JP2707764B2 - Polysilane compound, its production method and use - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel and useful polysilane compound, a method for producing the same, and a conductive material.

[Conventional technology]

Conventionally, metals are exclusively used as materials requiring conductivity, and organic polymer compounds are generally handled as insulating materials. However, in recent years, among organic polymer compounds that have been recognized as insulating materials, it has been found that a polymer compound containing a silicon atom has conductivity, and such a silicon-containing polymer compound is used as a conductive material. Attempts have been made to use it.

For example, in 1981, a compound having a crosslinked structure was obtained by irradiating light to methylphenylpolysilane, which is a kind of polysilane, and a compound having high conductivity was obtained by adding a dopant (doping agent) to the compound. That has been found. As the above dopants
A compound such as AsF ₅ is used, and by using such a dopant, the silicon-containing compound is
It is disclosed that it exhibits a conductivity of about 0.5 S / cm (JA
mer. Chem. Soc., 103 , 7352-7354 (1981)).

However, in order to use such a silicon-containing compound as a conductive material, highly toxic AsF ₅ must be used as a dopant. Further, there is also a problem that when producing the silicon-containing compound as described above, it is difficult to control light irradiation, and it is difficult to produce a compound having good characteristics with good reproducibility.

Further, in JP-A-62-59632, without using AsF _5, a matrix of polyalkyl silane exhibits excellent conductivity is disclosed. Here, it is shown that the polyalkylsilane has a conductivity of about 10 ⁻⁵ to 10 S / cm by including sulfate ions as a dopant in the polyalkylsilane.

However, there is still room for improvement in the properties such as conductivity and the manufacturing method of the conductive material made of polyalkylsilane as described above.

[Problems to be solved by the invention]

An object of the present invention is to provide a new and useful polysilane compound.

Another object of the present invention is to propose a production method for easily and efficiently producing the polysilane compound.

Another object of the present invention is to provide a conductive material comprising the above polysilane compound, which exhibits excellent conductivity, has good reproducibility, and is easy to produce.

[Means for solving the problem]

The present invention has the following general formula [I] (Wherein, R ¹ and R ² each independently represent a group selected from the group consisting of an alkyl group, an aryl group and an aralkyl group, and R ³ and R ⁴ each independently represent a hydrogen atom, or an alkyl group, an aryl group, Represents a group selected from the group consisting of an aralkyl group and an alkoxy group, and n represents an integer of 2 or more.), A method for producing the same, and a conductive material comprising the polysilane compound.

R ¹ and R ^{2 in} the general formula [I] are groups selected from the group consisting of an alkyl group, an aryl group and an aralkyl group, and R ¹ and R ² may be the same or different.

Examples of the alkyl group represented by R ¹ and R ² include those having 1 to 6, preferably 1 to 3 carbon atoms. The alkyl group may be linear or branched. Specific examples of such an alkyl group include a linear alkyl group such as a methyl group, an ethyl group, an n-propyl group and an n-butyl group; an isopropyl group, a sec-butyl group,
ec-amyl group and other secondary alkyl groups; tert-butyl group, ter
and tertiary alkyl groups such as t-amyl group.

Examples of the aryl group represented by R ¹ and R ² include a monovalent aryl group having at least one aromatic ring. This aromatic ring may have a substituent. Specific examples of such an aryl group include a phenyl group, a naphthyl group, a tolyl group, and a xylyl group.

Examples of the aralkyl group represented by R ¹ and R ² include a monovalent aralkyl group in which an aliphatic hydrocarbon is substituted with at least one aromatic ring. This aromatic ring may have a substituent. Specific examples of such an aralkyl group include a benzyl group, a phenethyl group, an α-methylbenzyl group, and a tolylmethyl group.

When the polysilane compound of the present invention is used as a conductive material, R ¹ and R ² are preferably a combination of groups selected from the group consisting of a methyl group, an ethyl group, a phenyl group and a benzyl group, particularly a combination of methyl groups, Combinations of methyl and phenyl groups are preferred.

