JP2012214704A - Method for producing aromatic polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an aromatic polymer with molecular weight higher than that obtained by a conventional production method.SOLUTION: The method for producing the aromatic polymer includes a step to mix an aromatic monomer represented by formula (A): X-Ar-X(A) (in formula, Xis one of formulas (1)-(6), and Aris a 6-36C divalent aromatic hydrocarbon group) and an aromatic monomer represented by formula (B): X-Ar-X(B) (Xis a chlorine atom etc., and Aris a 6-36C divalent aromatic hydrocarbon group) in the presence of a base, a palladium compound, a monoalkyl diphenyl phosphine optionally having a substituent on the phenyl group, and an aprotic organic solvent.

Description

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

Aromatic polymers having π-conjugated aromatic rings are useful, for example, for organic electronic materials. As a method for producing an aromatic polymer, a method for producing an aromatic monomer by a Suzuki coupling reaction is known.
Specifically, for example, from 9,9-di-n-octylfluorene-2,7-diboronic acid and pinacol in the presence of palladium acetate, tris (2-methoxyphenyl) phosphine, tetraethylammonium hydroxide aqueous solution and toluene. And the bis (4-bromophenyl) [4- (methylpropyl) phenyl] amine as an aromatic monomer and polymerizing the corresponding aromatic polymer with a molecular weight (Mw) 3 A method of manufacturing at 0.0 × 10 ⁵ is described in Patent Document 1.

JP 2007-126652 A (Synthesis Example 4)

  In the conventional production method, the molecular weight of the obtained aromatic polymer is not always satisfactory.

で表わされる基を表わし、Ａｒ^１は、炭素数６〜３６の２価の芳香族炭化水素基を表わす。当該芳香族炭化水素基に含まれる炭素原子は、ヘテロ原子又はカルボニル基で置換されていてもよく、当該芳香族炭化水素基に含まれる水素原子は、フッ素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、置換基を有してもよい複素環基、置換基を有してもよいアミノ基、置換基を有してもよいシリル基、アシル基、炭素原子−窒素原子二重結合を部分構造として有する置換基、酸イミド基、アルコキシカルボニル基、カルボキシル基、ニトリル基又はニトロ基で置換されていてもよい。）
で表わされる芳香族モノマーと、
式（Ｂ）
Ｘ^２−Ａｒ^２−Ｘ^２ （Ｂ）
（式中、Ｘ^２は、塩素原子、臭素原子又はヨウ素原子を表わし、Ａｒ^２は、炭素数６〜３６の２価の芳香族炭化水素基を表わす。当該芳香族炭化水素基に含まれる炭素原子は、ヘテロ原子又はカルボニル基で置換されていてもよく、当該芳香族炭化水素基に含まれる水素原子は、フッ素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、置換基を有してもよい複素環基、置換基を有してもよいアミノ基、置換基を有してもよいシリル基、アシル基、炭素原子−窒素原子二重結合を部分構造として有する置換基、酸イミド基、アルコキシカルボニル基、カルボキシル基、ニトリル基又はニトロ基で置換されていてもよい。）
で表わされる芳香族モノマーとを、
塩基、パラジウム化合物、式（Ｃ）

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立に、水素原子、フッ素原子、炭素数１〜２０のフルオロアルキル基、炭素数１〜２０のアルコキシカルボニル基、炭素数２〜２０のアシル基、シアノ基及びニトロ基、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基又は炭素数１〜２０のジアルキルアミノ基を表わし、Ａは、炭素数１〜２０のアルキル基を表す。）
で表されるホスフィン及び非プロトン性有機溶媒の存在下に混合する工程を含むことを特徴とする芳香族ポリマーの製造方法（以下、本発明製造方法という）；
２．非プロトン性有機溶媒が、エーテル溶媒、芳香族炭化水素溶媒及び脂肪族炭化水素溶媒からなる群から選ばれる少なくとも１種の非プロトン性有機溶媒であることを特徴とする前項１記載の芳香族ポリマーの製造方法；
３．パラジウム化合物が、パラジウム（０）錯体またはパラジウム（II）錯体であることを特徴とする前項１又は２記載の芳香族ポリマーの製造方法；
４．式（Ｄ）

（式中、Ｒ^６は、炭素数１〜２０のアルコキシ基を表し、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、それぞれ独立に、水素原子、フッ素原子、炭素数１〜２０のフルオロアルキル基、炭素数１〜２０のアルコキシカルボニル基、炭素数２〜２０のアシル基、シアノ基、ニトロ基、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基又は炭素数１〜２０のジアルキルアミノ基を表わす。）
で表されるホスフィン；
５．式（Ｅ）

