JPH0673180A - Production of polysilane - Google Patents

Abstract

PURPOSE:To obtain a polysilane safely, readily in a short time and in high yield without danger of environmental pollution by subjecting a halosilane to electrode reaction using a specific supporting electrolyte and a specific cathode. CONSTITUTION:A halosilane of formula I ((m) is 1-3; R is H, alkyl, etc.; X is halogen) is subjected to electrode reaction by using an alkali metal salt of perchloric acid (preferably lithium perchlorate) as a supporting electrolyte, an aprotic solvent (preferably 1,2-dimethoxyethane or THF) as a solvent and Mg as a cathode to give a polysilane of formula II ((n) is 10-11,000). The reaction is preferably carried out by supplying the halosilane of formula I and the supporting electrolyte together with the solvent, deoxidizing and stirring in a dried nitrogen or an inert gas atmosphere. The amount of electric current sent is sufficiently >=1F/mol based on the halogen in the halosilane generally.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing polysilane.

[0002]

2. Description of the Related Art Polysilane is drawing attention as a ceramic precursor, an optical / electronic material, and the like.

Conventionally, as a method for producing polysilane, an alkali metal such as sodium metal is used, and dialkyldichlorosilane or dichlorotetraalkyldisilane in a toluene solvent is agitated at a temperature of 100 ° C. or higher for a long time and reductively reduced. A method for coupling is known {J. Am. Chem. Soc., 103 (1981) 7352}. However,
This method requires severe reaction conditions (for example, long-time heating is required), the molecular weight cannot be controlled at all, and a large amount of alkali metal is used in production on an industrial scale. Therefore, it has drawbacks such as a large safety problem.

As a method for overcoming such drawbacks, a production method under mild conditions has been proposed in which polyalkylsilane is produced by subjecting a dialkyldichlorosilane or the like to electrode reduction at room temperature {J. Organomet. Chem. , 212 (1981) 155
}. This manufacturing method uses mercury or cadmium for the anode in an H-type cell with a diaphragm, and platinum, mercury, lead for the cathode,
Titanium or iron is used, tetra-n-butylammonium perchlorate is used as a supporting electrolyte, and 1,2 as a solvent.
-Using dimethoxyethane. The electrode reduction method is expected not only to solve the above problems but also to be effective in controlling the molecular weight and the molecular weight distribution. However, this method has not yielded anything that can be confirmed to be polysilane.

[0005]

Means for Solving the Problems As a result of intensive studies in view of the above-mentioned conventional state of the art, the present inventor has used halosilane as an alkali metal perchlorate salt as a supporting electrolyte, and It has been found that the problems of the prior art can be substantially eliminated or significantly reduced by subjecting them to an electrode reaction used as an anode.

Further, in such an electrode reaction, it was also found that the reaction efficiency is greatly improved by switching the polarities of both electrodes at a constant time interval.

Furthermore, in the case of irradiating the reactor or the reaction solution with ultrasonic waves during the electrode reaction as described above, the reaction time can be greatly shortened and the yield of the reaction product can be increased. I found it.

[0008] That is, the present invention provides the following method for producing polysilane:

[0009]

[Chemical 9]

(In the formula, m is 1 to 3; R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group. When m = 1, two R's represent m = Two
In case of, 4 Rs, in case of m = 3, 6 Rs,
They may be the same or different in two or more: X represents a halogen atom. ) Is used in an electrode reaction in which an alkali metal perchlorate is used as a supporting electrolyte, an aprotic solvent is used as a solvent, and Mg is used as an anode.

[0011]

[Chemical 10]

A process characterized by forming a polysilane represented by the formula (wherein R is the same as above corresponding to the starting materials; n is 10 to 11000).

A method for producing polysilane, comprising the general formula:

[0014]

[Chemical 11]

(In the formula, m is 1 to 3; R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group. When m = 1, two R's represent m = Two
In case of, 4 Rs, in case of m = 3, 6 Rs,
They may be the same or different in two or more: X represents a halogen atom. ) Under the irradiation of ultrasonic waves, by using an alkali metal perchlorate salt as a supporting electrolyte, an aprotic solvent as a solvent, and subjecting it to an electrode reaction using Mg as an anode, formula

[0016]

[Chemical 12]

A process characterized by forming a polysilane represented by the formula (wherein R is the same as above corresponding to the starting materials; n is 10 to 11000).

