JPH05323298A - Carbazole ring-containing monomer, carbazole ring-containing polymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain the carbazole ring-contg. polymer having excellent solubility in general-purpose solvents and workability by polymerizing the specific carbazole ring-contg. monomer. CONSTITUTION:The carbazole ring-contg. monomer expressed by formula I (where R1, R2 denote a substituent, such as hydrogen atom, lower alkyl group; R3 denotes a hydrogen atom, lower alkyl group, lower alkoxy group, halogen atom, hydroxyl group, cyano group, nitro group; X denotes 2 to 15 alkylene group), by which the carbazole ring-contg. polymer expressed by formula II (where m is 2000 to 1000000) is obtd. This polymer exhibits the excellent solubility in not only the general-purpose low boiling solvents, such as chloroform, tetrahydrofuran, benzene and toluene, but also high boiling org. solvents, such as chlorobenzene and dimethyl formamide. Since the liquid crystalline structure is incorporated into the polymer, the polymer has excellent orientability and has excellent photosensitiveness and photoelectric conversion characteristics.

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, carbazole ring-containing polymer and a process for producing them, and more specifically, an organic photosensitive material having a carbazole group introduced into a part of a mesogen group, a photoelectric conversion material, It is an object of the present invention to provide a carbazole ring-containing polymer having properties useful as an organic conductive material and having excellent solubility in solvents and processability.

[0002]

2. Description of the Related Art Conventionally, polyvinylcarbazole has been known as an example of an organic photosensitive material, but in order to improve the performance of the polymer as a photosensitive material, it is important to arrange carbazole rings in the polymer. Is. Known methods for arranging carbazole rings include synthesis of stereoregular polymers and blending with liquid crystal compounds.

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention 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 point organic solvent, and it is dissolved in a high-boiling point organic solvent before pouring. In the case of molding, there is a problem that the high boiling point solvent is likely to remain in the cast product, and the desired performance cannot be obtained due to the residual solvent, and the melting point is too high even when attempting melt molding. There are problems such as poor workability. or,
When it is used by blending with a liquid crystal compound, the compatibility with the liquid crystal compound is low, and even if it is further blended, the concentration of the carbazole group in the blended product is lowered, and the performance as a photosensitive material is deteriorated. There's a problem. Therefore, 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 excellent in solubility in a general-purpose solvent and processability.

[0004]

The above object can be achieved by the present invention described below. That is, the present invention relates to 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 the same. Is a manufacturing method.

[Chemical 4]

[Chemical 5] (R ₁ and R ₂ in the above formula are hydrogen atoms 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 or a nitro group. , X has 2 to 2 carbon atoms which may have a branched chain.
15 is an alkylene group, and m has 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 not only in general-purpose low boiling point solvents such as chloroform, tetrahydrofuran, benzene and toluene but also in high boiling point organic solvents such as chlorobenzene and dimethylformamide. With good processability, and in a molded article made of the polymer, since the liquid crystalline structure is incorporated in the polymer, the orientation of the carbazole ring is excellent, and the excellent photosensitivity and photoelectric conversion characteristics are obtained. Etc. are shown.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the 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) and an aniline derivative represented by the following structural formula (2) to a condensation reaction, and acryl-containing the resulting condensation product. 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 aniline derivative (2) can be synthesized according to the following reaction sequence. Besides, 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, with a methyl group being particularly preferred. Further, X is not particularly limited as long as it is an alkylene group having 2 to 15 carbon atoms and optionally having a branched chain. 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 of both is carried out according to the reaction of general aldehyde and amine,
For example, it is carried out by dissolving both in an anhydrous solvent such as absolute ethanol or anhydrous benzene in an approximately equimolar ratio, and heating and stirring as necessary to react them. Further, the reaction of the reaction product with acrylic acid or methacrylic acid or a functional derivative thereof is carried out according to a general esterification reaction with a hydroxyl group and a carboxyl group or a functional derivative thereof, for example, an inert gas such as chloroform. The reaction product and a base such as triethylamine are allowed to exist in a solvent, and an acid chloride such as acrylic acid or methacrylic acid is added dropwise to the reaction product at a low temperature, for example, 0 ° C., and the mixture is stirred at room temperature to cause a reaction. The carbazole ring-containing monomer of is obtained. Of course, the present invention is not limited to the above manufacturing method.