（式中、Ｒ^１１は炭素数１〜２０のアルコキシ基を表し、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５は、それぞれ独立に、水素原子、フッ素原子、炭素数１〜２０のフルオロアルキル基、炭素数１〜２０のアルコキシカルボニル基、炭素数２〜２０のアシル基、シアノ基、ニトロ基、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基又は炭素数１〜２０のジアルキルアミノ基を表わす。但し、Ｒ^１２〜Ｒ^１５がすべて水素原子になることはない。）
で表されるホスフィン；
６．前項４記載のホスフィンと第１０族遷移金属化合物とを接触させて得られる遷移金属錯体；
７．前項５記載のホスフィンと第１０族遷移金属化合物とを接触させて得られる遷移金属錯体；
等を提供するものである。 Under such circumstances, the present inventors diligently studied a method for producing a high molecular weight aromatic polymer by polymerization by the Suzuki coupling reaction, and as a result, the present invention has been achieved as follows.
That is, the present invention
1. Formula (A)
^{X 1 -Ar 1 -X 1 (A} )
(In the formula, X ¹ represents the formulas (1) to (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 substituted 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. , Aryl group, aryloxy group, arylthio group, arylalkylthio group, arylalkenyl group, arylalkynyl group, heterocyclic group which may have a substituent, amino group which may have a substituent, It may be substituted with a silyl group, an acyl group, a substituent having a carbon atom-nitrogen atom double bond as a partial structure, an acid imide group, an alkoxycarbonyl group, a carboxyl group, a nitrile group or a nitro group. )
An aromatic monomer represented by:
Formula (B)
^{X 2 -Ar 2 -X 2 (B} )
(In the formula, X ² 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. Carbon contained in the aromatic hydrocarbon group The atom may be substituted 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. , 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, Substituted with a substituent having a carbon atom-nitrogen double bond as a partial structure, an acid imide group, an alkoxycarbonyl group, a carboxyl group, a nitrile group or a nitro group Good.)
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 C 1-20 fluoroalkyl group, a C 1-20 alkoxycarbonyl group, C2-C20 acyl group, cyano group and nitro group, C1-C20 alkyl group, C1-C20 alkoxy group, C6-C20 aryl group, or C1-C20 dialkylamino Represents a group, and A represents an alkyl group having 1 to 20 carbon atoms.)
A method for producing an aromatic polymer comprising the step of mixing in the presence of a phosphine represented by formula (1) and an aprotic organic solvent (hereinafter referred to as the production method of the present invention);
2. 2. The aromatic polymer according to item 1, wherein the aprotic organic solvent is at least one aprotic organic solvent selected from the group consisting of ether solvents, aromatic hydrocarbon solvents, and aliphatic hydrocarbon solvents. Manufacturing method of
3. The method for producing an aromatic polymer according to item 1 or 2, wherein the palladium compound is a palladium (0) complex or a palladium (II) complex;
4). Formula (D)

(In the formula, 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 having 1 to 20 carbon atoms. Group, C1-C20 alkoxycarbonyl group, C2-C20 acyl group, cyano group, nitro group, C1-C20 alkyl group, C1-C20 alkoxy group, C6-C20 An aryl group or a C 1-20 dialkylamino group.)
A phosphine represented by
5. Formula (E)

(In the formula, 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. , C1-C20 alkoxycarbonyl group, C2-C20 acyl group, cyano group, nitro group, C1-C20 alkyl group, C1-C20 alkoxy group, C6-C20 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 contacting the phosphine according to item 4 with a Group 10 transition metal compound;
7). A transition metal complex obtained by contacting the phosphine according to the preceding item 5 with a Group 10 transition metal compound;
Etc. are provided.

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

<Aromatic monomer>
The aromatic monomer used in the production method of the present invention has the formula (A)
^{X 1 -Ar 1 -X 1 (A} )
An aromatic monomer represented by the formula (hereinafter sometimes referred to as aromatic monomer (A)), and a formula (B)
^{X 2 -Ar 2 -X 2 (B} )
It is an aromatic monomer represented by (Hereinafter, it may be described as an aromatic monomer (B).).

Ar ¹ and Ar ² each independently represent a divalent aromatic hydrocarbon group having 6 to 36 carbon atoms. Examples of the aromatic hydrocarbon group include a phenylene group, for example, a condensed aromatic hydrocarbon group such as a naphthalene group, an anthracene group, and a fluorene group. Further, as a different example, the aromatic hydrocarbon group forming the main chain of the resulting aromatic polymer, such as an aromatic hydrocarbon group in which a phenylene group is a single bond such as a biphenylene group, is a single bond with each other, Examples include those linked by a hetero atom 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, for example.

  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 that may have a substituent. A ring group, an amino group that may have a substituent, a silyl group that may have a substituent, an acyl group, a substituent having a carbon atom-nitrogen atom double bond as a partial structure, and a substituent There may be mentioned a heterocyclic group, an acid imide group, an alkoxycarbonyl group, a carboxyl group, a nitrile group or a nitro group. In addition, the hydrogen atom contained in the substituent further includes 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, and 2 to 20 carbon atoms. It may be substituted with an acyl group or a nitrile group.

  Examples of the “alkyl group” include an alkyl group having 1 to 20 carbon atoms. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-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- A dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, etc. can be mentioned.

  Examples of the “alkoxy group” include an alkoxy group having 1 to 20 carbon atoms. Specifically, for example, 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 Group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy, n-icosyloxy group and the like. .

  Examples of the “alkylthio group” include an alkylthio group having 1 to 20 carbon atoms. Specifically, for example, methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, s-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group Group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, dodecylthio group, trifluoromethylthio group and the like.

  As an aryl group, a C6-C20 aryl group etc. can be mentioned, for example. Specific examples include phenyl group, 4-methylphenyl group, 2-methylphenyl group, 1-naphthyl group, 2-naphthyl group, 3-phenanthryl group, 2-anthryl group and the like.

  As an aryloxy group, the group etc. which the oxygen atom couple | bonded with the said C6-C20 aryl group can be mentioned, for example. Specific examples include a phenoxy group, a naphthyloxy group, a phenanthryloxy group, and an anthryloxy group.

  As an arylthio group, the group etc. which the sulfur atom couple | bonded with the said C6-C20 aryl group can be mentioned, for example. Specific examples include a phenylthio group and a naphthylthio group.

  As an arylalkylthio group, the group etc. which the sulfur atom couple | bonded with the said C1-C20 alkyl group substituted by the said C6-C20 aryl group can be mentioned, for example. Specific examples include a phenylmethylthio group and a naphthylmethylthio group.

Examples of the arylalkenyl group include a phenylalkenyl group and a naphthylalkenyl group.
Examples of the alkenyl group include a 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 a 1-octenyl group.

  Examples of the arylalkynyl group include a phenylalkynyl group and a 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 thereof include a 1-octynyl group.

