JP2002128891A - Novel alternating copolymer and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel alternating copolymer which is excellent in solubility in a solvent, can easily form a thin film, is useful as an electronic material and other resin materials, and a method for producing the same. SOLUTION: The alternating copolymer of the present invention comprises a repeating unit represented by the following general formula (1). This alternating copolymer is obtained by copolymerizing a specific aniline derivative and a dihalogenated organic compound in the presence of a catalyst and a base. Embedded image [In the general formula (1), R ¹ is a substituted or unsubstituted carbazolyl group or a carbazolylaryl group, or a group represented by —NHR ² or —N (R ³ ) ₂ (provided that R ² and R ³ represents a substituted or unsubstituted aryl group.), And X ¹ represents a divalent organic group. ]

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel alternating copolymer and a method for producing the same, and more particularly, to an alternating copolymer useful as an electronic material such as a charge transport material and other resin materials, and a method for producing the same. Things.

[0002]

2. Description of the Related Art Conventionally, various organic polymer materials have been used as electronic parts and other electronic materials. Examples of such organic polymer materials include side chain polymers such as polyvinylcarbazole and polyamine, polyphenylenevinylene, and the like.
Thermoplastic polymers such as main-chain polymers such as polyfluorene, polythiophene, polyaniline, and polypyrrole are known. As polymers having excellent charge transporting properties, polyphenylene, alkoxy-substituted polyphenylenevinylene, polyfluorene copolymer having a bulky substituent, and the like have been developed. However, the above-mentioned organic polymer material generally has low solubility in a solvent and it is difficult to prepare a coating solution, so that it has been extremely difficult to form a thin film using the organic polymer material.

[0003] For these reasons, as a material for forming a thin film, a thermosetting resin precondensate or a low-molecular compound is used. However, in the thermosetting resin precondensate, it is possible to form a thin film having excellent heat resistance, but it takes a considerable time for molding, and the thermosetting resin precondensate reacts. At this time, since low molecular condensates such as water are generated, there is a great limitation when used as an electronic material. In addition, addition-type oligomers and the like have been developed as materials that do not generate low-molecular condensates.However, when preparing a coating solution, a very special reaction solvent is required, and when forming a thin film, In addition, there is a problem that productivity is extremely low because heat treatment at a high temperature is required. Further, it is difficult to form a thin film having excellent heat resistance with a low molecular compound.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made based on the above circumstances, and its object is to provide:
An object of the present invention is to provide a novel alternating copolymer which is excellent in solubility in a solvent, can easily form a thin film, and is useful as an electronic material and other resin materials. Another object of the present invention is to provide a method capable of producing a novel alternating copolymer which is excellent in solubility in a solvent, can easily form a thin film, and is useful as an electronic material and other resin materials. It is in.

[0005]

Means for Solving the Problems The alternating copolymer of the present invention comprises a repeating unit represented by the following general formula (1).

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[In the general formula (1), R ¹ represents a substituted or unsubstituted carbazolyl group or carbazolylaryl group, or —NHR ² or —N (R
³⁾ ₂ group represented by (wherein, R ² and R ³ represents a substituted or unsubstituted aryl group.) Indicates, X ¹ is
Shows a divalent organic group. ]

In the alternating copolymer of the present invention, the group X ¹ in the general formula (1) is replaced by a group represented by the following general formula (2), a group represented by the following general formula (3) or It is preferably a group represented by the general formula (4).

[0008]

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[In the general formulas (2) to (4),
R ^{4 to} R ¹¹ each independently represent an alkyl group, an aryl group or a halogen atom, and X ² represents a single bond, —O
Represents-, -CO-, -COO- or -S-. m is 0
And k is an integer of 0 to 3. ]

Further, in the alternating copolymer of the present invention,
In the general formula (1), the group R ¹ is preferably a group represented by the following general formula (5).

[0011]

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[In the general formula (5), R ¹² and R ¹³
Represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom or a group represented by the following general formula (6). ]

[0013]

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[In the general formula (6), R ¹⁴ and R ¹⁵
Each independently represents an alkyl group. j is an integer of 0 to 2. ]

Further, the alternating copolymer of the present invention preferably comprises a repeating unit represented by the following general formula (7), (8) or (9).

