JP2007016229A - Method for producing reactive aromatic polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method by which an aromatic polymer having characteristic groups can simply be produced, and to provide a method by which an aromatic polymer having bromo groups can simply be produced. <P>SOLUTION: This method for producing the reactive aromatic polymer comprises subjecting a polymer which contains one or more kinds of repeating units represented by the general formula (1): -Ar<SP>1</SP>- (Ar<SP>1</SP>represents an arylene group having at least one C-H bond on the aromatic ring, or the like) and in which the total amount of the repeating units of the general formula (1) is 0.1 to 100 mol.% based on the total amount of all the repeating units, to an aromatic electrophilic substitution reaction to obtain the polymer containing repeating units having characteristic groups X. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

Aromatic polymer compounds having an aromatic ring in the main chain exhibit specific properties such as electronic properties such as charge transport and light emission, and mechanical properties such as rigidity and thermal stability. In the field of electronic materials, chemistry, energy materials, medicine, etc., its application has been actively promoted especially for electronic devices (see, for example, Non-Patent Document 1). For example, polyarylene polymer compounds such as polyfluorene and polyparaphenylene derivatives, and polyarylene vinylene polymer compounds are known as materials used as high molecular weight light emitting materials (polymer phosphors) ( For example, refer nonpatent literature 2). In order to improve the characteristics of these polymer compounds, various introductions of substituents to the aromatic ring side chains of the aromatic polymer compounds have been studied. For example, a method in which an aromatic polymer compound having a characteristic group that enables a reaction for introducing the substituent is used as an intermediate has been studied. In recent years, a method for producing an aromatic polymer compound having a characteristic group by polymerizing a monomer having the characteristic group under a condition that the characteristic group is not lost has been proposed (see Patent Document 1). Among them, an aromatic polymer compound having a halogen group such as a bromo group is similar to a halide of a low molecular weight aromatic compound because a halogen group as a substituent can be converted into another substituent. For example, it is useful as an intermediate for conductive polymers, ion exchange resins, flame retardants, ion conductive polymers, insulating materials and the like. Conventionally, as a method for brominating an aromatic polymer compound, a method using an excessive amount of a brominating agent is known (see, for example, Patent Document 2 or Non-Patent Document 3).
Journal of Polymer Science Part A (Volume 39), page 1533 (2001) Progress in Polymer Science 28, 875 (2003) Polymer. Volume 30, page 1137 (1989) Japanese Unexamined Patent Publication No. 2003-253001 Japanese Patent Publication No. 2001-517256

However, the method for producing an aromatic polymer compound having a characteristic group by polymerization (Patent Document 2), which is the conventional production method described above, requires that the characteristic group does not react during polymerization. The characteristic group possessed by the aromatic polymer compound is limited. For example, when Suzuki coupling or Yamamoto coupling, which is useful as a method for synthesizing an aromatic polymer compound, is used, it is difficult to produce an aromatic polymer compound having a halogen group as a characteristic group. Further, depending on the type of the characteristic group, there is a possibility that the reactivity may be lowered during the production of the main chain polymer.
The first object of the present invention is to provide a method capable of easily producing an aromatic polymer compound having a characteristic group. Further, in the above bromination reaction of the aromatic polymer compound (Non-patent Document 3 and Patent Document 2), the reaction proceeds by using a large excess of brominating agent, so the bromination yield is high. Low, it may be difficult to control the rate of bromination; it is necessary to remove a large excess of brominating agent; the aromatic polymer compound has a linking group such as an ether bond in the main chain In some cases, an iron-based catalyst or a solid catalyst such as aluminum chloride was used for bromination to a compound having a relatively low activity with respect to electrophilic substitution even though bromination under mild conditions was possible. There is an industrial problem that a reaction at a high temperature is required and the purification of the brominated compound becomes complicated due to the removal of the solid catalyst.
The second object of the present invention is to form an aromatic polymer compound having a bromo group that is relatively less susceptible to electrophilic substitution reaction in a high yield and a high bromination yield under mild conditions. An object of the present invention is to provide a method that can be easily manufactured while controlling the ratio of the generated amount.

  As a result of intensive investigations to solve the above problems, the present inventors have used a polymer compound containing a repeating unit represented by the following general formula (1) as a raw material, and the C—H bond on the aromatic ring is subjected to a halogenation reaction. It has been found that a polymer compound containing a repeating unit having a characteristic group X represented by the following general formula (2) can be easily produced by conversion by a representative aromatic electrophilic substitution reaction. Furthermore, the present inventors further have an organic solvent of 5 mol times or more based on the total of the repeating units with respect to the polymer compound having one or more repeating units represented by the following general formula (1) in an organic solvent. By allowing bromine to act as a brominating agent in the presence of a strong acid, an aromatic polymer compound having a bromo group is brominated in a high yield and a high bromination yield under mild conditions. The inventors found that it can be easily produced while controlling the ratio, and completed the present invention.

（式中、Ａｒは炭素数６〜６０の炭化水素基を表し、Ｒ”は水素原子、アルキル基、アリール基、及び１価の複素環基からなる群から選ばれる置換基を表す。）で示される非共役部分を含む連結基、及び／又はそれらが２つ以上組み合わされた基を、上記式（１）及び（１ａ）で示される繰り返し単位の合計に対して、４０モル％以下含んでいてもよい）を原料とし、芳香環上のＣ−Ｈ結合をハロゲン化、ニトロ化、フリーデル−クラフツ（Friedel-Crafts）アルキル化、ハロメチル化、フリーデル−クラフツ（Friedel-Crafts）アシル化、ガッターマン（Gattermann）アルデヒド合成、及びヴィルスマイヤー（Vilsmeier）ホルミル化からなる群から選ばれる芳香族求電子置換反応により変換することにより、一般式（２）

（式中、Ｘは前記芳香族求電子置換反応により導入された特性基、又はそれらから誘導された特性基を表し、Ａｒ²はＡｒ¹の有する芳香環上のＣ−Ｈ結合のうちｎ個がＣ−Ｘ結合に変換されたｎ＋２価のアリーレン基、ｎ＋２価の複素環基、又はｎ＋２価の芳香族アミン基を示し、ｎは１〜４の整数を表す。）で示される、特性基Ｘを有する繰り返し単位を含む高分子化合物を得ることを特徴とする高分子化合物の製造方法に関する。 That is, the present invention provides the following general formula (1)
-Ar ^1- (1)
(In the formula, Ar ¹ represents an arylene group, a divalent heterocyclic group or a divalent aromatic amine group having at least one C—H bond on the aromatic ring.) A polymer compound in which the total of repeating units represented by formula (1) is 0.1 mol% or more and 100 mol% or less of the total of all repeating units (herein, the polymer compound is represented by formula (1) In addition to the repeating units shown, the general formula (1a)
—Ar ⁰ − (1a)
(In the formula, Ar ⁰ represents an arylene group, a divalent heterocyclic group or a divalent aromatic amine group that does not have a C—H bond on the aromatic ring). Well, furthermore, the following formulas X-1 to X-11

(In the formula, Ar represents a hydrocarbon group having 6 to 60 carbon atoms, and R ″ represents a substituent selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and a monovalent heterocyclic group). 40 mol% or less of the linking group containing the non-conjugated moiety shown and / or the group in which two or more of them are combined with respect to the total of the repeating units represented by the above formulas (1) and (1a) The C—H bond on the aromatic ring is halogenated, nitrated, Friedel-Crafts alkylated, halomethylated, Friedel-Crafts acylated, By converting by an aromatic electrophilic substitution reaction selected from the group consisting of Gattermann aldehyde synthesis and Vilsmeier formylation, the general formula (2)

(In the formula, X represents a characteristic group introduced by the aromatic electrophilic substitution reaction or a characteristic group derived therefrom, and Ar ² represents n of C—H bonds on the aromatic ring of Ar ^1. Represents an n + 2 valent arylene group, n + 2 valent heterocyclic group, or n + 2 valent aromatic amine group converted into a C—X bond, and n represents an integer of 1 to 4. The present invention relates to a method for producing a polymer compound comprising obtaining a polymer compound containing a repeating unit having X.

  According to the production method of the present invention, an aromatic polymer compound containing a repeating unit having a characteristic group can be easily produced. Furthermore, even in the case of an aromatic polymer compound in which bromination does not proceed at all by a conventionally known method or bromination proceeds only under strong conditions, the brominated aromatic polymer compound is subjected to mild conditions. Can be easily produced while controlling the bromination rate with good yield.

  In the production method of the present invention, the aromatic polymer compound as a raw material contains one or more types of repeating units represented by the above formula (1), and the total number of repeating units represented by the formula (1) is all repeating units. It is a high molecular compound which is 0.1 mol% or more and 100 mol% or less in total. The polymer compound may contain a repeating unit represented by the above formula (1a), and further includes a linking group containing a non-conjugated moiety represented by the above formulas X-1 to X-11 and / or two of them. The group combined above may be contained in an amount of 40 mol% or less based on the total of repeating units represented by the above formulas (1) and (1a).

In the repeating unit of the formula (1) used in the present invention, Ar ¹ represents an arylene group, a divalent heterocyclic group or a divalent aromatic amine group. The Ar ¹ has at least one C—H bond on the aromatic ring. Ar ¹ may have a substituent.

  An arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, having a condensed ring, two or more independent benzene rings or condensed rings bonded directly or via a group such as vinylene Also included. The arylene group may have a substituent. Carbon number of the part except the substituent in an arylene group is about 6-60 normally, Preferably it is 6-20. Moreover, the total carbon number including the substituent of an arylene group is about 6-100 normally. Examples of the arylene group include formulas 1A-1 to 1A-20 shown below.

In Ar ¹ represented by the above formulas 1A-1 to 1A-20, R represents a hydrogen atom, a bond, or a substituent. Any two of a plurality of Rs represent a bond, and any one or more of them represent a hydrogen atom. When a plurality of substituents represented by R are present, they may be the same or different. Ra represents a hydrogen atom or a substituent. When a plurality of substituents represented by Ra are present, they may be the same or different. When two Ras exist on the same atom, they may be combined to form an oxo group or a thioxo group, or may be bonded to each other to form a ring.

  In addition, the substituent represented by R is a 5- to 7-membered aliphatic ring which may include heteroatoms such as an oxygen atom, a sulfur atom and a nitrogen atom among the substituents on adjacent atoms, Alternatively, a 5- to 7-membered aromatic ring may be formed.

As the arylene group represented by Ar ¹ , among the above formulas 1A-1 to 1A-14, a phenylene group (formula 1A-1), a naphthalene-diyl group (formula 1A-2), an anthracene-diyl group (1A- 3), dihydrophenanthrene-diyl group (formula 1A-10), fluorene-diyl group (formula 1A-13), benzofluorene-diyl group (formula 1A-14), biphenylene group (formula 1A-15), terphenylene group (Formula 1A-16 to 1A-18) are preferred, phenylene group (Formula 1A-1), naphthalene-diyl group (Formula 1A-2), dihydrophenanthrene-diyl group (Formula 1A-10), fluorene-diyl group ( Formula 1A-13), benzofluorene-diyl group (Formula 1A-14), biphenylene group (Formula 1A-15), terphenylene group (Formula 1A-16 to 1A-18) Among them, a phenylene group (formula 1A-1), a naphthalene-diyl group (formula 1A-2), a fluorene-diyl group (formula 1A-13), and a benzofluorene-diyl group (formula 1A-14) are more preferred. .

  A divalent heterocyclic group is a remaining atomic group obtained by removing two hydrogen atoms from a heterocyclic compound, having a condensed ring, an independent monocyclic heterocyclic compound or two or more condensed rings directly or Those bonded through a group such as vinylene are also included. In addition, a combination of a heterocyclic compound and an aromatic hydrocarbon is also included. The divalent heterocyclic group may have a substituent. Carbon number of the part except the substituent in a bivalent heterocyclic group is about 4-60 normally, Preferably it is 2-20. Moreover, the total carbon number including the substituent of a bivalent heterocyclic group is about 2-100 normally. Here, a heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, and boron in the ring. Say. Examples of the divalent heterocyclic group include formulas 2A-1 to 2A-53 and 2A-101 to 2A-116 shown below.

In Ar ¹ represented by the formula 2A-1-2A-53 and 2A-101~2A-116,, R represents a hydrogen atom, bond or a substituent. Any two of a plurality of Rs represent a bond, and any one or more of them represent a hydrogen atom. When a plurality of substituents represented by R are present, they may be the same or different. Ra represents a hydrogen atom or a substituent. When a plurality of substituents represented by Ra are present, they may be the same or different. When two Ras exist on the same atom, they may be combined to form an oxo group or a thioxo group, or may be bonded to each other to form a ring.

  The substituent represented by R is a substituent on adjacent atoms, a 5- to 7-membered aliphatic ring containing a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom, or an oxygen atom A 5- to 7-membered aromatic ring which may contain a heteroatom such as sulfur atom or nitrogen atom may be formed.

The divalent heterocyclic group represented by Ar ^1, of the formula 2A-1~2A-53, and 2A-101~2A-116, pyridine - diyl group (formula 2A-1), quinoline - diyl Group (formula 2A-6), isoquinoline-diyl group (formula 2A-7), quinoxaline-diyl group (formula 2A-8), phenanthroline-diyl group (2A-18), thiophene-diyl group (formula 2A-22) , An imidazole-diyl group (2A-24), an oxazole-diyl group (formula 2A-26), a thiazole-diyl group (2A-27), containing nitrogen, sulfur, oxygen or selenium as a hetero atom, and a condensed benzene ring 5-membered heterocyclic groups (formulas 2A-30 to 2A-32 and 2A-34 to 2A-40) having a fluorene-like skeleton containing silicon, nitrogen, oxygen, or sulfur as a hetero atom Groups (formulas 2A-41 to 2A-44 and 2A-46 to 2A-47), heterocyclic groups having a condensed ring structure represented by formulas 2A-48 to 2A-53, diazaphenylene groups (formulas 2A-101) ), A compound group in which a phenyl group or a thienyl group is bonded to the 2,5-position of a 5-membered heterocyclic group containing nitrogen, oxygen, or sulfur as a hetero atom (formula 2A-103, 2A-105 to 2A-106, And 2A-108 to 2A-110), a compound group (formula 2A-111) containing nitrogen, oxygen, or sulfur as a hetero atom, and a phenyl group or thienyl group bonded to a 5-membered heterocyclic group condensed with a benzene ring To 2A-116), pyridine-diyl group (formula 2A-1), quinoline-diyl group (formula 2A-6), isoquinoline-diyl group (formula 2A-7), quinoxaline-diyl group (formula 2A-8) ), Fena A heterocyclic group having a fluorene-like skeleton containing a nitrone-diyl group (2A-18) and silicon, nitrogen, oxygen, or sulfur as a hetero atom (formulas 2A-41 to 2A-44 and 2A-46 to 2A-47) , A heterocyclic group having a condensed ring structure represented by formulas 2A-48 to 2A-53, a diazaphenylene group (formula 2A-101), a 5-membered heterocyclic group containing nitrogen, oxygen, or sulfur as a hetero atom Compound groups (formula 2A-103, 2A-105 to 2A-106, and 2A-108 to 2A-110) having a phenyl group bonded at the 2,5-position, containing nitrogen, oxygen, or sulfur as a hetero atom, A compound group (formula 2A-111-2A-116) in which a phenyl group is bonded to a 5-membered heterocyclic group having a condensed ring is more preferable, and a fluorine containing silicon, nitrogen, oxygen, or sulfur as a hetero atom. Heterocyclic groups having a similar skeleton (formulas 2A-41 to 2A-44 and 2A-46 to 2A-47), heterocyclic groups having a condensed ring structure represented by formulas 2A-48 to 2A-53, heteroatoms As a compound group (formula 2A-103, 2A-105 to 2A-106, and 2A-108 to 2A-) in which a phenyl group is bonded to the 2,5-position of a 5-membered heterocyclic group containing nitrogen, oxygen, or sulfur as 110), and a compound group (formula 2A-111-2A-116) containing nitrogen, oxygen or sulfur as a hetero atom and having a phenyl group bonded to a 5-membered heterocyclic group condensed with a benzene ring.