  The “heterocyclic group which may have a substituent” means a group in which a hydrogen atom in the heterocyclic compound is a bond. Here, as the “heterocyclic group”, for example, 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, isoquinolyl group and the like. Examples of the “substituent” possessed by the heterocyclic group include an alkyl group.

“Amino group optionally having substituent (s)” means a group represented by —N (R ′) ₂ . Here, as “R ′”, for example, each independently a hydrogen atom, 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, etc. Can be mentioned. Preferable examples include an amino group having a substituent (that is, at least one R ′ is a substituent other than a hydrogen atom).

  Specific examples of the “amino group optionally having substituent (s)” include, for example, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropyl Amino group, butylamino group, isobutylamino group, s-butylamino group, t-butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group 3,7-dimethyloctylamino group, dodecylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, naphthylamino group, pyridyl Amino group, pyridazinylamino group, pyrimidylamino group, pyrazinylamino group, and a triazinylamino group.

“The silyl group which may have a substituent” means a group represented by —Si (R ′) ₃ . Here, as “R ′”, for example, each independently a hydrogen atom, 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, etc. Can be mentioned. Preferable examples include a silyl group having a substituent (that is, at least one R ′ is a substituent other than a hydrogen atom).
Specific examples of the “silyl group which may have a substituent” include, for example, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tri-isopropylsilyl group, a dimethyl-isopropylsilyl group, and a diethyl-isopropylsilyl group. T-butylsilyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7 -Dimethyloctyl-dimethylsilyl group, dodecyldimethylsilyl group, phenylalkylsilyl group, alkoxyphenylalkylsilyl group, alkylphenylalkylsilyl group, naphthylalkylsilyl group, phenyl-allyldimethylsilyl group, Triphenylsilyl group, tri -p- Kishirirushiriru group, tribenzylsilyl group diphenylmethyl silyl group, t- butyl diphenyl silyl group and a 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 substituent having a carbon atom-nitrogen atom double bond as a partial structure” is derived from an imine compound having a partial structure represented by at least one of the formula: H—N═C <and the formula: —N═CH—. Means a group in which a hydrogen atom in the partial structure is a bond (hereinafter sometimes referred to as an imine residue). For example, a ring is formed based on the above-mentioned “carbon atom-nitrogen atom double bond”. The thing which is not formed can be mentioned. Here, as the “imine compound”, for example, a compound in which a hydrogen atom bonded to a nitrogen atom in aldimine, ketimine, and aldimine is substituted with an alkyl group, aryl group, arylalkyl group, arylalkenyl group, arylalkynyl group, or the like Can be mentioned. The carbon number of the imine residue is usually 2 to 20, preferably 2 to 18, and more preferably about 2 to 16.
As the “imine residue”, for example, the formula: —CR ″ = N—R ′ ″ or the formula: —N═C (R ′ ″) ₂ (where R ″ is a hydrogen atom) , An alkyl group, an aryl group, an arylalkyl group, an arylalkenyl group, and an arylalkynyl group, and R ′ ″ independently represents an alkyl group, an aryl group, an arylalkyl group, an arylalkenyl group, and an arylalkynyl group. However, when two R ′ ″ are present, the two R ′ ″ are bonded to each other to form a divalent group such as an ethylene group, a trimethylene group, a tetramethylene group, a pentane group. And a group represented by a C2-C18 alkylene group such as a methylene group and a hexamethylene group.
Specific examples of the “imine residue” include groups represented by the following structural formulas.

“Acid imide group” means a residue in which a hydrogen atom bonded to a nitrogen atom contained in an acid imide is a bond. As carbon number of an acid imide group, 4-20 etc. can be mentioned, for example. Preferably, about 4-18, for example, More preferably, about 4-16 can be mentioned. Specific examples of the “acid imide group” include the following groups.

  Examples of the “alkoxycarbonyl group” include a group in which a carbonyl group is bonded to the alkoxy group. Specifically, for example, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, s-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyl Oxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group Trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, Perfluorooctyl group, phenoxycarbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group and the like.

式中、Ｒは置換基を意味する。当該置換基としては、Ａｒ^１及びＡｒ^２の水素原子に置換されてもよい置換基として例示されたものと同様の基を挙げることができる。ｎは０〜４の整数を表わす。 Examples of the aromatic hydrocarbon group include divalent groups represented by the formulas (a) to (e).

In the formula, R means a substituent. As the said substituent, the group similar to what was illustrated as a substituent which may be substituted by the hydrogen atom of Ar < ¹ > and Ar < ² > can be mentioned. n represents an integer of 0 to 4.

（式中、Ｒは置換基を意味する。当該置換基としては、Ａｒ^１及びＡｒ^２の水素原子に置換されてもよい置換基として例示されたものと同様の基を挙げることができる。ｎは０〜２の整数を表わす。ＹはＮ、Ｓ、Ｃ＝Ｏを表わす。） 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 the formulas (f) to (z). it can.

(In the formula, R means a substituent. Examples of the substituent include the same groups as those exemplified as the substituent which may be substituted by the hydrogen atoms of Ar ¹ and Ar ^2. Represents an integer of 0 to 2. Y represents N, S, C = O.)

Examples of the aromatic hydrocarbon group connected to each other by a hetero atom or a carbonyl group include divalent groups represented by the formulas (aa) to (ae).

Ar ¹ in the aromatic monomer (A) used in the production method of the present invention and Ar ² in the aromatic monomer (B) may be the same or different.
Preferred examples of Ar ¹ and Ar ² include, for example, formulas (a), (b), (c), (d), (e), (m) (Y in (m) is preferably S), (y ), Groups represented by (aa), and the like.

