JP3200467B2 - Carbazole ring-containing monomer, carbazole ring-containing polymer and methods for producing them - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel carbazole ring-containing monomer, a carbazole ring-containing polymer and a method for producing the same, and more particularly, to an organic photosensitive material in which a carbazole group is partially introduced into a mesogen group, a photoelectric conversion material, An object of the present invention is to provide a carbazole ring-containing polymer that has useful properties as an organic conductive material and the like, and is excellent in solubility in a solvent, workability, and the like.

[0002]

2. Description of the Related Art Conventionally, polyvinyl carbazole is known as an example of an organic photosensitive material. In order to improve the performance of the polymer as a photosensitive material, it is important to arrange carbazole rings in the polymer. It is. As a method of arranging the carbazole ring, synthesis of a stereoregular polymer, blending with a liquid crystal compound, and the like are known.

[0003]

In the case of the stereoregular polymer according to the prior art as described above, it is difficult to dissolve it in a versatile low-boiling organic solvent and dissolve it in a high-boiling organic solvent. In the case of molding, the high boiling solvent tends to remain in the casting, and there is a problem that desired performance cannot be obtained due to the residual solvent. There are problems such as poor workability. or,
When used in a blend with a liquid crystal compound, the compatibility with the liquid crystal compound is low, and even when blended, the concentration of the carbazole group in the blended product is reduced, and the performance as a photosensitive material is reduced. There's a problem. Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a carbazole ring-containing polymer having excellent solubility in general-purpose solvents and excellent processability.

[0004]

The above object is achieved by the present invention described below. That is, the present invention provides a carbazole ring-containing monomer represented by the following structural formula (A), a carbazole ring-containing polymer represented by the following structural formula (B) obtained by polymerizing the monomer, and It is a manufacturing method of.

Embedded image

Embedded image (R ₁ and R ₂ in the above formula are a hydrogen atom or a lower alkyl group, and R ₃ is a substituent such as a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a hydroxyl group, a cyano group, and a nitro group. , X has 2 to 2 carbon atoms which may have a branched chain.
And m is a number average molecular weight of 2,0.
(It is a numerical value that becomes 00 to 1,000,000)

[0005]

The carbazole ring-containing polymer provided by the present invention has excellent solubility in not only general-purpose low-boiling solvents such as chloroform, tetrahydrofuran, benzene and toluene, but also high-boiling organic solvents such as chlorobenzene and dimethylformamide. In a molded article made of the polymer, a liquid crystal structure is incorporated in the polymer, so that the orientation of the carbazole ring is excellent, and excellent photosensitivity and photoelectric conversion characteristics are obtained. And the like.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments. The carbazole ring-containing monomer of the present invention is obtained by subjecting an aldehyde compound represented by the following structural formula (1) to a condensation reaction with an aniline derivative represented by the following structural formula (2), and then subjecting the obtained condensation product to acryl It is obtained by reacting an acid or methacrylic acid or a functional derivative thereof. In the above method, the aldehyde compound, aniline derivative and acrylic acid or methacrylic acid or their functional derivatives are all known compounds, and the aldehyde compound (1) and the aniline derivative (2) can be synthesized according to the following reaction sequence. It can be obtained from the market and used in the present invention.

[0007]

Embedded image Reaction sequence

Preferred groups for R ₂ in the above compounds are a hydrogen atom, a methyl group, an ethyl group, a propyl group and a butyl group, and a methyl group is particularly preferred. X is not particularly limited as long as it is an alkylene group which may have a branched chain having 2 to 15 carbon atoms. R ₃ is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a hydroxyl group,
It is a substituent such as a nitro group and a cyano group. The reaction itself is carried out according to a general reaction between an aldehyde and an amine,
For example, in an anhydrous solvent such as anhydrous ethanol or anhydrous benzene, the two are dissolved in an approximately equimolar ratio, and if necessary, heated and stirred to cause a reaction. The reaction between the above reaction product and acrylic acid or methacrylic acid or a functional derivative thereof is carried out in accordance with a general esterification reaction with a hydroxyl group and a carboxyl group or a functional derivative thereof. The reaction product and a base such as triethylamine are present in a solvent, and an acid chloride such as acrylic acid or methacrylic acid is added dropwise thereto at a low temperature, for example, 0 ° C., and the mixture is stirred and reacted at room temperature. A carbazole ring-containing monomer of the formula Of course, the present invention is not limited to the above manufacturing method.