A method for producing polysilane, comprising the general formula:

[0019]

[Chemical 13]

(In the formula, m is 1 to 3; R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group. When m = 1, two R's represent m = Two
In case of, 4 Rs, in case of m = 3, 6 Rs,
They may be the same or different in two or more: X represents a halogen atom. ) Is used as a supporting electrolyte, an alkali metal perchlorate is used as a supporting electrolyte, an aprotic solvent is used as a solvent, and Mg is used as one electrode, and a conductive material of the same or different type as these is used as the other electrode. As a general formula by subjecting the electrode reaction to switch the polarity of the electrode at certain time intervals as

[0021]

[Chemical 14]

A process characterized by forming a polysilane represented by the formula (wherein R is the same as above corresponding to the starting materials; n is 10 to 11000).

A method for producing polysilane, comprising the general formula:

[0024]

[Chemical 15]

(In the formula, m is 1 to 3; R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group. When m = 1, two R's represent m = Two
In case of, 4 Rs, in case of m = 3, 6 Rs,
They may be the same or different in two or more: X represents a halogen atom. ) Under the irradiation of ultrasonic waves with halosilane, an alkali metal perchlorate salt is used as a supporting electrolyte, an aprotic solvent is used as a solvent, and Mg is used as one electrode, and the same or different conductivity as those of these is used. By subjecting the conductive material to the other electrode in the electrode reaction that switches the polarity of the electrode at regular time intervals, the general formula

[0026]

[Chemical 16]

A process characterized by forming a polysilane represented by the formula (wherein R is the same as above corresponding to the starting materials; n is 10 to 11000).

In the following, the above inventions will be referred to as the first invention to the fourth invention of the present application, respectively, and these will be collectively referred to as the present invention.

In the present invention, the halosilane used as a starting material has the general formula

[0030]

[Chemical 17]

(In the formula, m is 1 to 3; R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group. When m = 1, two R's represent m = Two
In case of, 4 Rs, in case of m = 3, 6 Rs,
They may be the same or different in two or more: X represents a halogen atom. ).

The reaction product of the present invention has the general formula

[0033]

[Chemical 18]

(Wherein R is the same as above corresponding to the starting materials; n is 10 to 11000).

In the general formula (1), m is 1 to 3, and the hydrogen atom, amino group and organic substituent represented by R may be the same or different in two or more. May be. More specifically, when m = 1, 2
One R may be the same as four Rs when m = 2 or six Rs when m = 3, or two or more Rs may be different from each other. As the compound represented by the general formula (1), it is more preferable that m is 1 or 2. Examples of the alkyl group include those having about 1 to 10 carbon atoms, and among these, those having 1 to 6 carbon atoms are more preferable. As the aryl group, a phenyl group, a carbon number 1
Examples thereof include a phenyl group having one or more alkyl groups of 6 as a substituent and a p-alkoxyphenyl group. Examples of the alkoxy group include those having 1 to 10 carbon atoms, and among these, those having 1 to 6 carbon atoms are more preferable. When R is the above amino group or organic substituent, at least one of the hydrogen atoms may be substituted with another functional group such as an alkyl group, an aryl group or an alkoxy group.

In the general formula (1), X represents a halogen atom (Cl, F, Br, I). Cl is more preferable as the halogen atom.

In the method of the present invention, one kind of the halosilane represented by the general formula (1) may be used alone, or two or more kinds thereof may be mixed and used. Halosilane is preferably as pure as possible, for example,
It is preferable to dry it with calcium hydride before use and distill it before use.

In the reaction, halosilane is used by dissolving it in a solvent. As the solvent, aprotic solvents can be widely used, and more specifically, propylene carbonate, acetonitrile, dimethylformamide, dimethyl sulfoxide, 1,2-dimethoxyethane, bis (2-
Examples of the solvent include methoxyethyl) ether, p-dioxane, tetrahydrofuran and methylene chloride. These solvents can be used alone or as a mixture of two or more kinds. As the solvent, it is preferable to use an ether solvent such as 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, p-dioxane, or tetrahydrofuran alone or in combination with another solvent. Particularly preferred solvents are 1,2-dimethoxyethane and tetrahydrofuran. If the concentration of halosilane in the solvent is too low, the current efficiency will decrease, whereas if it is too high, the supporting electrolyte may not dissolve. Therefore, the concentration of halosilane in the solvent is
It is usually about 0.05 to 20 mol / l, more preferably about 0.2 to 15 mol / l, particularly preferably 0.3.
It is about 13 mol / l.