  The divalent aromatic amine group is a remaining atomic group obtained by removing two hydrogen atoms from an aromatic amine. The divalent aromatic amine group may have a substituent. The carbon number of the part except the substituent in a bivalent aromatic amine group is about 4-60 normally. As a bivalent aromatic amine group, group shown by the following general formula (1-2) is mentioned, for example.

（式中、Ａｒ³、Ａｒ⁴、Ａｒ⁵及びＡｒ⁶はそれぞれ独立にアリーレン基、又は２価の複素環基を示す。Ａｒ⁷、Ａｒ⁸及びＡｒ⁹はそれぞれ独立にアリール基、又は１価の複素環基を示す。Ａｒ³、Ａｒ⁴、Ａｒ⁵、Ａｒ⁶、Ａｒ⁷、Ａｒ⁸及びＡｒ⁹は置換基を有していてもよい。ｒ及びｒｒはそれぞれ独立に０又は１を示す。）

(In the formula, Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ each independently represent an arylene group or a divalent heterocyclic group. Ar ⁷ , Ar ⁸ and Ar ⁹ each independently represent an aryl group or a monovalent group. Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ and Ar ⁹ may have a substituent, and r and rr each independently represent 0 or 1 .)

  Specific examples of the divalent aromatic amine group include groups represented by the following formulas 3A-1 to 3A-8.

In Ar ¹ represented by the above formulas 3A-1 to 3A-8, R represents a hydrogen atom, a bond, or a substituent. Any two of a plurality of Rs represent a bond, and any one or more of them represent a hydrogen atom. When a plurality of substituents represented by R are present, they may be the same or different.

Examples of the divalent aromatic amine group represented by Ar ^1, of the formula 3A-. 1-3A-8, divalent aromatic amine group represented by the formula 3A-1~3A-4 are preferred, wherein The divalent aromatic amine group represented by 3A-1 to 3A-3 is more preferred, and the groups represented by Formulas 3A-2 and 3A-3 are more preferred.

  The substituent represented by R is a substituent on adjacent atoms, a 5- to 7-membered aliphatic ring containing a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom, or an oxygen atom A 5- to 7-membered aromatic ring which may contain a heteroatom such as sulfur atom or nitrogen atom may be formed.

As the group represented by Ar ¹ , an arylene group, a divalent heterocyclic group, and a divalent aromatic amine group, an arylene group and a divalent heterocyclic group are preferable, and an arylene group is more preferable.

  Examples of the substituent represented by R or Ra include an alkyl group, an aryl group, an aralkyl group, a monovalent heterocyclic group, an arylalkenyl group, an arylalkynyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, Examples include an arylthio group, an aralkylthio group, a substituted amino group, a substituted silyl group, a sulfonic acid group, a phosphono group, a cyano group, and a nitro group.

The alkyl group represented by R or Ra may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples thereof include methyl group, ethyl group Group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl Group, decyl group, 3,7-dimethyloctyl group, dodecyl group, octadecyl group and the like.
From the viewpoint of solubility in organic solvents and ease of synthesis, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group , Isopentyl group, hexyl group, cyclohexyl group, heptyl group, cyclohexylmethyl group, octyl group, 2-ethylhexyl group, 2-cyclohexylethyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, and dodecyl group are preferable. , Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl Group, nonyl group, decyl group, and 3,7-dimethyloctyl group are more preferable, propyl group Isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, and 3 More preferred is a 7,7-dimethyloctyl group.

The aryl group is an atomic group obtained by removing one hydrogen atom on an aromatic ring from an aromatic hydrocarbon, and includes those having a condensed ring. The aryl group usually has about 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include a phenyl group and a C _{1 to} C ₁₂ alkylphenyl group (C _{1 to} C ₁₂ have 1 to The same applies to the following.), 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group and the like.
From the viewpoints of solubility in an organic solvent and ease of synthesis, a C _{1 to} C ₁₂ alkylphenyl group is preferred.
C ₁ -C ₁₂ specifically alkylphenyl group include a methylphenyl group, ethylphenyl group, dimethylphenyl group, dimethyl -t- butylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, isopropylphenyl radical, n -Butylphenyl group, isobutylphenyl group, s-butylphenyl group, t-butylphenyl group, pentylphenyl group, isopentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, 3,7-dimethyloctylphenyl group, dodecylphenyl group and the like are exemplified, and dimethylphenyl group, dimethyl-t-butylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, isopropylphenyl group, n-butylphenyl group ,I Butylphenyl group, s-butylphenyl group, t-butylphenyl group, pentylphenyl group, isopentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, 3,7-dimethyl Octylphenyl and dodecylphenyl groups are preferred.

Aralkyl groups, usually about 7 to 60 carbon atoms, preferably 7 to 48, and examples thereof include phenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ Examples include alkyl groups, 1-naphthyl-C ₁ -C ₁₂ alkyl groups, 2-naphthyl-C ₁ -C ₁₂ alkyl groups, and the like.
Solubility in organic solvents, from the viewpoint of easiness of synthesis, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group are preferable.

The monovalent heterocyclic group is a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 4 to 60 carbon atoms, preferably 4 to 20 carbon atoms. The carbon number of the heterocyclic group does not include the carbon number of the substituent. Here, the heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, etc. in the ring. Say. Specifically, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, piperidyl group, quinolyl group, isoquinolyl group and the like.
Solubility in organic solvents, from the viewpoint of easiness of synthesis and the like, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, and C ₁ -C ₁₂ alkyl pyridyl group are preferable.

The arylalkenyl group has a carbon number of usually about 8 to 60, specifically, a phenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkenyl group, 1- Examples include a naphthyl-C ₂ -C ₁₂ alkenyl group, a 2-naphthyl-C ₂ -C ₁₂ alkenyl group, and the like.
Solubility in organic solvents, from the viewpoint of easiness of synthesis, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkenyl groups are preferred.

The arylalkynyl group has a carbon number of usually about 8 to 60, specifically, a phenyl -C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group, 1- Examples thereof include a naphthyl-C ₂ -C ₁₂ alkynyl group and a 2-naphthyl-C ₂ -C ₁₂ alkynyl group.
Solubility in organic solvents, from the viewpoint of easiness of synthesis, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group are preferable.

The alkoxy group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples thereof include a methoxy group, an ethoxy group, and a propyloxy group. , Isopropyloxy group, n-butoxy group, isobutoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, dodecyloxy group and the like can be mentioned.
From the viewpoints of solubility in an organic solvent and ease of synthesis, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a decyloxy group, and a 3,7-dimethyloctyloxy group are preferable. .

The aryloxy group usually has about 6 to 60 carbon atoms, preferably 7 to 48. Specific examples thereof include a phenoxy group, a C _{1 to} C ₁₂ alkylphenoxy group, a 1-naphthyloxy group, and 2-naphthyl. An oxy group etc. are illustrated.
From the viewpoints of solubility in an organic solvent and ease of synthesis, a C _{1 to} C ₁₂ alkylphenoxy group is preferable.
Specific examples of the C ₁ -C ₁₂ alkylphenoxy group include methylphenoxy group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-trimethylphenoxy group, methylethylphenoxy group, isopropylphenoxy group, n- Examples include butylphenoxy, isobutylphenoxy, t-butylphenoxy, pentylphenoxy, isopentylphenoxy, hexylphenoxy, heptylphenoxy, octylphenoxy, nonylphenoxy, decylphenoxy, dodecylphenoxy The

The aralkyloxy group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include a phenylmethoxy group, a phenylethoxy group, a phenyl-n-butoxy group, and a phenylpentyloxy group. , phenylhexyloxy group, phenyl heptyloxy group, phenyl -C ₁ -C ₁₂ alkoxy groups such as a phenyl octyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy groups, 1-naphthyl -C ₁ ~ C ₁₂ alkoxy groups, 2-naphthyl -C ₁ -C ₁₂ alkoxy groups.
Solubility in organic solvents, from the viewpoint of easiness of synthesis, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy group are preferable.

The alkylthio group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples thereof include a methylthio group, an ethylthio group, a propylthio group, Isopropylthio group, n-butylthio group, isobutylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7- Examples thereof include dimethyloctylthio group and dodecylthio group.
From the viewpoints of solubility in an organic solvent and ease of synthesis, a pentylthio group, a hexylthio group, an octylthio group, a 2-ethylhexylthio group, a decylthio group, and a 3,7-dimethyloctylthio group are preferable.

The arylthio group has a carbon number of usually about 3 to 60, and specific examples thereof include a phenylthio group, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group and 2-naphthylthio groups.
From the viewpoints of solubility in an organic solvent and ease of synthesis, a C _{1 to} C ₁₂ alkylphenylthio group is preferred.

Arylalkylthio group, usually about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms, and examples thereof include phenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group, 1-naphthyl -C ₁ -C ₁₂ alkylthio group, 2-naphthyl -C ₁ -C ₁₂ alkylthio groups.
Solubility in organic solvents, from the viewpoint of easiness of synthesis, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group are preferable.

Examples of the substituted amino group include an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group, and usually has about 1 to 60 carbon atoms, Preferably it is C2-C48.
Specifically, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, n-butylamino group, isobutylamino group, t-butyl Amino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, dodecylamino group, cyclopentylamino group, cyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, diphenylamino group, (C ₁ -C ₁₂ alkylphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino group, 1- Fuchiruamino group, 2-naphthylamino group, pyridylamino group, pyridazinylamino group, pyrimidylamino group, Pirajiruamino group, triazyl amino group, phenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) amino groups, 1-naphthyl -C ₁ -C ₁₂ alkylamino group, 2-naphthyl -C ₁ -C ₁₂ Examples include alkylamino groups.
From the viewpoints of solubility in an organic solvent, ease of synthesis, and the like, disubstituted amino groups such as a dimethylamino group, a diethylamino group, a diphenylamino group, and a di (C _{1 to} C ₁₂ alkylphenyl) amino group are preferable. Diarylamino groups such as diphenylamino groups and di (C ₁ -C ₁₂ alkylphenyl) amino groups are more preferred.

Examples of the substituted silyl group include a silyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group. The substituted silyl group usually has about 1 to 60 carbon atoms, preferably 3 to 48 carbon atoms.
Specifically, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, dimethylisopropylpropylsilyl group, diethylisopropylsilyl 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, phenyl-C _1- C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylsilyl group, 1-naphthyl -C ₁ -C ₁₂ alkylsilyl group, 2-naphthyl -C ₁ -C ₁₂ alkylsilyl group, phenyl -C ₁ -C ₁₂ alkyl dimethicone Silyl group, triphenyl silyl group, tri -p- methylphenyl silyl group, tribenzylsilyl group, diphenylmethylsilyl group, t- butyl diphenyl silyl group, dimethyl phenyl silyl groups.

When the substituent represented by R or Ra includes an aryl group or a monovalent heterocyclic group, the hydrogen atom on the aryl group or monovalent heterocyclic group is an aryl group, an aralkyl group, or a monovalent group. Heterocyclic group, arylalkenyl group, arylalkynyl group, alkoxy group, aryloxy group, aralkyloxy group, alkylthio group, arylthio group, aralkylthio group, substituted amino group, substituted silyl group, sulfonic acid group, phosphono group, cyano It may be substituted by a group or a nitro group. Among them, aryl groups, aralkyl groups, monovalent heterocyclic groups, alkoxy groups, aryloxy groups, aralkyloxy groups, alkylthio groups, arylthio groups, aralkylthio groups, substituted amino groups, substituted silyl groups, sulfonic acid groups, phosphono groups, A cyano group and a nitro group are preferable, and an alkyl group, an aryl group, an aralkyl group, a monovalent heterocyclic group, an alkoxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, an arylthio group, an aralkylthio group, and a substituted amino group Are more preferable, and an alkoxy group and an alkylthio group are even more preferable.
Specifically, for example, C ₁ -C ₁₂ alkoxyphenyl group, C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkynyl groups, C ₁ -C ₁₂ alkoxyphenoxy groups, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy groups, C ₁ -C ₁₂ alkoxyphenyl-thio groups, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkoxyphenyl amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino groups, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylamino groups, di (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, C ₁ -C such C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylsilyl group And a group having ₁₂ alkoxy substituent groups. Specific examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, propyloxy, isopropyloxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy , 2-ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, dodecyloxy and the like.

In addition, when the substituent represented by R or Ra includes an alkylene chain, any —CH ₂ — group in the alkylene chain includes a divalent heteroatom such as oxygen, sulfur, nitrogen, or a heteroatom. It may be substituted with a divalent group or a divalent group in which two or more of them are combined. Examples of the divalent group containing a divalent hetero atom and a hetero atom include groups represented by the formulas X-1 to X-5 and X-7 to X-10.

  Examples of the divalent group in which two or more divalent groups containing a divalent hetero atom or a hetero atom are combined include groups represented by the following formulas XX-1 to XX-4. .

上記式Ｘ−１〜Ｘ−５、Ｘ−６〜Ｘ−１０、及びＸＸ−１〜ＸＸ−４の中では、式Ｘ−１、Ｘ−２、Ｘ−３、Ｘ−５、及びＸ−７で示される基が好ましく、式Ｘ−１、及びＸ−２で示される基がより好ましく、式（Ｘ−１）で示される基がさらに好ましい。具体的には、メトキシメチルオキシ基、２−メトキシエチルオキシ基などが例示される。

Among the formulas X-1 to X-5, X-6 to X-10, and XX-1 to XX-4, the formulas X-1, X-2, X-3, X-5, and X- 7 is preferred, the groups represented by formulas X-1 and X-2 are more preferred, and the group represented by formula (X-1) is more preferred. Specific examples include a methoxymethyloxy group and a 2-methoxyethyloxy group.

Examples of the substituent represented by R in the group represented by Ar ¹ include an alkyl group, aryl group, aralkyl group, monovalent heterocyclic group, alkoxy group, aryloxy group, aralkyloxy group, alkylthio group, arylthio group, aralkyl. Thio group, substituted amino group, substituted silyl group, sulfonic acid group, phosphono group, cyano group, and nitro group are preferred, alkyl group, aryl group, aralkyl group, monovalent heterocyclic group, alkoxy group, aryloxy group, Aralkyloxy groups, alkylthio groups, arylthio groups, aralkylthio groups, and substituted amino groups are more preferred, alkyl groups, alkoxy groups, and alkylthio groups are more preferred, and alkyl groups are most preferred.

Examples of the substituent represented by Ra in the group represented by Ar ¹ include an alkyl group, an aryl group, an aralkyl group, a monovalent heterocyclic group, an alkoxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, an arylthio group, and an aralkyl group. A thio group, a substituted amino group, a substituted silyl group, an oxo group and a thioxo group are preferred, an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an oxo group and a thioxo group are more preferred, and an alkyl group and an alkoxy group are preferred. More preferred is an alkyl group.

In the repeating unit represented by the formula (1a) that may be contained in the polymer compound used as a raw material in the present invention, Ar ⁰ represents an arylene group, a divalent heterocyclic group or a divalent aromatic amine group. . The Ar ⁰ does not have a C—H bond on the aromatic ring. Ar ⁰ may have a substituent.