R ³ and R ^{4 in} the general formula (I) are a hydrogen atom or a group selected from the group consisting of an alkyl group, an aryl group, an aralkyl group and an alkoxy group, and R ³ and R ⁴ may be the same or different. Good.

Examples of the alkyl group represented by R ³ and R ⁴ include those having 1 to 8, preferably 1 to 6 carbon atoms. The alkyl group may be linear or branched. Specific examples of such an alkyl group include a linear alkyl group such as a methyl group, an ethyl group, an n-propyl group and an n-butyl group; an isopropyl group, a sec-butyl group,
ec-amyl group and other secondary alkyl groups; tert-butyl group, ter
and tertiary alkyl groups such as t-amyl group.

Examples of the aryl group represented by R ³ and R ⁴ include a monovalent aryl group having at least one aromatic ring. This aromatic ring may have a substituent. Specific examples of such an aryl group include a phenyl group, a naphthyl group, a tolyl group, and a xylyl group.

Examples of the aralkyl group represented by R ³ and R ⁴ include a monovalent aralkyl group in which an aliphatic hydrocarbon is substituted with at least one aromatic ring. This aromatic ring may have a substituent. Specific examples of such an aralkyl group include a benzyl group, a phenethyl group, an α-methylbenzyl group, and a tolylmethyl group.

Examples of the alkoxy group represented by R ³ and R ⁴ include those having 1 to 8, preferably 1 to 6 carbon atoms. The alkoxy group may be linear or branched. Examples of such an alkoxy group include linear alkoxy groups such as methoxy group, ethoxy group, n-propoxy group and n-butoxy group; and secondary alkoxy groups such as isopropoxy group, sec-butoxy group and sec-amyloxy group. Group; te
and tertiary alkyl groups such as rt-butoxy group and tert-amyloxy group.

When the polysilane compound of the present invention is used as a conductive material, a combination in which R ³ and R ⁴ are selected from the group consisting of hydrogen, methyl, ethyl, phenyl, benzyl and methoxy is preferred.

N in the general formula [I] is an integer of 2 or more. When using the polysilane compound of the present invention as a conductive material,
It is preferable that n is 10 or more and the average molecular weight is 2000 to 3000 or more.

The polysilane compound of the present invention has the following general formula (II) (Wherein, R ¹ and R ² each independently represent a group selected from the group consisting of an alkyl group, an aryl group and an aralkyl group, and R ³ and R ⁴ each independently represent a hydrogen atom, or an alkyl group, an aryl group, And a group selected from the group consisting of an aralkyl group and an alkoxy group.) A 2,5-bis (chlorosilyl) thiophene derivative represented by the following formula: is reacted with an alkali metal.

Specific examples of the 2,5-bis (chlorosilyl) thiophene derivative represented by the general formula [II] include, for example, 2,5-bis (chlorodimethylsilyl) thiophene,
-Bis (chloromethylethylsilyl) thiophene, 2,5
-Bis (chloromethylphenylsilyl) thiophene, 2,
5-bis (chloromethyltolylsilyl) thiophene, 2,5
-Bis (chloromethylphenylsilyl) -3-methylthiophene and the like.

When the polysilane compound of the present invention is used as a conductive material, among the 2,5-bis (chlorosilyl) thiophene derivatives, 2,5-bis (chlorodimethylsilyl) is particularly preferred.
It is preferred to use thiophene or 2,5-bis (chloromethylphenylsilyl) thiophene.

The 2,5-bis (chlorosilyl) thiophene derivative is usually used alone, but for example, two or more kinds can be used in combination for the purpose of adjusting the conductivity of the obtained polysilane compound.

The 2,5-bis (chlorosilyl) thiophene derivative represented by the general formula [II] may be, for example, a substituent (R ³ , R ^3
The monochloro-substituted hydrosilanes having predetermined substituents (R ¹ , R ² ) are reacted with 2,5-thienylenedimagnesium bromide synthesized from 2,5-dibromothiophene having ⁴ ) and magnesium, and A 5-bis (substituted hydrosilyl) thiophene can be produced by stirring the mixture in room temperature or under heating in the presence of palladium chloride (PdCl ₂ ) in carbon tetrachloride.