The carbazole ring-containing polymer of the present invention is obtained by polymerizing the carbazole ring-containing monomer obtained as described above. In the polymerization, the processability of a polymer obtained by partially copolymerizing other general monomers copolymerizable with an acryloyl group or a methacryloyl group can be further improved. Preferred monomers as other general monomers are acrylic acid, methacrylic acid or their alcohol esters, and electron acceptor monomers having a cyano group or a nitro group. When these other monomers are copolymerized, the content of these other monomers is preferably not more than 80% by mole of the whole monomers. Decrease. Polymerization conditions may be the same conditions as ordinary radical polymerization, cationic polymerization, anionic polymerization, etc., for example, suspension polymerization, solution polymerization, emulsion polymerization, bulk polymerization, etc., may be a conventionally known method,
For the initiation of polymerization, in addition to a general polymerization initiator such as an organic initiator such as azobisisobutyronitrile and an inorganic initiator such as potassium persulfate, the polymerization can be carried out also by irradiation with ultraviolet rays or electron beams. .

The resulting carbazole ring-containing polymer is
By appropriately selecting a polymerization method and a chain transfer agent, it is possible to arbitrarily synthesize a polymer having a relatively low molecular weight to a relatively high molecular weight. When used for the purpose, the number average molecular weight is 2,000 to 1,000,00
It is preferable to select the polymerization conditions so as to be 0, more preferably in the range of 4,000 to 100,000. The carbazole ring-containing polymer of the present invention obtained as described above is useful for various applications, particularly useful as a constituent material of a photoreceptor used for electrophotography and the like, and a constituent material of a photoelectric converter. By blending a copolymer with an electron acceptor monomer and an electron acceptor polymer composed of the monomer, it is also useful as an organic conductive material or the like.

[0011]

Next, the present invention will be described more specifically with reference to examples. Example 1 While stirring a mixture of 90 g (0.45 mol) of 2-nitrobiphenyl, 4 g of ferric oxide and 100 ml of water at 35 to 40 ° C, 96 g (0.6 mol) of bromine was added dropwise, and the mixture was heated at the same temperature. 2 hours, further raised to 100 ° C and reacted for 4 hours,
Excess bromine was removed. The reaction product was extracted with ether, the ether layer was washed with an aqueous sodium carbonate solution, the ether was removed by evaporation, and the product was obtained by distillation under reduced pressure. This was washed with ethanol to obtain 2-nitro-4'-bromobiphenyl (melting point: 63 to 65 ° C). Compound 45 above
g (0.162 mol) and 107.7 g of triethyl phosphite
(0.648 mol) under a nitrogen atmosphere at 160
Reaction was carried out by heating and stirring at 15 ° C. for 15 hours. After cooling to room temperature, the mixture was poured into a mixture of 1,200 ml of methanol and 120 ml of water, the precipitate was filtered, and the residue obtained by filtration was dried under reduced pressure.
Bromocarbazole (mp 243-246 ° C) was obtained.
Next, while stirring a mixture of 82 g (0.333 mol) of 2-bromocarbazole, 80 ml of a 66% aqueous potassium hydroxide solution and 600 ml of acetone, 109 g (0.864 mol) of dimethylsulfuric acid was slowly added dropwise thereto for 5 minutes. Stirred.