As the arylene group, divalent heterocyclic group, or divalent aromatic amine group represented by Ar ⁰ , the arylene group, divalent heterocyclic group, or divalent aromatic amine represented by Ar ¹ may be used. In the group, R is defined to represent a bond or a substituent. In the arylene group, divalent heterocyclic group, or divalent aromatic amine group represented by Ar ⁰ , any two of a plurality of Rs represent a bond, and the other represents a substituent. . When a plurality of substituents represented by R are present, they may be the same or different. Ra represents a hydrogen atom or a substituent. When a plurality of substituents represented by Ra are present, they may be the same or different. When two Ra are present on the same atom, they may be combined to form an oxo group or a thioxo group, or may be bonded to each other to form a ring.

（式中Ｒａは前記と同様の意味を表す。） In addition, examples of the divalent heterocyclic group represented by Ar ⁰ include groups of the following formulas 4A-1 to 4A-4.

(In the formula, Ra represents the same meaning as described above.)

In the linking group represented by the formulas X-1 to X-11, which may be included in the polymer compound used as a raw material in the present invention, Ar represents a hydrocarbon group having 6 to 60 carbon atoms, and R ″ represents Represents a group selected from a hydrogen atom, an alkyl group, an aryl group, and a monovalent heterocyclic group, and examples of the hydrocarbon group represented by Ar include formulas 1A-1 to 1A-14 in the examples of the arylene group in Ar ¹ . alkyl group in which an aromatic ring structure represented in is represented by is exemplified .R ", with respect to the aryl group, or a monovalent heterocyclic group, an alkyl group in the illustrative substituents R in the Ar ^1, aryl group, or Examples thereof are the same groups as the monovalent heterocyclic group.

The group in which two or more linking groups represented by the formulas X-1 to X-11 are combined may have a group represented by the formulas XX-1 to XX-4, a straight chain or a branched structure. , optionally C ₁ -C ₂₀ alkyl chains contain a cyclic structure, and any -CH ₂ - C ₁ -C ₂₀ alkyl chain exemplary group is interrupted by a group represented by the formula X-1 to X-15 Is done. Examples of the C ₁ -C ₂₀ alkyl chain include a methylene group, an ethylene group, a propyl-1,3-diyl group, a butyl-1,4-diyl group, a pentyl-1,5-diyl group, and a hexyl-1,6-diyl group. Group, octyl-1,8-diyl group, decyl-1,10-diyl group, octadecyl-1,18-diyl group, butyl-2,3-diyl group, 2,6-dimethyloctyl-1,8-diyl Group, cyclohexyl-1,4-diyl group, cyclohexyl-1,4-dimethyl-1′-1 ″ -diyl group and the like.

  Among the linking groups containing a non-conjugated moiety represented by the formulas X-1 to X-11 and XX-1 to XX-4, the formulas X-3, X-5, X-6, and X-8 to A linking group represented by X-11 is preferred, and linking groups represented by formulas X-3, X-5, X-6, and X-8 to X-10 are more preferred, and formulas X-3, X-5, And a linking group represented by X-6 is more preferred.

  In the method for producing an aromatic polymer compound of the present invention, the aromatic polymer compound as a raw material has the above formulas X-1 to X with respect to the total of repeating units represented by the above formulas (1) and (1a). The total of the linking groups including a non-conjugated moiety represented by -11 is required to be 40 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less, and more preferably 10 mol%. More preferably, it is particularly preferable that the linking group containing the non-conjugated moiety is not included.

  Here, as the total of the linking groups of the non-conjugated portion, the linking groups are counted as one linking group represented by the above formulas X-1 to X-11, and when two or more linking groups are combined, The total decomposed into the linking groups represented by the above formulas X-1 to X-11 shall be counted. For example, the linking group represented by the formula X-12 is counted as two. Moreover, in the branched alkyl chain, the minimum number of linking groups at the portion connecting the repeating units is counted. For example, the number of 2,6-dimethyloctyl-1,8-diyl groups is counted as eight.

Next, the conversion reaction of the C—H bond on the aromatic ring in the production method of the present invention will be described.
Examples of the conversion reaction of the C—H bond on the aromatic ring include those shown in Table 1 below.

  More specifically, the reaction conditions will be described. In the halogenation reaction, a halogenating agent such as bromine, chlorine, iodine, iodine monochloride, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide or the like having an equivalent amount to 10 equivalents or less of the halogen group to be introduced is used. Depending on the reactivity, 0.01 to 50 equivalents of an acid such as acetic acid, sulfuric acid, trifluoroacetic acid, trifluoromethanesulfonic acid may be added and reacted. As the solvent, an organic solvent such as chloroform, dichloromethane, 1,2-dichloroethane, N, N-dimethylformamide, tetrahydrofuran or the like is preferably used, but an acid such as acetic acid or sulfuric acid may be used as the solvent. The reaction can proceed at a reaction temperature of usually about 0 to 100 ° C. The reaction time is, for example, 5 minutes to 100 hours, but may be a time for which the reaction proceeds sufficiently, and since it is not necessary to leave for a long time after the reaction is completed, it is preferably 10 minutes to 50 hours. . If the concentration during the reaction is too dilute, the efficiency of the reaction is poor, and if it is too thick, it becomes difficult to control the reaction due to the precipitation of the polymer compound. It is usually in the range of 0.1 wt% to 30 wt%. The halogenation method is described in, for example, Polymer, Volume 30, page 1137 (1989), Japanese Patent Application Laid-Open No. 2002-241493, and the like.

  The nitration reaction is suitably performed at a temperature of 0 ° C. or higher and a boiling point or lower using a nitration reagent such as mixed acid, concentrated nitric acid, concentrated nitric acid-acetic acid or the like.

In Friedel-Crafts alkylation, halomethylation, and Friedel-Crafts acylation reactions, alkyl halides, terminal alkenes, alkylating reagents such as alcohols, halomethylating reagents such as formaldehyde and hydrogen chloride, acid chlorides, acid anhydrides, An acylating reagent such as carboxylic acid is appropriately reacted at a temperature of about room temperature to about 200 ° C. in the presence of an acid catalyst such as AlCl ₃ , FeCl ₃ , BF ₃ , and ZnCl ₂ . For example, these reactions are described in Organic Reactions, Volume 2, page 114, (1944).

In Gattermann aldehyde synthesis, formylation can be carried out by reacting hydrogen cyanide, Zn (CN) ₂ , triazine or the like with hydrogen chloride in the presence of a Lewis acid such as AlCl ₃ . For example, this reaction is described in Organic Reactions, Vol. 9, page 37, (1957), Chemical Review, Vol. 63, page 526 (1963).

  In the Vilsmeier formylation reaction, formylation can be carried out by appropriately reacting 1 to 5 equivalents of POCl 3 at about −20 ° C. to 40 ° C. in N, N-dimethylformamide. For example, this reaction is described in New Experimental Chemistry Course, Vol. 14, 688 (1977).

  Step (A) also includes a reaction that further induces the group introduced by the above various reactions to various characteristic groups by various reactions. Further, as the reaction to be induced, various known functional group conversion reactions can be used, and examples thereof include known reactions shown in Table 2 below.

  The conversion reaction of the C—H bond on the aromatic ring is preferably a halogenation reaction from the viewpoint of easy control of reactivity and introduction amount.

  After completion of the reaction, the reaction solution may be used for the next reaction as it is, but after completion of the reaction, the obtained polymer compound may be subjected to acid washing, alkali washing, neutralization, water washing, organic solvent washing, if necessary. It may be subjected to conventional separation operations such as reprecipitation, centrifugation, extraction, column chromatography, purification operations, drying and other operations. From the viewpoint of improving the yield of the next reaction, it is preferable to perform a separation operation, a purification operation, and drying.

In the repeating unit represented by the formula (2) in Step A of the production method of the present invention, the characteristic group represented by X includes a halogen atom, —OSO ₂ Q ¹ , —B (OQ ² ) ₂ , —Sn. (Q ³ ) ₃ , Z ¹ (Z ² ) m, —OH, —CH ₂ Z ³ , —CHQ ⁴ —P ⁺ (Q ⁵ ) ₃ Z ⁴ , —CHQ ⁶ —P (═O) (OQ ⁷ ) ₂ , groups such as —C (═O) Q ⁸ , —NH ₂ and diazonio groups.
Q ¹ is a hydrocarbon group, Q ² is a hydrogen atom or a hydrocarbon group, and two Q ^{2 s} may be the same or different, and may be bonded to each other to form a ring. Q ³ is a hydrocarbon group, and three Q ³ may be the same or different. Q ⁴ is a hydrogen atom or a hydrocarbon group, Q ⁵ is a hydrocarbon group, and the three Q ^{5 s} may be the same or different from each other. Q ⁶ is a hydrogen atom or a hydrocarbon group, Q ⁷ is a hydrocarbon group, and two Q ^{7 s} may be the same or different from each other. Q ⁸ is a hydrogen atom or a hydrocarbon group. Z ¹ is a metal atom or metal ion, Z ² is a counter anion, and m represents an integer of 0 or more. Z ³ represents a halogen atom or a cyano group. Z ⁴ represents a monovalent counter anion.

The reactions in Table 2 will be described more specifically. It is known that a —NO ₂ group can be reduced to a —NH ₂ group by allowing a metal such as zinc, iron or tin to react with an acid such as hydrochloric acid. It is known that the —NH ₂ group can be diazotized with a nitrous acid purified by the action of an acid such as NaNO ₂ and hydrochloric acid and derived into a diazonium salt.
It is known that a diazonium salt can be converted into a halogen atom by a Sandmeyer reaction or the like, for example, by reacting hydrochloric acid, hydrobromic acid or the like in the presence of copper (I) halide. This reaction is described in, for example, Organic Synthesis, Collective Volume, Vol. 3, 185 (1955), Organic Synthesis, Collective Volume, Vol. 1, 33. (1973). In addition, it is known that diazonium salts can be converted to —OH groups by heating in the presence of water under acidic conditions.

As a conversion reaction of a halogen atom to a -Z ¹ (Z ² ) m group, it is known that it can be lithiated by a lithiation reagent such as n-alkyllithium, and metal magnesium, zinc, etc. It is known that it can be converted into a magnesium halide group, a zinc halide group, or the like by a metallation reaction by the action of Gr, and a Grignard exchange reaction with isopropyl (i-Pr) MgCl or the like. For example, these reactions are described in Angew. Chem. Int. Ed. Vol. 37, p. 1701 (1998). The Grignard reaction is described, for example, in Bulletin of Chemical Society of Japan, Vol. 51, p. 2091 (1978), Chemistry Letters, p. ing.
Further, a halogen atom, a hexaalkyl stannane in the presence of a palladium catalyst, it is known that can be converted into a group represented by -Sn (Q ^{₃₎ 3.} For example, this reaction is described in Angew. Chem. Int. Ed. Vol. 25, p. 508 (1986).

A group represented by —Z ¹ (Z ² ) m such as —Li, —MgCl, —MgBr, etc. can be derived into a —B (OH) ₂ group by hydrolysis with, for example, trimethoxyborane. It is also known that it can be derived into a boronic ester group by the action of isopropoxypinacol borane. For example, this reaction can be performed as described in Journal of American Chemical Society Vol. 126, p. 7041 (2004).
A group represented by -Z ¹ (Z ² ) m, such as -Li, -MgCl, and -MgBr, is derived into -OH group by, for example, oxidative decomposition with hydrogen peroxide after acting trialkoxyborane. It is known that it can be done.
It is known that a group represented by —Z ¹ (Z ² ) m such as —Li, —MgCl, and —MgBr can be converted into a —CHO group by acting, for example, DMF or N-formylpiperidine. Yes. For example, this reaction is described in Synthesis, p. 228 (1984).

It is known that a methyl group can be converted into a halomethyl group such as —CH ₂ Cl and —CH ₂ Br by the action of SOCl ₂ , SOBr ₂ and the like. Further, it is known that a halomethyl group can be derived into a group represented by -CHQ ⁴ -P ⁺ (Q ⁵ ) ₃ Z ⁴ by the action of triphenylphosphine, and phosphorous acid can be obtained by an Arbuzov reaction. by the action of such trialkyl, it can be guided to the group represented by ^{-CHQ 6 -P (= O) (} OQ 7) 2.

  In the repeating unit represented by the above formula (2), among the characteristic groups represented by X, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom, a bromine atom, and an iodine atom Are preferable, a chlorine atom and a bromine atom are more preferable, and a bromine atom is still more preferable.

In the above formula, examples of the hydrocarbon group in the group represented by Q ¹ , Q ² , Q ³ , Q ⁴ , Q ⁵ , Q ⁶ , Q ⁷ , and Q ⁸ include, for example, a methyl group, an ethyl group, and a propyl group. An alkyl group having about 1 to 50 carbon atoms such as isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, nonyl group, dodecyl group, pentadecyl group, octadecyl group, docosyl group; A cyclic saturated hydrocarbon group having about 3 to 50 carbon atoms such as cyclobutyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group, cyclododecyl group, norbornyl group, adamantyl group, etc .; ethenyl group, propenyl group, 3- Alkene having about 2 to 50 carbon atoms such as butenyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-nonenyl, 2-dodecenyl Phenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl Aryl groups having about 6 to 50 carbon atoms such as 4-butylphenyl group, 4-t-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, 4-adamantylphenyl group, 4-phenylphenyl group, etc. Phenylphenyl group, 1-phenyleneethyl group, 2-phenylethyl group, 1-phenyl-1-propyl group, 1-phenyl-2-propyl group, 2-phenyl-2-propyl group, 1-phenyl-3- 7 to 50 carbon atoms such as propyl group, 1-phenyl-4-butyl group, 1-phenyl-5-pentyl group, 1-phenyl-6-hexyl group A degree of aralkyl group. As this hydrocarbon group, a C1-C20 hydrocarbon group is preferable, More preferably, it is a C1-C12 hydrocarbon group, More preferably, it is a C1-C8 hydrocarbon group. The hydrocarbon group may have a substituent.

Q ¹ in -OSO ₂ Q ¹ is a hydrocarbon group which may have a substituent, examples of the hydrocarbon group, the hydrocarbon group, and examples of the substituent include fluorine atom and a nitro group, Is mentioned.
Examples of the group represented by —OSO ₂ Q ¹ include an alkyl sulfonate group, an aryl sulfonate group, and an aryl alkyl sulfonate group. Examples of the alkyl sulfonate group include a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group. Examples of the aryl sulfonate group include a benzene sulfonate group, a p-toluene sulfonate group, a p-nitrobenzene sulfonate group, and an o-nitrobenzene sulfonate group. Examples of the aryl alkyl sulfonate group include a benzyl sulfonate group. Preferable examples include a trifluoromethanesulfonate group, a benzenesulfonate group, a p-toluenesulfonate group, and a p-nitrobenzenesulfonate group, and more preferable examples include a trifluoromethanesulfonate group.

-B (OQ ²⁾ Q ² in ₂ is a hydrogen atom, or an optionally substituted hydrocarbon group, forming two Q ² is may be the same or different and bonded to each other to form a ring You may do it. Examples of the hydrocarbon group include the hydrocarbon groups described above, and an alkyl group is preferable, and a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, and nonyl group are more preferable. More preferred are methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group. In the case of forming a ring, as the bifunctional hydrocarbon group consisting of two Q ² , 1,2-ethylene group, 1,1,2,2-tetramethyl-1,2-ethylene group, 1, 3-propylene group, 2,2-dimethyl-1,3-propylene group, and 1,2-phenylene group are preferred. Examples of the substituent include an amino group.
Examples of the group represented by —B (OQ ² ) ₂ include groups represented by the following formulae.