The carbazole ring-containing polymer of the present invention can be obtained by polymerizing the carbazole ring-containing monomer obtained as described above. During the polymerization, the processability of the polymer obtained by partially copolymerizing other general monomers copolymerizable with the acryloyl group or the methacryloyl group can be further improved. Preferred 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, it is preferable to keep these other monomers in an amount of 80 mol% or less in the total monomers, and when the amount is more than this, the carbazole ring-containing polymer obtained has properties such as photosensitivity. Is reduced. 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, or,
For the initiation of polymerization, in addition to general polymerization initiators such as organic initiators such as azobisisobutyronitrile and inorganic initiators such as potassium persulfate, it can be polymerized by irradiation with ultraviolet rays or electron beams. ..

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

[0011]

EXAMPLES 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 at the same temperature. 2 hours, further raise the temperature to 100 ℃ and react 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 triethyl phosphite 107.7 g
The mixture with (0.648 mol) was added under nitrogen atmosphere to 160
After heating and stirring at 15 ° C. for 15 hours to cause reaction, and 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 filtration residue was dried under reduced pressure.
Bromocarbazole (melting point 243-246 ° C) was obtained.
Next, while stirring a mixture of 82 g (0.333 mol) of 2-bromocarbazole, 80 ml of 66% aqueous potassium hydroxide solution and 600 ml of acetone, 109 g (0.864 mol) of dimethylsulfate was slowly dropped into this mixture for 5 minutes. It was stirred.

The reaction mixture was poured into 4 liters of ice water, the precipitate was filtered and purified by recrystallization with ethanol, and 2-bromo-9-methylcarbazole (melting point 83.3-84.
5 ° C.) was obtained. Then, 35 g (0.135 mol) of 2-bromo-9-methylcarbazole was added to 200 ml of anhydrous toluene, and butyl lithium 54 was added under a nitrogen atmosphere.
ml (2.5 mol hexane solution) and anhydrous ether 100
-20 ml of the mixture was added dropwise, and the mixture was stirred at room temperature for 1 hour.
Cooled to ° C. Anhydrous dimethylformaldehyde 9.84g (0.135mol), anhydrous toluene 50ml
And a mixture of 15 ml of anhydrous ether were added within 10 minutes, the temperature was returned to room temperature, and a saturated aqueous solution of ammonium chloride 150 m was added.
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), caustic potash 16.8 g (0.3 mol),
A small amount of potassium iodide, 60 ml of ethanol and 60 ml of water were mixed and heated under reflux to dissolve, and 6-chloro-
After 32.8 g (0.24 mol) of 1-hexanol was added dropwise, the mixture was heated under reflux for 20 hours, cooled to room temperature, and extracted with ethyl acetate. The ethyl acetate layer was washed with water and then with a saturated aqueous sodium chloride solution, the ethyl acetate was distilled off, and the residue was recrystallized and purified with toluene to give 4 (6-hydroxyhexyloxy).
Obtained nitrobenzene. 47.8 g (0.15 mol) of 4 (6-hydroxyhexyloxy) nitrobenzene,
Sodium sulfide nonahydrate 96.1 g (0.3 mol), sulfur 12.83 g (0.3 mol), ethanol 150 ml
And 150 ml of water were mixed and 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 sodium chloride solution, the ethyl acetate layer was dried over anhydrous sodium sulfate, the ethyl acetate was distilled off, and the residue was recrystallized and purified with ethyl acetate to give 4 (6-hydroxyhexyloxy). I got aniline.

