4-two Bromobenzene, 1,3-dibromobenzene, 1,4-dibromo-2-ethylbenzene, 1,4-dibromo-2-methoxybenzene, dimethyl 2,5-dibromophthalate, 1,4-Dibromonaphthalene, 3,5-dibromopyridine, 1,1'-di-19- 201245262 bromo-4,4'-biphenyl, 2,5-dibromopyridine, I,4.dibromo · 2,5·dihexyloxybenzene, 1-bromo-4-chlorobenzene, 1-bromo-4-chlorotoluene, 1-bromo-4-chloro-2-propylbenzene, 2,5-dibromo-4 '-Phenoxydiphenyl ketone, 2,5-dibromo-3-hexyl thiophene, 2,5-dibromo-3, 2,5-dibromo-3-octylthiophene-dodecyl thiophene, 2,5·dichloro-3-hexylthiophene, 5,5′-dibromo-2,2′·dithiophene, 5,5′-dibromo-3,3′-dihexyl-2,2′- Dithiophene, bis(4-bromophenyl)-4-(4-tert-butyl Aniline, bis(4-bromophenyl)-4-(1-methylpropyl)aniline, bis(4-bromophenyl)-4-aniline, N,N'-bis(4-bromophenyl) )-N,N'-bis(4-n-butylphenyl)-1,4-phenylenediamine, 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-phenylenediamine, N , N'-bis(4-bromophenyl)-N,N'-bis[4-(1,1-dimethylethyl)-2,6-dimethylphenyl]-1,4·benzene Diamine, 4,7-dibromo-2,1,3-benzothiadiazole, 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, anthracene, 3-benzothiazepine Oxazole, 4,7-bis(5-bromo-3-methyl-2.thienyl)-2,1,3-benzothiadiazole, 3,7-dibromo-10-( 4-11-butyl Phenyl)-1011-morphothione, 3,7-dibromo-1〇-(4-11-butylphenyl)-10H·phenoxypyridazine ring, 3,3'-[ 1,1 '-Biphenyl- 4,4'-diylbis[(4-bromophenyl)imido]]dibenzoic acid diethyl ester, and 4,4'-bis[(4-bromophenyl)anilinoyl 〕 Benzene. Preferred is 2,7-dibromo-9,9-dihexyl-9H-indole, 2,7-dibromo-9,9-dioctyl-9H-indole, 2,7-dibromo-9,9 - bis(dodecyl)-9Η·芴, 1,4-dibromobenzene, 1,3·dibromobenzene, 2,5-dibromo-3-hexylthiophene, and bis(4-bromophenyl) 4-aniline. In the production method of the present invention, two or more kinds of aromatic mono-20-201245262 (B) can be used. The use of the aromatic monomer (B) in the production method of the present invention is usually in the range of 0.8 mol to 1 for the aromatic monomer (A), and preferably in the range of 0.9 mol to K1 mol. &lt;Test&gt; As an examination, for example, an inorganic base and an organic base are mentioned. As the inorganic base, there are an alkali metal hydroxide, an alkaline earth metal hydrogen, an alkali metal carboxylate, an alkaline earth metal carboxylate, an alkali metal carbonate metal carbonate, an alkali metal hydrogencarbonate, an alkaline earth metal hydrogencarbonate phosphate, And an alkaline earth metal phosphate, preferably a ruthenium metal carbonate metal phosphate. Specific examples of the inorganic base include lithium hydroxide, potassium hydroxide hydride, hydrogen peroxide, calcium hydroxide, barium hydroxide, potassium formate, calcium formate, sodium acetate, potassium acetate, sodium carbonate, and potassium carbonate. Calcium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate and phosphoric acid are preferably sodium carbonate, potassium carbonate, carbonic acid planing, sodium phosphate and potassium phosphate. As the organic base, for example, an alkyl ammonium hydroxide, an alkyl carbonic acid ammonium bicarbonate, an alkyl ammonium borate, a 1,5-diindole bicyclo [4.3.0 olefin (DBN), 1,8-diindole bicyclo [5.4] .0] eleven-7-ene (, 1,4-dioxabicyclo[2.2.2] octane (DABCO), dimethylamine (DMAP), pyridine, trialkylamine, and tetraalkylammonium fluoride And ammonium fluoride, preferably tetraalkylammonium hydroxide such as tetramethylammonium hydroxide or tetraethylammonium hydroxide propylammonium hydroxide. Amount, phase 2 mole oxide, alkaline earth, gold salt And alkalized sodium, sodium, methyl, potassium carbonate, ammonium, sulphate-5-DBU) pyridine alkyl, tetra-n--21 - 201245262