-Sn (Q ³⁾ Q ³ in ₃ is a hydrocarbon group which may have a substituent, three Q ³ are may be the same or different. Examples of the hydrocarbon group include the hydrocarbon groups described above, and an alkyl group is preferable, and a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, and a nonyl group are more preferable. More preferred are a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Examples of the substituent include an amino group and an alkoxy group.
Examples of the group represented by —Sn (Q ³ ) ₃ include a tri (n-butyl) tin group and a triphenyltin group.

In Z ¹ (Z ² ) m, Z ¹ is a metal atom or metal ion, Z ² is a counter anion, and m is an integer of 0 or more. Specific examples of Z ¹ include Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Pb, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Ag, Cd, La, Ce, Sm, Eu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Atoms or ions such as Hg can be mentioned. Preferred are Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Pb, Sc, Ti, Cu, Zn, Y, Zr, Ag, and Hg. More preferably Li, Na, K, Rb, Cs, Be, Mg, Ca, In, Tl, Pb, Cu, Zn, Zr, Ag, and Hg, and more preferably Li, Na, K, Mg, Ca, Cu, and Zn.

As Z ² , a conjugate base of Bronsted acid is usually used, and specific examples include fluoride ion, chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, carbonate ion, perchlorate ion. , Tetrafluoroborate ion, hexafluorophosphate ion, methanesulfonate ion, trifluoromethanesulfonate ion, toluenesulfonate ion, acetate ion, trifluoroacetate ion, propionate ion, benzoate ion, hydroxide ion, oxidation A product ion, a methoxide ion, an ethoxide ion, and the like. Preferably chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, carbonate ion, methanesulfonate ion, trifluoromethanesulfonate ion, toluenesulfonate ion, acetate ion, trifluoroacetate ion, propionate ion, And benzoate ion, more preferably chloride ion, bromide ion, iodide ion, methanesulfonate ion, trifluoromethanesulfonate ion, toluenesulfonate ion, acetate ion, trifluoroacetate ion, propionate ion, benzoate Acid ions, and more preferably chloride ions, bromide ions, iodide ions, methanesulfonate ions, trifluoromethanesulfonate ions, acetate ions, and trifluoroacetate ions.

Ｚ¹(Ｚ²)ｍ部分を＋１価として、下記一般式（２−３）

で示される部分を−ｎ価としてみなし、Ｚ¹(Ｚ²)ｍ部分と残りの部分とはイオン結合しているとみなした方が好ましい。
Ｚ¹(Ｚ²)ｍで示される原子団としては、ハロゲン化亜鉛基、アルカリ金属原子、ハロゲン化アルカリ土類金属基などが例示される。ハロゲン化亜鉛基としては、塩化亜鉛基、臭化亜鉛基、ヨウ化亜鉛基などが例示され、好ましくは塩化亜鉛基、及び臭化亜鉛基が挙げられる。アルカリ金属原子としては、リチウム、ナトリウム、カリウムなどが例示され、好ましくは、リチウム、及びナトリウムが挙げられる。ハロゲン化アルカリ土類金属基としては、塩化マグネシウム基、臭化マグネシウム基、ヨウ化マグネシウム基、塩化カルシウム基、臭化カルシウム基、ヨウ化カルシウム基などが例示される。好ましくは、塩化マグネシウム基、臭化マグネシウム基、及びヨウ化マグネシウム基が挙げられる。 m is determined so as to be electrically neutral as the aromatic compound represented by the general formula (I). When the characteristic group represented by X is Z ¹ (Z ² ) m, that is, when the repeating unit represented by the general formula (2) is represented by the following formula (2-2),

When the Z ¹ (Z ² ) m portion is +1 valent, the following general formula (2-3)

It is preferable that the portion represented by the formula ( ¹ ) is regarded as -n valence, and the Z ¹ (Z ² ) m portion and the remaining portion are regarded as being ionically bonded.
Examples of the atomic group represented by Z ¹ (Z ² ) m include a zinc halide group, an alkali metal atom, and a halogenated alkaline earth metal group. Examples of the zinc halide group include a zinc chloride group, a zinc bromide group, and a zinc iodide group, and a zinc chloride group and a zinc bromide group are preferable. Examples of the alkali metal atom include lithium, sodium, potassium and the like, preferably lithium and sodium. Examples of the alkaline earth metal halide group include a magnesium chloride group, a magnesium bromide group, a magnesium iodide group, a calcium chloride group, a calcium bromide group, and a calcium iodide group. Preferably, a magnesium chloride group, a magnesium bromide group, and a magnesium iodide group are mentioned.

Z ³ in -CH ₂ Z ³ represents a halogen atom or a cyano group. Examples of the halogen atom represented by Z ³ include a chlorine atom, a bromine atom, and an iodine atom, and among them, a chlorine atom and a bromine atom are preferable.

^{-CHQ 4 -P + (Q 5)} Q 4 in ₃ Z ⁴ is a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include the above-described hydrocarbon groups, and a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, and the like are preferable. Q ⁵ is a hydrocarbon group which may have a substituent, and three Q ³ may be the same or different. Examples of the hydrocarbon group include the hydrocarbon groups described above, and a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group are preferable. Z ⁴ represents a monovalent counter anion. As the monovalent counter anion represented by Z ⁴ , a conjugate base of Bronsted acid is usually used. Specific examples include fluoride ion, chloride ion, bromide ion, iodide ion, sulfate ion, nitric acid. Ion, carbonate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, methanesulfonate ion, trifluoromethanesulfonate ion, toluenesulfonate ion, acetate ion, trifluoroacetate ion, propionate ion, benzoic acid An acid ion, a hydroxide ion, an oxide ion, a methoxide ion, an ethoxide ion, etc. are mentioned. Preferred are chloride ion, bromide ion, iodide ion, tetrafluoroborate ion, and trifluoromethanesulfonate ion, and more preferred are chloride ion and bromide ion. Examples of the group represented by —CHQ ⁴ —P ⁺ (Q ⁵ ) ₃ Z ⁴ include the following groups.

^{-CHQ 6 -P (= O) Q} 6 in (OQ ⁷⁾ ₂ is a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include the above-described hydrocarbon groups, and a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, and the like are preferable. Q ⁷ is a hydrocarbon group which may have a substituent, and two Q ³ may be the same or different. Examples of the hydrocarbon group include the hydrocarbon groups described above, and a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group are preferable.

Q ⁸ in -C (= O) Q ⁸ is a hydrogen atom, or a hydrocarbon group. Examples of the hydrocarbon group include the above-described hydrocarbon groups, and a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a phenyl group, a benzyl group, and the like are preferable. Examples of the group represented by —C (═O) Q ⁸ include a formyl group, an acetyl group, a benzoyl group, a benzylcarbonyl group, and the like, and a formyl group and a benzoyl group are preferable.

Examples of the diazonio group include groups such as —N ₂ ⁺ Br ⁻ , —N ₂ ⁺ Cl ⁻ , —N ₂ ⁺ (HSO ₄ ) ⁻ , —N ₂ ⁺ (BF ₄ ) ⁻ .

The characteristic group X introduced by the production method of the present invention includes —OSO ₂ Q ¹ , which is a halogen atom and a group derived from a halogen atom because of the reactivity during introduction and ease of control of the amount introduced. _{^{, -B (OQ 2) 2,}} -Sn (Q 3) 3, Z 1 (Z 2) m, -OH, -C (= O) is preferably a group such as Q ^8, a halogen atom, -OSO ₂ Q ¹ , —B (OQ ² ) ₂ , —Sn (Q ³ ) ₃ , Z ¹ (Z ² ) m, and —CHO are more preferable, and a halogen atom is most preferable.

  Next, a method for producing an aromatic polymer compound having a bromo group in the production method of the present invention in a high yield under a mild condition and controlling the bromination rate with a high bromination yield Will be described. In the organic solvent, the aromatic polymer compound containing one or more types of repeating units represented by the general formula (1) is added to an organic strong acid at least 5 moles relative to the total of the repeating units. It is characterized by allowing a brominating agent to act in the presence of.

  Examples of strong organic acids used include strong organic acids such as trifluoroacetic acid, trifluoromethanesulfonic acid, nonafluoro-n-butanesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, p-nitrobenzenesulfonic acid, and the like. And trifluoromethanesulfonic acid are preferred, and trifluoroacetic acid is more preferred from the viewpoint of ease of purification of the brominated aromatic polymer compound obtained by the production method of the present invention.

  The amount of the strong organic acid used is required to be 5 moles or more with respect to the total of the repeating units in the aromatic polymer compound containing one or more repeating units represented by the general formula (1). It is preferable to use 10 mol times or more, and more preferably 15 mol times or more. The upper limit is preferably such that the solubility of the aromatic polymer compound to be used is not hindered, and is preferably 30% by weight or less, more preferably 20% by weight or less based on the organic solvent used. If the amount of the strong organic acid used is less than the lower limit, the reactivity may be reduced, and if it exceeds the upper limit, the solubility of the aromatic polymer compound may be hindered.

  As the brominating agent, bromine is preferable from the viewpoints of economy, reactivity of bromination reaction, and ease of purification of the brominated aromatic polymer compound obtained by the production method of the present invention.

  Since the production method of the present invention has a high bromination yield, the bromination rate of the aromatic polymer compound can be controlled by the amount of the brominating agent used. Therefore, the amount of brominating agent to be used is selected depending on the desired ratio of bromination, and is preferably 1 mol% or more with respect to the total of repeating units represented by the above formula (1). It is less than mol times. In order to accurately control the bromination rate, the ratio of bromination is preferably 100% or less, more preferably 80% or less, further preferably 60% or less, and 50% or less. It is particularly preferred that In the present invention, the ratio of bromination is the number of bromine atoms introduced relative to the total number of repeating units represented by the above formula (1) contained in the aromatic polymer compound as a raw material. The bromination yield represents the ratio of the number of moles of bromine atoms introduced into the aromatic polymer compound to the number of moles of bromine used as the halogenating agent.

  As the organic solvent used here, halogenated methanes or halogenated ethanes are preferable. Here, the halogenated methanes mean a compound group in which 1 to 4 of the 4 hydrogen atoms of methane are substituted with halogen atoms. The same meaning is also applied to halogenated ethanes. Among them, methylene chloride, chloroform, and 1,2-dichloroethane are preferable as the organic solvent to be used. In the selection of the organic solvent, it is preferable that the aromatic polymer compound to be used has a high solubility, preferably 0.1% by weight or more of the aromatic polymer compound, and 0.5% by weight. It is more preferable that it is soluble above, and it is even more preferable that it is 1% by weight or more.

  The amount of the organic solvent used is appropriately selected from 10 times by weight to 1000 times by weight and 20 times by weight with respect to the aromatic polymer compound as the raw material in consideration of the reactivity and solubility of the raw material. Preferably, it is more than 40 times by weight. As an upper limit, it is preferable that it is 500 weight times or less, and it is more preferable that it is 300 weight times or less.

  The bromination reaction temperature is appropriately selected from 0 ° C. to the boiling point of the solvent depending on the solubility of the aromatic polymer compound used as a raw material and the boiling point of the strong organic acid used, and may be refluxed. When the boiling point of the strong organic acid is lower than the boiling point of the solvent, the reaction is preferably carried out below the boiling point of the strong organic acid. In order to suppress side reactions other than bromination, it is preferably carried out in the range of 0 ° C to 30 ° C.

  The reaction time of the bromination reaction varies depending on the reaction temperature and other conditions, but is usually 10 minutes or longer, preferably about 1 to 200 hours.

  The bromination rate of the aromatic polymer compound can be determined by usual means such as NMR measurement and organic element analysis.

The aromatic polymer compound containing a repeating unit having the characteristic group X obtained by the production method of the present invention contains a repeating unit represented by the above formula (2). Ar ² in the above formula (2) represents an n + 2 valent arylene group or an n + 2 valent heterocyclic group in which n of C—H bonds on the aromatic ring of Ar ¹ are converted to C—X bonds, Represents an integer of 1 to 4.

  In the above formula (2), n represents an integer of 1 to 4, preferably 1 or 2, and more preferably 1.

  In the production method of the present invention, the aromatic polymer compound containing the repeating unit having the characteristic group X to be produced, and the aromatic polymer compound as a raw material are random, block or graft copolymers. Alternatively, it may be a polymer having an intermediate structure thereof, for example, a random copolymer having a block property. The case where the main chain is branched and there are three or more terminal portions is also included.

In the production method of the present invention, the aromatic polymer compound containing a repeating unit having the characteristic group X and the aromatic polymer compound as a raw material typically have a polystyrene-equivalent number average molecular weight of 10 is ³ to 10 ^8, preferably from 5x10 ³ ~5x10 ^7.

  As a method for extracting and purifying an aromatic polymer compound containing a repeating unit having a characteristic group X obtained by the production method of the present invention, a usual method can be used. For example, an aromatic polymer compound containing a repeating unit having a characteristic group X is precipitated by adding a reaction solution into a poor solvent, and the target product is taken out by filtration, washed with water, It is possible to carry out reprecipitation purification using a solvent.

  Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.

(Number average molecular weight and weight average molecular weight)
Here, regarding the number average molecular weight (Mn), the weight average molecular weight (Mw), and the peak top molecular weight (Mp), the number average molecular weight (Mn), the weight average molecular weight (Mw), and the peak top molecular weight (Mp) converted to polystyrene by GPC. )
<GPC Measurement Method A> By GPC (manufactured by Shimadzu Corporation: LC-10Avp (trade name)), two TSKgel SuperHM-H (trade name) (manufactured by Tosoh) and one TSKgel SuperH2000 (trade name) (manufactured by Tosoh) are used. Using columns connected in series, tetrahydrofuran was used as a developing solvent, and flowed at a flow rate of 0.6 mL / min, and measurement was performed at 40 ° C. A differential refractive index detector (manufactured by Shimadzu Corporation: RID-10A (trade name)) was used as the detector.
<GPC measurement method B> By using PL-GPC210 system (trade name) (RI detection) manufactured by Polymer Laboratories, PLgel 10um MIXED-B (trade name) 3 manufactured by Polymer Laboratories was used as a column, and o-dichlorobenzene (2, 6-di-t-butyl-4-methylphenol 0.01% w / v) was used as a developing solvent at 70 ° C.
<GPC Measurement Method C> Tetrahydrofuran was developed using a column in which three TSKgel SuperHM-H (trade name) (manufactured by Tosoh) were directly connected by the Tosoh HLC-8220 GPC system (trade name) (RI detection). The solvent was flowed at a flow rate of 0.5 mL / min and measured at 40 ° C. A differential refractive index detector was used as the detector.

(NMR measurement)
The NMR measurement was performed at room temperature using an INOVA300 nuclear magnetic resonance apparatus manufactured by Varian as a deuterated tetrahydrofuran solution.

