JPS614725A - Production of polymer of carbazole compound - Google Patents

Abstract

PURPOSE:To produce a polymer which is moldable, excellent in oxidation resistance and useful as an organic semiconductor material, by polymerizing a carbazole compound in the presence of a halide of a specified element. CONSTITUTION:1mol of a carbazole compound of formula I (wherein R is H or a 10C or lower alkyl) and 0.0001-10mol of a halide of at least one element selected from among B, Si, As, Sb, and P (e.g., AsF5) are dissolved in a suitable solvent and polymerized at a temperature <= the boiling or sublimation temperature of the carbazole compound, or alternatively, the carbazole compound and a complex of a halide of an element of formula II (wherein n<=5, Y is P, I, S, or Se, X is AsF6, BF4, PF6, or SbF6, R3 is H, a halogen or a 10C or lower hydrocarbon group) are placed in the same reactor and polymerized by irradiation with light of a wavelength <=1,000nm.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polymer of a carbazole compound that is moldable and useful as an organic semiconductor material with excellent oxidative stability.

Poly(N-
Alkyl-3,6-carbazolediyl) is an organic photoconductive material (JP-A-58-88422) and a conductive material [J,
of Physique, 44.03-1377 (19
83)] is already known to be useful.

However, the method for synthesizing a polymer of carbazole compounds disclosed in the above-mentioned known literature first synthesizes 9-alkyl-3,6-cyhalocarbazole, and then synthesizes this compound using magnesium and a Ni complex as a catalyst. Since a complicated method of reaction is used, there is a drawback that if a polymer of a carbazole compound is produced industrially by this method, it will be extremely expensive.

In view of the above points, the present inventors have conducted intensive studies on industrial production methods for polymers of carbazole compounds, and have found that when carbazole compounds are polymerized in the presence of a halide of a specific element, molding is possible. The present inventors have discovered that a polymer of a carbazole compound that can be processed and is useful as an organic semiconductor material with excellent oxidation stability can be easily obtained, and that the resulting polymer exhibits high electrical conductivity, resulting in the present invention. .

That is, the present invention provides a carbazole compound represented by the general formula (wherein R is a hydrogen atom or an alkyl group having 10 or less carbon atoms) using B, Si, As.
.

The present invention relates to a method for producing a polymer of a carbazole compound, which comprises polymerizing in the presence of a halide of at least one element selected from sb and P.

The carbazole compound polymer obtained by the method of the present invention is linear and soluble in an appropriate solvent, and its electrical conductivity is in the semiconductor to metal range, so it cannot be left in the air for a long time. Because its electrical conductivity does not change even when exposed to heat, it is useful as an organic semiconductor material that is moldable and has good oxidation stability.

The carbazole compound used in the present invention is represented by the general formula (wherein R is a hydrogen atom or an alkyl group having 10 or less carbon atoms), and specific examples thereof include carbazole and N-methyl-carbazole. , N-ethyl-carbazole, N-butyl-carbazole, N-hexyψcarbazole, and the like. Among these cal/<sol type compounds, N-alkyl-carbazole is preferred.

The element halide used in the present invention is B
, Si, As, Sb and P. Among the halides of these elements, halides of elements selected from B, , As, Sb and P are preferred; As and sb Particularly preferred are halides of elements selected from: Examples of the halogen include fluorine, bromine, chlorine and iodine, with fluorine and chlorine being preferred, and fluorine being particularly preferred. Typical examples of halides of these elements are A
sF5. SbF5. AsF3゜BF3. Examples include PF5 and S iFa.

Of course, it is possible to carry out the polymerization using only one type of halide of these elements, but there is no problem even if two or more types are used in combination.

In addition, among the halides of the elements used in the present invention, there are general formulas (where n is a positive integer of 5 or less, Y is a phosphorus atom, iodine Atom, sulfur atom, or selenium atom.X is AsFe, BF4.PF6.SbF6.
It is a hydrocarbon group of 0 or less. ) also includes complexes of halides of elements represented by

Representative examples of complexes of halides of these elements include the following compounds.

Of course, it is possible to carry out polymerization using only one type of complex of halides of these elements, but there is no problem even if two or more types are used in combination.