The amount of the base to be used is usually, for example, 〇·5 equivalents to 20 equivalents, and is a base for neutralizing hydrogen ions having the same mass as the total of the aromatic monomers (B) c. The range of the ratio of X2 contained in the group monomer (B) is preferably 〇.5 equivalent to 6 when J &lt; related mobile catalyst&gt; In the production method of the present invention, it is used as a base. Use related mobile catalysts. As a related mobile catalyst, ammonium hydride, tetraalkylammonium hydrogen sulfate, and tetraalkylammonium hydroxide octyl hydroxychloride (tricaprylmethylammonium) are Aliquat (registered trademarks such as tetraalkylammonium halides) by Sigma-Aldrich. The amount of the relevant mobile catalyst used is usually 0.001 (the so-called equivalent is used to neutralize the mass of the hydrogen ion equivalent to the total mass of the X2 contained in the aromatic single, relative to the aromatic monomer. The range of the ratio of the mass of the material to be counted in (B) is preferably in the range of 0.01. &lt;Aprotic organic solvent&gt; "Aprotic organic solvent" is a non-radical or carboxyl group in the molecule. An organic solvent having an active hydrogen group and means an organic solvent capable of dissolving (A) and an aromatic monomer (B). Equivalent (the mass of the X2 theoretical substance contained herein, the range of t of the total mass of the substance. In the case of a base, for example, a tetraalkyl halide, preferably, a trichloride) can be obtained in an equivalent amount of 1 to 1 equivalent of the base in the form (B), and the equivalent of X2 is 0.5 to 0.5. Has a hydroxyl group, an amine-decomposed aromatic monomer-22- 20124526 2 Examples of the aprotic organic solvent include an ether solvent such as an acyclic ether solvent or a cyclic ether solvent, an aprotic polar solvent, an aromatic hydrocarbon solvent, and an aliphatic hydrocarbon solvent. Examples of the aprotic polar solvent include, for example, an aprotic polar solvent. N-methylpyrrolidone, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, dimethyl hydrazine, and acetonitrile. As a non-cyclic ether solvent, for example, diethyl Ether, diisopropyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether. Examples of the cyclic ether solvent include 1,4-dioxane and tetrahydrofuran. As an aromatic hydrocarbon solvent, for example For example, benzene, toluene, xylene, and mesitylene. Examples of the aliphatic hydrocarbon solvent include hexane, heptane, and cyclohexane. The viewpoints on the solubility of aromatic monomers (Α) and aromatic monomers (Β) Preferred are toluene, xylene, mesitylene, diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 1,4-dioxane. And tetrahydrofuran. If necessary, two or more kinds of aprotic organic solvents may be mixed, for example, tetrahydrofuran and a mixed solvent of benzene and a mixed solvent of ethylene glycol dimethyl ether and toluene. &lt;Palladium compound&gt; Examples of the palladium compound include a palladium (ruthenium) complex and a palladium (11) complex. 0) a complex compound, for example, dibenzylideneacetone is a complex complexed with valence palladium, that is, a dibenzylideneacetone-palladium(0) complex. Specifically, for example, bis(benzylideneacetone) An example of dipalladium (0), ginseng (di-mercaptoacetone) dipalladium (0) chloroform adduct and bis(dibenzylideneacetone)palladium (〇-23-201245262 as palladium(II) complex] For example, palladium carboxylate (II), trifluoroacetic acid IS (II), palladium carboxylate (II), etc.; palladium chloride (11), palladium (II) bromide, palladium iodide (U), etc. Palladium halide; and propyl ruthenium (π) dimer, bis(2-methylallyl)palladium(11) chloride, dichloro(1,5•cyclooctadiene) A palladium halide complex of palladium, dichlorobis(ethyl bromide) ruthenium (II), dichlorobis(benzonitrile)palladium (U) or the like. Among them, preferred are bis(dibenzylideneacetone)dipalladium, bis(indenylacetone)palladium (iridium), palladium chloride (ruthenium), palladium (II) bromide and palladium(II) acetate. The amount of the pin compound used is usually in the range of 0.0001 mol to 0.8 mol with respect to the aromatic monomer (B) 1 mol. It is preferably in the range of from 〇〇1 mol to 0.2 mol. &lt;phosphine represented by formula (C)&gt; The phosphine represented by formula (C) is represented by formula (C)