In the present invention, an alkali metal perchlorate such as sodium perchlorate or lithium perchlorate is used as the supporting electrolyte. These supporting electrolytes may be used alone or in combination of two or more kinds. Among these supporting electrolytes, lithium perchlorate is most preferable. If the concentration of the supporting electrolyte is too low, the reaction does not proceed sufficiently because the ionic conductivity given to the reaction solution is low, whereas if it is too high, an excessive current flows and the reaction is necessary for the reaction. The electric potential cannot be obtained. Therefore, the concentration of the supporting electrolyte in the solvent is usually 0.05 to 5 mol.
It is about 1 / l, more preferably about 0.1 to 3 mol / l, and particularly preferably about 0.15 to 1.2 mol / l.

In the first invention of the present application, Mg is used as the anode.
Alternatively, an alloy containing Mg as a main component is used (however, in the present specification, Mg and an alloy containing Mg as a main component are simply referred to as Mg). The cathode is not particularly limited as long as it is a material capable of passing an electric current.
It is preferable to use any one of g, Cu, Zn, Sn, Al, Ni and Co, or an alloy containing these metals as a main component. The shape of the electrode is not particularly limited as long as the current can be stably supplied, but a rod shape, a plate shape, a cylinder shape, a coiled shape of a plate shape, or the like is preferable. It is preferable to remove the oxide film as much as possible from the surface of the electrode. The oxide film can be removed from the electrode by any method. For example, the electrode is washed with acid, then washed with ethanol and ether, and dried under reduced pressure, or the electrode is polished under a nitrogen atmosphere. It can be performed by a method or a combination of these methods.

In carrying out the first invention of the present application, the halosilane represented by the general formula (1) and the supporting electrolyte are housed together with a solvent in a sealable reaction container provided with an anode and a cathode, preferably mechanically or magnetically. The electrode reaction is performed by applying a predetermined amount of current while stirring. The reaction vessel may have a dry atmosphere, but a dry nitrogen or inert gas atmosphere is more preferable, and a deoxygenated and dry nitrogen or inert gas atmosphere is most preferable. The amount of electricity is
Based on the halogen atom in halosilane, usually 1F /
The molecular weight can be controlled by adjusting the amount of electric current, as long as it is about mol or more. Also, 0.1 F / mol
It is also possible to take out the polysilane generated with an energization amount of about a certain amount or more, and collect the remaining raw material halosilane for reuse. The reaction time may vary depending on the amount of the raw material halosilane, the resistance of the electrolytic solution related to the amount of the supporting electrolyte, the desired molecular weight of polysilane, and the like, and may be appropriately determined as necessary. The temperature during the reaction may be within the temperature range not higher than the boiling point of the solvent used. In the first invention of the present application, the diaphragm, which is indispensable for the usual electrode reduction reaction, need not be used, which is advantageous because the operation is simplified.

The second invention of the present application, except for irradiating ultrasonic waves to the reaction container or reaction solution during the electrode reaction,
There is no substantial difference from the first invention of the present application. The method of irradiating ultrasonic waves during the electrode reaction is not particularly limited, but a method of irradiating by accommodating the reactor in an ultrasonic bath, a method of inserting and irradiating an ultrasonic transducer in the reactor Are exemplified. The frequency of ultrasonic waves is preferably about 10 to 70 kHz. The output of ultrasonic waves is the type of raw material, the amount of reaction solution, the shape and size of the reaction vessel and the electrode,
It may be appropriately determined according to the reaction conditions such as the material and surface area of the electrode, but usually 0.01 to 24 k per 1 l of the reaction solution.
Within the range of about W. By such ultrasonic irradiation, the reaction time is greatly shortened to about 1/3 to 2/3 that in the case where ultrasonic waves are not irradiated. In the second invention of the present application,
Stirring is satisfactorily performed by ultrasonic irradiation, but if necessary, mechanical means stirring may be used in combination.