The amount of the elemental halide or the elemental halide complex to be used is not particularly limited, but is usually 0.0001 to 10 mol per mol of the carbazole compound (monomer). Even if more than 10 moles of elemental halide or complex of elemental halide are used per mole of monomer, a large amount of unreacted elemental halide or complex of elemental halide remains, and there is no particular advantage. . Furthermore, if the amount of elemental halide or complex of elemental halide is less than 0.0001 mol per mol of monomer, a large amount of unreacted monomer remains and is not particularly advantageous.

When using a complex of an elemental halide, it is necessary to irradiate it with light, but the wavelength of the light used in the light irradiation used in the present invention is in a wavelength range in which the complex of an elemental halide is decomposed by the light. There are no particular limitations, and it is usually preferable to use light with a wavelength of 1000 mm (nanometers) or less.

In the present invention, the polymerization temperature is not particularly limited, but it is usually carried out below the Ura point or sublimation temperature of the carbazole compound.

In the present invention, there are no particular restrictions on the method of contacting the elemental halide and the carbazole compound, but for example, (1) the elemental halide and the cal/<zole compound may be brought into direct contact to form a carbazole compound. (2) A method of dissolving a carbazole compound in a suitable solvent and then contacting it with an elemental halide to produce a polymer of the carbazole compound. In addition, in the present invention, there are no particular limitations on the method of contacting the complex of the elemental halide with the carbazole compound and the method of light irradiation, but for example, (1) the complex of the carbazole compound and the elemental halide are placed in the same reactor. (2) A method in which a complex of an elemental halide is irradiated with light in the presence of an appropriate solvent to polymerize a carbazole compound. can.

The carbazole compound polymer obtained by the method of the present invention is linear and soluble in an appropriate solvent, and its electrical conductivity is in the semiconductor to metal range, and it can be left in the air for a long time. Because its electrical conductivity does not change,
It is extremely useful industrially as an organic semiconductor material that is moldable and has good oxidation stability.

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples in any way.

Example 1 18.9 g of N-methyl-carbazole (
55 mmol) and vacuum degassed at room temperature for 2 days. After cooling the reaction vessel with liquid nitrogen, 0.89 arsenic pentafluoride
g (5.2 mmol) was introduced into the reaction vessel, and then the liquid nitrogen was replaced with dry ice methanol and the mixture was heated at -78°C for 3.
Time polymerization was performed. After the polymerization reaction was completed, a black powder was obtained. Unreacted upper sulfur was removed by dissolving it in toluene,
Then, it was vacuum dried to obtain 7.8 g of a black powdery polymer. This black powdery polymer has 3
．． It was found that the polymer was polymerized at the 6th position. Also,
The degree of polymerization was found to be approximately 23 by GPc.

On the other hand, according to elemental analysis, the sonocomposition is C: H: N: A
s:F=1. OO: 0.85: 0.08:
0.07:0.3B (molar ratio).

The electrical conductivity (DC 4 terminal method) of the obtained black powdery polymer was 1.3X 10'Ω-1・Cll1-1te,
Even when the conopolymer was left in the air for one week, its electrical conductivity did not change.

Example 2 Instead of arsenic pentafluoride used in Example 1, 254 n
Polymerization was carried out in exactly the same manner as in Example 1, except that the polymer was irradiated with light of m, to obtain a polymer of N-methyl-carbazole that was exactly the same as in Example 1.

Example 3 Carbasol was used instead of N-methyl-carbazole used in Example 1, and 1 SbF5 was used instead of arsenic pentafluoride.
．． Polymerization was carried out in exactly the same manner as in Example 1 except that 00 g was used to obtain a black carbazole polymer.

Example 4 When polymerization was carried out at 25°C in Example 1, the degree of polymerization of the obtained N-methyl-carbazole polymer was about 18.

Claims (1)

[Claims] A carbazole compound represented by the general formula ▲ includes numerical formulas, chemical formulas, tables, etc. ▼ (wherein R is a hydrogen atom or an alkyl group having 10 or less carbon atoms), B, Si, As,
1. A method for producing a polymer of a carbazole compound, which comprises polymerizing in the presence of a halide of at least one element selected from Sb and P.