不活性雰囲気下、３００ｍｌ三つ口フラスコに１‐ナフタレンボロン酸５．００ｇ（２９ｍｍｏｌ）、２−ブロモベンズアルデヒド６．４６ｇ（３５ｍｍｏｌ）、炭酸カリウム１０.０ｇ（７３ｍｍｏｌ）、トルエン３６ｍｌ、及びイオン交換水３６ｍｌを入れ、室温で撹拌しつつ２０分間アルゴンバブリングした。続いてテトラキス（トリフェニルホスフィン）パラジウム１６．８ｍｇ（０.１５ｍｍｏｌ）を入れ、さらに室温で撹拌しつつ１０分間アルゴンバブリングした。１００℃に昇温し、２５時間反応を行った。室温まで冷却後、トルエンで有機層を抽出、硫酸ナトリウムで乾燥後、溶媒を留去した。トルエン：シクロヘキサン＝１：２混合溶媒を展開溶媒としたシリカゲルカラムで生成することにより、化合物Ａ ５.１８ｇ（収率８６％）を白色結晶として得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ７．３９〜７．６２（ｍ、５Ｈ）、７．７０（ｍ、２Ｈ）、７．９４（ｄ、２Ｈ）、８．１２（ｄｄ、２Ｈ）、９．６３（ｓ、１Ｈ）
ＭＳ（ＡＰＣＩ（＋））：（Ｍ＋Ｈ）⁺ ２３３ Synthesis example 1
<Synthesis of Compound F>
(Synthesis of Compound A)

Under an inert atmosphere, in a 300 ml three-necked flask, 5.00 g (29 mmol) of 1-naphthaleneboronic acid, 6.46 g (35 mmol) of 2-bromobenzaldehyde, 10.0 g (73 mmol) of potassium carbonate, 36 ml of toluene, and ion-exchanged water 36 ml was added, and argon was bubbled for 20 minutes while stirring at room temperature. Subsequently, 16.8 mg (0.15 mmol) of tetrakis (triphenylphosphine) palladium was added, and argon was bubbled for 10 minutes while stirring at room temperature. The temperature was raised to 100 ° C. and the reaction was carried out for 25 hours. After cooling to room temperature, the organic layer was extracted with toluene, dried over sodium sulfate, and the solvent was distilled off. By producing with a silica gel column using a mixed solvent of toluene: cyclohexane = 1: 2 as a developing solvent, 5.18 g of Compound A (yield 86%) was obtained as white crystals.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 7.39-7.62 (m, 5H), 7.70 (m, 2H), 7.94 (d, 2H), 8.12 (dd, 2H), 9.63 (s, 1H)
MS (APCI (+)): (M + H) ^<+> 233

不活性雰囲気下で３００ｍｌの三つ口フラスコに化合物Ａ ８．００ｇ（３４.４ｍｍｏｌ）と脱水ＴＨＦ４６ｍｌを入れ、−７８℃まで冷却した。続いてｎ−オクチルマグネシウムブロミド（１.０ｍｏｌ／ｌＴＨＦ溶液）５２ｍｌを３０分かけて滴下した。滴下終了後０℃まで昇温し、１時間撹拌後、室温まで昇温して４５分間撹拌した。氷浴して１Ｎ塩酸２０ｍｌを加えて反応を終了させ、酢酸エチルで有機層を抽出、硫酸ナトリウムで乾燥した。溶媒を留去した後トルエン：ヘキサン＝１０：１混合溶媒を展開溶媒とするシリカゲルカラムで精製することにより、化合物Ｂ ７．６４ｇ（収率６４％）を淡黄色のオイルとして得た。ＨＰＬＣ測定では２本のピークが見られたが、ＬＣ−ＭＳ測定では同一の質量数であることから、異性体の混合物であると判断した。 (Synthesis of Compound B)

Under an inert atmosphere, 8.00 g (34.4 mmol) of Compound A and 46 ml of dehydrated THF were placed in a 300 ml three-necked flask and cooled to -78 ° C. Subsequently, 52 ml of n-octylmagnesium bromide (1.0 mol / l THF solution) was added dropwise over 30 minutes. After completion of dropping, the temperature was raised to 0 ° C., stirred for 1 hour, then warmed to room temperature and stirred for 45 minutes. The reaction was terminated by adding 20 ml of 1N hydrochloric acid in an ice bath, and the organic layer was extracted with ethyl acetate and dried over sodium sulfate. After distilling off the solvent, the residue was purified by a silica gel column using a mixed solvent of toluene: hexane = 10: 1 as a developing solvent to obtain 7.64 g (yield: 64%) of Compound B as a pale yellow oil. Although two peaks were observed in the HPLC measurement, they were determined to be a mixture of isomers because they were the same mass number in the LC-MS measurement.

不活性雰囲気下、５００ｍｌ三つ口フラスコに化合物Ｂ（異性体の混合物）５.００ｇ（１４.４ｍｍｏｌ）と脱水ジクロロメタン７４ｍｌを入れ、室温で撹拌、溶解させた。続いて、三フッ化ホウ素のエーテラート錯体を室温で１時間かけて滴下し、滴下終了後室温で４時間撹拌した。撹拌しながらエタノール１２５ｍｌをゆっくりと加え、発熱がおさまったらクロロホルムで有機層を抽出、２回水洗し、硫酸マグネシウムで乾燥した。溶媒を留去後、ヘキサンを展開溶媒とするシリカゲルカラムで精製することにより、化合物Ｃ ３．２２ｇ（収率６８％）を無色のオイルとして得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９０（ｔ、３Ｈ）、１．０３〜１．２６（ｍ、１４Ｈ）、２．１３（ｍ、２Ｈ）、４．０５（ｔ、１Ｈ）、７．３５（ｄｄ、１Ｈ）、７．４６〜７．５０（ｍ、２Ｈ）、７．５９〜７．６５（ｍ、３Ｈ）、７．８２（ｄ、１Ｈ）、７．９４（ｄ、１Ｈ）、８．３５（ｄ、１Ｈ）、８．７５（ｄ、１Ｈ）
ＭＳ（ＡＰＣＩ（＋））：（Ｍ＋Ｈ）⁺ ３２９ (Synthesis of Compound C)

Under an inert atmosphere, 5.00 g (14.4 mmol) of Compound B (mixture of isomers) and 74 ml of dehydrated dichloromethane were placed in a 500 ml three-necked flask and stirred and dissolved at room temperature. Subsequently, an etherate complex of boron trifluoride was added dropwise at room temperature over 1 hour, and after completion of the addition, the mixture was stirred at room temperature for 4 hours. While stirring, 125 ml of ethanol was slowly added. When the exotherm subsided, the organic layer was extracted with chloroform, washed twice with water, and dried over magnesium sulfate. After distilling off the solvent, the residue was purified by a silica gel column using hexane as a developing solvent to obtain 3.22 g (yield 68%) of Compound C as a colorless oil.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 3H), 1.03-1.26 (m, 14H), 2.13 (m, 2H), 4.05 (t, 1H), 7.35 (dd, 1H), 7 .46-7.50 (m, 2H), 7.59-7.65 (m, 3H), 7.82 (d, 1H), 7.94 (d, 1H), 8.35 (d, 1H) ), 8.75 (d, 1H)
MS (APCI (+)): (M + H) ^<+> 329

不活性雰囲気下２００ｍｌ三つ口フラスコにイオン交換水２０ｍｌを入れ、撹拌しながら水酸化ナトリウム１８．９ｇ（０.４７ｍｏｌ）を少量ずつ加え、溶解させた。水溶液が室温まで冷却した後、トルエン２０ｍｌ、化合物Ｃ ５.１７ｇ（１５.７ｍｍｏｌ）、及び臭化トリブチルアンモニウム１．５２ｇ（４.７２ｍｍｏｌ）を加え、５０℃に昇温した。臭化ｎ−オクチルを滴下し、滴下終了後５０℃で９時間反応させた。反応終了後トルエンで有機層を抽出し、２回水洗し、硫酸ナトリウムで乾燥した。ヘキサンを展開溶媒とするシリカゲルカラムで精製することにより、化合物Ｄ ５．１３ｇ（収率７４％）を黄色のオイルとして得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．５２（ｍ、２Ｈ）、０．７９（ｔ、６Ｈ）、１．００〜１．２０（ｍ、２２Ｈ）、２．０５（ｔ、４Ｈ）、７．３４（ｄ、１Ｈ）、７．４０〜７．５３（ｍ、２Ｈ）、７．６３（ｍ、３Ｈ）、７．８３（ｄ、１Ｈ）、７．９４（ｄ、１Ｈ）、８．３１（ｄ、１Ｈ）、８．７５（ｄ、１Ｈ）
ＭＳ（ＡＰＣＩ（＋））：（Ｍ＋Ｈ）⁺ ４４１ (Synthesis of Compound D)

Under an inert atmosphere, 20 ml of ion-exchanged water was placed in a 200 ml three-necked flask, and 18.9 g (0.47 mol) of sodium hydroxide was added little by little with stirring to dissolve. After the aqueous solution was cooled to room temperature, 20 ml of toluene, 5.17 g (15.7 mmol) of Compound C, and 1.52 g (4.72 mmol) of tributylammonium bromide were added, and the temperature was raised to 50 ° C. N-Octyl bromide was added dropwise, and after completion of the addition, the mixture was reacted at 50 ° C. for 9 hours. After completion of the reaction, the organic layer was extracted with toluene, washed twice with water, and dried over sodium sulfate. By purifying with a silica gel column using hexane as a developing solvent, 5.13 g (yield 74%) of Compound D was obtained as a yellow oil.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.52 (m, 2H), 0.79 (t, 6H), 1.00-1.20 (m, 22H), 2.05 (t, 4H), 7.34 (d, 1H), 7 40 to 7.53 (m, 2H), 7.63 (m, 3H), 7.83 (d, 1H), 7.94 (d, 1H), 8.31 (d, 1H), 8. 75 (d, 1H)
MS (APCI (+)): (M + H) ^<+> 441

空気雰囲気下、５０ｍｌの三つ口フラスコに化合物Ｄ４．００ｇ（９．０８ｍｍｏｌ）と酢酸：ジクロロメタン＝１：１混合溶媒５７ｍｌを入れ、室温で撹拌、溶解させた。続いて三臭化ベンジルトリメチルアンモニウム７．７９ｇ（２０．０ｍｍｏｌ）を加えて撹拌しつつ、塩化亜鉛を三臭化ベンジルトリメチルアンモニウムが完溶するまで加えた。室温で２０時間撹拌後、５％亜硫酸水素ナトリウム水溶液１０ｍｌを加えて反応を停止し、クロロホルムで有機層を抽出、炭酸カリウム水溶液で２回洗浄し、硫酸ナトリウムで乾燥した。ヘキサンを展開溶媒とするフラッシュカラムで２回精製した後、エタノール：ヘキサン＝１：１、続いて１０：１混合溶媒で再結晶することにより、化合物Ｅ ４．１３ｇ（収率７６％）を白色結晶として得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．６０（ｍ、４Ｈ）、０．９１（ｔ、６Ｈ）、１．０１〜１．３８（ｍ、２０Ｈ）、２．０９（ｔ、４Ｈ）、７．６２〜７．７５（ｍ、４Ｈ）、７．８９（ｓ、１Ｈ）、８．２０（ｄ、１Ｈ）、８．４７（ｄ、１Ｈ）、８．７２（ｄ、１Ｈ）
ＭＳ（ＡＰＰＩ（＋））：Ｍ⁺ ５９６ (Synthesis of Compound E)

Under an air atmosphere, 4.00 g (9.08 mmol) of Compound D and 57 ml of a mixed solvent of acetic acid: dichloromethane = 1: 1 were placed in a 50 ml three-necked flask, and the mixture was stirred and dissolved at room temperature. Subsequently, while adding 7.79 g (20.0 mmol) of benzyltrimethylammonium tribromide and stirring, zinc chloride was added until benzyltrimethylammonium tribromide was completely dissolved. After stirring at room temperature for 20 hours, the reaction was stopped by adding 10 ml of 5% aqueous sodium bisulfite solution, and the organic layer was extracted with chloroform, washed twice with aqueous potassium carbonate solution, and dried over sodium sulfate. After purification twice with a flash column using hexane as a developing solvent, 4.13 g (yield 76%) of Compound E was obtained by recrystallization from ethanol: hexane = 1: 1, followed by a 10: 1 mixed solvent. Obtained as crystals.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.60 (m, 4H), 0.91 (t, 6H), 1.01-1.38 (m, 20H), 2.09 (t, 4H), 7.62-7.75 (m, 4H), 7.89 (s, 1H), 8.20 (d, 1H), 8.47 (d, 1H), 8.72 (d, 1H)
MS (APPI (+)): M ⁺ 596

アルゴンガス雰囲気下、５００ｍＬの三つ口フラスコに化合物Ｅ１１．９７ｇ（２０．０ｍｍｏｌ）、市販脱水テトラヒドロフラン２００ｍＬ、及び市販脱水ジエチルエーテル２００ｍＬを仕込み、室温で攪拌して溶解させた後、−７８℃に冷却した中へ、ｎ−ブチルリチウムのヘキサン溶液（１．５４ｍｏｌ／Ｌ）１２．９９ｍＬ（２０．０ｍｍｏｌ）を３０分かけて、ゆっくりと滴下した。−７８℃で５０分間攪拌した後に、２−イソプロポキシ−４，４，５，５−テトラメチル−［１，３，２］ジオキサボロラン４．９０ｍＬ（２４．０ｍｍｏｌ）を１５分かけて滴下した。−７８℃で１時間攪拌した後、室温まで１．５時間かけて昇温し、２規定塩酸２００ｍＬ中へ反応マスを室温で滴下した。室温にて３０分攪拌した後に、油層を分液し、水層からジエチルエーテル４０ｍＬで抽出・分液し、得られた油層を合一した後に、蒸留水、５％炭酸水素ナトリウム水溶液、蒸留水で順次洗浄したのちに、無水硫酸ナトリウムで乾燥し、濃縮することで、淡黄色油状物として粗生成物を得た（１５．３ｇ）。得られた油状物をテトラヒドロフランに溶解し、メタノールを滴下して晶析させるという操作を３回繰り返すことにより、化合物Ｆ １１．０ｇ（収率８５％）を白色結晶として得た。
¹Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ₃）：
δ０．４０〜０．６０（ｍ、４Ｈ）、０．８０（ｔ、６Ｈ）、０．９０〜１．２０（ｍ、２０Ｈ）、１．４５（ｓ、１２Ｈ）、１．９４〜２．１７（ｍ、４Ｈ）、７．５４〜７．６４（ｍ、４Ｈ）、８．０３（ｓ、１Ｈ）、８．１９（ｄ、１Ｈ）、８．６６（ｄ、１Ｈ）、８．９２（ｄ、１Ｈ）
ＭＳ（ＡＰＰＩ（＋））：Ｍ⁺ ６４４ (Synthesis of Compound F)

In an argon gas atmosphere, 11.97 g (20.0 mmol) of compound E, 200 mL of commercially available dehydrated tetrahydrofuran, and 200 mL of commercially available dehydrated diethyl ether were charged into a 500 mL three-necked flask and dissolved by stirring at room temperature. While cooling, 12.99 mL (20.0 mmol) of a hexane solution (1.54 mol / L) of n-butyllithium was slowly added dropwise over 30 minutes. After stirring at −78 ° C. for 50 minutes, 4.90 mL (24.0 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl- [1,3,2] dioxaborolane was added dropwise over 15 minutes. After stirring at −78 ° C. for 1 hour, the temperature was raised to room temperature over 1.5 hours, and the reaction mass was dropped into 200 mL of 2N hydrochloric acid at room temperature. After stirring at room temperature for 30 minutes, the oil layer is separated, extracted and separated from the aqueous layer with 40 mL of diethyl ether, and the obtained oil layer is combined, and then distilled water, 5% aqueous sodium hydrogen carbonate solution, distilled water After washing sequentially with, dried over anhydrous sodium sulfate and concentrated to obtain a crude product as a pale yellow oil (15.3 g). The operation of dissolving the obtained oil in tetrahydrofuran and crystallizing it dropwise by adding methanol was repeated three times to obtain 11.0 g (yield 85%) of Compound F as white crystals.
¹ H-NMR (270 MHz / CDCl ₃ ):
δ 0.40 to 0.60 (m, 4H), 0.80 (t, 6H), 0.90 to 1.20 (m, 20H), 1.45 (s, 12H), 1.94 to 2. 17 (m, 4H), 7.54 to 7.64 (m, 4H), 8.03 (s, 1H), 8.19 (d, 1H), 8.66 (d, 1H), 8.92 (D, 1H)
MS (APPI (+)): M ⁺ 644