The reaction mixture was poured into 4 liters of ice water, and the precipitate was filtered and purified by recrystallization from ethanol to give 2-bromo-9-methylcarbazole (melting point: 83.3 to 84.
5 ° C.). Then, 35 g (0.135 mol) of the above 2-bromo-9-methylcarbazole was added to 200 ml of anhydrous toluene, and butyllithium was added under nitrogen atmosphere.
ml (2.5 molar hexane solution) and anhydrous ether 100
ml of the mixture was added dropwise and stirred at room temperature for 1 hour,
Cooled to ° C. To this, 9.84 g (0.135 mol) of anhydrous dimethylformaldehyde and 50 ml of anhydrous toluene
And a mixture of 15 ml of anhydrous ether within 10 minutes.
1 was added. The organic layer of the reaction solution was washed with water, dried over anhydrous sodium sulfate, filtered, and the solvent was removed. Carboxaldehyde (mp 69.5-71.0) was obtained.

On the other hand, 27.8 g of p-nitrophenol
(0.2 mol), 16.8 g (0.3 mol) of potassium hydroxide,
A small amount of potassium iodide, 60 ml of ethanol and 60 ml of water were mixed and dissolved by heating under reflux, and 6-chloro-
32.8 g (0.24 mol) of 1-hexanol was added dropwise, and the mixture was further heated under reflux for 20 hours, then returned to room temperature and extracted with ethyl acetate. The ethyl acetate layer is washed with water and then with a saturated aqueous solution of sodium chloride, the ethyl acetate is distilled off, and the residue is purified by recrystallization with toluene to give 4 (6-hydroxyhexyloxy).
Nitrobenzene was obtained. 47.8 g (0.15 mol) of the above 4 (6-hydroxyhexyloxy) nitrobenzene,
96.1 g (0.3 mol) of sodium sulfide nonahydrate, 12.83 g (0.3 mol) of sulfur, 150 ml of ethanol
And 150 ml of water, and the mixture was heated under reflux for 18 hours, then returned to room temperature and extracted with ethyl acetate. The ethyl acetate layer was washed with water and then with a saturated aqueous solution of sodium chloride. The ethyl acetate layer was dried over anhydrous sodium sulfate, the ethyl acetate was distilled off, and the residue was purified by recrystallization with ethyl acetate to give 4 (6-hydroxyhexyloxy). Aniline was obtained.

6.28 g (0.03 mol) of 9-methyl-2-carbazolylcarboxaldehyde synthesized above
And 4. (6-hydroxyhexyloxy) aniline 6.28
g (0.03 mol) in 30 ml of absolute ethanol.
The reaction was carried out at 0 ° C. for 2 hours, and the temperature was returned to room temperature. The precipitated solid was filtered and purified by recrystallization with ethanol to obtain 4 (6-hydroxyhexyloxy) -N- (9-methyl-2-carbazolylmethylene) aniline. 13.7 g (0.0342 mol) of 4 (6-hydroxyhexyloxy) -N- (9-methyl-2-carbazolylmethylene) aniline, 10.4 g (0.10 mol) of triethylamine and 130 ml of chloroform were mixed. Then, a mixture of 4.6 g (0.0513 mol) of acrylic acid chloride and 40 ml of chloroform was slowly added dropwise thereto, and the mixture was cooled to 0 ° C.
The mixture was reacted at 2 ° C. for 2 hours, then returned to room temperature and reacted for 4 hours. The reaction mixture was washed with a 1% aqueous sodium hydrogen carbonate solution, water and a saturated aqueous sodium chloride solution in that order, and the chloroform layer was dried over anhydrous sodium sulfate. After filtration, chloroform was removed by evaporation, and the residue was purified by recrystallization three times with ethanol. The carbazole ring-containing monomer of the present invention, 4 (6-acryloyloxyhexyloxy) -N- listed in Table 1 below, was used.
(9-Methyl-2-carbazolylmethylene) aniline (A6Cz) was obtained.

Example 2 In the same manner as in Example 1, carbazole ring-containing monomers of the present invention shown in Table 1 below were obtained.