In the third invention of the present application, Mg or Mg
With the first invention of the present application, except that the polarity of the electrode is switched at a constant time interval using an alloy containing as a main component as one pole and a conductive material (Ni, Co, etc.) of the same type or different types as these as the other pole. The reaction is performed by the same operation. By switching the polarity, the current value is stabilized and the reaction proceeds smoothly, and the reaction time per the same amount of current is shortened. The polarity switching is usually performed at intervals of about 0.01 second to 60 minutes, more preferably at intervals of about 1 second to 10 minutes, and particularly preferably at intervals of about 10 seconds to 3 minutes. When switching the polarities, it is necessary to configure the two electrodes with the same kind of metal, because metal ions (eg, Mg ²⁺ ) are dissolved between the two electrodes and the migration is performed.
This is preferable for synthesizing a high molecular weight polysilane because the consumption of electrodes is reduced and the energization time can be extended. Also in the third invention of the present application, it is not necessary to use a diaphragm.

In the fourth invention of the present application, ultrasonic waves are applied to the reaction container or the reaction solution during the electrode reaction. The fourth invention of the present application is the same as that of the third invention of the present application, except that ultrasonic waves are applied.
There is no substantial difference from the invention. Also, the irradiation of ultrasonic waves may be performed in the same manner as in the second invention of the present application. In the fourth invention of the present application, the reaction time is shortened and the yield is improved by the combination of the polarity switching and the ultrasonic irradiation. Fourth application
Also in the invention, if necessary, agitation by mechanical means may be used together.

In the present invention, in order to suppress oxygen content in the main chain, it is desirable to remove water in the solvent and supporting electrolyte in advance. For example, when tetrahydrofuran or 1,2-dimethoxyethane is used as the solvent, it is preferable to previously dry it with sodium-benzophenone ketyl.
Further, in the case of the supporting electrolyte, it is preferable that the support electrolyte is dried by heating under reduced pressure or the water is removed by adding a substance that easily reacts with the water and can be easily removed (for example, trimethylchlorosilane).

The polysilane represented by the general formula (2) obtained by the present invention usually has an average molecular weight of 1000 to 100.
10,000 (that is, in the general formula (2), n = 10
It is about 11000). When polysilane is used as an optical / electronic material, it is usually used in the form of a thin film.
In this case, n needs to be 30 or more. According to the method of the present invention, polysilane useful as an optoelectronic material having n of 30 or more can be easily obtained.

[0047]

According to the present invention, the following remarkable effects are achieved.

(A) Since mercury or cadmium is not used as the electrode, polysilane can be produced safely and easily without the risk of environmental pollution.

(B) Since no alkali metal is used, polysilane can be produced safely and easily even in industrial scale production.

(C) By adjusting the amount of electricity supplied,
The molecular weight of the polysilane produced can be controlled.

(D) The formation of Si-O-Si bonds in the main chain can be greatly suppressed. (E) Since it is not necessary to use a diaphragm, the diaphragm is not clogged and the operation is simple.

(F) When ultrasonic waves are applied during the electrode reaction, the reaction time is greatly shortened and the yield is remarkably improved.

[0053]

EXAMPLES Examples will be shown below to further clarify the features of the present invention.

Example 1 Three-way cock and Mg electrode (1 cm × 1 cm × 5 cm;
After washing with dilute sulfuric acid, washing with ethanol and ether, drying under reduced pressure, and polishing under a nitrogen atmosphere,
Inner volume 30 with 2 pieces (excluding oxide film on the surface)
0.64 g of anhydrous lithium perchlorate was placed in a 3-ml flask (hereinafter referred to as a reactor), heated to 50 ° C. and decompressed to 1 mmHg (6 hours), and dried to remove lithium perchlorate. The dried nitrogen thus prepared was introduced into the reactor, and further 15 ml of tetrahydrofuran previously dried with sodium-benzophenone ketyl was added. 0.97 ml of methylphenyldichlorosilane, which had been previously dried with calcium hydride and distilled, was added with a syringe, and the reactor was kept at room temperature by a water bath, and electricity was supplied by a constant voltage power source. At this time, using a commutator to convert the polarities of the two electrodes every minute, energize for about 96 hours so that the energization amount is 5.4 F / mol based on chlorine in methylphenyldichlorosilane. did.

After the reaction, the reaction solution was added with 1N hydrochloric acid (150 m).
After the addition of l, the mixture was extracted with ether, and reprecipitated with a poor solvent 2-propanol and a good solvent tetrahydrofuran.

As a result, polysilane having a weight average molecular weight of 5,540 was obtained. The oxygen content in the main chain of this polysilane was 0.1% or less, and it was confirmed that the oxygen content was extremely low.