Examples of the alkali metal include sodium metal,
Metal lithium, metal potassium, and the like can be given. Among them, it is preferable to use metallic sodium. These alkali metals can be used alone or in combination of two or more.

An example of the reaction between a 2,5-bis (chlorosilyl) thiophene derivative and an alkali metal is shown below.

(In the formula, R ^{1 to} R ⁴ and n are the same as described above.) As shown in the above formula [III], in the reaction between the 2,5-bis (chlorosilyl) thiophene derivative and the alkali metal, Is preferably used in such an amount as to react with a chlorine atom in at least the 2,5-bis (chlorosilyl) thiophene derivative, and usually 1.2 to 5 mol, preferably 1.2 to 5 mol per mol of the 2,5-bis (chlorosilyl) thiophene derivative. Is preferably used in the range of 2 to 4 mol.

According to the reaction mechanism of the above formula [III], the repeating unit represented by the above general formula [I] can be represented by the following general formula [IV], but is substantially the same as a polymer.

(In the formula, R ^{1 to} R ⁴ and n are the same as described above.) The alkali metal is usually dispersed in a solvent inert to the alkali metal and used in the form of a dispersion (dispersion liquid). It is desirable.

Therefore, the reaction between the 2,5-bis (chlorosilyl) thiophene derivative and the alkali metal is usually performed as a liquid phase reaction using a solvent. As described above, a solvent that is not reactive with alkali metals and is inert, and at the same time, inert to the starting material 2,5-bis (chlorosilyl) thiophene derivative, should be used. Is desirable. Specific examples of such a solvent include, for example, aromatic hydrocarbon solvents such as benzene, toluene, and xylene; saturated hydrocarbon solvents such as n-decane; unsaturated hydrocarbon solvents; ether solvents and the like. I can give it. In particular, aromatic hydrocarbon solvents such as toluene, benzene and xylene or saturated hydrocarbon solvents such as n-decane are preferably used. These solvents may be used alone or in combination with two or more.
Mixtures of more than one type can also be used.

The reaction is preferably carried out at a reaction temperature of usually -20C to -180C, preferably 0 to 150C. The polymerization reaction can be carried out under reduced pressure or under increased pressure, and the reaction pressure is not limited, but is usually from reduced pressure to 60 kg / cm ² · G, preferably 0 to 30 kg / cm ² · G, particularly preferably 0 to 30 kg / cm ² · G. 5kg / cm ²
-The range of G is preferable. The reaction time is appropriately set in consideration of the reaction temperature and the reaction pressure.
0 hours, preferably 1 to 10 hours is desirable.

The reaction can be carried out while irradiating a super-warm wave. In this case, the reaction temperature is usually −20 to 100 ° C., preferably 0 to 50 ° C.
℃, the reaction time is usually 5 minutes to 50 hours, preferably 1 to 20 hours, the reaction pressure is usually 0 to 30 kg / cm ² · G, preferably 0 to
5 kg / cm ² · G is desirable.

The reaction is usually desirably performed in an inert atmosphere. As the inert atmosphere, for example, an argon or nitrogen atmosphere is used.

The polysilane compound produced in this manner has, as a repeating unit, one represented by the general formula (I),
The terminal group includes the raw materials used and those derived from the reaction of the formula [III].

After completion of the reaction, a polysilane compound is obtained by, for example, hydrolyzing the alkali metal, extracting with a solvent such as chloroform or benzene, and adding an alcohol such as ethanol or isopropanol to reprecipitate.

In this way, the polysilane compound represented by the general formula (I) obtained by the present invention has a conductivity σ of usually 10 ⁻⁸ S / cm or less, but by adding a dopant, the conductivity σ becomes Usually, it is about 0.01 to 10 S / cm. Therefore, the polysilane compound of the present invention can be used as a conductive material.

Although the reason why the polysilane compound of the present invention exhibits conductivity is not clear, it is presumed that it has both a silicon-silicon bond and a thiophene ring.