で表わされる基を表わす。
芳香族モノマー（Ａ）におけるＸ^１は、同一でも異なっていてもよいが、同一のＸ^１であると、芳香族モノマー（Ａ）の調製が容易であることから好ましい。好ましいＸ^１は、式（３）で表わされる基である。 X ¹ of the aromatic monomer (A) is represented by the formulas (1) to (6)

Represents a group represented by
X ¹ in the aromatic monomer (A) may be the same or different, but the same X ¹ is preferable because the preparation of the aromatic monomer (A) is easy. Preferred X ¹ is a group represented by the formula (3).

  Specific examples of the aromatic monomer (A) include 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 3,2-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-dii ) 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-phenylene) 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-dioxaborolane-2 -Yl) thiophene, 2,5-bis (1,3,2-dioxaborinan-2-yl) thiophene, 2,5-bis (5,5-dimethyl-1,3,2-dioxaborinan-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′-biphenyl 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, 5,5'-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -2,2'-bithiophene, etc. Can be mentioned. Preferably, for example, 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- Oxaborolane), 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, 5,5′-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- Yl) -2,2′-bithiophene and the like.

  In the production method of the present invention, a plurality of types of aromatic monomers (A) having different aromatic monomers (A) may be used.

X ² of the aromatic monomer (B) represents a chlorine atom, a bromine atom or an iodine atom.
X ² in the aromatic monomer (B) may be the same or different, but the same X ² is preferable because the preparation of the aromatic polymer (B) is easy. Preferred X ² is a bromine atom.

  Specific examples of the aromatic monomer (B) include 2,7-dibromo-9,9-dihexyl-9H-fluorene, 2,7-dibromo-9,9-dioctyl-9H-fluorene, 2,7 -Dibromo-9,9-didodecyl-9H-fluorene, 2,7-dichloro-9,9-dihexyl-9H-fluorene, 2,7-dichloro-9,9-dioctyl-9H-fluorene, 2,7-dichloro -9,9-didodecyl-9H-fluorene, 2-bromo-7-chloro-9,9-dihexyl-9H-fluorene, 2-bromo-7-chloro-9,9-dioctyl-9H-fluorene, 2-bromo -7-chloro-9,9-didodecyl-9H-fluorene, 1,4-dibromobenzene, 1,3-dibromobenzene, 1,4-dibromo-2-ethylbenzene, 1,4 Dibromo-2-methoxybenzene, 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-t-butyl) benzenamine, bis (4-bromophenyl) -4- (1-methylpropyl) benzenamine, bis (4-bromo Phenyl) -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-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) -2,1,3-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, 4,4′-bis [(4-bromophenyl) Eniruamino] biphenyl, and the like. Preferably, for example, 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, bis (4-bromophenyl) -4-benzeneamine and the like can be mentioned.

  In the production method of the present invention, a plurality of types of aromatic monomers (B) having different aromatic monomers (B) may be used.

  As usage-amount of the aromatic monomer (B) in this invention manufacturing method, the range of 0.8 mol-1.2 mol can be mentioned with respect to 1 mol of aromatic monomers (A), for example. Preferably, the range of 0.9 mol-1.1 mol is mentioned, for example.

<Base>
Examples of the base used in the production method of the present invention include inorganic bases and organic bases.
Examples of inorganic bases include alkali metal or alkaline earth metal hydroxides, carboxylates, carbonates, bicarbonates, phosphates, and the like. Preferable examples include alkali metal carbonates and phosphates.
Specific examples include, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, barium hydroxide, sodium formate, potassium formate, calcium formate, sodium acetate, potassium acetate, sodium carbonate, potassium carbonate Cesium carbonate, calcium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate and the like. Preferable examples include sodium carbonate, potassium carbonate, cesium carbonate, sodium phosphate, and potassium phosphate.
Examples of the organic base include alkyl ammonium hydroxide, alkyl ammonium carbonate, alkyl ammonium bicarbonate, alkyl ammonium 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, trialkyl Examples thereof include alkylammonium fluorides such as amines and tetraalkylammonium fluorides. Preferable examples include tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetra-n-propylammonium hydroxide.

The amount of base used relative to aromatic monomer (B) 1 mole, for example, 0.5 equivalents to 20 equivalents (Here, the equivalent, the total material X ² that is included in the aromatic monomer (B) The range of the theoretical substance amount of the base necessary for neutralizing hydrogen ions equal to the amount). Preferably, the range of 0.5 equivalent-6 equivalent is mentioned, for example.

<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. Examples of the phase transfer catalyst include tetraalkyl ammonium halide, tetraalkyl ammonium hydrogen sulfate, and tetraalkyl ammonium hydroxide. Preferable examples include tetraalkylammonium halides such as tricaprylylmethyl ammonium chloride (available as ALIQUAT® 336 from Sigma-Aldrich).

The amount of the phase transfer catalyst used is, for example, 0.001 equivalent to 1 equivalent (here, equivalent) with respect to 1 mol of the total number of moles of the aromatic monomer (A) and the aromatic monomer (B). can be given a range of aromatic monomer represents the ratio of the theoretical amount of substance of the bases required to neutralize the same hydrogen ions to the total amount of substance of X ² contained in (B).). Preferably, 0.01 equivalent-0.5 equivalent is mentioned, for example.

<Aprotic organic solvent>
The aprotic organic solvent used in the production method of the present invention has no active hydrogen bonded to, for example, a hydroxyl group, an amino group, a carboxyl group, or the like in the molecule, and the aromatic monomer (A) and the aromatic monomer It means an organic solvent capable of dissolving (B).
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.
Here, specific examples of the “aprotic polar solvent” include N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, acetonitrile and the like. Specific examples of the “acyclic ether solvent” include diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and the like. Specific examples of the “cyclic ether solvent” include 1,4-dioxane, tetrahydrofuran and the like. Specific examples of the “aromatic hydrocarbon solvent” include benzene, toluene, xylene, mesitylene and the like. Specific examples of the “aliphatic hydrocarbon solvent” include hexane, heptane, cyclohexane and the like.
Preferred “aprotic organic solvents” are, for example, toluene, xylene, mesitylene, diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether from the viewpoint of the solubility of the aromatic monomer (A) and aromatic monomer (B). 1,4-dioxane, tetrahydrofuran and the like.
In addition, as for an aprotic organic solvent, you may mix and use 2 or more types of aprotic organic solvents as needed. Specific examples include a mixed solvent of tetrahydrofuran and toluene, a mixed solvent of ethylene glycol dimethyl ether and toluene, and the like.

