JP2008169263A - Method for producing polyarylene - Google Patents

Abstract

A method for producing polyarylene is provided.
A mixture comprising nickel halide and a bidentate nitrogen ligand and a solvent (hereinafter abbreviated as solution A), a mixture comprising one or more aromatic monomers, zinc and a solvent (hereinafter abbreviated as solution B). ) Are mixed and reacted to produce a polyarylene.
The aromatic monomer is, for example, the formula (1)
^{X 1} -Ar-X ¹
(In the formula, Ar represents an arylene group or a divalent heterocyclic group, and X ¹ represents a chlorine, bromine or iodine atom), and the polyarylene has the formula (2)
-Ar-
It is a polyarylene containing the repeating unit shown by.
[Selection figure] None

Description

  The present invention relates to a method for producing polyarylene.

  The reaction in which polyarylene is obtained by polymerizing a dihalogenoaromatic monomer in the presence of a nickel compound is called Yamamoto Polymerization (Non-Patent Document 1). In general, this reaction proceeds in the presence of a stoichiometric amount of a zerovalent nickel compound with respect to the aromatic monomer. However, the use of a stoichiometric amount of an unstable and expensive zero-valent nickel compound is not preferable in terms of productivity and manufacturing cost.

It has also been found that polyarylene can be obtained from stable and inexpensive nickel chloride (Non-Patent Document 2). In this method, nickel chloride, nitrogen or phosphorus ligand and zinc are heated in a solvent to generate a zerovalent nickel compound in a solution, and then a monomer is charged and polymerized. However, since the prepared zero-valent nickel compound is unstable, sufficient care is required for handling.
Macromolecules 1992, 25, 1214 Macromolecules 2004, 37, 4748

  An object of the present invention is to provide a technique capable of efficiently producing polyarylene from dihalogenoaromatic monomers using stable and inexpensive nickel halide.

  The inventors of the present invention have continually studied to solve the above problems. Under such circumstances, it was found that polyarylene can be obtained by mixing a solution containing nickel halide and its ligand and a solution containing dihalogenoaromatic monomer and zinc, and the present invention was completed. .

That is, the present invention
Mixing a mixture of nickel halide and bidentate nitrogen ligand and solvent (hereinafter abbreviated as solution A) and a mixture of one or more aromatic monomers, zinc and solvent (hereinafter abbreviated as solution B). It is intended to provide a method for producing polyarylene, which is characterized in that the reaction is carried out.

According to the present invention, there is no need to separately prepare an unstable zero-valent nickel compound, and a simple and efficient method for producing polyarylene can be provided.

Hereinafter, the present invention will be described in detail.
In the present invention,
As an aromatic monomer, the formula (1)
^{X 1} -Ar-X ¹
(In the formula, Ar represents an arylene group or a divalent heterocyclic group, and X ¹ represents a chlorine, bromine or iodine atom.)
One or more aromatic monomers represented by:
As polyarylene, the formula (2)
-Ar-
The polyarylene containing the repeating unit shown by these is mentioned.
In the aromatic monomer represented by the formula (1), X ¹ represents a chlorine, bromine or iodine atom, preferably a chlorine atom.

Ar represents an arylene group or a divalent heterocyclic group, and may be substituted with the following substituents. It may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. A good C1-C20 alkyl group;
It may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. A good C1-C20 alkoxy group;
An aryl group having 6 to 20 carbon atoms which may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms ;
A C6-C20 aryloxy optionally substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, a C1-C20 alkoxy group and a C6-C20 aryloxy group A group; and
It may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. A good acyl group having 2 to 20 carbon atoms;
It may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. A good C1-C20 alkoxysulfonyl group;
It may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. A good C1-C20 alkoxycarbonyl group;
It may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. A good C1-C20 arylsulfonyl group;
It may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. A good C1-C20 arylcarbonyl group;
It may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. A good C1-C20 aminosulfonyl group;
It may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. A good C1-C20 aminocarbonyl group;
It may be substituted with at least one substituent selected from the group consisting of

Specific examples of the aromatic monomer represented by the formula (1) include, for example, 1,4-dichlorobenzene, 4,4′-dichlorobiphenyl, 1,4-dichloronaphthalene, 2,7-dichlorofluorene, 2,5 -Dichlorothiophene and the like are exemplified, among which 1,4-dichlorobenzene and 4,4'-dichlorobiphenyl are preferable. In addition, these aromatic monomers include one or more methyl group, methoxy group, phenyl group, phenoxy group, acetyl group, methoxysulfonyl group, methoxycarboxy group, phenoxysulfonyl group, phenoxycarbonyl group, diethylaminooxysulfonyl group, diethylaminooxy The carbonyl group may be substituted.

Such aromatic monomers may be used alone or in admixture of two or more. Among these, a dihalogenobenzene compound or a dihalogenobiphenyl compound is preferable, and a compound substituted with a sulfonic acid ester or amide represented by the following formula (3) or (4) is particularly preferable.

（式中、Ａは、１つもしくは２つの炭化水素基で置換され、該炭化水素基の炭素数の合計が１〜２０であるアミノ基、又は炭素数１〜２０のアルコキシ基を表わす。ここで、前記炭化水素基及び炭素数１〜２０のアルコキシ基は、フッ素原子、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基及びシアノ基からなる群から選ばれる少なくとも一つの基で置換されていてもよい。
Ｒ^１は、水素原子、フッ素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基又はシアノ基を表わす。ここで、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基及び炭素数２〜２０のアシル基は、フッ素原子、シアノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基及び炭素数６〜２０のアリールオキシ基からなる群から選ばれる少なくとも一つの置換基で置換されていてもよい。また、Ｒ¹が複数の場合、Ｒ^１は同一の基であってもよいし、異なる基であってもよい。また、隣接する２つのＲ¹が結合して環を形成していてもよい。
Ｘ^２は塩素原子、臭素原子又はヨウ素原子を表わす。ｍは１又は２を表わし、ｋは４−ｍを表わす。）
で示されるジハロゲノベンゼン化合物について説明する。 Next, Formula (3)