Expressed. In the formula (C), Ri, R2, R3, R4 and R5 are each independently represented by a hydrogen atom, a fluoroalkyl group having 1 to 20 carbon atoms or a dialkylamino group having 1 to 20 carbon atoms, and A is represented by a carbon number of 1. ~20 alkyl. Examples of the fluoroalkyl group having 1 to 20 carbon atoms include monofluoromethyl, difluoromethyl-24-201245262, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, and perfluoro. The -η-propyl group and the perfluoroisopropyl group are preferably a fluoroalkyl group having 1 to 4 carbon atoms, more preferably a trifluoromethyl group. The dialkylamino group having 1 to 20 carbon atoms is an amine group substituted with 2 alkyl groups having 1 to 20 carbon atoms, and specifically, for example, a dimethylamino group, a diethylamino group, a di-η-propylamino group, Diisopropylamino, di-η-butylamino, di-sec-butylamino and di-tert-butylamino, preferably a dialkylamino group having 1 to 8 carbon atoms, more preferably a carbon number of 1 More preferably, it is a 1-4 aminoalkyl group. The alkyl group having 1 to 20 carbon atoms represented by A may be a linear chain, a branched chain or a cyclic chain. Specific examples are methyl, ethyl, η-propyl, isopropyl, η-butyl, isobutyl ' sec-butyl, tert-butyl, η-pentyl, 2,2-dimethylpropyl Base, cyclopentyl, η-hexyl, cyclohexyl, η-heptyl, 2-methylpentyl, η-octyl, 2-ethylhexyl, η-fluorenyl, η-fluorenyl, 1-adamantane Base, η-undecyl group, η-dodecyl group, η·tridecyl group, η-tetradecyl group, η-fiute building, η-hexadecanyl group, η-seventeenth base , η-eighteen yard base, η-nine yard base and η-twist yard base, preferably a court base having a carbon number of 1 to 8, more preferably tert-butyl, cyclopentyl and cyclohexyl. As the phosphine represented by the formula (C), for example, a phosphine represented by the formula (C) wherein A is an alkyl group having 1 to 8 carbon atoms; A is a phosphine represented by the formula (C) of tert-butyl group; a phosphine represented by the formula (C) of a cyclopentyl group; a phosphine represented by the formula (C) wherein A is a cyclohexyl group; and a formula wherein the hydrogen atom 'r3 is a dimercaptoamine group having a carbon number of 1 to 4 (C) The phosphine shown; -25- 201245262 R2, R3, R4 and R5 are a hydrogen atom, R1 is a phosphine of the formula (C) having a dialkylamino group having 1 to 4 carbon atoms; A is a carbon number of 1~ 8 is an alkyl group, R1, R2, R4 and R5 are a hydrogen atom, and R3 is a phosphine represented by the formula (C) having a dialkylamino group having 1 to 4 carbon atoms; A is tert-butyl, R1, R2 R4 and R5 are a phosphine represented by the formula (C) wherein a hydrogen atom 'R3 is a dialkylamino group having 1 to 4 carbon atoms; A is a cyclopentyl group, R1, ! ^2! ^4 and R5 are a hydrogen atom, R3 is a phosphine represented by the formula (C) having a dialkylamino group having 1 to 4 carbon atoms; A is a cyclohexyl group, R1, R2, R4 and R5 are a hydrogen atom, and R3 is a carbon. a phosphine represented by the formula (C) having 1 to 4 dialkylamino groups; A is an alkyl group having 1 to 8 carbon atoms; R 2 , R 3 , R 4 and R 5 are a hydrogen atom, and R 1 is a carbon number of 1 to 4; a phosphine represented by the formula (C) of a dialkylamino group; A is a tert-butyl group, and R2, R3, R4 and R5 are a hydrogen atom 'R1 is a dialkylamino group having a carbon number of 1 to 4 (C) a phosphine; A is a cyclopentyl group, R2, R3, R4 and R5 are a hydrogen atom, and R1 is a phosphine of