6.28 g (0.03 mol) of 9-methyl-2-carbazolylcarboxaldehyde synthesized above
And 4 (6-hydroxyhexyloxy) aniline 6.28
g (0.03 mol) and 7 in 30 ml 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. The mixture was cooled to 0 ° C., and a mixture of 4.6 g (0.0513 mol) of acrylic acid chloride and 40 ml of chloroform was slowly added dropwise to this,
The reaction was carried out at 0 ° C. for 2 hours, then the temperature was returned to room temperature and the reaction was carried out 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 this order, and the chloroform layer was dried over anhydrous sodium sulfate. After filtration, chloroform was removed by evaporation, and the product was recrystallized and purified with ethanol three times to obtain 4 (6-acryloyloxyhexyloxy) -N- which is the carbazole ring-containing monomer of the present invention shown in Table 1 below.
(9-Methyl-2-carbazolylmethylene) aniline (A6Cz) was obtained.

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

[Chemical 7]

[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. Ronitrile 0.00722 g (0.000044
Mol) in 2.3 ml of benzene, put in 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. The carbazole ring-containing polymers having various molecular weights shown in Table 2 below were obtained by changing the polymerization conditions. Example 4 In the same manner as in Example 3, the carbazole ring-containing monomer obtained in Example 2 was polymerized to obtain a carbazole ring-containing polymer of the present invention. The carbazole ring-containing polymers having various molecular weights shown in Table 2 below were obtained by changing the polymerization conditions.

[0017]

[Chemical 8]

[Table 2]

The various physical properties shown in Tables 1 and 2 were measured by the following methods. Molecular weight : GPC (Tosoh Corporation HLC-802
It was measured in A) using THF as a solvent. Phase transition temperature : DSC (Perkin Elmer DSC7)
In Table 1, the cooling rate was 10 K / min.
In Table 2, the heating rate was 10K / mi when heating twice.
n. Polarizing microscope (Olympus Optical Industry B
HS-751P), hot stage (MET80, FP80HT), control unit (METT)
The phase transition was confirmed using LER FP82HT). Although the acryloyl group was used as the polymerizable group in the above examples, similar results were obtained when a methacryloyl group was used.

[0019]

INDUSTRIAL APPLICABILITY The carbazole ring-containing polymer provided by the present invention is excellent not only for general-purpose low boiling point solvents such as chloroform, tetrahydrofuran, benzene and toluene but also for high boiling point organic solvents such as chlorobenzene and dimethylformamide. In the molded product which is soluble and has good processability, and in which the polymer has a liquid crystalline structure incorporated therein, the orientation of the carbazole ring is excellent, and thus the excellent photosensitivity and photoelectric property are obtained. The characteristics such as conversion characteristics are shown.

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[Procedure amendment]

[Submission date] February 18, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Title of invention

[Correction method] Change

[Correction content]

Title: Carbazole ring-containing monomer, carbazole ring-containing polymer, and methods for producing the same

Claims (4)

[Claims] 1. A carbazole ring-containing monomer represented by the following structural formula (A): [Chemical 1] (R ₁ and R ₂ in the above formula are hydrogen atoms 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 or a nitro group. , X has 2 to 2 carbon atoms which may have a branched chain.
15 is an alkylene group) 2. A carbazole ring-containing polymer represented by the following structural formula (B). [Chemical 2] (R ₁ and R ₂ in the above formula are hydrogen atoms 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 or a nitro group. , X has 2 to 2 carbon atoms which may have a branched chain.
15 is an alkylene group, and m has a number average molecular weight of 2,0.
(It is a numerical value that becomes 00 to 1,000,000) 3. An aldehyde compound represented by the following structural formula (1) and an aniline derivative represented by the following structural formula (2) are subjected to a condensation reaction, and then acrylic acid or methacrylic acid or a functional derivative thereof is added. The method for producing a carbazole ring-containing monomer according to claim 1, wherein the method comprises reacting. [Chemical 3] (R ₁ and R ₂ in the above formula are hydrogen atoms 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 or 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.