(In the formula, A represents an amino group substituted with one or two hydrocarbon groups, and the hydrocarbon group has a total carbon number of 1 to 20, or an alkoxy group having 1 to 20 carbon atoms. And the hydrocarbon group and the alkoxy group having 1 to 20 carbon atoms are a fluorine atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a carbon number. It may be substituted with at least one group selected from the group consisting of 2 to 20 acyl groups and cyano groups.
R ¹ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or 2 carbon atoms. Represents ˜20 acyl groups or cyano groups. Here, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an acyl group having 2 to 20 carbon atoms are It may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. Good. Further, when R ¹ is plural, R ¹ may be the same group or different groups. Further, two adjacent R ¹ may be bonded to form a ring.
X ² represents a chlorine atom, a bromine atom or an iodine atom. m represents 1 or 2, and k represents 4-m. )
The dihalogenobenzene compound represented by the above will be described.

A represents an amino group substituted with one or two hydrocarbon groups, and the hydrocarbon group having 3 to 20 carbon atoms in total, or an alkoxy group having 1 to 20 carbon atoms.

Examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and 2,2-dimethylpropyl group. N-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n -Pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, phenyl group, 1,3-butadiene-1,4-diyl group, butane-1,4 -Hydrocarbon groups having 1 to 20 carbon atoms such as a diyl group, a pentane-1,5-diyl group, a biphenyl-2,2′-diyl group, and an o-xylylene group.

Examples of the amino group substituted with one or two hydrocarbon groups and having a total carbon number of 1 to 20 include methylamino group, dimethylamino group, ethylamino group, diethylamino group, n-propyl Amino group, di-n-propylamino group, isopropylamino group, diisopropylamino group, n-butylamino group, di-n-butylamino group, sec-butylamino group, di-sec-butylamino group, tert-butyl Amino group, di-tert-butylamino group, n-pentylamino group, 2,2-dimethylpropylamino group, n-hexylamino group, cyclohexylamino group, n-heptylamino group, n-octylamino group, n- Nonylamino group, n-decylamino group, n-undecylamino group, n-dodecylamino group, n-tridecylamino , N-tetradecylamino group, n-pentadecylamino group, n-hexadecylamino group, n-heptadecylamino group, n-octadecylamino group, n-nonadecylamino group, n-icosylamino group, pyrrolyl group, pyrrolidinyl group , Piperidinyl group, carbazolyl group, dihydroindolyl group, dihydroisoindolyl group and the like, and diethylamino group and n-dodecylamino group are preferable.

Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, 2,2 -Dimethylpropoxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-icosyloxy group Linear, branched or cyclic alkoxy groups having 3 to 20 carbon atoms such as isobutoxy Group, 2,2-dimethyl-propoxy group, and a cyclohexyloxy group are preferable.

The hydrocarbon group and the alkoxy group having 1 to 20 carbon atoms include a fluorine atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and 2 to 2 carbon atoms. It may be substituted with at least one group selected from the group consisting of 20 acyl groups and cyano groups.

Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, 2,2-dimethylpropoxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, 2-methylpentyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy Group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n- Heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-ico Aryloxy groups such as a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms can be mentioned.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 1-naphthyl group, 2-naphthyl group, 3-phenanthryl group, 2-anthryl group and the like. Examples of the aryloxy group having 6 to 20 carbon atoms include those having 6 to 20 carbon atoms such as phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 3-phenanthryloxy group, and 2-anthryloxy group. The thing comprised from an aryl group and an oxygen atom is mentioned.

Examples of the acyl group having 2 to 20 carbon atoms include aliphatic or aromatic acyl groups having 2 to 20 carbon atoms such as acetyl group, propionyl group, butyryl group, isobutyryl group, benzoyl group, 1-naphthoyl group, and 2-naphthoyl group. Is mentioned.

Among them, as A, an unsubstituted alkoxy group having 3 to 20 carbon atoms is preferable, and an isobutoxy group, a 2,2-dimethylpropoxy group, and a cyclohexyloxy group are more preferable.

R ¹ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or 2 carbon atoms. Represents ˜20 acyl groups or cyano groups.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2, 2-dimethylpropyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, 2-methylpentyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n- Directly such as undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, etc. A linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms is exemplified.

Examples of the alkoxy group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, the aryloxy group having 6 to 20 carbon atoms, and the acyl group having 2 to 20 carbon atoms are the same as those described above.

Such an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms and an acyl group having 2 to 20 carbon atoms are fluorine atoms. , A cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms, and may be substituted with at least one substituent selected from the group consisting of Examples of the alkoxy group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the aryloxy group having 6 to 20 carbon atoms are the same as those described above.

When R ¹ is plural, R ¹ may be the same group or different groups. Further, two adjacent R ¹ may be bonded to form a ring.
Among these, as R ¹ , a hydrogen atom is preferable.

X ² represents a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom or a bromine atom. m represents 1 or 2, and k represents 4-m. Preferably m represents 1.