<Palladium compound>
Examples of the palladium compound used in the production method of the present invention include a palladium (0) complex and a palladium (II) complex.
Examples of the palladium (0) complex include a complex in which dibenzylideneacetone is coordinated to zerovalent palladium, a so-called dibenzylideneacetone-palladium (0) complex, and the like. Specific examples include tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) chloroform adduct, bis (dibenzylideneacetone) palladium (0), and the like.
Examples of the palladium (II) complex include palladium carboxylates such as palladium (II) acetate, palladium (II) trifluoroacetate, palladium (II) acetylacetonate, such as palladium chloride (II), palladium bromide ( II), palladium halides such as palladium (II) iodide, such as allyl palladium (II) chloride dimer, bis 2-methylallyl palladium (II) chloride dimer, dichloro (1,5-cyclooctadiene) palladium (II) ), Dichlorobis (acetonitrile) palladium (II), dichlorobis (benzonitrile) palladium (II), and the like.
Specific examples of preferred palladium compounds include tris (dibenzylideneacetone) dipalladium (0), bis (dibenzylideneacetone) palladium (0), palladium (II) chloride, palladium (II) bromide, and palladium acetate. (II) etc. can be mentioned.

  As the usage-amount of a palladium compound, the range of 0.0001 mol-0.8 mol can be mentioned with respect to an aromatic monomer (B), for example. Preferably, the range of 0.001 mol-0.2 mol is mentioned, for example.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立に、水素原子、フッ素原子、炭素数１〜２０のフルオロアルキル基、炭素数１〜２０のアルコキシカルボニル基、炭素数２〜２０のアシル基、シアノ基、ニトロ基、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基及び炭素数１〜２０のジアルキルアミノ基を表わし、Ａは、炭素数１〜２０のアルキル基を表す。）
で表されるホスフィンである。 <Phosphine represented by formula (C)>
The phosphine represented by the formula (C) used in the production method of the present invention is represented by the formula (C)

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a fluorine atom, a C 1-20 fluoroalkyl group, a C 1-20 alkoxycarbonyl group, C2-C20 acyl group, cyano group, nitro group, C1-C20 alkyl group, C1-C20 alkoxy group, C6-C20 aryl group, and C1-C20 dialkylamino Represents a group, and A represents an alkyl group having 1 to 20 carbon atoms.)
It is a phosphine represented by.

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, or 2 to 2 carbon atoms. A 20-acyl group, 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, and a dialkylamino group having 1 to 20 carbon atoms. Specific examples of the C1-C20 fluoroalkyl group include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, Examples thereof include a fluoro-n-propyl group and a perfluoroisopropyl group. Specific examples of the alkoxycarbonyl group having 1 to 20 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, and s-butoxycarbonyl. Group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxy Boniru group, perfluorohexyloxy carbonyl group, perfluorooctyloxy carbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group, and pyridyloxycarbonyl group. Examples of the acyl group having 2 to 20 carbon atoms include aliphatic acyl groups such as acetyl group, propionyl group, butyryl group, isobutyryl group, and aromatic acyl groups such as benzoyl group and naphthoyl group. Can do. Specific examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-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, 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. Specific examples of the alkoxy group having 1 to 20 carbon atoms include 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 can be exemplified. Specific 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, 2 -Anthryl group etc. can be mentioned. Specific examples of the dialkylamino group having 1 to 20 carbon atoms include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, and di-sec. -A butylamino group, a di-tert- butylamino group, etc. can be mentioned.

  A represents an alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-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, Examples thereof include an n-nonadecyl group and an n-icosyl group. Preferably, for example, a t-butyl group and a cyclohexyl group are exemplified.

  Examples of the phosphine represented by the formula (C) include tert-butyldiphenylphosphine, tert-butylbis (4-fluorophenyl) phosphine, tert-butylbis (2-fluorophenyl) phosphine, and 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-trifluorophenyl) phosphine, tert-butylbis (3,5-dimethyl-4-methoxyphenyl) phosphine, tert-butylbis (4-acetylphenyl) phosphine, tert-butylbis (4-carbomethoxyphenyl) 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-methylphenyl) phos , 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-trifluorophenyl) phosphine, cyclohexyl Bis (2,5-dimethyl-4-methoxyphenyl) phosphine, cyclohexylbis (4-acetylphenyl) phosphine, cyclohexylbis (4-carbomethoxyphenyl) 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, cyclohexylbis (2-methylphenyl) phosphine and the like.