アルゴン雰囲気下、ジムロートを接続した１Ｌ三つ口フラスコに化合物Ｆ１０．０ｇ（１５．５ｍｍｏｌ），酢酸パラジウム１７３．９ｍｇ、及びトリシクロヘキシルホスフィン４３５．１ｍｇを加えた後、アルゴンガスにより容器内を置換した。ここにトルエン６２０ｍｌ、及びｎ−オクチルベンゼン（内部標準物質）８．６ｇを加え、１１０℃で１０分間攪拌した。このモノマー溶液に、２０重量％の水酸化テトラエチルアンモニウム水溶液８０ｍｌを注加し、１１０℃で１６ｈｒ攪拌した。液体クロマトグラフィーにて化合物Ｆが消失したのを確認した後、室温まで冷却し、有機層を水層と分離した。有機層を約２００ｍＬに濃縮後、エタノール１．８Ｌに加え、ポリマーを沈殿させた。沈殿物をろ過、減圧乾燥し粉末を得た。この粉末をトルエンに溶解させ、シリカゲルとアルミナのカラムに通液させ、溶液を乾固して、粉末を得た。この粉末をクロロホルム１３０ｍＬに溶解させ、エタノール１．５Ｌに滴下しポリマーを沈殿させ、沈殿物をろ過後乾燥し、重合体（以後、芳香族系高分子化合物１と呼ぶ）を６．４ｇ（収率９４．１％）得た。また、ポリスチレン換算の数平均分子量及び重量平均分子量は、それぞれＭｎ＝１．５×１０⁴、Ｍｗ＝３．１×１０⁴であった（ＧＰＣ測定法Ｂ）。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：δ ０．８３（ｂｓ）、１．１６（ｂｓ）、２．１９（ｂｓ）、７．３〜９．１（ｍ）、積分比は（アルキル基に由来するプロトン）／（アリール基に由来するプロトン）＝４．１９であった。 Synthesis example 2
<Synthesis of Aromatic Polymer Compound 1>

Under an argon atmosphere, 10.0 g (15.5 mmol) of compound F, 173.9 mg of palladium acetate, and 435.1 mg of tricyclohexylphosphine were added to a 1 L three-necked flask connected to a Dimroth, and the inside of the container was replaced with argon gas. . To this, 620 ml of toluene and 8.6 g of n-octylbenzene (internal standard substance) were added and stirred at 110 ° C. for 10 minutes. To this monomer solution, 80 ml of a 20 wt% tetraethylammonium hydroxide aqueous solution was added, and the mixture was stirred at 110 ° C. for 16 hours. After confirming the disappearance of Compound F by liquid chromatography, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer. The organic layer was concentrated to about 200 mL and then added to 1.8 L of ethanol to precipitate the polymer. The precipitate was filtered and dried under reduced pressure to obtain a powder. This powder was dissolved in toluene, passed through a column of silica gel and alumina, and the solution was dried to obtain a powder. This powder is dissolved in 130 mL of chloroform and added dropwise to 1.5 L of ethanol to precipitate a polymer. The precipitate is filtered and dried, and 6.4 g of polymer (hereinafter referred to as aromatic polymer compound 1) is collected. (Rate 94.1%). The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 1.5 × 10 ⁴ and Mw = 3.1 × 10 ⁴ (GPC measurement method B).
¹ H-NMR (300 MHz / CDCl ₃ ): δ 0.83 (bs), 1.16 (bs), 2.19 (bs), 7.3 to 9.1 (m), integral ratio is (alkyl group (Proton derived from) / (proton derived from aryl group) = 4.19.

不活性ガス雰囲気下、５０ｍＬフラスコに、芳香族系高分子化合物１（４００ｍｇ、ベンゾフルオレン繰り返し単位換算で０．９１２ｍｍｏｌ）、及びクロロホルム２０ｍＬを仕込み、室温にて攪拌して溶解させた後に、トリフルオロ酢酸１．４０ｍＬ（１８．２ｍｍｏｌ、ベンゾフルオレン単位に対して２０モル倍）、及び臭素１９．６μＬ（０．３８ｍｍｏｌ、ベンゾフルオレン単位に対して４２モル％）を順次仕込み、遮光下で１６時間攪拌した。反応マスをメタノール２００ｍＬに攪拌下で滴下することにより、沈殿化させた。得られた沈殿をろ過、メタノールで洗浄、減圧乾燥することで、重合体４０５ｍｇを得た。得られた重合体をブロモ化芳香族系高分子化合物１と呼ぶ。得られたブロモ化芳香族系高分子化合物１のポリスチレン換算の数平均分子量は、Ｍｎ＝１．５×１０⁴、重量平均分子量は、Ｍｗ＝３．２×１０⁴、ピークトップ分子量は、Ｍｐ＝３．３×１０⁴、分散度は、Ｍｗ／Ｍｎ＝２．１であった。（ＧＰＣ測定法Ｂ）
元素分析の結果、Ｂｒ基を有する繰り返し単位（式Ｐ−２）とＢｒ基を含有しない繰り返し単位（式Ｐ−１）の比率は（Ｐ−１）／（Ｐ−２）＝６２／３８に相当し、ブロモ化された割合は３８％、ブロモ化収率は９０％に相当する。
元素分析測定値：Ｃ ８４．３３％、Ｈ ８．８２％、Ｎ＜０．３％、Ｂｒ ６．４９％
元素分析計算値：Ｃ ８４．５５％、Ｈ ８．９６％、Ｎ ０％、Ｂｒ ６．４９％（（Ｐ−１）／（Ｐ−２）＝６２／３８での計算値）
¹Ｈ−ＮＭＲ測定の結果、高磁場側のアルキル基のプロトンに由来するピークは変化せず、低磁場側のアリール基のプロトンに由来するピークに変化が見られ、さらに、アリール基プロトンのアルキル基プロトンに対する積分比の低下が見られ、Ｂｒ基はベンゾフルオレンの芳香環部分に導入されていることが判明した。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：δ ０．８３（ｂｓ）、１．１６（ｂｓ）、２．１９（ｂｓ）、７．３〜９．３（ｍ）、積分比は（アルキル基に由来するプロトン）／（アリール基に由来するプロトン）＝４．４０であり、¹Ｈ−ＮＭＲ測定によるブロモ化された割合は３４％であり、ブロモ化収率は８１％であった。 Example 1
<Synthesis of Brominated Aromatic Polymer Compound 1: Bromination of Aromatic Polymer Compound 1>

In an inert gas atmosphere, an aromatic polymer compound 1 (400 mg, 0.912 mmol in terms of benzofluorene repeating units) and 20 mL of chloroform were charged in a 50 mL flask, and dissolved by stirring at room temperature. 1.40 mL of acetic acid (18.2 mmol, 20 mol times with respect to the benzofluorene unit) and 19.6 μL of bromine (0.38 mmol, 42 mol% with respect to the benzofluorene unit) were sequentially charged and stirred for 16 hours under light shielding. did. The reaction mass was precipitated by dropwise addition to 200 mL of methanol with stirring. The obtained precipitate was filtered, washed with methanol, and dried under reduced pressure to obtain 405 mg of a polymer. The resulting polymer is referred to as brominated aromatic polymer compound 1. The number average molecular weight of polystyrene conversion of the obtained brominated aromatic polymer compound 1 is Mn = 1.5 × 10 ⁴ , the weight average molecular weight is Mw = 3.2 × 10 ⁴ , and the peak top molecular weight is Mp. = 3.3 × 10 ⁴ , and the degree of dispersion was Mw / Mn = 2.1. (GPC measurement method B)
As a result of elemental analysis, the ratio of the repeating unit having a Br group (formula P-2) to the repeating unit not containing a Br group (formula P-1) is (P-1) / (P-2) = 62/38 The brominated proportion corresponds to 38% and the bromination yield corresponds to 90%.
Elemental analysis measured values: C 84.33%, H 8.82%, N <0.3%, Br 6.49%
Elemental analysis calculated values: C 84.55%, H 8.96%, N 0%, Br 6.49% (calculated value at (P-1) / (P-2) = 62/38)
As a result of ¹ H-NMR measurement, the peak derived from the proton of the alkyl group on the high magnetic field side did not change, and the peak derived from the proton of the aryl group on the low magnetic field side changed, and further the alkyl of the aryl group proton A decrease in the integration ratio with respect to the group proton was observed, and it was found that the Br group was introduced into the aromatic ring portion of benzofluorene.
¹ H-NMR (300 MHz / CDCl ₃ ): δ 0.83 (bs), 1.16 (bs), 2.19 (bs), 7.3 to 9.3 (m), integral ratio is (alkyl group a proton) = 4.40 derived from protons) / (aryl group derived from, brominated been proportions by the ¹ H-NMR measurement is 34%, bromo yield of was 81%.

Example 2
<Synthesis of Brominated Aromatic Polymer Compound 2: Bromination of Aromatic Polymer Compound 1>
In an inert gas atmosphere, an aromatic polymer compound 1 (20.0 mg, 0.0456 mmol in terms of benzofluorene repeating unit) and 1.0 mL of chloroform were charged into a 4 mL screw tube and dissolved by stirring at room temperature. After that, 70 μL of trifluoroacetic acid (0.91 mmol, 20 mol times with respect to the benzofluorene unit) and 0.7 μL of bromine (0.014 mmol, 30 mol% with respect to the benzofluorene unit) were sequentially added, sealed, light-shielded Stirred under for 16 hours. The reaction mass was precipitated by dropping into 20 mL of methanol with stirring. The obtained precipitate was filtered, washed with methanol, and dried under reduced pressure to obtain 19.9 mg of a polymer. The resulting polymer is referred to as brominated aromatic polymer compound 2. The number average molecular weight of polystyrene conversion of the obtained brominated aromatic polymer compound 2 is Mn = 1.3 × 10 ⁴ , the weight average molecular weight is Mw = 3.1 × 10 ⁴ , and the peak top molecular weight is Mp. = 3.2 × 10 ⁴ , and the degree of dispersion was Mw / Mn = 2.3. (GPC measurement method B)
As a result of elemental analysis, the ratio of the repeating unit having a Br group (formula P-2) to the repeating unit not containing a Br group (formula P-1) is (P-1) / (P-2) = 72/28 The brominated proportion corresponds to 28% and the bromination yield corresponds to 93%.
Elemental analysis measurements: C 85.39%, H 9.07%, N <0.3%, Br 4.79%
Calculated value of elemental analysis: C 86.07%, H 9.14%, N 0%, Br 4.79% (calculated value at (P-1) / (P-2) = 72/28)
^The integral ratio by ¹ H-NMR (300 MHz / CDCl ₃ ) corresponds to (proton derived from alkyl group) / (proton derived from aryl group) = 4.34, and brominated by ¹ H-NMR measurement. The proportion corresponds to 22% and the bromination yield corresponds to 73%.

Example 3
<Synthesis of Brominated Aromatic Polymer Compound 3: Bromination of Aromatic Polymer Compound 1>
In an inert gas atmosphere, an aromatic polymer compound 1 (20.0 mg, 0.0456 mmol in terms of benzofluorene repeating unit) and 1.0 mL of chloroform were charged into a 4 mL screw tube and dissolved by stirring at room temperature. After that, 70 μL of trifluoroacetic acid (0.91 mmol, 20 mol times with respect to the benzofluorene unit) and 1.6 μL of bromine (0.032 mmol, 70 mol% with respect to the benzofluorene unit) were sequentially added, sealed, light-shielded Stirred under for 16 hours. The reaction mass was precipitated by dropping into 20 mL of methanol with stirring. The obtained precipitate was filtered, washed with methanol, and dried under reduced pressure to obtain 21.4 mg of a polymer. The resulting polymer is referred to as brominated aromatic polymer compound 3. The number average molecular weight of polystyrene conversion of the obtained brominated aromatic polymer compound 3 is Mn = 1.3 × 10 ⁴ , the weight average molecular weight is Mw = 3.1 × 10 ⁴ , and the peak top molecular weight is Mp. = 3.3 × 10 ⁴ , and the degree of dispersion was Mw / Mn = 2.3. (GPC measurement method B)
As a result of elemental analysis, the ratio of the repeating unit having a Br group (formula P-2) to the repeating unit not containing a Br group (formula P-1) is (P-1) / (P-2) = 35/65 The brominated proportion corresponds to 65% and the bromination yield corresponds to 93%.
Elemental analysis measurements: C 79.11%, H 8.42%, N <0.3%, Br 10.61%
Elemental analysis calculated values: C 80.87%, H 8.52%, N 0%, Br 10.61% (calculated values at (P-1) / (P-2) = 35/65)
^The integral ratio according to ¹ H-NMR (300 MHz / CDCl ₃ ) is (proton derived from alkyl group) / (proton derived from aryl group) = 4.53, and the ratio of bromination by ¹ H-NMR measurement Was 56% and the bromination yield was 80%.

Example 4
<Synthesis of Brominated Aromatic Polymer Compound 4: Bromination of Aromatic Polymer Compound 1>
In an inert gas atmosphere, an aromatic polymer compound 1 (20.4 mg, 0.0465 mmol in terms of benzofluorene repeat unit) and 1.0 mL of chloroform were charged in a 4 mL screw tube and dissolved by stirring at room temperature. After that, 70 μL of trifluoroacetic acid (0.91 mmol, 20 mol times with respect to the benzofluorene unit) and 2.3 μL of bromine (0.045 mmol, 96 mol% with respect to the benzofluorene unit) were sequentially added, sealed, and light-shielded Stirred under for 16 hours. The reaction mass was precipitated by dropping into 20 mL of methanol with stirring. The obtained precipitate was filtered, washed with methanol, and dried under reduced pressure to obtain 22.7 mg of a polymer. The resulting polymer is referred to as brominated aromatic polymer compound 4. The resulting brominated aromatic polymer compound 4 has a polystyrene-equivalent number average molecular weight of Mn = 1.5 × 10 ⁴ , a weight average molecular weight of Mw = 3.2 × 10 ⁴ , and a peak top molecular weight of Mp = 3.3 × 10 ⁴ , and the degree of dispersion was Mw / Mn = 2.2. (GPC measurement method B)
As a result of elemental analysis, the ratio of the repeating unit having a Br group (formula P-2) to the repeating unit not containing a Br group (formula P-1) is (P-1) / (P-2) = 13/87. The brominated proportion corresponds to 87% and the bromination yield corresponds to 91%.
Elemental analysis measurements: C 78.18%, H 8.20%, N <0.3%, Br 13.75%
Elemental analysis calculated value: C 78.07%, H 8.18%, N 0%, Br 13.75% (calculated value at (P-1) / (P-2) = 13/87)
^The integral ratio according to ¹ H-NMR (300 MHz / CDCl ₃ ) is (proton derived from alkyl group) / (proton derived from aryl group) = 4.78, and the ratio of bromination by ¹ H-NMR measurement Was 94% and the bromination yield was 98%.

Example 5
<Synthesis of Brominated Aromatic Polymer Compound 5: Bromination of Aromatic Polymer Compound 1>
In an inert gas atmosphere, a 4 mL screw tube was charged with aromatic polymer compound 1 (20.0 mg, 0.0456 mmol in terms of benzofluorene repeating units) and 1.0 mL of dehydrated tetrahydrofuran and dissolved by stirring at room temperature. After that, 70 μL of trifluoroacetic acid (0.91 mmol, 20 mol times with respect to the benzofluorene unit) and 2.3 μL of bromine (0.045 mmol, 98 mol% with respect to the benzofluorene unit) were sequentially charged, Stir for 16 hours in the dark. The reaction mass was precipitated by dropping into 20 mL of methanol with stirring. The obtained precipitate was filtered, washed with methanol, and dried under reduced pressure to obtain 19.6 mg of a polymer. The resulting polymer is referred to as brominated aromatic polymer compound 5. The number average molecular weight of polystyrene conversion of the obtained brominated aromatic polymer compound 5 is Mn = 1.5 × 10 ⁴ , the weight average molecular weight is Mw = 3.1 × 10 ⁴ , and the peak top molecular weight is Mp. = 3.3 × 10 ⁴ , and the degree of dispersion was Mw / Mn = 2.1. (GPC measurement method B)
^The integral ratio according to ¹ H-NMR (300 MHz / CDCl ₃ ) is (proton derived from alkyl group) / (proton derived from aryl group) = 4.29, and the ratio of bromination by ¹ H-NMR measurement Was 13% and the bromination yield was 13%.