Examples of the dihalobenzene compound (3) include isopropyl 2,5-dichlorobenzenesulfonate, isobutyl 2,5-dichlorobenzenesulfonate, 2,5-dichlorobenzenesulfonate (2,2-dimethylpropyl), 2,5- Cyclohexyl dichlorobenzenesulfonate, n-octyl 2,5-dichlorobenzenesulfonate, n-pentadecyl 2,5-dichlorobenzenesulfonate, n-icosyl 2,5-dichlorobenzenesulfonate, N, N-diethyl-2, 5-dichlorobenzenesulfonamide, N, N-diisopropyl-2,5-dichlorobenzenesulfonamide, N- (2,2-dimethylpropyl) -2,5-dichlorobenzenesulfonamide, Nn-dodecyl-2, 5-dichlorobenzenesulfonamide, Nn-ikoshi -2,5-dichlorobenzenesulfonamide, isopropyl 3,5-dichlorobenzenesulfonate, isobutyl 3,5-dichlorobenzenesulfonate, 3,5-dichlorobenzenesulfonate (2,2-dimethylpropyl), 3,5 -Cyclohexyl benzene sulfonate, n-octyl 3,5-dichlorobenzene sulfonate, n-pentadecyl 3,5-dichlorobenzene sulfonate, n-icosyl 3,5-dichlorobenzene sulfonate, N, N-diethyl-3 , 5-dichlorobenzenesulfonamide, N, N-diisopropyl-3,5-dichlorobenzenesulfonamide, N- (2,2-dimethylpropyl) -3,5-dichlorobenzenesulfonamide, Nn-dodecyl-3 , 5-dichlorobenzenesulfonamide, Nn-ico Le -3,5-dichlorobenzene sulfonamide,

Isopropyl 2,5-dibromobenzenesulfonate, isobutyl 2,5-dibromobenzenesulfonate, 2,5-dibromobenzenesulfonate (2,2-dimethylpropyl), cyclohexyl 2,5-dibromobenzenesulfonate, 2,5 -N-octyl dibromobenzenesulfonate, n-pentadecyl 2,5-dibromobenzenesulfonate, n-icosyl 2,5-dibromobenzenesulfonate, N, N-diethyl-2,5-dibromobenzenesulfonamide, N, N-diisopropyl-2,5-dibromobenzenesulfonamide, N- (2,2-dimethylpropyl) -2,5-dibromobenzenesulfonamide, Nn-dodecyl-2,5-dibromobenzenesulfonamide, N- n-Icosyl-2,5-dibromobenzenesulfonamide Isopropyl 3,5-dibromobenzenesulfonate, isobutyl 3,5-dibromobenzenesulfonate, 3,5-dibromobenzenesulfonate (2,2-dimethylpropyl), cyclohexyl 3,5-dibromobenzenesulfonate, 3,5 -N-octyl dibromobenzenesulfonate, n-pentadecyl 3,5-dibromobenzenesulfonate, n-icosyl 3,5-dibromobenzenesulfonate, N, N-diethyl-3,5-dibromobenzenesulfonamide, N, N-diisopropyl-3,5-dibromobenzenesulfonamide, N- (2,2-dimethylpropyl) -3,5-dibromobenzenesulfonamide, Nn-dodecyl-3,5-dibromobenzenesulfonamide, N- n-Icosyl-3,5-dibromobenzenesulfonami ,

Isopropyl 2,5-diiodobenzenesulfonate, isobutyl 2,5-diiodobenzenesulfonate, 2,5-diiodobenzenesulfonic acid (2,2-dimethylpropyl), cyclohexyl 2,5-diiodobenzenesulfonate N-octyl 2,5-diiodobenzenesulfonate, n-pentadecyl 2,5-diiodobenzenesulfonate, n-icosyl 2,5-diiodobenzenesulfonate, N, N-diethyl-2,5- Diiodobenzenesulfonamide, N, N-diisopropyl-2,5-diiodobenzenesulfonamide, N- (2,2-dimethylpropyl) -2,5-diiodobenzenesulfonamide, Nn-dodecyl-2 , 5-Diiodobenzenesulfonamide, Nn-icosyl-2,5-diiodobenzenesulfonamide Isopropyl 3,5-diiodobenzenesulfonate, isobutyl 3,5-diiodobenzenesulfonate, 3,5-diiodobenzenesulfonic acid (2,2-dimethylpropyl), cyclohexyl 3,5-diiodobenzenesulfonate N-octyl 3,5-diiodobenzenesulfonate, n-pentadecyl 3,5-diiodobenzenesulfonate, n-icosyl 3,5-diiodobenzenesulfonate, N, N-diethyl-3,5- Diiodobenzenesulfonamide, N, N-diisopropyl-3,5-diiodobenzenesulfonamide, N- (2,2-dimethylpropyl) -3,5-diiodobenzenesulfonamide, Nn-dodecyl-3 , 5-Diiodobenzenesulfonamide, Nn-icosyl-3,5-diiodobenzenesulfonamide ,

2,4-dichlorobenzenesulfonic acid (2,2-dimethylpropyl), 2,4-dibromobenzenesulfonic acid (2,2-dimethylpropyl), 2,4-diiodobenzenesulfonic acid (2,2-dimethylpropyl) ), 2,4-dichloro-5-methylbenzenesulfonic acid (2,2-dimethylpropyl), 2,5-dichloro-4-methylbenzenesulfonic acid (2,2-dimethylpropyl), 2,4-dibromo- 5-methylbenzenesulfonic acid (2,2-dimethylpropyl), 2,5-dibromo-4-methylbenzenesulfonic acid (2,2-dimethylpropyl), 2,4-diiodo-5-methylbenzenesulfonic acid (2 , 2-dimethylpropyl), 2,5-diiodo-4-methylbenzenesulfonic acid (2,2-dimethylpropyl), 2,4-dichloro- -Methoxybenzenesulfonic acid (2,2-dimethylpropyl), 2,5-dichloro-4-methoxybenzenesulfonic acid (2,2-dimethylpropyl), 2,4-dibromo-5-methoxybenzenesulfonic acid (2, 2-dimethylpropyl), 2,5-dibromo-4-methoxybenzenesulfonic acid (2,2-dimethylpropyl), 2,4-diiodo-5-methoxybenzenesulfonic acid (2,2-dimethylpropyl), 2, Examples include 5-diiodo-4-methoxybenzenesulfonic acid (2,2-dimethylpropyl), 1- (2,5-dichlorobenzenesulfonyl) pyrrolidine.