The polysilane compound of the present invention exhibits better conductivity by adding a dopant. For this reason, when the polysilane compound of the present invention is used as a conductive material, it is common to add an appropriate dopant. The dopant is not particularly limited, and conventionally known halogens; Lewis acids; electron-withdrawing compounds such as transition metal halogen compounds; and electron-donating compounds such as alkali metals can be used. Specific examples of the dopant include, for example, I ₂ , SO ₃ , AsF ₅ , SbF ₅ , and SbCl ₅ . Preferably SbF ₅ Of these. These dopants can be used alone or in combination of two or more.

The method of adding the dopant to the polysilane compound is not particularly limited.For example, after forming the polysilane compound into an arbitrary shape, for example, a film shape, a method of applying a dopant to the molded body, any method after adding the dopant to the polysilane compound, Various methods such as a method of forming into a shape can be adopted. The molding method and the shape of the molded body at this time are not particularly limited, and can be formed into an arbitrary shape such as a film shape or a linear shape by a known method according to the shape of the intended conductive material.

The polysilane compound of the present invention can be used not only as a conductive material as described above, but also as a photosensitive material, for example, by utilizing the photofunctionality of a silicon-silicon bond.

〔The invention's effect〕

According to the present invention, a novel and useful polysilane compound having a repeating unit represented by the general formula [I] can be obtained. Such a posilirane compound has the general formula (II)
Can be easily and efficiently produced by reacting a 2,5-bis (chlorosilyl) thiophene derivative represented by the following formula with an alkali metal.

Further, according to the present invention, a conductive material having excellent conductivity can be easily obtained with good reproducibility.