Example 2 An electrode reaction was carried out in the same manner as in Example 1 except that the amount of tetrahydrofuran was 7.5 ml and the amount of electricity applied was 4.8 F / mol based on chlorine in methylphenyldichlorosilane. .

As a result, a polysilane having a weight average molecular weight of 21,900 was obtained.

Example 3 Example 3 except that 1.5 g of 1,2-dichlorotrimethylphenyldisilane was used as the raw material represented by the general formula (1) and the electrification amount was 4.4 F / mol based on the chlorine component. The electrode reaction was carried out in the same manner as in 1. The energizing time is
It was about 168 hours.

As a result, polysilane having a weight average molecular weight of 11,400 was obtained with a yield of 5%.

Example 4 An electrode reaction was carried out in the same manner as in Example 1 except that methyl-n-hexyldichlorosilane was used as the raw material represented by the general formula (1).

As a result, the corresponding polysilane was obtained.

Example 5 An electrode reaction was carried out in the same manner as in Example 1 except that dimethoxydichlorosilane was used as the raw material represented by the general formula (1).

As a result, the corresponding polysilane was obtained.

Example 6 An electrode reaction was carried out in the same manner as in Example 1 except that methyl-p-biphenyldichlorosilane was used as the raw material represented by the general formula (1).

As a result, the corresponding polysilane was obtained.

Example 7 A Mg electrode (1 cm × 1 cm × 5 cm) was used as an anode, and a Ni electrode (1 cm × 0.1 cm × 5 c) was used as a cathode.
Example 1 except that m) is used and no polarity conversion is performed.
The electrode reaction of methylphenyldichlorosilane was carried out in the same manner as in.

As a result, the same polysilane as in Example 1 was obtained 139 hours after the start of the reaction.

Example 8 An electrode reaction of methylphenyldichlorosilane was carried out in the same manner as in Example 1 except that 15 ml of 1,2-dimethoxyethane which had been dried with sodium benzophenone ketyl was used as a solvent.

As a result, the same polysilane as in Example 1 was obtained.

Example 9 An electrode reaction was carried out in the same manner as in Example 1 except that 1.94 ml of methylphenyldichlorosilane was used and the amount of electricity applied was 3.2 F / mol based on the chlorine component. The energization time was about 118 hours.

After completion of the reaction, reprecipitation was carried out with a poor solvent ethanol and a good solvent benzene, and a weight average molecular weight of 8 was obtained.
960 polysilanes were obtained with a yield of 22%.

Example 10 The same as Example 9 except that the reactor was immersed in an ultrasonic cleaner having an output of 60 W and a frequency of 45 kHz, ultrasonic waves were applied, and the energization amount was 4.0 F / mol based on the chlorine component. Then, the electrode reaction was carried out. The energization time was about 85 hours.

After completion of the reaction, reprecipitation was carried out with a poor solvent ethanol and a good solvent benzene, and a weight average molecular weight of 9 was obtained.
780 polysilanes were obtained with a yield of 33%.

Example 11 The same as Example 3 except that the reactor was immersed in an ultrasonic cleaner having an output of 60 W and a frequency of 45 kHz, ultrasonic waves were applied, and the energization amount was 4.0 F / mol based on the chlorine component. Then, the electrode reaction was carried out. The energization time was about 72 hours.

After completion of the reaction, reprecipitation was carried out with a poor solvent ethanol and a good solvent benzene, and a weight average molecular weight of 8 was obtained.
100 polysilanes were obtained with a yield of 15%.

Example 12 Anhydrous lithium perchlorate was dried using trimethylchlorosilane, and the amount of electricity applied was 2.0 F / m based on the chlorine component.
The electrode reaction was performed in the same manner as in Example 10 except that the amount was 1.

After completion of the reaction, reprecipitation was carried out with a poor solvent ethanol and a good solvent benzene, and a weight average molecular weight of 1 was obtained.
1500 polysilane was obtained with a yield of 65%.

Example 13 The electrode reaction was carried out in the same manner as in Example 10 except that 3.9 ml of methylphenyldichlorosilane and 4.0 ml of tetrahydrofuran were used and the amount of electricity applied was 0.4 F / mol based on the chlorine content. It was

After completion of the reaction, reprecipitation was carried out with a poor solvent ethanol and a good solvent benzene, and a weight average molecular weight of 5 was obtained.
5500 polysilanes were obtained with a yield of 15%.