Among them, 2,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl), 2,5-dichlorobenzenesulfonic acid isobutyl, 2,5-dichlorobenzenesulfonic acid cyclohexyl, N, N-diethyl-2,5- Dichlorobenzenesulfonamide and Nn-dodecyl-2,5-dichlorobenzenesulfonamide, 2,5-dibromobenzenesulfonic acid (2,2-dimethylpropyl), isobutyl 2,5-dibromobenzenesulfonate, 2,5 Preferred are cyclohexyl dibromobenzenesulfonate, N, N-diethyl-2,5-dibromobenzenesulfonamide, and Nn-dodecyl-2,5-dibromobenzenesulfonamide.

（式中、Ａ、Ｒ^１、ｋ、ｍ及びＸ^２は上記と同一の意味を表わす。）
で示されるジハロゲノビフェニル化合物としては、
例えば、４，４’−ジクロロビフェニル−２，２’−ジスルホン酸ジメチル、４，４’−ジクロロビフェニル−２，２’−ジスルホン酸ジエチル、４，４’−ジクロロビフェニル−２，２’−ジスルホン酸ジ（ｎ−プロピル）、４，４’−ジクロロビフェニル−２，２’−ジスルホン酸ジイソプロピル、４，４’−ジクロロビフェニル−２，２’−ジスルホン酸ジ（ｎ−ブチル）、４，４’−ジクロロビフェニル−２，２’−ジスルホン酸ジイソブチル、４，４’−ジクロロビフェニル−２，２’−ジスルホン酸ジ（２，２−ジメチルプロピル）、４，４’−ジクロロビフェニル−２，２’−ジスルホン酸ジシクロヘキシル、４，４’−ジクロロビフェニル−２，２’−ジスルホン酸ジ（ｎ−オクチル）、４，４’−ジクロロビフェニル−２，２’−ジスルホン酸ジ（ｎ−ペンタデシル）、４，４’−ジクロロビフェニル−２，２’−ジスルホン酸ジ（ｎ−イコシル）、 Next, Formula (4)

(In the formula, A, R ¹ , k, m and X ² represent the same meaning as described above.)
As the dihalogenobiphenyl compound represented by
For example, dimethyl 4,4′-dichlorobiphenyl-2,2′-disulfonate, diethyl 4,4′-dichlorobiphenyl-2,2′-disulfonate, 4,4′-dichlorobiphenyl-2,2′-disulfone Acid di (n-propyl), 4,4′-dichlorobiphenyl-2,2′-disulfonic acid diisopropyl, 4,4′-dichlorobiphenyl-2,2′-disulfonic acid di (n-butyl), 4,4 '-Dichlorobiphenyl-2,2'-disulfonic acid diisobutyl, 4,4'-dichlorobiphenyl-2,2'-disulfonic acid di (2,2-dimethylpropyl), 4,4'-dichlorobiphenyl-2,2 '-Disulfonic acid dicyclohexyl, 4,4'-dichlorobiphenyl-2,2'-disulfonic acid di (n-octyl), 4,4'-dichlorobiphenyl-2,2'-disulfonic acid di (n Pentadecyl), 4,4'-dichloro-2,2'-disulfonate, di (n- eicosyl),

N, N-dimethyl-4,4′-dichlorobiphenyl-2,2′-disulfonamide, N, N-diethyl-4,4′-dichlorobiphenyl-2,2′-disulfonamide, N, N-di ( n-propyl) -4,4′-dichlorobiphenyl-2,2′-disulfonamide, N, N-diisopropyl-4,4′-dichlorobiphenyl-2,2′-disulfonamide, N, N-di (n -Butyl) -4,4'-dichlorobiphenyl-2,2'-disulfonamide, N, N-diisobutyl-4,4'-dichlorobiphenyl-2,2'-disulfonamide, N-di (2,2- Dimethylpropyl) -4,4′-dichlorobiphenyl-2,2′-disulfonamide, N-di (n-octyl) -4,4′-dichlorobiphenyl-2,2′-disulfonamide, N-disulfonamide n-dodecyl) -4,4'-dichlorobiphenyl-2,2'-disulfonamide, N-di (n-icosyl) -4,4'-dichlorobiphenyl-2,2'-disulfonamide, N, N- Diphenyl-4,4′-dichlorobiphenyl-2,2′-disulfonamide,

3,3′-dimethyl-4,4′-dichlorobiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl), 5,5′-dimethyl-4,4′-dichlorobiphenyl-2,2 '-Disulfonic acid di (2,2-dimethylpropyl), 6,6'-dimethyl-4,4'-dichlorobiphenyl-2,2'-disulfonic acid di (2,2-dimethylpropyl), 3,3' -Dimethoxy-4,4'-dichlorobiphenyl-2,2'-disulfonic acid di (2,2-dimethylpropyl), 5,5'-dimethoxy-4,4'-dichlorobiphenyl-2,2'-disulfonic acid Di (2,2-dimethylpropyl), 6,6′-dimethoxy-4,4′-dichlorobiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl), 3,3′-diphenyl-4 , 4'-jiku Robiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl), 3,3′-diacetyl-4,4′-dichlorobiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl) ), 5,5′-diacetyl-4,4′-dichlorobiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl),

4,4'-dibromobiphenyl-2,2'-disulfonic acid dimethyl, 4,4'-dibromobiphenyl-2,2'-disulfonic acid diethyl, 4,4'-dibromobiphenyl-2,2'-disulfonic acid dicarboxylic acid (N-propyl), 4,4′-dibromobiphenyl-2,2′-disulfonic acid diisopropyl, 4,4′-dibromobiphenyl-2,2′-disulfonic acid di (n-butyl), 4,4′- Dibromobiphenyl-2,2′-disulfonic acid diisobutyl, 4,4′-dibromobiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl), 4,4′-dibromobiphenyl-2,2′- Dicyclohexyl disulfonate, 4,4′-dibromobiphenyl-2,2′-disulfonic acid di (n-octyl), 4,4′-dibromobiphenyl-2,2′- Sulfone, di (n- pentadecyl), 4,4'-dibromo-2,2'-disulfonate, di (n- eicosyl),