the formula (C) having a dialkylamino group having 1 to 4 carbon atoms; A is a cyclohexyl group. , R2, R3, R4 and R5 are a hydrogen atom, R1 is a phosphine represented by the formula (C) having a dialkylamino group having 1 to 4 carbon atoms; R' 'R2 'R4 R R5 is a hydrogen atom, and R3 is a carbon a phosphine represented by the formula (C) having a fluoroalkyl group of 1 to 4; R2, R3, R4 and R5 are a phosphine represented by the formula (C) wherein the hydrogen atom 'R1 is a fluoroalkyl group having 1 to 4 carbon atoms; A is a C 1-8 alkyl group, and R1, R2, R4 and R5 are a phosphine represented by the formula (C) wherein a hydrogen atom 'R3 is a fluoroalkyl group having 1 to 4 carbon atoms; -26- 201245262 A is tert -butyl, R丨, R2, R4 and R5 are hydrogen R3 is a phosphine represented by the formula (C) having a fluoroalkyl group having 1 to 4 carbon atoms; A is a cyclopentyl group, and R1, R2, R4 and R5 are a hydrogen atom 'R3 is a fluorocarbon having a carbon number of 1 to 4 a phosphine represented by the formula (C); A is a cyclohexyl group, and R1, R2, R4 and R5 are a phosphine of the formula (C) wherein a hydrogen atom 'R3 is a fluoroalkyl group having 1 to 4 carbon atoms; a phosphine having a carbon number of 1 to 8 and R 2 , R 3 , R 4 and R 5 being a hydrogen atom, and R 1 being a fluoroalkyl group having 1 to 4 carbon atoms; (a) is a tert-butyl group; R3, R4 and R5 are a hydrogen atom, R1 is a phosphine represented by the formula (C) having a fluoroalkyl group having 1 to 4 carbon atoms; A is a cyclopentyl group, R2, R3, R4 and R5 are a hydrogen atom, and R1 is a carbon atom. a phosphine represented by the formula (C) of 1 to 4 fluoroalkyl groups; and A is a cyclohexyl group, and R 2 , R 3 , R 4 and R 5 are a hydrogen atom ' R 1 is a fluoroalkyl group having 1 to 4 carbon atoms (C) ) the phosphine shown. Specific examples of the phosphine represented by the formula (C) include, for example, dicyclohexylphenylphosphine, dicyclohexyl[4-(N,N-dimethylamino)phenyl]phosphine, and dicyclohexyl [2-( N,N-dimethylamino)phenyl]phosphine, dicyclohexyl (4-trifluoromethylphenyl)phosphine, dicyclohexyl (2-trifluoromethylphenyl)phosphine, di-tert-butyl Phenylphosphine, [4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine, [2-(N,N-dimethylamino)phenyl]di-tert-butyl Phosphine, tert-butyl (4·trifluoromethylphenyl)phosphine, bis(tert-butyl)(2-trifluoromethylphenyl)phosphine, dicyclopentylphenylphosphine, bicyclo Pentyl [4-( &gt;1, dimethylamino)phenyl]phosphine, dicyclopentyl [2-(叱^1-dimethylamino)phenyl]phosphine, dicyclopentyl (4- Trifluoromethylphenylphosphine and dicyclopentyl-27- 201245262 (2-trifluoromethylphenyl)phosphine. &lt;phosphine represented by formula (D)&gt; The phosphine represented by formula (D) is represented by formula (D):

Expressed. In the formula (D), R6, R7, R8, R9 and Rl() are each independently represented by a hydrogen atom, a fluoroindenyl group having 1 to 20 carbon atoms or a divalent amine group having 1 to 20 carbon atoms. However, R6 to R1() are not the case where all of the numbers are hydrogen atoms. As the fluoroalkyl group having 1 to 20 carbon atoms, for example, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, perfluoro·η-propyl The group and the perfluoroisopropyl group are preferably a fluoroalkyl group having 1 to 4 carbon atoms, more preferably a trifluoromethyl group. The dialkylamino group having 1 to 20 carbon atoms is an amine group substituted with 2 alkyl groups having 1 to 20 carbon atoms, and specific examples thereof include a dimethylamino group, a diethylamino group, a di-n-propylamino group, Diisopropylamino, di-η-butylamino, di-sec-butylamino and di-tert-butylamino, preferably a dialkylamino group having 1 to 8 carbon atoms, more preferably a carbon number of 1 More preferably, it is a 1-4 aminoalkyl group. As the