Example 6
<Synthesis of Brominated Aromatic Polymer Compound 6: Bromination of Aromatic Polymer Compound 1>
In an inert gas atmosphere, a 4 mL screw tube was charged with aromatic polymer compound 1 (20.0 mg, 0.0456 mmol in terms of benzofluorene repeating units) and 1.0 mL of chloroform and dissolved by stirring at room temperature. After that, 70 μL of trifluoroacetic acid (0.91 mmol, 20 mol times with respect to the benzofluorene unit) and 2.4 μL of bromine (0.047 mmol, 103 mol% with respect to the benzofluorene unit) were sequentially added, sealed, and shielded from light Stirred under for 16 hours. The reaction mass was precipitated by dropping into 20 mL of methanol with stirring. The obtained precipitate was filtered, washed with methanol, and dried under reduced pressure to obtain 17.6 mg of a polymer. The resulting polymer is referred to as brominated aromatic polymer compound 6. The number average molecular weight of polystyrene conversion of the obtained brominated aromatic polymer compound 6 is Mn = 1.5 × 10 ⁴ , the weight average molecular weight is Mw = 3.1 × 10 ⁴ , and the peak top molecular weight is Mp. = 3.3 × 10 ⁴ , and the degree of dispersion was Mw / Mn = 2.1. (GPC measurement method B)
^The integral ratio according to ¹ H-NMR (300 MHz / CDCl ₃ ) is (proton derived from alkyl group) / (proton derived from aryl group) = 4.49, and the ratio of bromination by ¹ H-NMR measurement Was 49% and the bromination yield was 48%.

Example 7
<Synthesis of Brominated Aromatic Polymer Compound 7: Bromination of Aromatic Polymer Compound 1>
In an inert gas atmosphere, a 4 mL screw tube was charged with aromatic polymer compound 1 (30.0 mg, 0.0685 mmol in terms of benzofluorene repeating unit) and 1.5 mL of chloroform and dissolved by stirring at room temperature. Thereafter, 105 μL of trifluoroacetic acid (0.91 mmol, 20 mol times with respect to the benzofluorene unit) and 12.2 mg of N-bromosuccinimide (0.068 mmol, 100 mol% with respect to the benzofluorene unit) were sequentially added, The mixture was stirred for 16 hours in a sealed stopper and protected from light. The reaction mass was precipitated by dropping into 20 mL of methanol with stirring. The obtained precipitate was filtered, washed with methanol, and dried under reduced pressure to obtain 31.9 mg of a polymer. The resulting polymer is referred to as brominated aromatic polymer compound 7. The number average molecular weight of polystyrene conversion of the obtained brominated aromatic polymer compound 7 is Mn = 1.4 × 10 ⁴ , the weight average molecular weight is Mw = 2.9 × 10 ⁴ , and the peak top molecular weight is Mp. = 3.1 × 10 ⁴ , and the degree of dispersion was Mw / Mn = 2.1. (GPC measurement method B)
^The integral ratio according to ¹ H-NMR (300 MHz / CDCl ₃ ) is (proton derived from alkyl group) / (proton derived from aryl group) = 4.47, and the ratio of bromination by ¹ H-NMR measurement Was 45% and the bromination yield was 45%.

１００ｍＬ４口丸底フラスコをアルゴンガス置換後、合成例１における化合物Ｅと同様に合成した化合物Ｅ（３．２ｇ、５．３ｍｍｏｌ）、ビスピナコーラートジボロン（３．８ｇ、１４．８ｍｍｏｌ）、ＰｄＣｌ₂（ｄｐｐｆ）（０．３９ｇ、０．４５ｍｍｏｌ）、 ビス（ジフェニルホスフィノ）フェロセン（０．２７ｇ、０．４５ｍｍｏｌ）、酢酸カリウム（３．１ｇ、３２ｍｍｏｌ）を仕込み、脱水ジオキサン４５ｍｌを加えた。アルゴン雰囲気下、１００℃まで昇温し、３６時間反応させた。放冷後、セライト２gをプレコートで濾過を実施し、濃縮したところ黒色液体を取得した。ヘキサン５０gに溶解させて活性炭で着色成分を除去し３７ｇの淡黄色液体を取得した (濾過時、ラヂオライト（昭和科学工業株式会社製）５ｇプレコート実施)。酢酸エチル６ｇ、脱水メタノール１２ｇ、ヘキサン２ｇを加え、ドライアイス−メタノール浴に浸して、化合物Ｉ２．１ｇの無色結晶を取得した。 Synthesis example 3
<Synthesis of Compound G>

After replacing the 100 mL 4-neck round bottom flask with argon gas, compound E (3.2 g, 5.3 mmol) synthesized in the same manner as compound E in Synthesis Example 1, bispinacholate diboron (3.8 g, 14.8 mmol), PdCl _{2 (dppf) (0.39g, 0.45mmol} ), bis (diphenylphosphino) ferrocene (0.27 g, 0.45 mmol), were charged potassium acetate (3.1 g, 32 mmol), was added anhydrous dioxane 45 ml. In an argon atmosphere, the temperature was raised to 100 ° C. and reacted for 36 hours. After standing to cool, 2 g of Celite was filtered with a precoat and concentrated to obtain a black liquid. Dissolved in 50 g of hexane to remove colored components with activated carbon to obtain 37 g of pale yellow liquid (radiolite (made by Showa Kagaku Kogyo Co., Ltd.) 5 g pre-coating was performed during filtration). 6 g of ethyl acetate, 12 g of dehydrated methanol and 2 g of hexane were added and immersed in a dry ice-methanol bath to obtain 2.1 g of colorless crystals of Compound I.

芳香族系高分子化合物２ Synthesis example 4
<Synthesis of Aromatic Polymer Compound 2>
Under a argon atmosphere, to a 200 mL flask connected with a Dimroth, compound E37.7 g (63 mmol) synthesized in the same manner as in Synthesis Example 2 and compound G43.6 g (63 mmol) synthesized in the same manner as in Synthesis Example 6 were added, After dissolving in 70 mL of toluene, degassing was performed by bubbling argon gas. Thereto, 42 mg of palladium acetate and 266 mg of tris (o-methoxyphenyl) phosphine were added, and 283.4 mL of a bis (tetraethylammonium) carbonate aqueous solution (33 wt%) was added dropwise while raising the temperature, and the mixture was refluxed for 24 hours. 10.8 g of bromobenzene was added and refluxed for an additional hour, and then 8.9 g of phenylboronic acid was added and refluxed for an additional hour. The oil layer was washed twice with 2N aqueous hydrochloric acid, twice with 10% aqueous acetic acid and twice with water, filtered through Celite, and concentrated under reduced pressure to cause precipitation by dropping into methanol. The obtained solid was collected by filtration, dried under reduced pressure, then dissolved again in toluene, reprecipitated in methanol, and dried under reduced pressure twice to obtain a polymer (hereinafter referred to as aromatic polymer compound 2). 22.4 g was obtained. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 7.3 × 10 ⁴ and Mw = 1.8 × 10 ⁵ (GPC measurement method C).

Aromatic polymer 2

Example 8
<Synthesis of Brominated Aromatic Polymer Compound 8: Bromination of Aromatic Polymer Compound 2>
In an argon gas atmosphere, a 500 mL flask was charged with aromatic polymer compound 2 (5.00 g, 11.4 mmol in terms of benzofluorene repeat unit) and 150 mL of chloroform and dissolved by stirring at room temperature. mL and bromine 236 μL (4.6 mmol, 40 mol% with respect to the benzofluorene unit) were sequentially added, and the mixture was stirred for 24 hours under light shielding. The reaction mass was precipitated by dropwise addition to 1250 mL of methanol with stirring. The obtained precipitate was filtered, washed with methanol, and dried under reduced pressure to obtain 5.29 g of a polymer. The resulting polymer is referred to as brominated aromatic polymer compound 8. The number average molecular weight in terms of polystyrene is Mn = 7.5 × 10 ⁴ , the weight average molecular weight is Mw = 1.6 × 10 ⁵ , the peak top molecular weight is Mp = 1.2 × 10 ⁵ , and the dispersity is Mw / Mn = 2.1. (GPC measurement method C).
From the results of elemental analysis, the ratio of the repeating unit having a Br group (formula P-2) to the repeating unit not containing a Br group (formula P-1) is (P-1) / (P-2) = 61/39. The brominated proportion corresponds to 39% and the bromination yield corresponds to 98%.
Elemental analysis measured values: C84.93%, H9.06%, N <0.3%, Br6.57%
Elemental analysis calculated values: C84.48%, H8.94%, N0%, Br6.57% (calculated values at (P-1) / (P-2) = 61/39)

（芳香族系高分子化合物３） Synthesis example 5
<Synthesis of Aromatic Polymer Compound 3: Condensation Polymerization of 2,7-Dibromo-9,9-di-n-octylfluorene and 2,7-dibromo-9,9-bis (3-methylbutyl) fluorene>
2,6.3 g of 2,7-dibromo-9,9-di-n-octylfluorene, 5.6 g of 2,7-dibromo-9,9-bis (3-methylbutyl) fluorene and 22 g of 2,2′-bipyridyl were dehydrated. After dissolving in 1600 mL of the resulting tetrahydrofuran, the system was purged with nitrogen by bubbling with nitrogen. Under a nitrogen atmosphere, bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (40.66 g) was added to this solution, the temperature was raised to 60 ° C., and the mixture was stirred for 8 hours. Reacted. After the reaction, this reaction solution was cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% ammonia water 1200 mL / methanol 1200 mL / ion-exchanged water 1200 mL, and stirred for 0.5 hour, and then the deposited precipitate was filtered. And then dried under reduced pressure for 2 hours, and then dissolved in 1110 mL of toluene, followed by filtration. Toluene was added to the filtrate to make a solution of about 2800 mL, and then 1 ml of 1N hydrochloric acid was used for 1 hour with 4% aqueous ammonia. The organic layer was washed with 2200 mL for 1 hour, ion-exchanged water 1000 mL for 10 minutes, and ion-exchanged water 1000 mL for 10 minutes. The organic layer was concentrated under reduced pressure to 592 g at 50 ° C., then dropped into 3330 mL of methanol and stirred for 0.5 hour, the deposited precipitate was filtered, washed twice with 500 mL of methanol, And dried under reduced pressure for 5 hours. The yield of the obtained copolymer was 12.6 g. This copolymer is referred to as aromatic polymer compound 3. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 8.4 × 10 ⁴ and Mw = 1.6 × 10 ⁵ (GPC analysis method C). In the aromatic polymer compound 3, the ratio of the repeating units of 9,9-di-n-octylfluorene and 9,9-bis (3-methylbutyl) fluorene inferred from the charging ratio is 80:20.

(Aromatic polymer 3)

Example 9
<Synthesis of Brominated Aromatic Polymer Compound 9: Bromination of Aromatic Polymer Compound 3>
In an argon gas atmosphere, a 200 mL flask was charged with aromatic polymer compound 3 (2.00 g, 5.38 mmol in terms of fluorene repeat unit) and chloroform (100 mL), stirred and dissolved at room temperature, and then 8.3 mL of trifluoroacetic acid. Then, 104 μL of bromine (2.05 mmol, 38 mol% with respect to the fluorene repeating unit) was sequentially added and stirred for 20 hours under light shielding. The reaction mass was precipitated by dropwise addition to 500 mL of methanol with stirring. The obtained precipitate was filtered, washed with methanol, and dried under reduced pressure to obtain 2.17 g of a polymer. The resulting polymer is referred to as brominated aromatic polymer compound 9. The number average molecular weight in terms of polystyrene is Mn = 9.2 × 10 ⁴ , the weight average molecular weight is Mw = 1.7 × 10 ⁵ , the peak top molecular weight is Mp = 1.4 × 10 ⁵ , and the dispersity is Mw / Mn = 1.90. (GPC measurement method C).
From the results of elemental analysis, the ratio of the combination of repeating units having a Br group (formula P-7) and the combination of repeating units not containing a Br group (formula P-6) is (P-6) / (P-7) = 63/37, the brominated proportion is 37% and the bromination yield is 97%.
Elemental analysis measured values: C82.48%, H9.25%, N <0.3%, Br7.44%
Elemental analysis calculated values: C83.21%, H9.35%, N0%, Br7.44% (calculated values at (P-6) / (P-7) = 63/37)

化合物L-1
不活性雰囲気下１ｌの三つ口フラスコにベンゾフラン(23.2ｇ、137.9mmol)と酢酸(232ｇ)を入れ、室温で撹拌、溶かした後、７５℃まで昇温した。昇温後、臭素(92.6ｇ、579.3mmol)を酢酸(54ｇ)で希釈したものを滴下した。滴下終了後、温度を保持したまま３時間撹拌し、放冷した。ＴＬＣで原料の消失を確認した後、チオ硫酸ナトリウム水を加え反応を終了させ、室温で１時間撹拌した。撹拌後、ろ過を行いケーキをろ別し、さらにチオ硫酸ナトリウム水、水で洗浄した後、乾燥した。得られた粗生成物をヘキサンにて再結晶し、目的物を得た。（収量：21.8ｇ、収率：49％）
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ７．４４（ｄ、２Ｈ）、７．５７（ｄ、２Ｈ）、８．０３（ｓ、２Ｈ） Synthesis Example 6
<Synthesis of Compound L>
(Synthesis of Compound L-1)

Compound L-1
Benzofuran (23.2 g, 137.9 mmol) and acetic acid (232 g) were placed in a 1 l three-necked flask under an inert atmosphere, stirred and dissolved at room temperature, and then heated to 75 ° C. After raising the temperature, bromine (92.6 g, 579.3 mmol) diluted with acetic acid (54 g) was added dropwise. After completion of the dropwise addition, the mixture was stirred for 3 hours while maintaining the temperature and allowed to cool. After confirming disappearance of the raw material by TLC, sodium thiosulfate water was added to terminate the reaction, and the mixture was stirred at room temperature for 1 hour. After stirring, the mixture was filtered to separate the cake, further washed with aqueous sodium thiosulfate and water, and dried. The obtained crude product was recrystallized from hexane to obtain the desired product. (Yield: 21.8 g, Yield: 49%)
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 7.44 (d, 2H), 7.57 (d, 2H), 8.03 (s, 2H)