〔Example〕

Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 (I) Synthesis of 2,5-bis (chlorodimethylsilyl) thiophene 4.2 ml of 2,5-dibromothiophene (0.0281) in 40 ml of a 1: 1 mixed solvent of tetrahydrofuran (THF) and benzene.
Mol) and 1.6 g (0.0694 mol) of magnesium, and 10 g of dimethylchlorosilane (0.106 mol) was added to 2,5-thienylenedimagnesium bromide, stirred at room temperature for 10 hours, and then hydrolyzed. Further, the oil layer was separated, dried and distilled under reduced pressure to obtain 2,5-bis (dimethylsilyl) thiophene 4.0 (yield 71%). The boiling point of this compound is 100 ° C / 1
It was 6 mmHg, and the results of the instrumental analysis are shown below. ¹ H nuclear magnetic resonance spectrum (measured in a CCl ₄ solvent, δ ppm) 0,39 (d, 12 H, J-4 Hz, CH ₃ Si); 5.55 (sept, 2 H, J = 4 Hz, HSi); 8.31 (s, 2H, ring protons) infrared absorption spectrum νSi-H; 2130cm ^-1 mass spectrum m / e200 (M ⁺⁾ as the element analysis (C ₈ H ₁₆ SSi ₂₎ Found C, 47.64; H, 8.00 calculated C, 47.94 ; H, 8.05 2,5-bis (dimethylsilyl) thiophene obtained above in carbon tetrachloride in the presence of catalytic amount of palladium chloride
Stirred at room temperature for 20 hours. Then, after carbon tetrachloride was distilled off, the remaining liquid was distilled under reduced pressure to obtain 4.7 g of 2,5-bis (chlorodimethylsilyl) thiophene (yield 66%). The boiling point of this compound is 125 ° C./15 mmHg, and the results of instrumental analysis are shown below. ¹ H nuclear magnetic resonance spectrum (measured in CCl ₄ solvent, δ ppm) 0.70 (s, 12 H, CH ₃ Si); 7.23 (s, 2 H, ring protons) ¹³ C nuclear magnetic resonance spectrum (measured in CDCl ₃ solvent, δpp
m) 3.3,136.7,143.5 Mass spectrum m / e268 (M ⁺⁾ as the element analysis _{(C 8 H 14 Cl 2 SSi} 2) Found C, 35.45; H, 5.20 Calculated C, 35.68; H, 5.24 ( II) Polymerization of 2,5-bis (chlorodimethylsilyl) thiophene 1.1 g (0.0478 mol) of sodium was added to 70 ml of n-decane, dispersed by stirring, and 4.7 g of 2,5-bis (chlorodimethylsilyl) thiophene ( 0.0175 mol). 13
After stirring at 0 ° C. for 10 hours, the mixture was hydrolyzed, extracted with chloroform and dried, and the solvent was distilled off. The residue was reprecipitated in benzene / ethanol to obtain 2.2 g of a polymer. As a result of measuring the molecular weight using GPC, the weight average molecular weight (Mw) was 1700
At 0, the melting point was 155-161 ° C. The results of the instrumental analysis are shown below. ¹ H nuclear magnetic resonance spectrum (measured in CDCl ₃ solvent, δ ppm) 0.34 (s, 12 H, CH ₃ Si); 7.14 (s, 2 P, ring protons) ¹³ C nuclear magnetic resonance spectrum (measured in CDCl ₃ solvent, δpp
m) -2.5,135.6,143.9 Example 2 (I) Synthesis of 2,5-bis (chloromethylphenylsilyl) thiophene 4.2 ml of 2,5-dibromothiophene (0.0281 in 30 ml of THF)
Mol) and 1.6 g (0.0694 mol) of magnesium, and 15 g (0.0958 mol) of chloromethylphenylsilane were added to 2,5-thienylenedimagnesium bromide, and the mixture was heated with stirring at 50 ° C. for 3 hours. Hydrolysis, extraction with hexane, drying over anhydrous magnesium sulfate, evaporation of the solvent and distillation under reduced pressure gave 7.9 g of 2,5-bis (methylphenylsilyl) thiophene (yield 84%). . The boiling point of this compound is 125 to 128 ° C./0.2 mmHg, and the results of instrumental analysis are shown below. ¹ H nuclear magnetic resonance spectrum (measured in CCl ₄ solvent, δppm) 0.64 (d, 6H , J = 4Hz, CH 3 Si); 5.01 (sept, 2H, J = 4Hz, HSi); 7.04-7.64 (m, 12H, ring protons) infrared absorption spectrum νSi-H; as 2130 cm ^-1 mass spectrum m / e324 (M ⁺⁾ elemental analysis (C ₁₈ H ₂₀ SSi ₂₎ Found C, 66.57; H, 6.18 calculated C, 66.21 ; H, 6.21 2,5-bis (methylphenylsilyl) obtained above
The thiophene was treated in the same manner as in Example 1 to obtain 7.2 g of 2,5-bis (chloromethylphenylsilyl) thiophene (yield: 75%). The boiling point of this compound was 190 ° C / 0.8 mmHg, and the results of instrumental analysis are shown below. ¹ Nuclear magnetic resonance spectrum (measured in CCl ₄ solvent, δppm) 0.94 (s, 6H, CH ₃ Si); 7.20-7.87 (m, 12H, ring protons) ¹³ C nuclear magnetic resonance spectrum (measured in CDCl ₃ solvent) , Δpp