phosphine represented by the formula (D), for example, R6, R7, R9 and RIQ are a hydrogen atom, and R8 is a phosphine represented by the formula (D) having a dialkylamino group having 1 to 4 carbon atoms; R7, R8, R9 and R1Q are a hydrogen atom, R6 is a dialkylamine having a carbon number of 1 to 4, and a scale of the formula (D) of the formula (D); R6, R7' R9 and R1G are a hydrogen atom, and R8 is a carbon number. a phosphine represented by the formula (D) of fluoroalkyl group of 1-4; and R7' R8, R9 and R1() are represented by the formula (D) wherein the hydrogen atom 'R6 is a fluoroalkyl group having a carbon number of 丨 to 4 phosphine. Specific examples of the phosphine represented by the formula (D) include, for example, dicyclopentylphenylphosphine 'dicyclopentyl[4-(N,N-dimethylamino)phenyl]phosphine, dicyclopentyl [ 2-(N,N-dimethylamino)phenyl]phosphine, dicyclopentyl (4-trifluoromethylphenyl)phosphine, and dicyclopentyl (2-trifluoromethylphenyl)phosphine. The phosphine represented by the formula (C) is preferably a phosphine represented by the formula (D). The amount of the phosphine represented by the formula (C) in the production method of the present invention is usually in the range of 0.1 mole to 10 moles, preferably 0.5 mole to 5 moles, per mole of the palladium compound. The adjacent formula (C) can be synthesized according to a known method such as J 〇 u r n a 1 〇 f Μ ο 1 e c u 1 a r Catalysis A: Chemical 2003, 200, 81-94. Further, it is intended to use a commercially available phosphine represented by the formula (C). &lt;Transition Metal Complex&gt; The transition metal complex can be prepared by contacting a phosphine represented by the formula (C) or a phosphine represented by the formula (D) with a Group 10 transition metal compound. The first steroidal transition metal compound is, for example, a nickel compound, a palladium compound or a lead compound, and is preferably a palladium compound. The palladium compound may, for example, be a palladium compound described in the &lt;Palladium compound &gt; column described above. A transition metal complex obtained by contacting a phosphine represented by the formula (C) or a phosphine represented by the formula (D) with a palladium compound, for example, according to the fifth edition of the -29-201245262 chemistry lecture (Japaneseization) The editor of the Society, issued by Nine Good (shares), 21 organic transition metal complexes, supramolecular complexes P308-327 (9.2 organic palladium complex), etc., are prepared by a known method. &lt;Polymerization step&gt; The polymerization step is a step of mixing an aromatic monomer (A) and an aromatic monomer (B) in the presence of a base, a palladium compound, a phosphine represented by the formula (C), and an aprotic organic solvent. In the step, the order of mixing is not limited, but examples thereof include (i) a palladium compound, a phosphine represented by the formula (C), a base, an aromatic monomer (A), an aromatic monomer (B), and an aprotic organic compound. a step of mixing the solvent together to carry out the polymerization; (ii) mixing the base, the aromatic monomer (A), the aromatic monomer (B) and the aprotic organic solvent, and then adding the palladium compound to the formula (C) The phosphine or the step of polymerizing the palladium compound and the phosphine represented by the formula (c) into a previously prepared complex and an aprotic organic solvent. The polymerization temperature in the polymerization step is usually in the range of 〇 ° C to 180 t, preferably in the range of 30 ° C to 1 0 0 ° C. The polymerization time as the polymerization step is usually in the range of from 1 hour to 96 hours, preferably in the range of from 3 hours to 4 hours. For example, 'the reaction mixture containing an aromatic polymer obtained by the