化合物L-2
不活性雰囲気下で５００ｍｌの四つ口フラスコに化合物L-1(16.6ｇ、50.9mmol)とテトラヒドロフラン(293ｇ)を入れ、−７８℃まで冷却した。ｎ−ブチルリチウム(80ml<1.6モルヘキサン溶液>、127.3mmol)を滴下した後、温度を保持したまま１時間撹拌した。この反応液を、不活性雰囲気下で１０００ｍｌの四つ口フラスコにトリメトキシボロン酸(31.7ｇ、305.5mmol)とテトラヒドロフラン(250ml)を入れ、−７８℃まで冷却したものに滴下した。滴下終了後、ゆっくり室温まで戻し、２時間室温で撹拌後、ＴＬＣで原料の消失を確認した。反応終了マスを、２０００ｍｌビーカーに濃硫酸(30g)と水(600ml)をいれたものに、注入し、反応を終了させた。トルエン(300ml)を加え、有機層を抽出し、さらに水を加えて洗浄した。溶媒を留去後、そのうち８ｇと酢酸エチル(160ml)を３００ｍｌの四つ口フラスコにいれ、つづいて３０％過酸化水素水(7.09g)を加え、４０℃で２時間撹拌した。この反応液を、１０００ｍｌのビーカーに硫酸アンモニウム鉄（II）(71g)と水(500ml)の水溶液に注入した。撹拌後、有機層を抽出し、有機層を水で洗浄した。溶媒を除去することにより、化合物L-2粗製物６．７２ｇを得た。
ＭＳスペクトル：Ｍ^＋ 200.0 (Synthesis of Compound L-2)

Compound L-2
Under an inert atmosphere, Compound L-1 (16.6 g, 50.9 mmol) and tetrahydrofuran (293 g) were placed in a 500 ml four-necked flask and cooled to -78 ° C. n-Butyllithium (80 ml <1.6 mol hexane solution>, 127.3 mmol) was added dropwise, and the mixture was stirred for 1 hour while maintaining the temperature. This reaction solution was added dropwise to a 1000 ml four-necked flask in an inert atmosphere, which was charged with trimethoxyboronic acid (31.7 g, 305.5 mmol) and tetrahydrofuran (250 ml) and cooled to -78 ° C. After completion of the dropwise addition, the temperature was slowly returned to room temperature, and after stirring at room temperature for 2 hours, disappearance of the raw material was confirmed by TLC. The reaction completed mass was poured into a 2000 ml beaker containing concentrated sulfuric acid (30 g) and water (600 ml) to complete the reaction. Toluene (300 ml) was added, the organic layer was extracted, and further washed with water. After distilling off the solvent, 8 g of the mixture and ethyl acetate (160 ml) were placed in a 300 ml four-necked flask, followed by addition of 30% aqueous hydrogen peroxide (7.09 g) and stirring at 40 ° C. for 2 hours. The reaction solution was poured into an aqueous solution of iron (II) ammonium sulfate (71 g) and water (500 ml) in a 1000 ml beaker. After stirring, the organic layer was extracted, and the organic layer was washed with water. By removing the solvent, 6.72 g of a crude compound L-2 was obtained.
MS spectrum: M ⁺ 200.0

化合物L-3
不活性雰囲気下で２００ｍｌの四つ口フラスコに上記と同様の方法で合成した化合物L-2(2.28ｇ、11.4mmol)とＮ，Ｎ−ジメチルホルムアミド(23ｇ)を入れ、室温で撹拌、溶かした後、炭酸カリウム(9.45ｇ、68.3mmol) を入れ６０℃まで昇温した。昇温後、臭化ｎ−オクチル(6.60ｇ、34.2mmol)をＮ，Ｎ−ジメチルホルムアミド(11ｇ)で希釈したものを滴下した。滴下終了後、６０℃まで昇温し、温度を保持したまま２時間撹拌し、ＴＬＣで原料の消失を確認した。水(20ml)を加え反応を終了させ、つづいてトルエン(20ml)を加え、有機層を抽出し、有機層を水で２回洗浄した。無水硫酸ナトリウムで乾燥後、溶媒留去した。得られた粗生成物をシリカゲルカラムで精製することにより、目的物を得た。（収量：1.84ｇ、収率：38％）
ＭＳスペクトル：Ｍ^＋ 425.3 (Synthesis of Compound L-3)

Compound L-3
In an inert atmosphere, compound L-2 (2.28 g, 11.4 mmol) and N, N-dimethylformamide (23 g) synthesized in the same manner as described above were placed in a 200 ml four-necked flask and dissolved by stirring at room temperature. Thereafter, potassium carbonate (9.45 g, 68.3 mmol) was added and the temperature was raised to 60 ° C. After heating, n-octyl bromide (6.60 g, 34.2 mmol) diluted with N, N-dimethylformamide (11 g) was added dropwise. After completion of the dropwise addition, the temperature was raised to 60 ° C., and the mixture was stirred for 2 hours while maintaining the temperature. Water (20 ml) was added to terminate the reaction, followed by addition of toluene (20 ml) to extract the organic layer, and the organic layer was washed twice with water. After drying over anhydrous sodium sulfate, the solvent was distilled off. The obtained crude product was purified by a silica gel column to obtain the desired product. (Yield: 1.84 g, Yield: 38%)
MS spectrum: M ⁺ 425.3

化合物Ｌ
不活性雰囲気下５００ｍｌ四つ口フラスコに上記と同様の方法で合成した化合物L-3(7.50ｇ、17.7mmol)とＮ，Ｎ−ジメチルホルムアミドを入れ、室温で撹拌、溶かした後、氷浴で冷却した。冷却後、Ｎ−ブロモスクシンイミド(6.38ｇ、35.9mmol)をＮ，Ｎ−ジメチルホルムアミド(225ml)で希釈したものを滴下した。滴下終了後、氷浴で１時間、室温で１８．５時間、４０℃まで昇温し、温度を保持したまま６．５時間撹拌し、液体クロマトグラフィーで原料の消失を確認した。溶媒を除去し、トルエン(75ml)を加え溶解した後、有機層を水で３回洗浄した。無水硫酸ナトリウムで乾燥後、溶媒留去した。得られた粗生成物の約半量をシリカゲルカラム及び液体クロマトグラフィー分取で精製することにより、目的物を得た。（収量：0.326ｇ）
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９０（ｔ、６Ｈ）、１．２６〜１．９５（ｍ、２４Ｈ）、４．１１（ｔ、４Ｈ）、７．３４（ｓ、２Ｈ）、７．７４（ｓ、２Ｈ）
ＭＳスペクトル：Ｍ^＋ 582.1 (Synthesis of Compound L)

Compound L
In a 500 ml four-necked flask under inert atmosphere, compound L-3 (7.50 g, 17.7 mmol) synthesized in the same manner as above and N, N-dimethylformamide were placed, stirred and dissolved at room temperature, and then placed in an ice bath. Cooled down. After cooling, a solution prepared by diluting N-bromosuccinimide (6.38 g, 35.9 mmol) with N, N-dimethylformamide (225 ml) was added dropwise. After completion of the dropwise addition, the mixture was heated to 40 ° C. for 1 hour in an ice bath, 18.5 hours at room temperature, stirred for 6.5 hours while maintaining the temperature, and disappearance of the raw materials was confirmed by liquid chromatography. The solvent was removed, toluene (75 ml) was added and dissolved, and the organic layer was washed 3 times with water. After drying over anhydrous sodium sulfate, the solvent was distilled off. About half of the resulting crude product was purified by silica gel column and liquid chromatography fractionation to obtain the desired product. (Yield: 0.326g)
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 6H), 1.26 to 1.95 (m, 24H), 4.11 (t, 4H), 7.34 (s, 2H), 7.74 (s, 2H)
MS spectrum: M ⁺ 582.1

Synthesis example 7
<Synthesis of Aromatic Polymer Compound 4>
Under a nitrogen atmosphere, 0.18 g of 3,8-dibromodibenzofuran, 0.719 g of compound L, and 0.578 g of 2,2′-bipyridyl were dissolved in 30 g of dehydrated tetrahydrofuran, and the temperature was raised to 60 ° C. To this solution, 1.040 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } was added and reacted at 60 ° C. for 3 hours. After the reaction, this reaction solution was cooled to room temperature, dropped into a mixed solution of 25 g ammonia water 9 g / methanol 95 g / ion exchanged water 50 g and stirred for 30 minutes, and then the deposited precipitate was filtered and dried under reduced pressure for 2 hours. And dissolved in 30 ml of toluene. After adding 30 g of 1N hydrochloric acid and stirring for 3 hours, the aqueous layer was removed. Next, 30 g of 4% aqueous ammonia was added to the organic layer and stirred for 3 hours, and then the aqueous layer was removed. Subsequently, the organic layer was dropped into 200 mL of methanol and stirred for 30 minutes, the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 30 mL of toluene. Then, it refine | purified through the alumina column (alumina amount 10g), and the collect | recovered toluene solution was dripped at methanol 200mL, it stirred for 30 minutes, the depositing precipitate was filtered and dried under reduced pressure for 2 hours. The yield of the obtained polymer was 0.456 g. This polymer is called aromatic polymer compound 4. The number average molecular weight in terms of polystyrene was Mn = 1.3 × 10 ⁵ , and the weight average molecular weight was Mw = 4.6 × 10 ⁵ (GPC measurement method A).
The aromatic polymer compound 4 contains dibenzofuran repeating units represented by the formulas (P-9) and (P-10), and the ratio estimated from the charging ratio is (P-9) / (P-10) = 80/20.

Example 10
<Synthesis of Brominated Aromatic Polymer Compound 10: Bromination of Aromatic Polymer Compound 4>
In an argon gas atmosphere, a 20 mL flask was charged with aromatic polymer compound 4 (150 mg, 0.404 mmol in terms of dibenzofuran repeating units) and chloroform 8 mL, and stirred and dissolved at room temperature. Then, 0.6 mL of trifluoroacetic acid, A solution obtained by diluting 5.2 μL of bromine with 1 mL of chloroform (0.10 mmol, 25 mol% with respect to the dibenzofuran repeating unit) was sequentially added and stirred for 20 hours under light shielding. The reaction mass was precipitated by dropwise addition to 38 mL of methanol with stirring. The resulting precipitate was filtered, washed with methanol, dried under reduced pressure for 2 hours, and then dissolved in 25 mL of toluene. The solution was passed through a silica gel column and an alumina column through which toluene was passed in advance, and after washing with toluene, the solution concentrated under reduced pressure was dropped into methanol to reprecipitate. The precipitate was filtered, washed with methanol, and dried under reduced pressure to obtain 152 mg of a polymer. This polymer is referred to as brominated aromatic polymer compound 10. The number average molecular weight in terms of polystyrene was Mn = 1.5 × 10 ⁵ , the weight average molecular weight was Mw = 3.8 × 10 ⁵ , the peak top molecular weight was Mp = 3.7 × 10 ⁵ , and the degree of dispersion was Mw / Mn = 2.6. (GPC measurement method C).
The brominated aromatic polymer compound 10 is considered to contain dibenzofuran repeating units represented by the formulas (P-9), (P-10), (P-9b), and (P-11).
Of the repeating unit having the Br group (formula P-9b), (formula P-11) and the repeating unit not containing the Br group (formula P-9), (formula P-10) The ratio is {(formula P-9) + (formula P-10)} / {(formula P-9b) + (formula P-11)} = 77/23, (all dibenzofuran repeating units) / Br group = It corresponds to 81/19.
Elemental analysis measurements: C 75.46%, H 7.93%, N <0.3%, Br 4.67%
Elemental analysis calculated values: C76.52%, H8.12%, N0%, Br4.67% ({(Formula P-9) + (Formula P-10)} / {(Formula P-9b) + (Formula P −11)} = calculated value at 77/23)

Claims (12)

General formula (1)
-Ar ^1- (1)
(In the formula, Ar ¹ represents an arylene group, a divalent heterocyclic group or a divalent aromatic amine group having at least one C—H bond on the aromatic ring.) A polymer compound in which the total of repeating units represented by formula (1) is 0.1 mol% or more and 100 mol% or less of the total of all repeating units (herein, the polymer compound is represented by formula (1) In addition to the repeating units shown, the general formula (1a)
—Ar ⁰ − (1a)
(In the formula, Ar ⁰ represents an arylene group, a divalent heterocyclic group or a divalent aromatic amine group that does not have a C—H bond on the aromatic ring). Well, furthermore, the following formulas X-1 to X-11

(In the formula, Ar represents a hydrocarbon group having 6 to 60 carbon atoms, and R ″ represents a substituent selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and a monovalent heterocyclic group). 40 mol% or less of the linking group containing the non-conjugated moiety shown and / or the group in which two or more of them are combined with respect to the total of the repeating units represented by the above formulas (1) and (1a) The C—H bond on the aromatic ring is halogenated, nitrated, Friedel-Crafts alkylated, halomethylated, Friedel-Crafts acylated, By converting by an aromatic electrophilic substitution reaction selected from the group consisting of Gattermann aldehyde synthesis and Vilsmeier formylation, the general formula (2)

(In the formula, X represents a characteristic group introduced by the aromatic electrophilic substitution reaction or a characteristic group derived therefrom, and Ar ² represents n of C—H bonds on the aromatic ring of Ar ^1. Represents an n + 2 valent arylene group, n + 2 valent heterocyclic group, or n + 2 valent aromatic amine group converted into a C—X bond, and n represents an integer of 1 to 4. A method for producing a polymer compound, comprising obtaining a polymer compound containing a repeating unit having X. Characteristic group represented by X is a halogen ^{_{atom, -OSO 2 Q 1, -B (}} OQ 2) 2, -Sn (Q 3) 3, Z 1 (Z 2) m, -OH, -CH 2 Z ³ , —CHQ ⁴ —P ⁺ (Q ⁵ ) ₃ Z ⁴ , —CHQ ⁶ —P (═O) (OQ ⁷ ) ₂ , —C (═O) Q ⁸ , —NH ₂ , and a diazonio group A characteristic group selected from (Q ¹ is a hydrocarbon group, Q ² is a hydrogen atom or a hydrocarbon group, and two Q ^{2 s} may be the same or different, and are bonded to each other to form a ring. Q ³ is a hydrocarbon group, three Q ³ may be the same or different, Q ⁴ is a hydrogen atom or a hydrocarbon group, Q ⁵ is a hydrocarbon group, 3 one of Q ⁵ are each good .Q ⁶ be different hydrogen atoms at the same, or a hydrocarbon group, Q ⁷ is a hydrocarbon group, two Q ⁷ be the identical or different from each other .Q ⁸ is hydrogen atom or a hydrocarbon group .Z ¹ is a metal atom or a metal ion, Z ² is a counter anion, .Z ³ m is representing an integer of 0 or more halogen atoms or cyano The method according to claim 1, wherein Z ⁴ represents a monovalent counter anion.   The method according to claim 1, wherein the conversion reaction of the C—H bond on the aromatic ring is a halogenation reaction.   The halogenation reaction causes bromine to act as a brominating agent in an organic solvent in the presence of 5 times or more of a strong organic acid with respect to the total of the repeating units represented by the general formula (1). The method according to any one of claims 1 to 3, which is a characteristic bromination reaction. The characteristic group represented by X is selected from the group consisting of a halogen atom, —OSO ₂ Q ¹ , —B (OQ ² ) ₂ , —Sn (Q ³ ) ₃ , Z ¹ (Z ² ) m, and —CHO. chosen characteristic groups ^{(Q 1, Q 2, Q} 3, Z 1, Z 2, and m. to the same meaning as defined above) which is a process according to any one of claims 1 to 4.   The method according to claim 1, wherein the characteristic group represented by X is a halogen atom.   The method according to any one of claims 4 to 6, wherein the strong organic acid is trifluoroacetic acid.   The method according to any one of claims 4 to 7, wherein the organic solvent contains at least one selected from the group consisting of halogenated methanes and halogenated ethanes. The method according to any one of claims 1 to 8, wherein Ar ¹ represents an arylene group and Ar ² represents an n + divalent arylene group.   The method according to any one of claims 1 to 9, wherein n in formula (2) represents 1. The method according to any one of claims 1 to 10, wherein the polymer compound has a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ⁸ .   A polymer compound comprising a repeating unit represented by the general formula (2) having a characteristic group X, which is obtained by the production method according to any one of claims 1 to 11.