[0016]

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[In the general formulas (7) to (9),
R ⁶ and R ⁷ each independently represent an alkyl group, an aryl group or a halogen atom, and R ¹² and R ¹³ are
A hydrogen atom, an alkyl group, an aryl group, a halogen atom or a group represented by the above general formula (6) is shown. k is an integer of 0 to 3. ]

Further, in the alternating copolymer of the present invention,
The groups R ¹² and R ^{13 in the} general formula (7), the general formula (8) or the general formula (9) are preferably groups represented by the following formula (a).

[0019]

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Further, in the alternating copolymer of the present invention,
Weight average molecular weight is 1,000-
It is preferably in the range of 1,000,000.

The method for producing an alternating copolymer of the present invention is a method for producing an alternating copolymer comprising a repeating unit represented by the above general formula (1), and is represented by the following general formula (10). It is characterized in that an aniline derivative and a dihalogenated organic compound are copolymerized in the presence of a catalyst and a base.

[0022]

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[In the general formula (10), R¹Is it
A substituted or unsubstituted carbazolyl group or carb
Bazolylaryl group, or -NHR^TwoOr -N
(R^Three) _TwoA group represented by the formula (provided that R^TwoAnd R^ThreeIs
Represents a substituted or unsubstituted aryl group. ) And X¹
Represents a divalent organic group.

In the method for producing an alternating copolymer according to the present invention, the dihalogenated organic compound is represented by the following general formula (1)
The compound represented by 1), the compound represented by the following general formula (12) or the compound represented by the following general formula (13) is preferable.

[0025]

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[In the general formulas (10) to (12), R ^{4 to} R ¹¹ each independently represent an alkyl group, an aryl group or a halogen atom; X ² represents a single bond;
O -, - CO -, - COO- or -S- are shown, Z ¹
And Z ² represent a halogen atom. m is an integer of 0 to 4, and k is an integer of 0 to 3. ]

In the method for producing an alternating copolymer of the present invention, it is preferable to use a palladium compound as the catalyst, and it is particularly preferable to use a palladium compound and phosphine in combination.

[0028]

Embodiments of the present invention will be described below in detail. The alternating copolymer of the present invention is composed of a repeating unit represented by the general formula (1), and includes an aniline derivative represented by the general formula (10) (hereinafter, also referred to as a “specific aniline derivative”). ) And a copolymerizable compound with the specific aniline derivative.

In the general formulas (1) and (10), the group R ¹ is a carbazolyl group having or not having a substituent, a carbazolylphenyl group having or having no substituent, or the like. And a group represented by —NHR ² or —N (R ³ ) ₂ , wherein the groups R ² and R ³ are substituted or unsubstituted aryl groups, respectively. . Here, as a substituent of the carbazolyl group or the carbazolylaryl group, for example, a C1-8 alkyl group,
Examples include an aryl group such as a phenyl group, a halogen atom, and a group represented by the general formula (6). In the general formula (6), the group R ¹⁴ and the group R ¹⁵ are an alkyl group (preferably having 1 to carbon atoms). 8). As the substituent for the aryl group represented by the group R ³ , an alkyl group (preferably having 1 carbon atom)
To 8), an alkoxy group (preferably having 1 to 8 carbon atoms),
Examples include a halogen atom and a nitro group.

In the specific aniline derivative used for obtaining the alternating copolymer of the present invention, specific examples of the compound in which the group R ¹ in the general formula (10) is —NHR ² or —N (R ³ ) ₂ Are monophenylaminoaniline represented by the following formula (b), diphenylaminoaniline represented by the following formula (c), diphenylphenylaminoaniline represented by the following formula (d), triphenylphenylaminoaniline represented by the following formula (e), 2-tolylphenylaminoaniline represented by the following formula (f), 4-tolylphenylaminoaniline represented by the following formula (g), 2-methoxyphenylaminoaniline represented by the following formula (h), and 3 represented by the following formula (li) −
Methoxyphenylaminoaniline, 4-methoxyphenylaminoaniline represented by the following formula (nu), 4-nitrophenylaminoaniline represented by the following formula (ル), and the following formula (ヲ)
3-fluorophenylaminoaniline represented by the following formula (W), 4,4-difluorophenylaminoaniline represented by the following formula (F), 3,4 represented by the following formula (Y) 5-trifluorophenylaminoaniline, 2,3 represented by the following formula (T)
Examples thereof include 4,5-tetrafluorophenylaminoaniline, and 2,3,4,5,6-pentafluorophenylaminoaniline represented by the following formula (V).