Example 14 An electrode reaction was carried out in the same manner as in Example 12 except that naphthylmethyldichlorosilane was used as the raw material represented by the general formula (1).

After completion of the reaction, reprecipitation was carried out with a poor solvent ethanol and a good solvent benzene, and a weight average molecular weight of 1 was obtained.
0960 polysilane was obtained with a yield of 32%.

Example 15 An electrode reaction was carried out in the same manner as in Example 14 except that anisylmethyldichlorosilane was used as the raw material represented by the general formula (1).

After completion of the reaction, reprecipitation was carried out with a poor solvent ethanol and a good solvent benzene, and a weight average molecular weight of 6 was obtained.
930 polysilanes were obtained with a yield of 37%.

Example 16 An electrode reaction was carried out in the same manner as in Example 10 except that the energization time was 130 hours and the polarities of the two electrodes were not switched.

As a result, polysilane having a weight average molecular weight of 8300 was obtained in a yield of 26%. Example 17 An electrode reaction was carried out in the same manner as in Example 12 except that the time interval of polarity conversion of the two electrodes was changed to 15 seconds at the time when the energization amount became 1 F / mol based on the chlorine component.

As a result, polysilane having a weight average molecular weight of 12,300 was obtained in a yield of 68%.

Comparative Example 1 The electrode reaction of methylphenyldichlorosilane was carried out in the same manner as in Example 10 except that platinum (1 cm × 1 cm × 0.1 cm) was used as both electrodes.

After the completion of the reaction, reprecipitation was carried out using a poor solvent ethanol and a good solvent benzene, but almost no precipitate was obtained.

From this, it was found that when the electrode reaction is carried out in a reactor without a diaphragm using platinum as an electrode, only polysilane having a weight average molecular weight of 800 or less can be obtained.

Front page continued (72) Inventor Ryoichi Nishida 4-1-2 Hiranocho, Chuo-ku, Osaka, Osaka Gas Co., Ltd. (72) Shinichi Kawasaki 4-1-2 Hiranocho, Chuo-ku, Osaka Osaka Gas Co., Ltd. In the company

Claims (4)

[Claims] 1. A method for producing polysilane, which comprises the general formula: (In the formula, m is 1 to 3: R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group. When m = 1, two R's and m = 2 To 4
When one R is m = 3, the six Rs may be the same or different in two or more: X represents a halogen atom. ) Is used as a supporting electrolyte, an alkali metal perchlorate is used as a supporting electrolyte, an aprotic solvent is used as a solvent, and Mg is used as an anode. (Where R is the same as above corresponding to the starting material; n is 1
0 to 11000). 2. A method for producing polysilane, comprising the general formula: (In the formula, m is 1 to 3: R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group. When m = 1, two R's and m = 2 To 4
When one R is m = 3, the six Rs may be the same or different in two or more: X represents a halogen atom. ) Under the irradiation of ultrasonic waves, using a perchloric acid alkali metal salt as a supporting electrolyte, an aprotic solvent as a solvent, Mg
By subjecting the compound to an electrode reaction using as an anode, a compound of the general formula: (Where R is the same as above corresponding to the starting material; n is 1
0 to 11000). 3. A method for producing polysilane, comprising the general formula: (In the formula, m is 1 to 3: R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group. When m = 1, two R's and m = 2 To 4
When one R is m = 3, the six Rs may be the same or different in two or more: X represents a halogen atom. ) Is used as a supporting electrolyte, an alkali metal perchlorate is used as a supporting electrolyte, an aprotic solvent is used as a solvent, Mg is used as one electrode, and a conductive material of the same or different type as these is used as the other electrode. By subjecting it to an electrode reaction in which the polarity of the electrode is switched at regular time intervals, the general formula: (Where R is the same as above corresponding to the starting material; n is 1
0 to 11000). 4. A method for producing polysilane, comprising the general formula: (In the formula, m is 1 to 3: R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an amino group. When m = 1, two R's and m = 2 To 4
When one R is m = 3, the six Rs may be the same or different in two or more: X represents a halogen atom. ) Under the irradiation of ultrasonic waves, using a perchloric acid alkali metal salt as a supporting electrolyte, an aprotic solvent as a solvent, Mg
Is used as one pole, and the same or different conductive material as these is used as the other pole in the electrode reaction for switching the polarities of the electrodes at regular time intervals. (Where R is the same as above corresponding to the starting material; n is 1
0 to 11000).