N, N-dimethyl-4,4′-dibromobiphenyl-2,2′-disulfonamide, N, N-diethyl-4,4′-dibromobiphenyl-2,2′-disulfonamide, N, N-di ( n-propyl) -4,4′-dibromobiphenyl-2,2′-disulfonamide, N, N-diisopropyl-4,4′-dibromobiphenyl-2,2′-disulfonamide, N, N-di (n -Butyl) -4,4'-dibromobiphenyl-2,2'-disulfonamide, N, N-diisobutyl-4,4'-dibromobiphenyl-2,2'-disulfonamide, N-di (2,2- Dimethylpropyl) -4,4'-dibromobiphenyl-2,2'-disulfonamide, N-di (n-octyl) -4,4'-dibromobiphenyl-2,2'-disulfonamide, N-disulfonamide n-dodecyl) -4,4'-dibromobiphenyl-2,2'-disulfonamide, N-di (n-icosyl) -4,4'-dibromobiphenyl-2,2'-disulfonamide, N, N- And diphenyl-4,4′-dibromobiphenyl-2,2′-disulfonamide.

Among them, 4,4′-dichlorobiphenyl-2,2′-disulfonic acid diisopropyl, 4,4′-dichlorobiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl), 4,4′- Dibromobiphenyl-2,2′-disulfonic acid diisopropyl and 4,4′-dibromobiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl) are preferred.

The dihalobenzene compound (3) and the dihalogenobiphenyl compound (4) are usually obtained by reacting the corresponding acid chloride with an alcohol in the presence of a base. A commercially available acid chloride may be used. For example, Bull. Soc. Chim. Fr. 4, 49 (1931), 1047-1049, etc. may be used.

（式中、ａ、ｂ及びｃは同一又は相異なって、０又は１を表わし、ｎは５以上の整数を表わす。Ａｒ^１、Ａｒ^２、Ａｒ^３及びＡｒ^４は同一又は相異なって、２価の芳香族基を表わす。ここで、２価の芳香族基は、フッ素原子、シアノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基及び炭素数６〜２０のアリールオキシ基からなる群から選ばれる少なくとも一つの置換基で置換されていてもよい炭素数１〜２０のアルキル基；
フッ素原子、シアノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基及び炭素数６〜２０のアリールオキシ基からなる群から選ばれる少なくとも一つの置換基で置換されていてもよい炭素数１〜２０のアルコキシ基；
フッ素原子、シアノ基、炭素数１〜２０のアルコキシ基及び炭素数６〜１０のアリールオキシ基からなる群から選ばれる少なくとも一つの置換基で置換されていてもよい炭素数６〜２０のアリール基；
フッ素原子、シアノ基、炭素数１〜２０のアルコキシ基及び炭素数６〜２０のアリールオキシ基からなる群から選ばれる少なくとも一つの置換基で置換されていてもよい炭素数６〜２０のアリールオキシ基；及び、
フッ素原子、シアノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基及び炭素数６〜２０のアリールオキシ基からなる群から選ばれる少なくとも一つの置換基で置換されていてもよい炭素数２〜２０のアシル基からなる群から選ばれる少なくとも一つの置換基で置換されていてもよい。
Ｙ^１及びＹ^２は同一又は相異なって、単結合、カルボニル基、スルホニル基、２，２−イソプロピリデン基、２，２−ヘキサフルオロイソプロピリデン基又はフルオレン−９，９−ジイル基を表わす。
Ｚ^１及びＺ^２は同一又は相異なって、酸素原子又は硫黄原子を表わす。Ｘ^３は塩素原子、臭素原子又はヨウ素原子を表わす。）
で示されるジハロゲノアリール化合物を混合して用いても良い。 The monomer represented by the formula (1), the formula (3) or the formula (4) includes the formula (5).

(In the formula, a, b and c are the same or different and represent 0 or 1, n represents an integer of 5 or more. Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are the same or different and 2 And a divalent aromatic group includes a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryl having 6 to 20 carbon atoms. An alkyl group having 1 to 20 carbon atoms which may be substituted with at least one substituent selected from the group consisting of oxy groups;
It may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. A good C1-C20 alkoxy group;
An aryl group having 6 to 20 carbon atoms which may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 10 carbon atoms ;
A C6-C20 aryloxy optionally substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, a C1-C20 alkoxy group and a C6-C20 aryloxy group A group; and
It may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms. It may be substituted with at least one substituent selected from the group consisting of good acyl groups having 2 to 20 carbon atoms.
Y ¹ and Y ² are the same or different and each represents a single bond, a carbonyl group, a sulfonyl group, a 2,2-isopropylidene group, a 2,2-hexafluoroisopropylidene group, or a fluorene-9,9-diyl group.
Z ¹ and Z ² are the same or different and represent an oxygen atom or a sulfur atom. X ³ represents a chlorine atom, a bromine atom or an iodine atom. )
A dihalogenoaryl compound represented by the above formula may be used in combination.

Examples of the dihalogenoaryl compound (5) include compounds shown below and compounds in which the chlorine atoms at both ends of the compounds shown below are replaced by bromine atoms.

As the dihalogenoaryl compound (5), for example, one produced according to a known method such as Japanese Patent No. 2745727 may be used, or a commercially available one may be used. As what is marketed, Sumitomo Chemical Co., Ltd. Sumika Excel PES etc. are mentioned, for example.
As the dihalogenoaryl compound (5), those having a polystyrene-equivalent weight average molecular weight of 2,000 or more are preferably used, and more preferably 3,000 or more.

Next, a method for producing polyarylene, which is a polymer, will be described.
First, a method for preparing a mixture comprising nickel halide, a bidentate nitrogen ligand and a solvent (hereinafter abbreviated as solution A) will be described.
Examples of the nickel halide include divalent nickel compounds such as nickel fluoride, nickel chloride, nickel bromide, nickel iodide, and nickel chloride is preferable.