[0031]

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[0032]

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The compound in which the group R ¹ in the general formula (10) is a substituted or unsubstituted carbazolyl group (hereinafter, also referred to as “specific carbazolyl group-containing aniline derivative”) includes the following general formula (14) And a compound in which the group R ¹ in the general formula (10) is a substituted or unsubstituted carbazolylaryl group (hereinafter, also referred to as “specific carbazolylaryl group-containing aniline derivative”). Is preferably a compound represented by the following general formula (15).

[0034]

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[In the general formulas (13) and (14), R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group, an aryl group, a halogen atom or the above general formula (6). Represents a group. ]

Specific examples of the specific carbazolyl group-containing aniline derivative include p-N-carbazolylaniline and p-N-carbazolylaniline.
-(3,6-dimethyl-N-carbazolyl) aniline,
p- (3,6-diphenyl-N-carbazolyl) aniline, p- (3,6-dihalogeno-N-carbazolyl) aniline, p- (3,6-diarylamino-N-carbazolyl) aniline, p- (3 , 6-bis (phenyl-m
-Tolylamino) -N-carbazolyl) aniline, p-
(3,6- (n-butoxyphenyl-m-tolylamino) -N-carbazolyl) aniline and the like.
Specific examples of specific carbazolylaryl group-containing aniline derivatives include p-N-carbazolylphenylaniline, p- (3,6-dimethyl-N-carbazolyl) phenylaniline, and p- (3,6-diphenyl). -N-carbazolyl) phenylaniline, p- (3,6-dihalogeno-N-carbazolyl) phenylaniline, p- (3,6
-Diarylamino-N-carbazolyl) phenylaniline and the like.

As the specific aniline derivative, among the above compounds, a substituted or unsubstituted carbazolyl group is preferred in that an alternating copolymer having high solubility in a solvent and excellent heat resistance can be obtained. Are preferred.

In the general formula (1), the group X ¹ is a divalent organic group, preferably a group represented by the general formula (2), a group represented by the general formula (3) or a group represented by the general formula (3). It is a group represented by (4). In the general formulas (2) to (4), the groups R ⁴ to R ¹¹ each independently represent an alkyl group (preferably having 1 to 8 carbon atoms), an aryl group such as a phenyl group, or a halogen atom. , A group X ² is a single bond,
-O-, -CO-, -COO- or -S- is shown. Further, m is an integer of 0 to 4, and k is an integer of 0 to 3.

As the compound used for forming the group X ¹ , that is, the compound copolymerizable with the specific aniline derivative, it is preferable to use a dihalogenated organic compound, and particularly, a compound represented by the above general formula (11). Compound
The compound represented by the general formula (12) or the compound represented by the general formula (13) is preferable.

The compound represented by the general formula (11) is
Examples thereof include a biphenyl derivative, a diphenyl ether derivative, a benzophenone derivative, and a diphenyl sulfide derivative each having two halogen atoms. Specific examples thereof include dibromodiphenyl, 4,4′-dichlorodiphenylether, 4,4′-dibromodiphenylether, 4′-diiododiphenyl ether, 4,
4'-dibromobenzophenone and the like.

The compound represented by the general formula (12) is
A fluorene derivative having two halogen atoms,
Specific examples thereof include 2,7-dibromofluorene,
Examples thereof include 2,7-dichlorofluorene and 2,7-diiodofluorene. The compound represented by the general formula (13) is a spirofluorene derivative having two halogen atoms, and specific examples thereof include 2,7-dibromospirofluorene, 2,7-dichlorospirofluorene, and 2,7-dichlorospirofluorene. -Diiodospirofluorene and the like.

The average molecular weight of the alternating copolymer of the present invention is appropriately selected according to the purpose of use. However, in terms of obtaining good mechanical properties, the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography is not preferable. , 1,000
It is preferably from 5,000 to 1,000,000, and particularly from the viewpoint of obtaining good solubility and processing characteristics, from 5,000 to
Preferably it is 50,000.

The method for producing the alternating copolymer of the present invention comprises:
Although it is not particularly limited, as a method for easily producing an alternating copolymer, a specific aniline derivative and a dihalogenated organic compound are mixed in an appropriate polymerization solvent in the presence of a catalyst and a base. The method of copolymerization is preferred. Here, the ratio of the specific aniline derivative and the dihalogenated organic compound is usually a specific aniline derivative: dihalogenated organic compound = 0.5 to 1.5 in a molar ratio, and particularly a high molecular weight alternating copolymer. Is obtained, the specific aniline derivative: dihalogenated organic compound =
It is preferably from 0.9 to 1.1.

