JP3083613B2 - Manufacturing method of organic polygermane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a conductive material, a photoresist,
The present invention relates to a novel method for producing an organic polygermane useful as a polymerization initiator, a ceramic precursor, an electrophotographic photosensitive member, a carrier transfer agent, and the like.

[0002]

2. Description of the Related Art Conventionally, as a method for producing organic polygermane, there has been known a method in which an organic germanium dihalide is used as a starting material and dehalogenated and condensed with an alkali metal or the like (for example, M. Lesbre, P. Mazerolles, J. Am. .Satge,
“The Organic Compound of Germanium” John Wiley &
Sons (1971) and Fujino, JP-A-1-252637).

Embedded image Here, A and B are organic substituents, X is a halogen atom, M is an alkali metal, and z is 10 to 1000. General formula (II
The reaction of I) is a wurtz type reaction, in which electron transfer from sodium to germanium generates anion radicals of germane halide at the beginning of the reaction, and various germanium intermediates (for example, germanyl radical) that are subsequently formed , Germyl anion, germylene, germylene anion, germene, etc.) are considered to form organic polygermane. The molecular weight distribution of the thus produced organic polygermane is bimodal (bimod).
al) shows two broad peaks called distribution. Although the reason why the conventional production method gives a polymer having a molecular weight distribution having a plurality of peaks is not clear, the similar distribution is shown in the production of organic polysilane, so that it is considered only for polycondensation using an alkali metal. It is considered to be a unique phenomenon. Therefore, the above-mentioned production method has many disadvantages such as obtaining only a polymer having a molecular weight distribution of a plurality of peaks and low yield.

[0003]

An object of the present invention is to provide a method for producing an organic polygermane having a single peak molecular weight distribution in a high yield.

[0004]

The present invention provides the following formula (I)

Embedded image (Where R₁And R_TwoAre the same or different
May be, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
Substituted or unsubstituted aromatic groups and substituted or unsubstituted fats
It is selected from the group consisting of cyclic groups. However, al
The kill groups combine with each other to form a Ge-containing ring with Ge atoms.
It can also be done. Also, R_ThreeRepresents an aromatic substituent
You. ) To irradiate light to digermoxane
The following equation (II)

Embedded image (Where R₁And R_TwoIs the same as above. )
The present invention relates to a method for producing an organic polygermane comprising repeating units.

The production process of the present invention is carried out, for example, by dissolving digermoxane of the formula (I) in an organic solvent and irradiating the solution with light.

As the organic solvent used in the production method, ethers such as diethyl ether and tetrahydrofuran, hydrocarbons such as pentane, hexane and cyclohexane, and aromatic hydrocarbons such as benzene and toluene can be used. In carrying out the reaction, it is preferable to use these organic solvents after drying them in advance.
As a light source for light irradiation, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a laser, a xenon lamp, or the like can be used. Further, the reaction temperature can be in the range of -80C to 120C. In any case, the reaction is preferably performed under an inert gas to avoid a reaction with oxygen in the air.

In the above general formulas (I) and (II), the substituents R ₁ to R ₃ are methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl. ,
t-butyl group, n-pentyl group, i-pentyl group, neopentyl group, n-hexyl group, cyclohexyl group, n-
Examples include an alkyl group such as an octyl group and an n-dodecyl group, a substituted or unsubstituted phenyl group, a benzyl group, and a germanacyclohexyl group. Examples of the substituent for the phenyl group and the benzyl group include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group and a t-butyl group, a methoxy group, an ethoxy group, an n-propoxy group, And alkoxy, nitro, and cyano groups such as -butoxy group, and mono-, di-, and tri-substituted products of these alkyl groups, alkoxy groups, nitro groups, and cyano groups.

Next, specific examples of the organic polygermane obtained by the production method of the present invention are shown in the following Tables 1 to 5 in relation to the repeating unit of the formula (II). (Below)

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[0009]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Also,
All reactions in the following examples were performed under a nitrogen stream. Example 1 Dimethyl polygermane (Polymer No. 1)
3.75 g (0.01 mol) of bis (dimethylphenyl) digermoxane dissolved in 70 ml of tetrahydrofuran is placed in a 200 ml round bottom flask, and the atmosphere in the flask is replaced with nitrogen. This was irradiated with a low-pressure mercury lamp for 6 hours while blowing nitrogen gas at room temperature. Thereafter, the reaction product was extracted with toluene and dried over anhydrous magnesium sulfate. After removing toluene, vacuum drying was performed to obtain 1.20 g of dimethylpolygermane, a viscous liquid.

Example 2 Method for Producing Phenylmethyl Polygermane (Polymer No. 15) In a 200 ml round bottom flask, 5.00 g (0.01 mol) of bis (diphenylmethyl) digermoxane dissolved in 80 ml of tetrahydrofuran was placed. Replace with nitrogen. This was irradiated with a low-pressure mercury lamp for 10 hours while blowing nitrogen gas at room temperature. Thereafter, the reaction product was extracted with toluene and dried over anhydrous magnesium sulfate. After removing toluene, vacuum drying was performed, and the obtained product was dissolved in 10 ml of toluene.
To methanol to precipitate crystals. After suction filtration,
Vacuum drying was performed to obtain 0.74 g of phenylmethyl polygermane as white crystals.

Example 3 Preparation of diphenylpolygermane (Polymer No. 7) 6.23 hexaphenyldigermoxane dissolved in 80 ml of tetrahydrofuran in a 200 ml round bottom flask
g (0.01 mol), and the atmosphere in the flask is replaced with nitrogen. This was irradiated with a low-pressure mercury lamp for 4 hours while blowing nitrogen gas at room temperature. Thereafter, the reaction product was extracted with toluene and dried over anhydrous magnesium sulfate. After removing toluene, vacuum drying was performed to obtain 0.96 g of viscous liquid diphenyl polygermane.

[0012]

According to the present invention, a new process for producing an organic polygermane using, as a starting material, a digermoxane which is different from the conventional organogermanium compound is developed. According to the method of the present invention, an organic polygermane having a molecular weight of about 5000 and a small molecular weight distribution could be synthesized relatively easily. In addition, the method of the present invention was able to obtain organic polygermane with higher yield than the conventional method.

[Brief description of the drawings]

FIG. 1 is a GPC chart of phenylmethyl polygermane which is a polymer of Example 2 of the present invention.

FIG. 2 is an ultraviolet-visible absorption spectrum of phenylmethyl polygermane, a polymer of Example 2 of the present invention, in a toluene solution.

FIG. 3 is an infrared absorption spectrum of a phenylmethyl polygermane, which is a polymer of Example 2 of the present invention, measured by a reflection method.

Claims (2)

(57) [Claims] (1) The following formula (I): (Where R₁And R_TwoAre the same or different
May be, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
Substituted or unsubstituted aromatic groups and substituted or unsubstituted fats
It is selected from the group consisting of cyclic groups. However, al
The kill groups combine with each other to form a Ge-containing ring with Ge atoms.
It can also be done. Also, R_ThreeRepresents an aromatic substituent
You. ) To irradiate light to digermoxane
The following formula (II): (Where R₁And R_TwoIs the same as above. )
A method for producing organic polygermane consisting of repeating units. 2. The method for producing organic polygermane according to claim 1, wherein the method is carried out in the presence of an inert gas.