When the amount of nickel halide used is small, polyarylene having a small molecular weight is easily obtained, and when the amount used is large, polyarylene having a large molecular weight is easily obtained, depending on the molecular weight of the target polyarylene, What is necessary is just to determine the usage-amount of a nickel compound. The usage-amount of a nickel compound is 0.4-5 mol normally with respect to 1 mol of aromatic monomers.

Examples of the nitrogen-containing bidentate ligand include 2,2'-bipyridine, 1,10-phenanthroline, methylenebisoxazoline, N, N'-tetramethylethylenediamine, and 2,2'-bipyridine is preferable. The amount of the nitrogen-containing bidentate ligand used is usually 0.2 to 2 mol, preferably 1 to 1.5 mol, per 1 mol of the nickel compound.

The solution A may be in the form of a slurry or a uniform solution when the nickel halide or the bidentate nitrogen ligand is difficult to dissolve in the solvent.

Examples of the solvent of the solution A include ether solvents such as tetrahydrofuran and 1,4-dioxane; dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, hexamethylphosphoric Examples include aprotic polar solvents such as triamide. Such a solvent may be used independently and may be used in mixture of 2 or more types. Of these, an aprotic polar solvent is preferable, and dimethyl sulfoxide is more preferable. Although there is no restriction | limiting in particular in the usage-amount of a solvent, It is 1-100 weight times normally with respect to the monomer in a monomer composition, Preferably it is 3-50 weight times.

Next, a method for preparing a mixture composed of an aromatic monomer, zinc and a solvent (hereinafter abbreviated as solution B) will be described.
Zinc is usually used in powder form. The amount of zinc used is usually 1 mol or more with respect to 1 mol of the aromatic monomer, and the upper limit is not particularly limited. However, if it is too much, post-treatment after the polymerization reaction becomes troublesome and economically. Since it becomes disadvantageous, it is practically 10 mol or less, preferably 5 mol or less.

Solution B is in the form of a slurry because zinc is difficult to dissolve, but the aromatic monomer is preferably dissolved.

Examples of the solvent of the solution B include aromatic hydrocarbon solvents such as toluene and xylene; ether solvents such as tetrahydrofuran and 1,4-dioxane; dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, Examples include aprotic polar solvents such as N, N-dimethylacetamide and hexamethylphosphoric triamide; halogenated hydrocarbon solvents such as dichloromethane and dichloroethane. Such a solvent may be used independently and may be used in mixture of 2 or more types. Of these, ether solvents and aprotic polar solvents are preferable, and tetrahydrofuran, dimethyl sulfoxide, N-methyl-2-pyrrolidone and N, N-dimethylacetamide are more preferable. If the amount of the solvent used is too large, a polyarylene having a small molecular weight is likely to be obtained, and if it is too small, the properties of the reaction mixture are likely to be deteriorated. Therefore, it is usually 1 to 100 times the weight of the monomer in the monomer composition. The amount is preferably 3 to 50 times by weight.

The temperature of the solution A and the solution B is usually in the range of 0 to 250 ° C. However, if the temperature is too low, the reaction tends to be difficult to start, and if the temperature is too high, heat generation immediately after the start of the reaction is large and temperature control becomes difficult. Therefore, 30-100 degreeC is preferable and 40-80 degreeC is especially preferable.

The mixing order of the solution A and the solution B is not limited, but the solution A is preferably mixed with the solution B. At this time, the time required for mixing is preferably within 10 minutes, particularly preferably within 5 minutes.

The polymerization temperature after mixing is usually 0 to 250 ° C, preferably 30 to 100 ° C. The polymerization time is usually 0.5 to 48 hours.

After completion of the polymerization reaction, for example, the polyarylene is precipitated by mixing the reaction mixture with a solvent that hardly dissolves the generated polyarylene to precipitate the polyarylene, and separating the precipitated polyarylene from the reaction mixture by filtration. Can do. After mixing the reaction mixture with a solvent that does not dissolve or hardly dissolve the produced polyarylene, an aqueous solution of an acid such as hydrochloric acid may be added, and the precipitated polyarylene may be separated from the reaction mixture by filtration. The molecular weight and structure of the obtained polyarylene can be analyzed by ordinary analysis means such as gel permeation chromatography and NMR. Examples of the solvent that does not dissolve or hardly dissolve the generated polyarylene include water, methanol, ethanol, acetonitrile, and the like, and water and methanol are preferable.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. The obtained polyarylene was analyzed by gel permeation chromatography (analysis conditions were as follows), and the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene were calculated from the analysis results.
<Analysis conditions>
Measuring device: CTO-10A (manufactured by Shimadzu Corporation)
Column: TSK-GEL (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Mobile phase: N, N-dimethylacetamide containing lithium bromide (lithium bromide concentration: 10 mmol / dm ³ )
Flow rate: 0.5 mL / min Detection wavelength: 300 nm

[Example 1]
Anhydrous nickel chloride (0.162 g) and dimethyl sulfoxide (1.5 mL) were mixed and adjusted to an internal temperature of 70 ° C. To this, 0.215 g of 2,2′-bipyridine was added and stirred at the same temperature for 10 minutes to prepare Solution A.
To a solution obtained by dissolving 0.103 g of methyl N, N-diethyl-2,5-dichlorobenzoate in 0.5 mL of dimethyl sulfoxide, 0.123 g of zinc powder was added and adjusted to 70 ° C. Prepared. The solution A was poured into this, and a polymerization reaction was carried out at 70 ° C. for 4 hours. The molecular weight of the polymer obtained by the above method showed 9,400 g / mol Mw and 5,000 g / mol Mn.