In such a production method, it is preferable to use a palladium compound as a catalyst. The palladium compound is not particularly limited, and is, for example, a tetravalent palladium compound such as sodium hexachloropalladium (IV) tetrahydrate, potassium hexachloropalladium (IV); palladium chloride (I
I), palladium (II) bromide, palladium acetate (I
I), palladium acetylacetonate (II), dichlorobis (benzonitrile) palladium (II), dichlorobis (acetonitrile) palladium (II), dichlorobis (triphenylphosphine) palladium (I
I), dichlorotetraamminepalladium (II), dichloro (cycloocta-1,5-diene) palladium (II), palladium trifluoroacetate (II)
Divalent palladium compounds such as tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium chloroform complex (0), and tetravalent (triphenylphosphine) palladium (0) Can be mentioned.

The use amount of such a palladium compound is as follows:
Although not particularly limited, in view of the fact that the reaction can proceed reliably, 0.000 in terms of palladium relative to 1 mol of halogen atom in the dihalogenated organic compound.
It is preferably in the range of 01 to 20.0 mol%, and in particular, considering the economical efficiency because the palladium compound is expensive, 0.001 in terms of palladium relative to 1 mol of halogen atom in the dihalogenated organic compound. -10
Preferably it is mol%.

As a catalyst, it is preferable to use phosphine in combination with the above-mentioned palladium compound. The phosphine is not particularly limited, and examples thereof include triethylphosphine, tricyclohexylphosphine, triisopropylphosphine, tri-n-butylphosphine, triisobutylphosphine, and tri-se.
trialkylphosphines such as c-butylphosphine and tri-tert-butylphosphine; triphenylphosphine, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, tri (p-tolyl) phosphine, B
Examples include arylphosphines such as INAP, trimesitylphosphine, diphenylphosphinoethane, diphenylphosphinopropane, diphenylphosphinoferrocene, and the like. Among them, tri-tert-butylphosphine is preferred because of having high reaction activity. When a palladium compound and phosphine are used in combination as a catalyst, they may be separately added to the reaction system, or a palladium compound and phosphine complex may be prepared in advance and added to the reaction system. .

When a palladium compound and a phosphine are used in combination as a catalyst, the amount of the phosphine is 0.01 to 100 mol per mol of the palladium compound.
It is sufficient if it is in the range of 00 mol, and in particular, it is in the range of 0.1 to 10 mol per mol of the palladium compound in consideration of economy since phosphine is expensive.

Examples of the base for copolymerizing the specific aniline derivative and the dihalogenated organic compound include, for example, carbonates such as sodium carbonate and potassium carbonate, inorganic bases such as alkali metal alkoxide, and organic bases such as tertiary amine. And the like. Specific examples of preferable bases include sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, and lithium te.
Examples thereof include alkali metal alkoxides such as rt-butoxide, sodium-tert-butoxide, and potassium-tert-butoxide. These bases may be added to the reaction system as they are, but an alkali metal, an alkali metal hydride or an alkali metal hydroxide, and an alcohol are added to the reaction system, and the target base is obtained by reacting both. It may be prepared and subjected to a reaction.

The use amount of such a base is not particularly limited, but is preferably 0.5 mol or more per 1 mol of halogen atom in the dihalogenated organic compound. Even when the base is added excessively, the yield is not affected much, but the post-treatment operation after the completion of the reaction is complicated, so that the amount of the base used is based on 1 mol of the halogen atom in the dihalogenated organic compound. More preferably, it is 1.0 to 5 mol.

The polymerization solvent is not particularly limited as long as it is an inert solvent which does not significantly inhibit the reaction between the specific aniline derivative and the dihalogenated organic compound. Examples thereof include aromatic hydrocarbon solvents such as benzene, toluene and xylene mesitylene. Ether solvents such as diethyl ether, tetrahydrofuran and dioxane; acetonitrile, dimethylformamide, dimethylsulfoxide, hexamethylphosphotriamide and the like can be mentioned as preferred. Among these, benzene, toluene, xylene,
Aromatic hydrocarbon solvents such as mesitylene are particularly preferred.

In the production method of the present invention, the reaction between the specific aniline derivative and the dihalogenated organic compound is usually carried out by
It is carried out under normal pressure and in an atmosphere of an inert gas such as nitrogen or argon, but may be carried out under pressure. As specific reaction conditions, for example, the reaction temperature is preferably 20 ° C to 25 ° C.
The temperature may be selected from 0 ° C, more preferably from 50 ° C to 150 ° C, and the reaction time may be preferably selected from the range of several minutes to 24 hours.