（式中、Ｒ^６は、炭素数１〜２０のアルコキシ基を表し、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、それぞれ独立に、水素原子、フッ素原子、炭素数１〜２０のフルオロアルキル基、炭素数１〜２０のアルコキシカルボニル基、炭素数２〜２０のアシル基、シアノ基、ニトロ基、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基及び炭素数１〜２０のジアルキルアミノ基を表わす。）
で表されるホスフィンである。
Ｒ^６は、炭素数１〜２０のアルコキシ基を表し、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、それぞれ独立に、水素原子、フッ素原子、炭素数１〜２０のフルオロアルキル基、炭素数１〜２０のアルコキシカルボニル基、炭素数２〜２０のアシル基、シアノ基、ニトロ基、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基及び炭素数１〜２０のジアルキルアミノ基を表わす。
炭素数１〜２０のアルコキシ基としては、具体的に例えば、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｓ−ブトキシ基、ｔ−ブトキシ基、ｎ−ペンチルオキシ基、２，２−ジメチルプロポキシ基、ｎ−ヘキシルオキシ基、シクロヘキシルオキシ基、ｎ−ヘプチルオキシ基、ｎ−オクチルオキシ基、ｎ−ノニルオキシ基、ｎ−デシルオキシ基、ｎ−ウンデシルオキシ基、ｎ−ドデシルオキシ基、ｎ−トリデシルオキシ基、ｎ−テトラデシルオキシ基、ｎ−ペンタデシルオキシ基、ｎ−ヘキサデシルオキシ基、ｎ−ヘプタデシルオキシ基、ｎ−オクタデシルオキシ基、ｎ−ノナデシルオキシ基及びｎ−イコシルオキシ基等を挙げることができる。また、炭素数１〜２０のフルオロアルキル基としては、具体的には例えば、モノフルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、２，２，２−トリフルオロエチル基、ペンタフルオロエチル基、パーフルオロ−ｎ−プロピル基、パーフルオロイソプロピル基等を挙げることができる。また、炭素数１〜２０のアルコキシカルボニル基としては、具体的には例えば、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、イソプロポキシカルボニル基、ブトキシカルボニル基、イソブトキシカルボニル基、ｓ−ブトキシカルボニル基、ｔ−ブトキシカルボニル基、ペンチルオキシカルボニル基、ヘキシルオキシカルボニル基、シクロヘキシルオキシカルボニル基、ヘプチルオキシカルボニル基、オクチルオキシカルボニル基、２−エチルヘキシルオキシカルボニル基、ノニルオキシカルボニル基、デシロキシカルボニル基、３，７−ジメチルオクチルオキシカルボニル基、ドデシルオキシカルボニル基、トリフルオロメトキシカルボニル基、ペンタフルオロエトキシカルボニル基、パーフルオロブトキシカルボニル基、パーフルオロヘキシルオキシカルボニル基、パーフルオロオクチルオキシカルボニル基、フェノキシカルボニル基、ナフトキシカルボニル基、ピリジルオキシカルボニル基等を挙げることができる。また、炭素数２〜２０のアシル基としては、例えば、アセチル基、プロピオニル基、ブチリル基、イソブチリル基等の脂肪族アシル基、例えば、ベンゾイル基、ナフトイル基等の芳香族アシル基等を挙げることができる。また、炭素数１〜２０のアルキル基としては、具体的には例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、２，２−ジメチルプロピル基、シクロペンチル基、ｎ−ヘキシル基、シクロヘキシル基、ｎ−ヘプチル基、２−メチルペンチル基、ｎ−オクチル基、２−エチルヘキシル基、ｎ−ノニル基、ｎ−デシル基、ｎ−ウンデシル基、ｎ−ドデシル基、ｎ−トリデシル基、ｎ−テトラデシル基、ｎ−ペンタデシル基、ｎ−ヘキサデシル基、ｎ−ヘプタデシル基、ｎ−オクタデシル基、ｎ−ノナデシル基、ｎ−イコシル基等を挙げることができる。また、炭素数１〜２０のアルコキシ基としては、具体的に例えば、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｓ−ブトキシ基、ｔ−ブトキシ基、ｎ−ペンチルオキシ基、２，２−ジメチルプロポキシ基、ｎ−ヘキシルオキシ基、シクロヘキシルオキシ基、ｎ−ヘプチルオキシ基、ｎ−オクチルオキシ基、ｎ−ノニルオキシ基、ｎ−デシルオキシ基、ｎ−ウンデシルオキシ基、ｎ−ドデシルオキシ基、ｎ−トリデシルオキシ基、ｎ−テトラデシルオキシ基、ｎ−ペンタデシルオキシ基、ｎ−ヘキサデシルオキシ基、ｎ−ヘプタデシルオキシ基、ｎ−オクタデシルオキシ基、ｎ−ノナデシルオキシ基、ｎ−イコシルオキシ基等を挙げることができる。また、炭素数６〜２０のアリール基としては、具体的には例えば、フェニル基、４−メチルフェニル基、２−メチルフェニル基、１−ナフチル基、２−ナフチル基、３−フェナントリル基、２−アントリル基等を挙げることができる。また、炭素数１〜２０のジアルキルアミノ基としては、具体的には例えば、ジメチルアミノ基、ジエチルアミノ基、ジ−ｎ−プロピルアミノ基、ジイソプロピルアミノ基、ジ−ｎ−ブチルアミノ基、ジ−ｓｅｃ−ブチルアミノ基、ジ−ｔｅｒｔ−ブチルアミノ基等を挙げることができる。 <Phosphine represented by formula (D)>
The phosphine represented by the formula (D) used in the production method of the present invention is represented by the formula (D)

(In the formula, 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 having 1 to 20 carbon atoms. Group, C1-C20 alkoxycarbonyl group, C2-C20 acyl group, cyano group, nitro group, C1-C20 alkyl group, C1-C20 alkoxy group, C6-C20 An aryl group of 1 to 20 carbon atoms and a dialkylamino group having 1 to 20 carbon atoms.)
It is a phosphine represented by.
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, a C 1-20 fluoroalkyl group, or a carbon number. 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 aryl group having 6 to 20 carbon atoms, and Represents a dialkylamino group having 1 to 20 carbon atoms.
Specific examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, and 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. Specific 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, a perfluoroisopropyl group, etc. can be mentioned. Specific examples of the alkoxycarbonyl group having 1 to 20 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, and s-butoxycarbonyl. Group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxy Boniru group, perfluorohexyloxy carbonyl group, perfluorooctyloxy carbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group, and pyridyloxycarbonyl group. Examples of the acyl group having 2 to 20 carbon atoms include aliphatic acyl groups such as acetyl group, propionyl group, butyryl group, isobutyryl group, and aromatic acyl groups such as benzoyl group and naphthoyl group. Can do. Specific examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-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, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group , N-icosyl group and the like. Specific examples of the alkoxy group having 1 to 20 carbon atoms include 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, n-icosyloxy group and the like can be mentioned. Specific 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, 2 -Anthryl group etc. can be mentioned. Specific examples of the dialkylamino group having 1 to 20 carbon atoms include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, and di-sec. -A butylamino group, a di-tert- butylamino group, etc. can be mentioned.