[Example 2]
Anhydrous nickel chloride (0.162 g) and dimethyl sulfoxide (1.5 mL) were mixed and adjusted to an internal temperature of 70 ° C. To this, 0.215 g of 2,2′-bipyridine was added and stirred at the same temperature for 10 minutes to prepare Solution A.
To a solution obtained by dissolving 0.172 g of 2,5-dichloro-4′-phenoxybenzophenone in 0.5 mL of dimethyl sulfoxide, 0.123 g of zinc powder was added and adjusted to 70 ° C. to prepare Solution B. The solution A was poured into this, and a polymerization reaction was carried out at 70 ° C. for 4 hours. The molecular weight of the polymer obtained by the above method showed Mw of 28,100 g / mol and Mn of 9,100 g / mol.

で示されるスミカエクセルＰＥＳ ５２００Ｐ（住友化学株式会社製；Ｍｗ＝９４，０００、Ｍｎ＝４０，０００：上記分析条件で測定）０．５０ｇとをジメチルスルホキシド５ｍＬに溶解させて得られた溶液に、亜鉛粉末１．２３ｇを加え、７０℃に調整した。これに、前記ニッケル含有溶液を注ぎ込み、７０℃で４時間重合反応を行った。反応混合物をメタノール６０ｍＬ中に加え、次いで、６ｍｏｌ／Ｌ塩酸６０ｍＬを加え、１時間撹拌した。析出した固体を濾過により分離し、乾燥し、灰白色の下記

で示される繰り返し単位と下記

で示されるセグメントとを含むポリアリーレン１．６２ｇを得た。収率：９９％。
Ｍｗ＝１９１，０００、Ｍｎ＝６９，０００。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，δ（ｐｐｍ））：０．８０−１．０５（ｂｒ），３．８０−３．８９（ｂｒ），７．２５（ｄ），７．９７（ｄ），７．００−８．５０（ｃ） [Example 3]
1.62 g of anhydrous nickel chloride and 15 mL of dimethyl sulfoxide were mixed and adjusted to an internal temperature of 70 ° C. To this, 2.15 g of 2,2′-bipyridine was added and stirred at the same temperature for 10 minutes to prepare a nickel-containing solution.
1.49 g of 2,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl) and the following formula

In a solution obtained by dissolving 0.50 g of Sumika Excel PES 5200P (manufactured by Sumitomo Chemical Co., Ltd .; Mw = 94,000, Mn = 40,000: measured under the above analysis conditions) in 5 mL of dimethyl sulfoxide, Zinc powder 1.23g was added and it adjusted to 70 degreeC. The nickel-containing solution was poured into this, and a polymerization reaction was performed at 70 ° C. for 4 hours. The reaction mixture was added to 60 mL of methanol, and then 60 mL of 6 mol / L hydrochloric acid was added and stirred for 1 hour. The precipitated solid was separated by filtration, dried, and grayish white

The repeating unit indicated by

1.62 g of polyarylene containing the segment represented by Yield: 99%.
Mw = 191,000, Mn = 69,000.
¹ H-NMR (CDCl ₃ , δ (ppm)): 0.80 to 1.05 (br), 3.80 to 3.89 (br), 7.25 (d), 7.97 (d), 7.00-8.50 (c)

で示される繰り返し単位のみからなるポリアリーレン２．７ｇを得た。収率：９９％。
Ｍｗ＝２０１，０００、Ｍｎ＝５９，０００
^１Ｈ−ＮＭＲ（（ＣＤ_３）_２ＳＯ，δ（ｐｐｍ））：０．８０−１．０５（ｂｒ），３．８０−３．８９（ｂｒ），７．００−８．５０（ｃ） [Example 4]
3.89 g of anhydrous nickel chloride and 36 mL of dimethyl sulfoxide were mixed and adjusted to an internal temperature of 70 ° C. To this, 5.15 g of 2,2′-bipyridine was added and stirred at the same temperature for 10 minutes to prepare a nickel-containing solution.
To a solution obtained by dissolving 3.57 g of 2,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl) in 12 mL of dimethyl sulfoxide, 2.94 g of zinc powder was added and adjusted to 70 ° C. The nickel-containing solution was poured into this, and a polymerization reaction was performed at 70 ° C. for 4 hours. The reaction mixture was added to 120 mL of methanol, and then 120 mL of 6 mol / L hydrochloric acid was added and stirred for 1 hour. The precipitated solid was separated by filtration. The separated solid is dried and grayish white

Thus, 2.7 g of polyarylene consisting only of the repeating unit represented by the formula (1) was obtained. Yield: 99%.
Mw = 201,000, Mn = 59,000
¹ H-NMR ((CD ₃ ) ₂ SO, δ (ppm)): 0.80 to 1.05 (br), 3.80 to 3.89 (br), 7.00 to 8.50 (c)

で示される繰り返し単位のみからなるポリアリーレンを含む反応混合物を得た。ポリアリーレンのＭｗは１９９，０００、Ｍｎは９３，０００であった。 [Example 5]
Anhydrous nickel chloride (0.16 g) and dimethyl sulfoxide (1.5 mL) were mixed to adjust the internal temperature to 70 ° C. To this, 0.22 g of 2,2′-bipyridine was added and stirred at the same temperature for 10 minutes to prepare a nickel-containing solution.
To a solution obtained by dissolving 0.15 g of 3,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl) in 0.5 mL of dimethyl sulfoxide, 0.12 g of zinc powder was added and adjusted to 70 ° C. The nickel-containing solution was poured into this, and a polymerization reaction was performed at 70 ° C. for 4 hours.

A reaction mixture containing polyarylene consisting only of the repeating unit represented by Polyarylene had Mw of 199,000 and Mn of 93,000.

で示される繰り返し単位のみからなるポリアリーレンを含む反応混合物を得た。ポリアリーレンのＭｗは７，２００、Ｍｎは２，７００であった。 [Example 6]
In Example 5, except that 0.14 g of N, N-diethyl-2,5-dichlorobenzenesulfonamide was used instead of 0.15 g of 3,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl). Performed in the same manner as in Example 5 and

A reaction mixture containing polyarylene consisting only of the repeating unit represented by Polyarylene had Mw of 7,200 and Mn of 2,700.