The alternating copolymer thus obtained is
It can be used as it is as an electronic material or other resin material, but glass fiber, carbon fiber, talc,
The composition can also be used in the state of being mixed with fillers such as calcium carbonate and mica, various kinds of pigments, antioxidants, various kinds of stabilizers such as light stabilizers, and the like. In addition, polyethylene, polypropylene, polyvinyl chloride, general-purpose resins such as polystyrene, polyamide, engineering plastics such as modified polyphenylene ether, polyphenylene sulfide, polyphenylene sulfide ketone, polyimide, polyether imide, super engineering plastics such as liquid crystal polymer and other other It can be used in a state of being blended or alloyed with a polymer.

According to the alternating copolymer of the present invention, excellent solubility in a solvent can be obtained, and a coating solution for forming a thin film can be easily prepared. A thin film can be easily formed. Therefore,
The alternating copolymer of the present invention is useful as an electronic material and other resin materials, and is particularly suitable as a charge transport material because it has charge transport performance due to its chemical structure.

[0054]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples.

Example 1 In a 500 ml four-necked flask equipped with a cooling tube and a thermometer, p- (3,6-bis (phenyl-m-
Tolylamino) -N-carbazolyl) aniline 12.4
g (0.02 mol) and 9.48 g (0.02 g) of 2,7-dibromospirofluorene as a dihalogenated organic compound.
2 mol), 5.77 g of sodium tertiary butoxide (1.5 mol per 1 mol of bromine atom in the dihalogenated organic compound) as a base and 300 ml of mesitylene as a polymerization solvent were charged and mixed. In this system, 455 mg of tris (dibenzylideneacetone) dipalladium (an amount that becomes 2.5 mol in terms of palladium per mol of bromine atom in the dihalogenated organic compound) as a catalyst and tritertiarybutylphosphine 3
Mmol (6 moles per mole of palladium compound) was added under a nitrogen atmosphere. Thereafter, the temperature of the system is increased to 140 ° C. in a nitrogen atmosphere, and further increased to 140 ° C.
The reaction was carried out for 20 hours while stirring with heating. After completion of the reaction, 60 ml of water was added to the system, and the system was washed with water. Then, the solvent (organic layer) and water were separated by a separating funnel, and the organic phase was concentrated under reduced pressure to obtain a red solution. This solution was dropped into acetone to precipitate a pale yellow powder. The powder was collected by filtration and dried under reduced pressure to obtain 15.2 g of a pale yellow powder.

The obtained pale yellow powder was subjected to a nuclear magnetic resonance analyzer "JNM EX-90" (manufactured by JEOL Ltd.) and an infrared spectrometer "JIR-5500" (manufactured by JASCO Corporation). As a result, it was confirmed that the copolymer was an alternating copolymer comprising a repeating unit represented by the following formula (i). The nuclear magnetic resonance spectrum diagram and the infrared spectrum diagram are shown in FIGS. 1 and 2, respectively. The yield of the obtained alternating copolymer was 73%, and its weight average molecular weight was measured with a gel permeation chromatograph "HLC8120" (manufactured by Tosoh, tetrahydrofuran solvent).
600.

[0057]

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Example 2 In Example 1, the specific aniline derivative was p- (3,6-bis (phenyl-
Instead of m-tolylamino) -N-carbazolyl) aniline, p- (3,6-bis (n-butoxyphenyl-m
-Tolylamino) -N-carbazolyl) aniline 15.
By performing the same operation except that 3 g (0.02 mol) was used, 16.5 g of a pale yellow powder was obtained. The obtained pale yellow powder is subjected to a nuclear magnetic resonance analyzer “JNM EX
-90 "and infrared spectrometer" JIR-5500 "
As a result, it was confirmed that the copolymer was an alternating copolymer comprising a repeating unit represented by the following formula (ii).
FIGS. 3 and 4 show a nuclear magnetic resonance spectrum diagram and an infrared spectrum diagram, respectively. The yield of the obtained alternating copolymer was 81%, and the weight average molecular weight was
Gel permeation chromatograph "HLC81
20 ", it was 2 in terms of polystyrene.
It was 3,000.