polymerization step can be precipitated by adding a poor solvent, etc., and the aromatic polymer can be precipitated by a usual separation means such as filtration. The family polymer is extracted. In order to remove impurities such as metals, the anti--30-201245262 mixture is washed with an acidic solution such as hydrochloric acid, and the desired aromatic polymer can be extracted by the above method. The obtained aromatic polymer ' can be subjected to purification treatment by classification of a chromatogram or the like. [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited. The molecular weight of the obtained aromatic polymer was evaluated by gel permeation chromatography (hereinafter also referred to as GPC), and the weight average molecular weight (Mw) in terms of styrene was calculated from the analysis results.尙, GPC analysis conditions are as follows. &lt;GPC analysis conditions&gt; • GPC measurement device: CTO-20A (Column Oven, manufactured by Shimadzu Corporation), SPD-20A (detector manufactured by Shimadzu Corporation) • Column: PLgel 1 Ομιη MIXED- B 3 00 x 7.5mm (manufactured by POLYMER LABORATORIES Co., Ltd.) • Column temperature: 40 ° C • Mobile phase: tetrahydrofuran • Flow rate: 2 mL/min • Detection: UV detection (wavelength: 228 nm) -31 - 201245262 Example 1 A borate body (6.0 mmol) formed of 9,9-di-n-octyl acid and hydrazine at room temperature under a nitrogen atmosphere, bis(4[4-(methylpropyl)benzene) a ruthenium (6.0mnl〇i), a 20-fold aqueous solution of tetraethylammonium (20 m 1 ) and toluene (1 1 〇m 1 ) in a glass reaction vessel of a 7-cooling device. While raising the temperature (bath temperature of 100 ° C), after heating, di-tert-butyl(4.dimethylaminophenyl)phosphine)dichloropalladium (mol) and toluene (12 ml). The resulting mixture was polymerized at a bath temperature of 1 〇 C ° C for 4 hours. After the polymerization, the molecular weight of the aromatic polymer was confirmed by the GPC analysis to confirm that the molecular weight (Mw) was 6.4 x 105. Example 2 The same as Example 1, except that bis(di-tert-butylphenylphosphine)dichloropalladium bis(di-tert-butyl(4-dimethylaminophenyl)phosphine) was used. Implement the polymerization. The molecular weight of the obtained compound was determined by the above GPC measurement to confirm that the molecule fi (Mw) was 5·2χ105. Example 3 In addition to the use of bis(di-tert-butyl(4-trifluoromethylphenyldichloropalladium(II)) in place of bis(di-tert-butyl(4-dimethylphosphine)dichloropalladium(II) In the same manner as in Example 1, the amount of hydrazine-2,7-diboron-bromophenyl) i was % oxyhydrogen. The bis(II) was stirred while being equipped with r (3 U 丨 stirring, one obtained The measurement was carried out according to (II) to take II palladium (II)] aromatic polycondensation, the result of the base) phosphine) phenyl) polymerization. The molecular weight of the aromatic polymer obtained in -32-201245262, as determined by the GPC test, was confirmed to have a molecular weight (M w ) of 4.9 X 1 05. Example 4 Except that bis(-cyclohexylphenylphosphine) dichloropin (ruthenium) was used in place of bis(1-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium. 1 Polymerization was carried out in the same manner. The molecular weight of the obtained aromatic polymer was confirmed by the above GPC measurement to confirm that the molecular weight (Mw) was 2.4 x 105. Example 5 In addition to the use of bis(dicyclohexyl(4-(N,N-dimethylamino)phenyl)phosphine)-palladium (II) to replace bis(di-tert-butyl(4-dimethylamino) Polymerization was carried out in the same manner as in Example 1 except for phenylphosphinium)dichloropalladium (11). The molecular weight of the obtained aromatic polymer was confirmed by the above GPC measurement, and the molecular weight (Mw) was confirmed to be 2.5 x 