で示される繰り返し単位のみからなるポリアリーレンを含む反応混合物を得た。ポリアリーレンのＭｗは７，４００、Ｍｎは４，５００であった。 [Example 7]
In Example 5, in place of 0.15 g of 3,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl), 0.14 g of isobutyl 2,5-dichlorobenzenesulfonic acid was used. Implement the following

A reaction mixture containing polyarylene consisting only of the repeating unit represented by The polyarylene had an Mw of 7,400 and an Mn of 4,500.

で示される繰り返し単位のみからなるポリアリーレンを含む反応混合物を得た。ポリアリーレンのＭｗは、２１７，０００、Ｍｎは４９，０００であった。 [Example 8]
65 mg of anhydrous nickel chloride and 0.8 mL of dimethyl sulfoxide were mixed and adjusted to an internal temperature of 60 ° C. To this, 86 mg of 2,2′-bipyridine was added and stirred at the same temperature for 10 minutes to prepare a nickel-containing solution.
49 mg of zinc powder was added to a solution obtained by dissolving 105 mg of 4,4′-dichlorobiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl) in 0.8 mL of dimethyl sulfoxide, and the mixture was heated to 60 ° C. It was adjusted. The nickel-containing solution was poured into this, and a polymerization reaction was performed at 70 ° C. for 4 hours.

A reaction mixture containing polyarylene consisting only of the repeating unit represented by Polyarylene had Mw of 217,000 and Mn of 49,000.

[Comparative Example 1]
0.77 g of anhydrous nickel chloride, 1.02 g of 2,2′-bipyridine and 0.58 g of zinc powder were mixed with 7.0 mL of dimethyl sulfoxide, and the internal temperature was adjusted to 70 ° C. (solution 1).
A solution obtained by dissolving 0.70 g of 2,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl) in 3.5 mL of dimethyl sulfoxide was adjusted to 70 ° C., poured into Solution 1, and then at 70 ° C. for 4 hours. A polymerization reaction was performed. The molecular weight of the polymer obtained by the above method showed Mw of 4,200 g / mol and Mn of 3,700 g / mol.

Claims (11)

Mixing a mixture of nickel halide and bidentate nitrogen ligand and solvent (hereinafter abbreviated as solution A) and a mixture of one or more aromatic monomers, zinc and solvent (hereinafter abbreviated as solution B). A process for producing polyarylene, characterized in that The production method according to claim 1, wherein the reaction is performed by adding the solution A to the solution B. The method according to claim 1 or 2, wherein the nickel halide is nickel chloride. The production method according to claim 1, wherein the bidentate nitrogen ligand is 2,2′-bipyridyl. The production method according to claim 1, wherein the solution is a solution containing dimethyl sulfoxide. The temperature of the solution A and the solution B is 40 to 80 degreeC, The manufacturing method in any one of Claims 1-5. The aromatic monomer is represented by the formula (1)
^{X 1} -Ar-X ¹
(In the formula, Ar represents an arylene group or a divalent heterocyclic group, and X ¹ represents a chlorine, bromine or iodine atom.)
And one or more aromatic monomers represented by the formula (2):
-Ar-
The production method according to claim 1, wherein the polyarylene contains a repeating unit represented by the formula: The aromatic monomer is represented by the formula (3)

(In the formula, A represents an amino group substituted with one or two hydrocarbon groups, and the hydrocarbon group has a total carbon number of 1 to 20, or an alkoxy group having 1 to 20 carbon atoms. And the hydrocarbon group and the alkoxy group having 1 to 20 carbon atoms are a fluorine atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a carbon number. It may be substituted with at least one group selected from the group consisting of 2 to 20 acyl groups and cyano groups.
R ¹ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or 2 carbon atoms. Represents ˜20 acyl groups or cyano groups. Here, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an acyl group having 2 to 20 carbon atoms are It may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. Good. Further, when R ¹ is plural, R ¹ may be the same group or different groups. Further, two adjacent R ¹ may be bonded to form a ring.
X ² represents a chlorine atom, a bromine atom or an iodine atom. m represents 1 or 2, and k represents 4-m. )
The production method according to claim 1, which is a dihalogenobenzene compound represented by the formula: The aromatic monomer is represented by the formula (4)

(In the formula, A, R ¹ , k, m and X ² represent the same meaning as described above.)
The production method according to claim 1, which is a dihalogenobiphenyl compound represented by the formula: The aromatic monomer is a dihalogenobenzene compound represented by the formula (3) according to claim 8 and the formula (5).

(In the formula, a, b and c are the same or different and represent 0 or 1, n represents an integer of 5 or more. Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are the same or different and 2 Represents a divalent aromatic group, wherein the divalent aromatic group may be substituted with the following substituents.
It may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. A good C1-C20 alkyl group;
It may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. A good C1-C20 alkoxy group;
An aryl group having 6 to 20 carbon atoms which may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 10 carbon atoms ;
A C6-C20 aryloxy optionally substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, a C1-C20 alkoxy group and a C6-C20 aryloxy group A group; and
It may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms. It may be substituted with at least one substituent selected from the group consisting of good acyl groups having 2 to 20 carbon atoms.
Y ¹ and Y ² are the same or different and each represents a single bond, a carbonyl group, a sulfonyl group, a 2,2-isopropylidene group, a 2,2-hexafluoroisopropylidene group, or a fluorene-9,9-diyl group.
Z ¹ and Z ² are the same or different and represent an oxygen atom or a sulfur atom. X ³ represents a chlorine atom, a bromine atom or an iodine atom. )
The manufacturing method in any one of Claims 1-6 which is a mixture which consists of a dihalogenoaryl compound shown by these. The aromatic monomer is a mixture comprising a dihalogenobiphenyl compound represented by the formula (4) according to claim 9 and a dihalogenoaryl compound represented by the formula (5) according to claim 10. 6. The production method according to any one of 6 above.