[0059]

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Example 3 In a 500 ml four-necked flask equipped with a condenser and a thermometer, p- (3,6-bis (n-butoxyphenyl-m-tolylamino) was used as a specific aniline derivative at room temperature. -N-carbazolyl) aniline, 15.3 g (0.02 mol) of dihalogenated organic compound, 6.56 g (0.02 mol) of 4,4'-dibromodiphenyl ether as dihalogenated organic compound, 5.82 g of sodium tert-butoxide as base (dihalogenated organic compound) And 1.5 ml of mesitylene as a polymerization solvent. In this system, 455 mg of tris (dibenzylideneacetone) dipalladium (an amount of 2.5 mol in terms of palladium per mol of bromine atom in the dihalogenated organic compound) as a catalyst and 3 mmol of tritertiarybutylphosphine (palladium compound 6 mol per mol) was added under a nitrogen atmosphere.
Thereafter, the temperature of the system was increased to 120 ° C. under a nitrogen atmosphere, and the reaction was further performed at 120 ° C. for 24 hours while heating and stirring. After completion of the reaction, 60 ml of water was added to the system, and the system was washed with water. Then, the solvent (organic layer) and water were separated by a separating funnel, and the organic phase was concentrated under reduced pressure to obtain a red solution. This solution was mixed with a mixed solvent of tetrahydrofuran and methanol (the mixing weight ratio was tetrahydrofuran: methanol = 1: 1).
5) A light and pale powder was deposited by dropping into the mixture. The powder was collected by filtration and dried under reduced pressure to obtain 16.45 g of a pale yellow powder.

The obtained pale yellow powder was subjected to a nuclear magnetic resonance analyzer “JNM EX90” and an infrared spectrometer “JI
R-5500 ", it was confirmed that the copolymer was an alternating copolymer comprising a repeating unit represented by the following formula (iii). The nuclear magnetic resonance spectrum diagram and the infrared spectrum diagram are shown in FIGS. 5 and 6, respectively. Also,
The yield of the obtained alternating copolymer was 88%, and its weight average molecular weight was measured by a gel permeation chromatograph "HLC8120". As a result, it was 19,800 in terms of polystyrene.

[0062]

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Example 4 In a 500 ml four-necked flask equipped with a cooling tube and a thermometer, p- (3,6-bis (phenyl-m-
Tolylamino) -N-carbazolyl) aniline 12.4
g (0.02 mol), 6.56 g (0.4%) of 4,4'-dibromodiphenyl ether as a dihalogenated organic compound.
02 mol), 5.82 g of sodium tertiary butoxide (1.5 mol per 1 mol of bromine atom in the dihalogenated organic compound) as a base, and 150 ml of mesitylene as a polymerization solvent were charged and mixed. In this system, tris (dibenzylideneacetone) is used as a catalyst.
455 mg of dipalladium (an amount of 2.5 mol in terms of palladium based on 1 mol of a bromine atom in the dihalogenated organic compound) and 3 mmol of tritertiarybutylphosphine (an amount of 6 mol with respect to 1 mol of the palladium compound) Was added under a nitrogen atmosphere. Thereafter, the temperature of the system is increased to 120 ° C. in a nitrogen atmosphere, and
The reaction was carried out for 24 hours while heating and stirring at ℃. After completion of the reaction, 60 ml of water was added to the system, and the system was washed with water. Then, the solvent (organic layer) and water were separated by a separating funnel, and the organic phase was concentrated under reduced pressure to obtain a red solution. This solution was dropped into a mixed solvent of tetrahydrofuran and methanol (the mixing weight ratio was tetrahydrofuran: methanol = 1: 5) to precipitate a pale yellow powder. The powder was collected by filtration and dried under reduced pressure to obtain 14.4 g of a pale yellow powder.

The obtained pale yellow powder was subjected to a nuclear magnetic resonance analyzer “JNM EX90” and an infrared spectrometer “JI
R-5500 ", it was confirmed that the copolymer was an alternating copolymer comprising a repeating unit represented by the following formula (iv). FIGS. 7 and 8 show a nuclear magnetic resonance spectrum diagram and an infrared spectrum diagram, respectively. Also,
The yield of the obtained alternating copolymer was 90%, and its weight average molecular weight was measured by a gel permeation chromatograph "HLC8120". As a result, it was 19,800 in terms of polystyrene.