  Examples of the phosphine represented by the formula (D) include tert-butylbis (2-methoxyphenyl) phosphine, tert-butylbis (2,4-dimethoxyphenyl) phosphine, and tert-butylbis (2-methoxy-4-methylphenyl). ) Phosphine, tert-butylbis (2-methoxy-4-fluorophenyl) phosphine, tert-butylbis (2-methoxy-4-trifluorophenyl) phosphine, and the like.

（式中、Ｒ^１１は、炭素数１〜２０のアルコキシ基を表し、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５は、それぞれ独立に、水素原子、フッ素原子、炭素数１〜２０のフルオロアルキル基、炭素数１〜２０のアルコキシカルボニル基、炭素数２〜２０のアシル基、シアノ基、ニトロ基、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基又は炭素数１〜２０のジアルキルアミノ基を表わす。但し、Ｒ^１２〜Ｒ^１５がすべて水素原子になることはない。）
で表されるホスフィンである。 <Phosphine represented by formula (E)>
The phosphine represented by the formula (E) used in the production method of the present invention is represented by the formula (E)

(In the formula, 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 having 1 to 20 carbon atoms. Group, C1-C20 alkoxycarbonyl group, C2-C20 acyl group, cyano group, nitro group, C1-C20 alkyl group, C1-C20 alkoxy group, C6-C20 Or an aryl group having 1 to 20 carbon atoms, provided that R ^{12 to} R ¹⁵ are not all hydrogen atoms.)
It is a phosphine represented by.

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, a C 1-20 fluoroalkyl group, or a carbon number. 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 aryl group having 6 to 20 carbon atoms, or Represents a dialkylamino group having 1 to 20 carbon atoms. However, R ^{12 to} R ¹⁵ are not all hydrogen atoms.
Specific examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, and 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 , N-icosyloxy group and the like. Specific 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, a perfluoroisopropyl group, etc. can be mentioned. Specific examples of the alkoxycarbonyl group having 1 to 20 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, and s-butoxycarbonyl. Group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxy Boniru group, perfluorohexyloxy carbonyl group, perfluorooctyloxy carbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group, and pyridyloxycarbonyl group. Examples of the acyl group having 2 to 20 carbon atoms include aliphatic acyl groups such as acetyl group, propionyl group, butyryl group, isobutyryl group, and aromatic acyl groups such as benzoyl group and naphthoyl group. Can do. Specific examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-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, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group , N-icosyl group and the like. Specific examples of the alkoxy group having 1 to 20 carbon atoms include 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, n-icosyloxy group and the like can be mentioned. Specific 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, 2 -Anthryl group etc. can be mentioned. Specific examples of the dialkylamino group having 1 to 20 carbon atoms include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, and di-sec. -A butylamino group, a di-tert- butylamino group, etc. can be mentioned.

  Examples of the phosphine represented by the formula (E) include cyclohexyl bis (2,4-dimethoxyphenyl) phosphine, cyclohexyl bis (2-methoxy-4-methylphenyl) phosphine, and cyclohexyl bis (2-methoxy-4-fluoro). Phenyl) phosphine, cyclohexylbis (2-methoxy-4-trifluorophenyl) phosphine, and the like.

The phosphine represented by the formula (D) and the formula (E) can be used as a ligand for the Suzuki coupling reaction. For example, Metal-Catalyzed Cross-Coupling Reactions Second, Completely Revised and Enhanced Edition Volume 1, 2 (De Meijere Armin, edited by Dietrich Francois, 2004, published by Wiley-VCH). Specific examples include Stille coupling, Heck coupling, Hiyama coupling, Sonogashira coupling, Kumada coupling, Buchwald-Hartwig coupling, and the like.

As the usage-amount of the phosphine represented by Formula (C), the range of 0.1 mol-10 mol can be mentioned with respect to 1 mol of palladium compounds, for example. Preferably, the range of 0.5 mol-5 mol is mentioned.
The phosphine represented by the formula (C) is, for example, 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 is 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. be able to. Here, examples of the “Group 10 transition metal compound” include a nickel compound, a palladium compound, a platinum compound, and the like. Preferably, a palladium compound etc. are mentioned. Here, examples of the “palladium compound” include the palladium compounds described in the explanation section of the above <palladium compound>.
The transition metal complex composed of 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 is, for example, the 5th edition experimental chemistry course ( It can be prepared according to a known method such as 21 organic transition metal complex, supramolecular complex p308-327 (9.2 organic palladium complex), edited by The Chemical Society of Japan, published by Maruzen Co., Ltd.

<Polymerization process>
The polymerization step is not particularly limited. For example, (i) palladium compound, phosphine represented by formula (C), base, aromatic monomer (A), aromatic monomer (B), and aprotic organic (Ii) mixing the base together, the aromatic monomer (A), the aromatic monomer (B) and the aprotic organic solvent, and then mixing the palladium compound and the formula (C). Or a complex prepared in advance by a palladium compound and a complex prepared in advance with a phosphine represented by the formula (C), and an aprotic organic solvent.

As temperature in a superposition | polymerization process, the range of 0 degreeC-180 degreeC can be mentioned, for example. Preferably, the range of 30 degreeC-100 degreeC is mentioned, for example.
As polymerization time in a superposition | polymerization process, the range of 1 hour-96 hours can be mentioned, for example. Preferably, the range of 3 hours-48 hours is mentioned, for example.

