JPS5911603B2 - Method for producing polycarbazole derivatives - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel carbazole derivative useful as a photoconductor for electrophotographic light-sensitive materials and a method for producing a polymer thereof.

5 Polyvinylcarbazole and its derivatives are widely known as photoconductors for electrophotography, and have already been put into practical use in some areas.

However, conventional polyvinylcarbazole or its derivatives do not have sufficient film-forming ability when used alone, and have been made to have the film-forming ability by using a plasticizer or the like in combination. Furthermore, when the photoconductive layer is formed on a support, the adhesion to the support is poor, and therefore measures such as providing an adhesive layer between the support and the photoconductive layer have been taken. However, because the photoconductive layer is formed by using a plasticizer or by using an adhesive layer with the support 15, the excellent photoconductive properties inherent to polyvinylcarbazole have not been fully utilized until now. is the reality.

The purpose of the present invention is to eliminate such drawbacks20, and the produced polymer has sufficient film-forming ability and also exhibits sufficient adhesion to the support without intervening an adhesive layer.
Therefore, the present invention provides a method for producing a novel polycarbazole derivative (photoconductive material) that takes advantage of the various properties of a photoconductor.

25 That is, the characteristics of the method for producing the novel polycarbazole derivative of the present invention are that the carbazole represented by formula I and the formula
N-hydroxymethylac'゜□ ・・・・
・・・・・・．

,)CH2=CHC0NHCH20H・・・・・・・・・
By carrying out a condensation reaction with (■) 35lylamide in a solvent in the presence of a catalyst of p-toluenesulfonic acid, the formula ■
3. In carrying out this production method, the starting material carbazole (Formula 1) The appropriate blending ratio of N-hydroxymethylacrylamide (formula) is about 1 to 2 moles of N-hydroxymethylacrylamide per 1 mole of carbazole.

Although p-toluenesulfonic acid is used as a catalyst, it is difficult to promote the reaction with other catalysts. The amount of catalyst is 0.01 per mole of carbazole (formula 1)
~2.0 moles. In addition, the solvents used are chloroform, chlorinated hydrocarbons such as methylene chloride,
1,4-dioxane, acetonitrile, tetrahydrofuran and the like are preferred. As mentioned above, p-toluenesulfonic acid is used as a catalyst and is extremely effective in promoting the reaction. However, in order to prevent side reactions and advance the reaction more efficiently, it is necessary to add N, It is preferable to use N'-dicyclohexylcarbodiimide in combination. The appropriate amount of N,N'-dicyclohexylcarbodiimide to be added is such that the sum of the moles of p-toluenesulfonic acid and N,N5-dicyclohexylcarbodiimide is approximately 0.1 to 2.0 moles per mole of carbazole. be.
This reaction is an exothermic reaction, and since the reaction product (N-acrylamidomethylcarbazonol represented by the formula) tends to polymerize due to its double bonds, the reaction operation is carried out at room temperature without heating. It is desirable to do so.

In addition, if necessary, a small amount of polymerization inhibitor such as halodroquinone may be added. Carbazole (formula 1
) and N-hydroxymethylacrylamide (formula 11
) is easily available, but the obtained N-acrylamidomethylcarbazole (formula) is a novel compound with photoconductivity.

As mentioned above, this new compound easily undergoes radical polymerization to produce a high molecular weight polymer (formula). Therefore,
In the actual polymerization operation, N-atarylamide methylcarbazole is dissolved in, for example, N,N'-dimethylformamide, α,α'-azobisisobutyronitrile (polymerization initiator) is added thereto, and then 50~ while blowing
After maintaining the temperature at 150°C, preferably 80°C, for about 10 hours,
Simply pour it into a large amount of methanol or water, separate the resulting precipitate, and dry it.

The polymer represented by the above formula has photoconductivity and itself has film-forming ability.

Therefore, when this polymer is used, there is no need to consider the use of plasticizers, etc., and since the adhesion to the support is good, there is no need to use adhesives. Next, examples and monomer synthesis examples will be shown. Monomer synthesis example 1 Carbazole (16.771.0X10-1m0t), N-hydroxymethylacrylamide (12.1f1.2x10-
1m0t) was dissolved in tetrahydrofuran (250d) and kept at about 10°C.

Add p-toluenesulfonic acid (1Z2f1.0X
A solution of 10-1m0t) dissolved in tetrahydrofuran (30d) was added dropwise while keeping the temperature below about 15°C. After that, the temperature was gradually raised to room temperature, and after reacting at room temperature for 2 days, the reaction solution was poured into a large amount of water to remove the resulting precipitate.
It was separated, washed with water, and then dried. The obtained precipitate was repeatedly recrystallized with methanol to obtain colorless columnar crystals (3.3r yield 13%).
) was obtained. Melting point: 193-195°C (polymerized after melting point measurement) Elemental analysis: Cl6Hl4N2O, infrared absorption spectrum shows absorption based on secondary amide (32
40? -1,1660 (:!n-1,1560?-1)
1640F-1,990C:RfL-1 showed absorption of vinyl terminals.

From the above results, it can be seen that the desired monomer formula [) was obtained.

Monomer synthesis example 2 Carbazole (16.7t1.0×10-1m0t),
N-hydroxymethylacrylamide (11.1f11
．． 1 x 10-1 m0t), N,N'-dicyclohexylcarbodiimide (18.5t0.9 x 10-1m0t)
Dissolve in tetrahydrofuran (250ml) for about 10
It was kept at ℃.

On the other hand, p-toluenesulfonic acid (3.4V0.2×10
-1m0t) was dissolved in tetrahydrofuran (20mi), and this solution was added dropwise to the previous solution. After that, the temperature was gradually returned to room temperature and the reaction was allowed to proceed at room temperature for one day, after which the white precipitate formed in the reaction solution was separated, and the resulting solution was poured into a large amount of water.The resulting precipitate was washed with water and dried. . This precipitate was repeatedly recrystallized with methanol to give colorless columnar crystals (8.3
A V yield of 33% was obtained. It can be seen that even when this was mixed with the monomer obtained in Synthesis Example 1, the melting point did not decrease, and the desired monomer formula was obtained. Example (polymer synthesis example) Monomer (1.37) obtained in Synthesis Example 1 or 2, α
, N,N'-dimethylformamide (10ml) obtained by rectifying α'-azobisisobutyronitrile (3.0W9)
and heated to 80°C for 1 hour while blowing dry nitrogen gas.
I kept it for 0 hours.

Claims (1)

[Claims] 1 Carbazole represented by formula I and N-hydroxymethylacrylamide represented by formula II▲Mathematical formula, chemical formula,
There are tables, etc.▼・・・(I)CH_2=CHCON
HCH_2OH...(II) in a solvent with p-toluenesulfonic acid or p-toluenesulfonic acid and N,N
By carrying out a condensation reaction in the presence of a catalyst of '-dicyclohexylcarbodiimide, N-acrylamidomethylcarbazole represented by formula III is obtained (III), and then this N-acrylamidomethylcarbazole is obtained. A method for producing a polycarbazole derivative, which comprises radically polymerizing carbazole.