105. Example 6 In addition to the use of bis(dicyclopentylphenylphosphine)dichloropalladium (11) in place of bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium (11) Polymerization was carried out in the same manner as in Example 1. The molecular weight of the obtained aromatic polymer was confirmed by the above GPC measurement to confirm that the molecular weight (Mw) was 3.7 χ 105. -33- 201245262 Example 7 In addition to the use of bis(dicyclopentyl (4-trifluoromethylphenyl)phosphine) palladium (Π) to replace bis(di-tert-butyl (4-dimethylaminophenyl) The polymerization was carried out in the same manner as in Example 1 except for the palladium (II) chloride. The molecular weight of the obtained aromatic polymer was confirmed by the above GPC, and the molecular weight (Mw) was 3.2×10 5 . Example 8 A boronic ester (6.0 mmol) and 9,9-di-n-octyl formed from 9,9-di-n-octylindole-2,7-acid and hydrazine at room temperature under a nitrogen atmosphere. Dibromofluorene (5.9 mmol), 20% by weight of tetraethylammonium hydroxide in water (20 ml) and toluene (1 l〇ml) were added to a glass reaction vessel equipped with a cooling device. The obtained mixture was stirred while stirring (bath temperature 1 〇〇 ° C). After heating, bis(dicyclohexyl(N,N-dimethylamino)phenyl)-o-dichloropalladium (II) was added. (3// mol) Benzene (1 2 ml). The obtained mixture was stirred at a temperature of 100 ° C for 4 hours while stirring. After the polymerization, the molecular weight of the obtained aromatic compound was confirmed to be 3.5 x 105 by the GPC measurement. Example 9 Under a nitrogen atmosphere, bromophenyl hydrazine. 77 g and tetrahydrofuran 20 ml were placed in a reaction vessel equipped with a dropping funnel. After the obtained solution was cooled at 78 ° C, 3.0 ml of η-butyllithium (1.62 M / hexane solution) was added dropwise. — λ=( ~- phosphine) The obtained diboron-2,7- liquid (the temperature of the glass is increased by 4- (the temperature is polymerized with the temperature of the nail, and the mixture obtained in the mixture is added to the mixture at -34-201245262 at the same temperature 2 After that, a solution obtained by dissolving 1.00 g of chlorodicyclopentylphosphine in 13 ml of tetrahydrofuran was added dropwise to the obtained mixture at -78 t. The resulting mixture was stirred at room temperature. 5 hours. By diluting the obtained reaction mixture, dicyclopentylphenylphosphine as a concentrate (crude product) 1.55 g (viscous liquid) was obtained. Example 1 0 Under a nitrogen atmosphere 1.55 g of dicyclopentylphenylphosphine synthesized in Example 9, dichlorobis(acetonitrile)palladium (π) 〇.5 〇g, and 20 ml of ethanol were added to the reaction vessel. The obtained mixture was allowed to stand at room temperature. After stirring for 16 hours, the precipitated solid was extracted by filtration and washed three times with 12 ml of ethanol. The obtained solid was dried under reduced pressure at 50 ° C for 3 hours. Bis(dicyclopentylphenylphosphine)dichloropalladium(II) as a yellow solid, the desired transition metal complex 1.12g» *H-NMR ( δ : ppm, CDCl3 solvent, TMS basis) 7.7 (m, 2H), 7.4 (m, 3H), 2.8-2.9 (quin, 2H), 2.0-2.2 (m, 2H), L-5-2.0 (m, 1 4H) 31Ρ-ΝΜΙΙ (δ: ppm, CDC13 solvent) 29.0 Example 1 1 In addition to the use of 4-bromobenzotrifluoride 1.10 g instead of bromobenzene 0.77 g, and Example 9 The same operation was carried out to obtain 1.78 g of dicyclopentyl (4-trifluoromethylphenyl)phosphine as a concentrate (crude product) (viscous liquid - 35 - 201245262). Example 1 2 Nitrogen 1.78 g of difluoromethylphenylphosphine synthesized in Example 11 and 35 ml of dichlorobis(acetonitrile)palladium i ethanol were placed in a reaction vessel under an atmosphere. The obtained mixture was stirred for 14 hours. It was extracted by filtration and washed with ethanol 1 2 m 1 for 3 times. The obtained solid f was dried under reduced pressure for 3 hours to obtain a bis(dicyclopentyl) as a pale yellow solid transition metal complex. (4-Trifluoromethyldichloropalladium(II) 1.34g » iH-NMRejpm.CDCh Solvent, TMS Benchmark) 7.8 (m, 2H), 7.6 (m, 2H), 2.8-2.9 (quin, 2H), 2.1 -2. 