m) 2.1, 128.2, 130.9, 133.8, 137.1, 138.0, 142.5 Elemental analysis (as C ₁₈ H ₁₈ Cl ₂ SSi ₂ ) Found C, 66.57; H, 6.18 Calculated C, 66.61; H, 6.21 (II) 2 Polymerization of 1,5-bis (chloromethylphenylsilyl) thiophene Sodium 0.6G (0.0260 mol) was added to 18 ml of benzene and dispersed by stirring, and 3.0 g of 2,5-bis (chloromethylphenylsilyl) thiophene was added thereto. 0.00763 mol). The mixture was stirred at room temperature for 10 hours while being irradiated with ultrasonic waves.
After hydrolysis, the precipitate was reprecipitated once with chloroform / ethanol and chloroform / isopropanol once to obtain 1.79 g of a polymer. The melting point of this polymer was 68 to 74 ° C, and the weight average molecular weight (Mw) obtained by GPC was 58,000. The results of the instrumental analysis are shown below. ¹ H nuclear magnetic resonance spectrum (measured in CDCl ₃ solvent, δppm) 0.65 (s, 6H, CH ₃ Si); 7.12-7.34 (m, 12H, ring protons) ¹³ C nuclear magnetic resonance spectrum (in CDCl ₃ solvent) Measurement, δpp
m) −3.3, 127.8, 129.1, 134.7, 135.8, 137.5, 142.0 Elemental analysis (as C ₁₈ H ₁₈ SSi ₂ ) Found C, 67.28; H, 5.68 Calculated C, 67.02; H, 5.62 Example 3 (I ) Synthesis of 2,5-bis (chloromethyltrisilyl) thiophene 4.2 ml of 2,5-dibromothiophene (0.0281 in 50 ml of THF)
Mol) and 1.6 g (0.0694 mol) of magnesium, and 15 g (0.0880 mol) of chloromethyltolylsilane were added to 2,5-thienylenedimagnesium bromide.
Stirred for hours. After hydrolysis, the mixture was extracted with hexane and dried over anhydrous magnesium sulfate. The solvent was distilled off, and 2,5-bis (methyltolylsilyl) thiophene 7.4 was distilled under reduced pressure.
g was obtained (75% yield). The boiling point of this compound is 185 ℃ / 0.9mm
Hg, and the results of the instrumental analysis are shown below. ¹ H nuclear magnetic resonance spectrum (measured in CCl ₄ solvent, δ ppm) 0.63 (d, 6H, J = 4 Hz, CH ₃ Si); 2.30 (s, 6 H, P-Me); 4.96 (q, 2 H, J = 7.05 (d, 4H, J = 20Hz, tolyl ring protons); 7.19 (d, 4H, J = 70Hz, tolyl ring protons); 7.19 (s, 2H, thiophene ring protons) Infrared absorption spectrum νSi −H; 2130 cm ⁻¹ mass spectrum m / e352 (M ⁺ ) Elemental analysis (as C ₂₀ H ₂₄ SSi ₂ ) Found C, 68.02; H, 6.79 Calculated C, 68.12; H, 6.86 2 obtained above 5,5-Bis (methyltolylsilyl) thiophene was treated in the same manner as in Example 1 to obtain 6.4 g of 2,5-bis (chloromethyltolylsilyl) thiophene (yield: 72%). The boiling point of this compound was 190 ° C / 0.3 mmHg, and the results of instrumental analysis are shown below. ¹ Nuclear magnetic resonance spectrum (measured in CCl ₄ solvent, δ ppm) 0.93 (s, 6H, CH ₃ Si); 2.35 (s, 6H, P-Me); 7.17 (d, 4H, J = 18Hz, tolyl ring protons 7.26 (d, 4H, J = 18Hz, tolyl ring protons); 7.30 (s, 2H, thiophene ring protons) ¹³ C nuclear magnetic resonance spectrum (measured in CDCl ₃ solvent, δpp)
m) 2.2, 21.6, 129.0, 130.5, 133.9, 137.8, 141.1, 142.7 Mass spectrum m / e420 (M ⁺ ) Elemental analysis (as C ₂₀ H ₂₂ Cl ₂ SSi ₂ ) Measured value C, 56.92; H, 5.17 Calculated value C, 57.00; H, 5.26 (II) Polymerization of 2,5-bis (chloromethyltolylsilyl) thiophene 0.5 g (0.0217 mol) of sodium was added to 15 ml of benzene, and the mixture was dispersed by stirring, and 3.2 g of 2,5 was added. A solution of bis (chloromethyltolysilyl) thiophene (0.00759 mol) in 4 ml of benzene was added. The mixture was stirred at room temperature and irradiated with ultrasonic waves for 10 hours. After hydrolysis and extraction with chloroform, the extract was dried over anhydrous magnesium sulfate, the solvent was distilled off, and the residue was reprecipitated twice with chloroform / ethanol to obtain 1.2 g of a polymer (yield: 46%). The melting point of this polymer is 86-92 ° C, GP
The weight average molecular weight (Mw) measured by C was 62,000. The results of the instrumental analysis are shown below. ¹ Nuclear magnetic resonance spectrum (measured in CDCl ₃ solvent, δ ppm) 0.69 (s, 6H, CH ₃ Si); 2.29 (s, 6H, P-Me); 6.72-7.55 (m, 10H, ring protons) ¹³ C Nuclear magnetic resonance spectrum (measured in CDCl ₃ solvent, δpp
m) −3.1,21.5,128.7,132.3,132.4,134.9,137.4,138.9,14
2.1 Example 4 1 mg of the polymer obtained in Example 1 (polydisilanilenyleneenylene, R ¹ and R ² in the above formula [I] are methyl groups)
Was dissolved in 0.1 ml of a mixed solvent of dichloroethane and toluene 1: 1. Using this solution, a film having a thickness of 200 mm was formed on an insulating substrate by a spin coating solution.