[0065]

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Example 5 In a 500 ml four-necked flask equipped with a cooling tube and a thermometer, p- (3,6-bis (phenyl-m-
Tolylamino) -N-carbazolyl) aniline 12.4
g (0.02 mol) and 6.5 g (0.02 mol) of 2,7-dibromofluorene as a dihalogenated organic compound.
l), 5.77 g of sodium tert-butoxide as base (1.5 mol per 1 mol of bromine atom in dihalogenated organic compound) and xylene as polymerization solvent (o-form, m-form and p-form) Mixture)
150 ml was charged and mixed. In this system, 455 m of tris (dibenzylideneacetone) dipalladium was used as a catalyst.
g (an amount of 2.5 mol in terms of palladium based on 1 mol of a bromine atom in the dihalogenated organic compound) and 3 mmol of tritertiary butylphosphine (an amount of 6 mol per 1 mol of the palladium compound) with nitrogen Added under atmosphere. Then, the temperature of the system is reduced to 1 under a nitrogen atmosphere.
The temperature was raised to 40 ° C, and the reaction was further performed for 18 hours while heating and stirring at 140 ° C. After the reaction is completed, add 200 ml of water to the system.
Was added and washed with water, and the solid content was collected by filtration. This solid content is mixed with 30 ml of water and 30 ml of tetrahydrofuran.
And 30 ml of methanol in this order, and dried under reduced pressure to obtain 14.05 g of a white powder.

The obtained white powder was subjected to a nuclear magnetic resonance analyzer “JNM EX90” and an infrared spectrometer “JIR
As a result, the copolymer was confirmed to be an alternating copolymer comprising a repeating unit represented by the following formula (v). FIGS. 9 and 10 show a nuclear magnetic resonance spectrum diagram and an infrared spectrum diagram, respectively. Also,
The yield of the obtained alternating copolymer was 90%, and its weight average molecular weight was measured by a gel permeation chromatograph "HLC8120". As a result, it was 32,000 in terms of polystyrene.

[0068]

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Example 6 In Example 1, the specific aniline derivative was p- (3,6-bis (phenyl-
By performing the same operation except that 6.72 g (0.02 mol) of p- (3,5-diphenylphenylamino) aniline was used instead of m-tolylamino) -N-carbazolyl) aniline, a white powder was obtained. 9.1 g were obtained. The obtained white powder was converted into an infrared spectrometer "JIR-
As a result, the copolymer was confirmed to be an alternating copolymer comprising a repeating unit represented by the following formula (vi). FIG. 11 shows the infrared spectrum. The yield of the obtained alternating copolymer was 71%, and the weight-average molecular weight thereof was 8,900 in terms of polystyrene as measured by a gel permeation chromatograph "HLC8120".

[0070]

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[Solubility test] The alternating copolymers obtained in Examples 1 to 6 were evaluated for solubility in solvents as follows. 0.5 g of the alternating copolymer was added to 10 ml of toluene, and the mixture was stirred at a constant rotation speed. The solubility of the alternating copolymer in toluene was examined. did. As a comparative example, solubility of polyaniline was similarly evaluated. Table 1 shows the results.

[Thin Film Forming Test] The solution obtained in the above solubility test was used as a thin film forming coating solution, and this thin film forming coating solution was applied to the surface of a glass substrate by spin coating. By performing the drying treatment, a thin film was formed on the surface of the substrate and observed. The case where a thin film with a uniform thickness was formed was evaluated as ○, and the case where a thin film with a uniform thickness was not formed was evaluated as x. The results are shown in Table 1.

[0073]

[Table 1]

[0074]

As described above, the alternating copolymer of the present invention has excellent solubility in a solvent, can easily form a thin film, and is useful as an electronic material or other resin material. In particular, since it has charge transport performance due to its chemical structure, it is suitable as a charge transport material. ADVANTAGE OF THE INVENTION According to the manufacturing method of the alternating copolymer of this invention, it is excellent in the solubility with respect to a solvent, a thin film can be easily formed, and an alternating copolymer useful as an electronic material and other resin materials can be manufactured. .

[Brief description of the drawings]

FIG. 1 is a nuclear magnetic resonance spectrum of the alternating copolymer obtained in Example 1.

FIG. 2 is an infrared absorption spectrum diagram of the alternating copolymer obtained in Example 1.

FIG. 3 is a nuclear magnetic resonance spectrum of the alternating copolymer obtained in Example 2.

FIG. 4 is an infrared absorption spectrum of the alternating copolymer obtained in Example 2.

FIG. 5 is a nuclear magnetic resonance spectrum of the alternating copolymer obtained in Example 3.

FIG. 6 is an infrared absorption spectrum of the alternating copolymer obtained in Example 3.