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[Table 1]

Example 3 2 g (0.0044 mol) of 4 (6-acryloyloxyhexyloxy) -N- (9-methyl-2-carbazolylmethylene) aniline obtained in Example 1 and azobisisobutyi 0.00722 g of lonitrile (0.000044
Mol) in 2.3 ml of benzene, put into a polymerization tube,
After degassing and sealing using a vacuum line, polymerization was carried out at 70 ° C. for 20 hours. After returning to room temperature, the polymerization solution was poured into ether to precipitate a polymer, which was filtered and dried to obtain a carbazole ring-containing polymer of the present invention. By changing the polymerization conditions, carbazole ring-containing polymers having various molecular weights shown in Table 2 below were obtained. Example 4 In the same manner as in Example 3, each of the carbazole ring-containing monomers obtained in Example 2 was polymerized to obtain a carbazole ring-containing polymer of the present invention. By changing the polymerization conditions, carbazole ring-containing polymers having various molecular weights shown in Table 2 below were obtained.

[0017]

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[Table 2]

The physical properties in Tables 1 and 2 were measured by the following methods. Molecular weight : GPC (HLC-802 manufactured by Tosoh Corporation)
The measurement was performed using THF as a solvent in A). Phase transition temperature : DSC (PerkinElmer DSC7)
In Table 1, the cooling rate during cooling was 10 K / min.
In Table 2, the heating rate was 10 K / mi at the time of heating twice.
n. With a polarizing microscope (Olympus Optical Industry B
HS-751P), hot stage (FP80HT manufactured by METTLER), control unit (METT
The phase transition was confirmed using FP82HT manufactured by LER. In the above example, an acryloyl group was used as the polymerizable group. However, similar results were obtained when a methacryloyl group was used.

[0019]

The carbazole ring-containing polymer provided by the present invention is excellent not only for general-purpose low-boiling solvents such as chloroform, tetrahydrofuran, benzene and toluene, but also for high-boiling organic solvents such as chlorobenzene and dimethylformamide. In a molded article made of the polymer, which has solubility and good processability, and the liquid crystal structure is incorporated in the polymer, the orientation of the carbazole ring is excellent, and excellent photosensitivity and photoelectricity are obtained. It shows characteristics such as conversion characteristics.

──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C07D 209/86 C08F 20/36 G02F 1/1333 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. A carbazole ring-containing monomer represented by the following structural formula (A). Embedded image (R ₁ and R ₂ in the above formula are a hydrogen atom or a lower alkyl group, and R ₃ is a substituent such as a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a hydroxyl group, a cyano group, and a nitro group. , X has 2 to 2 carbon atoms which may have a branched chain.
15 alkylene groups) 2. A carbazole ring-containing polymer represented by the following structural formula (B). Embedded image (R ₁ and R ₂ in the above formula are a hydrogen atom or a lower alkyl group, and R ₃ is a substituent such as a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a hydroxyl group, a cyano group, and a nitro group. , X has 2 to 2 carbon atoms which may have a branched chain.
And m is a number average molecular weight of 2,0.
(It is a numerical value that becomes 00 to 1,000,000) 3. A condensation reaction between an aldehyde compound represented by the following structural formula (1) and an aniline derivative represented by the following structural formula (2), followed by acrylic acid or methacrylic acid or a functional derivative thereof. The method for producing a carbazole ring-containing monomer according to claim 1, wherein the reaction is carried out. Embedded image (R ₁ and R ₂ in the above formula are a hydrogen atom or a lower alkyl group, and R ₃ is a substituent such as a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a hydroxyl group, a cyano group, and a nitro group. , X has 2 to 2 carbon atoms which may have a branched chain.
15 is an alkylene group, and Y is a functional group such as a hydroxyl group, a halogen atom, and an alkoxy group.) 4. The method for producing a carbazole ring-containing polymer according to claim 2, wherein the carbazole ring-containing monomer according to claim 1 is polymerized.