2.0 (m, 4H), l .5-2_8 (m, l〇H) 31P-NMR (5: ppm, CDCl3 solvent 3〇. Industrial Applicability The polymer compound can be produced by the production method of the present invention. Cyclopentyl (4-tri(II) 0.50g and a mixture of solids at room temperature, and hidden at 50 ° C Alkyl phosphine) Aromatic poly-36-

Claims (1)

201245262 VII. Patent Application Range 1. A method for producing an aromatic polymer, which comprises an aromatic monomer represented by the following formula (A) and an aromatic monomer represented by the following formula (B) a step of mixing in the presence of a base, a palladium compound, a phosphine represented by the following formula (C), and an aprotic organic solvent, wherein the formula (A): X1 - Ar1--X1 (A) wherein X1 is each Independently shown as the base of (5) or (6), 1), (2), (3), (4) (4) (5) Ar1 is represented by a divalent aromatic hydrocarbon group having 6 to 36 carbon atoms, and a carbon atom contained in the aromatic hydrocarbon group may be substituted with a hetero atom or a carbonyl group, and a hydrogen atom contained in the aromatic hydrocarbon group may be through a fluorine atom or an alkane. Alkyl group, alkoxy group, alkylthio group, aryl 'aryloxy group, arylthio group, arylalkylthio group, aralkenyl group, arylalkynyl group, heterocyclic group which may have a substituent, an amine group which may have a substituent , a thiol group which may have a substituent, a fluorenyl group, a moiety which is a group having a carbon atom-nitrogen double bond, a quinone imine group, an alkoxycarbonyl group, a carboxyl group, a cyano group or a nitro group) -37- 201245262 Formula (B): X2—Ar2—X2 (B) (wherein, X2 is independently shown as a chlorine atom, a bromine atom or an iodine atom, and Ar2 is represented as a divalent aromatic hydrocarbon group having a carbon number of 6 to 36, and the aromatic The carbon atom contained in the hydrocarbon group may be substituted by 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 or an aromatic group. Thio group, aralkylthio group, aralkenyl group, aralkynyl group, heterocyclic group which may have a substituent, an amine group which may have a substituent a mercapto group which may have a substituent, a mercapto group, a moiety which is a group having a carbon atom-nitrogen double bond, a quinone imine group, an alkoxycarbonyl group, a carboxyl group, a cyano group or a nitro group, and a formula (C) : (C) (wherein, 1, 112, 3, 114 and R5 are each independently represented by a hydrogen atom, a fluoroalkyl group having 1 to 20 carbon atoms or a dialkylamino group having 1 to 20 carbon atoms, a being shown as Alkyl group having a carbon number of 1 to 20). 2. 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. 3. The production method according to claim 1 or 2, wherein the palladium compound is a palladium (ruthenium) complex or a palladium (II) complex. 4—a phosphine represented by the following formula (D), -38 - 201245262 (D) (wherein R6, R7, R8, R9 and R10 are 1 to 20 fluoroalkyl groups or carbon number 1 to 20 R 1 ° is not the case where all are hydrogen atoms) 5. A transition metal complex, 3 The phosphine of Group 4 and the transition metallization of Group 10 are independently shown as a hydrogen atom or a carbon. Dialkylamine group, but R6~ is obtained by contacting the patent application. -39- 201245262 IV. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the symbol of the representative figure is simple: No. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention. :no