After doping the film by supplying SbF ₅ in the gas phase, the conductivity of the film was measured. The conductivity was evaluated by applying a voltage to the film and measuring the flowing current and voltage by employing a four-point probe method. As a result, the conductivity σ of this film is
It was 5.47 S / cm.

Example 5 1 mg of the polymer obtained in Example 2 (polydisilanilenyleneenylene, R ¹ in the above general formula [I] is a methyl group and R ² is a phenyl group) was dissolved in 0.1 ml of dichloroethane. Using this solution, a film having a thickness of 6100 mm was formed on an insulating substrate by a spin coating solution.

After doping the film by supplying SbF ₅ in the gas phase, the conductivity of the film was measured. The conductivity was evaluated by applying a voltage to the film and measuring the flowing current and voltage by employing a four-point probe method. As a result, the conductivity σ of this film is
2.33 S / cm.

Example 6 1 mg of the polymer obtained in Example 3 (polydisilanilentenyleneene, R ¹ in the above general formula [I] is a methyl group and R ² is a tolyl group) was dissolved in 0.1 ml of dichloroethane. Using this solution, a film having a thickness of 2700 ° was formed on an insulating substrate by a spin coating solution.

After doping the film by supplying SbF ₅ in the gas phase, the conductivity of the film was measured. The conductivity was evaluated by applying a voltage to the film and measuring the flowing current and voltage by employing a four-point probe method. As a result, the conductivity σ of this film is
It was 0.01 S / cm.

Claims (3)

(57) [Claims] 1. The following general formula [I] (Wherein, R ¹ and R ² each independently represent a group selected from the group consisting of an alkyl group, an aryl group and an aralkyl group, and R ³ and R ⁴ each independently represent a hydrogen atom, or an alkyl group, an aryl group, And a group selected from the group consisting of an aralkyl group and an alkoxy group, and n represents an integer of 2 or more.) 2. The following general formula [II] (Wherein, R ¹ and R ² each independently represent a group selected from the group consisting of an alkyl group, an aryl group and an aralkyl group, and R ³ and R ⁴ each independently represent a hydrogen atom, or an alkyl group, an aryl group, A group selected from the group consisting of an aralkyl group and an alkoxy group.) A 2,5-bis (chlorosilyl) thiophene derivative represented by the following general formula [I]: (Wherein, R ¹ and R ² each independently represent a group selected from the group consisting of an alkyl group, an aryl group and an aralkyl group, and R ³ and R ⁴ each independently represent a hydrogen atom, or an alkyl group, an aryl group, A group selected from the group consisting of an aralkyl group and an alkoxy group, and n represents an integer of 2 or more.) 3. The following general formula: (Wherein, R ¹ and R ² each independently represent a group selected from the group consisting of an alkyl group, an aryl group and an aralkyl group, and R ³ and R ⁴ each independently represent a hydrogen atom, or an alkyl group, an aryl group, An electrically conductive material comprising a polysilane compound having as a repeating unit disilanilenyleneenylene represented by the following formula: wherein n is an integer selected from the group consisting of an aralkyl group and an alkoxy group. .