The reaction mixture containing the aromatic polymer obtained by the polymerization step may precipitate the aromatic polymer by adding a poor solvent, for example, and take out the aromatic polymer by solid-liquid separation such as filtration.
In order to remove impurities such as metals, the reaction mixture may be removed by the above method after being washed with an acidic solution such as hydrochloric acid.
The obtained aromatic polymer may be subjected to a 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 evaluated by performing gel permeation chromatography (hereinafter sometimes referred to as GPC), and calculating the weight average molecular weight (Mw) in terms of polystyrene 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 body (6.0 mmol) composed of 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% by weight tetraethylammonium hydroxide aqueous solution (20 ml) and toluene (110 ml) were added, and the temperature was raised with stirring. (Bath temperature 100 ° C.). After the temperature rise, bis (cyclohexylbis (2-methoxyphenyl) phosphine) dichloropalladium (II) (3 μmol) and toluene (12 ml) were added, and polymerization was carried out at a bath temperature of 100 ° C. for 4 hours while stirring. 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) phosphinephosphine) dichloropalladium (II) was used instead of bis (cyclohexylbis (2-methoxyphenyl) phosphine) dichloropalladium (II) The same operation was performed. 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) The same operation was performed. 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. Except that, the same operation as in Example 1 was performed. 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 ° C., 6.6 ml of n-butyllithium (1.62 M / hexane solution) was added dropwise to the obtained cooled product, and the 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, followed by stirring at −10 ° C. for 4 hours. The produced white solid was removed by filtration, the filtrate was concentrated, and then the resulting concentrate (crude product) was purified by silica gel column chromatography to obtain cyclohexylbis (2,4-dimethoxyphenyl) phosphine 0. 48 g (clear viscous liquid) was obtained.
1H-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)
31P-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 a reaction vessel at room temperature. Stir for 5 hours. After stirring, the precipitated solid was filtered 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 (ocher color) of bis (cyclohexylbis (2,4-dimethoxyphenyl) phosphine) dichloropalladium (II) as a desired transition metal complex. Solid).
1H-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)
31P-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 ° C., 7.6 ml of n-butyllithium (1.62 M / hexane solution) was added dropwise to the obtained cooled product, and the 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, followed by stirring at −10 ° C. for 4 hours. The produced white solid was removed by filtration, and the filtrate was concentrated to obtain 1.12 g (clear viscous liquid) of tert-butylbis (2-methoxyphenyl) phosphine 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 a reaction vessel at room temperature. Stir for hours. After stirring, the precipitated solid was filtered 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 (pale yellow) of bis (tert-butylbis (2-methoxyphenyl) phosphinephosphine) dichloropalladium (II) as a desired transition metal complex. Solid).
1H-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)
31P-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 ° C., 7.6 ml of n-butyllithium (1.62 M / hexane solution) was added dropwise to the obtained cooled product, and the 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, and the mixture was stirred at −10 ° C. for 1 hour. The produced white solid was removed by filtration, and the filtrate was concentrated to obtain 2.30 g (clear viscous liquid) of tert-butyl (2,4-dimethoxyphenyl) phosphine 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 a reaction vessel at room temperature. For 17 hours. After stirring, the precipitated solid was filtered 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) phosphinephosphine) dichloropalladium (II) as a desired transition metal complex. Ocher solids).
1H-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)
31P-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 (7)

Formula (A)
^{X 1 -Ar 1 -X 1 (A} )
(In the formula, X ¹ represents the formulas (1) to (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 substituted 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. , Aryl group, aryloxy group, arylthio group, arylalkylthio group, arylalkenyl group, arylalkynyl group, heterocyclic group which may have a substituent, amino group which may have a substituent, It may be substituted with a silyl group, an acyl group, a substituent having a carbon atom-nitrogen atom double bond as a partial structure, an acid imide group, an alkoxycarbonyl group, a carboxyl group, a nitrile group or a nitro group. )
An aromatic monomer represented by:
Formula (B)
^{X 2 -Ar 2 -X 2 (B} )
(In the formula, X ² 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. Carbon contained in the aromatic hydrocarbon group The atom may be substituted 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. , 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, Substituted with a substituent having a carbon atom-nitrogen double bond as a partial structure, an acid imide group, an alkoxycarbonyl group, a carboxyl group, a nitrile group or a nitro group Good.)
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 C 1-20 fluoroalkyl group, a C 1-20 alkoxycarbonyl group, carbon C2-C20 acyl group, cyano group, nitro group, C1-C20 alkyl group, C1-C20 alkoxy group, C6-C20 aryl group, or C1-C20 dialkylamino group 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 represented by formula (1) and an aprotic organic solvent The aromatic solvent according to claim 1, wherein the aprotic organic solvent is at least one aprotic organic solvent selected from the group consisting of an ether solvent, an aromatic hydrocarbon solvent, and an aliphatic hydrocarbon solvent. A method for producing a polymer. The method for producing an aromatic polymer according to claim 1 or 2, wherein the palladium compound is a palladium (0) complex or a palladium (II) complex. Formula (D)

(In the formula, 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 having 1 to 20 carbon atoms. Group, C1-C20 alkoxycarbonyl group, C2-C20 acyl group, cyano group, nitro group, C1-C20 alkyl group, C1-C20 alkoxy group, C6-C20 An aryl group or a C 1-20 dialkylamino group.)
A phosphine represented by Formula (E)

(In the formula, 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 having 1 to 20 carbon atoms. Group, C1-C20 alkoxycarbonyl group, C2-C20 acyl group, cyano group, nitro group, C1-C20 alkyl group, C1-C20 alkoxy group, C6-C20 Or an aryl 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.