FIG. 7 is a nuclear magnetic resonance spectrum of the alternating copolymer obtained in Example 4.

FIG. 8 is an infrared absorption spectrum of the alternating copolymer obtained in Example 4.

9 is a nuclear magnetic resonance spectrum of the alternating copolymer obtained in Example 5. FIG.

FIG. 10 is an infrared absorption spectrum of the alternating copolymer obtained in Example 5.

FIG. 11 is an infrared absorption spectrum of the alternating copolymer obtained in Example 6.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yasunori Negoro F-term (reference) 4J043 PA10 QB15 QB51 QB52 SA03 SA06 SA42 SA47 SA54 SA72 TA41 TA43 TA46 UA092 2-1-1-24 Tsukiji, Chuo-ku, Tokyo UA131 UA132 UA141 UA151 UA242 UA421 UB122 UB152 UB211 UB241 UB401 UB402 XB14 XB15 XB16 XB21 ZA23 ZA41 ZB47 ZB50

Claims (9)

[Claims] 1. An alternating copolymer comprising a repeating unit represented by the following general formula (1). Embedded image [In the general formula (1), R ¹ is a substituted or unsubstituted carbazolyl group or a carbazolylaryl group, or a group represented by —NHR ² or —N (R ³ ) ₂ (provided that R ² and R ³ represents a substituted or unsubstituted aryl group.), And X ¹ represents a divalent organic group. ] 2. The group X ¹ in the general formula (1) is a group represented by the following general formula (2), a group represented by the following general formula (3), or a group represented by the following general formula (4) The alternating copolymer according to claim 1, which is a group. Embedded image [In the general formulas (2) to (4), R ^{4 to} R
¹¹ each independently represents an alkyl group, an aryl group or a halogen atom; X ² represents a single bond, -O-, -CO
Represents-, -COO- or -S-. m is an integer of 0 to 4, and k is an integer of 0 to 3. ] 3. The alternating copolymer according to claim ¹ , wherein the group R ¹ in the general formula (1) is a group represented by the following general formula (5). Embedded image [In the general formula (5), R ¹² and R ¹³ represent a hydrogen atom, an alkyl group, an aryl group, a halogen atom or a group represented by the following general formula (6). [Formula 4] [In the general formula (6), R ¹⁴ and R ¹⁵ each independently represent an alkyl group. j is an integer of 0 to 2. ] 4. The alternating material according to claim 1, comprising a repeating unit represented by the following general formula (7), (8) or (9). Copolymer. Embedded image [In the general formulas (7) to (9), R ⁶ and R
⁷ independently represents an alkyl group, an aryl group or a halogen atom, and R ¹² and R ¹³ represent a hydrogen atom, an alkyl group, an aryl group, a halogen atom, or claim 3
And a group represented by the general formula (6). k is 0-3
Is an integer. ] 5. The group represented by the general formula (7), (8) or (9), wherein the groups R ¹² and R ¹³ are groups represented by the following formula (A). 5. The alternating copolymer according to 4. Embedded image 6. The alternating copolymer according to claim 1, wherein the weight average molecular weight is in the range of 1,000 to 1,000,000 in terms of polystyrene. 7. The method for producing the alternating copolymer according to claim 1.
A aniline derivative represented by the following general formula (10):
With a halogenated organic compound in the presence of a catalyst and a base.
A method for producing an alternating copolymer, which comprises polymerizing. Embedded image[In the general formula (10), R¹Is the replacement
Or unsubstituted carbazolyl group or carbazolylant
Or -NHR^TwoOr -N (R^Three) _TwoIn table
Group (provided that R^TwoAnd R^ThreeIs replaced or unplaced
And a substituted aryl group. ) And X¹Is divalent organic
Represents a group. ] 8. The method according to claim 1, wherein the dihalogenated organic compound is a compound represented by the following general formula (11), a compound represented by the following general formula (12) or a compound represented by the following general formula (13). The method for producing an alternating copolymer according to claim 7, characterized in that: Embedded image [In the general formulas (10) to (12), R ^{4 to} R
¹¹ independently represent an alkyl group, an aryl group or a halogen atom; X ² represents a single bond, -O-, -CO
-, -COO- or -S-, Z ¹ and Z
² represents a halogen atom. m is an integer of 0 to 4,
k is an integer of 0 to 3. ] 9. The method for producing an alternating copolymer according to claim 7, wherein a palladium compound is used as the catalyst.