JP3060857B2 - Polycyclic fused aromatic group pendant polysilanes, process for producing the same, and conductive polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polycyclic fused aromatic pendant polysilane useful as a photoconductive material, a conductive material and the like, a method for producing the same, and a conductive polymer.

[0002]

2. Description of the Related Art Conventional polysilanes mainly have an alkyl group typified by a methyl group or a phenyl group as a substituent (RW).
est et al. , J. et al. Am. Chem. So
c. , 103 , 7352 (1981)).

Then, hydrogen or reactive carbon is used as a substituent.
A polysilane having a substituent containing a carbon double bond, c
Polysilanes with alkylated alkyl groups will be synthesized
And it becomes possible to crosslink polysilane.
Expectations for applications have increased (R. West et.
al. , J. et al. Organomet. Chem. ,30
0, 327 (1986)).

In recent years, it has been reported that, as other substituents, a polysilane having a silyl group introduced therein (JP-A-63-12636) or a polysilane having a phenolic substituent introduced therein is applied to a resist material. (JP-A-63-113021).

The present inventors have also paid attention to the photoconductivity and conductivity of polysilane, and have developed a polysilane with suppressed photodegradability by introducing a carbazolyl group-containing substituent into the polysilane. (Japanese Unexamined Patent Publication No.
No. 2).

However, polysilanes having higher electric conductivity and being effectively used as a photoconductive material or a conductive material are desired.

[0007]

Means and Action for Solving the Problems The present inventors have
As a result of further study to meet the above demand, diorganohalogenosilane represented by the following general formula (2) and polycyclic condensed aromatic group-containing dihalogenosilane represented by the following general formula (3) or the following general formula By reacting the polycyclic fused aromatic group-containing dihalogenosilane of the formula (3) in an inert solvent in the presence of an alkali metal, a novel polycyclic fused aromatic represented by the following general formula (1) is obtained. The base pendant polysilanes are obtained, and the electric conductivity when the polycyclic fused aromatic group pendant polysilanes are doped with an oxidizing dopant such as iodine is, for example, 10 ^-4 to 10 ^-5 S /.
cm), and the electrical conductivity of dibutylpolysilane (3.5 × 10 ⁻⁸ S / cm) or methylphenylpolysilane (1.3 × 10 ⁻⁶ S / cm) having no polycyclic fused aromatic group. Have been further improved, and thus have been found to be effectively used as a photoconductive material or a conductive material, and have led to the present invention.

[0008]

Embedded image (Wherein R ¹ , R ² , R ³ , and R ⁴ are each a hydrogen atom or a monovalent hydrocarbon group, and at least one of R ³ and R ⁴
One is a monovalent hydrocarbon group containing a polycyclic fused aromatic group represented by the following formula. Also, k, m, and n are 0 ≦ k <1, 0
<M ≦ 1, k + m = 1, n ≧ 6. X is a halogen atom. )

R ⁵ -C _p H _2p- (wherein, R ⁵ is a polycyclic fused aromatic group, and p is 1 ≦ p ≦
It is an integer of 12. )

Accordingly, the present invention provides a polycyclic fused aromatic group pendant polysilane represented by the above general formula (1), a diorganohalogenosilane represented by the above general formula (2) and a compound represented by the above general formula (3). Reacting the polycyclic fused aromatic group-containing dihalogenosilane represented by formula (3) or the polycyclic fused aromatic group-containing dihalogenosilane of the formula (3) in an inert solvent in the presence of an alkali metal. Provided are a method for producing polysilanes, and a conductive polymer obtained by doping the polysilanes with an oxidizing dopant.

Now, the present invention will be described in further detail. The novel polycyclic fused aromatic group-pendant polysilane of the present invention is represented by the following general formula (1).

[(R ¹ R ² Si) _k (R ³ R ⁴ Si) _m ] _n (1) (where R ¹ , R ² , R ³ , and R ⁴ are each a hydrogen atom or a monovalent A hydrocarbon group, at least one of R ³ and R ⁴
One is a monovalent hydrocarbon group containing a polycyclic fused aromatic group represented by the following formula. Also, k, m, and n are 0 ≦ k <1, 0
<M ≦ 1, k + m = 1, n ≧ 6. )

R ⁵ -C _p H _2p- (wherein, R ⁵ is a polycyclic fused aromatic group, and p is 1 ≦ p ≦
12, preferably an integer of 1 ≦ p ≦ 6. )

Here, the monovalent hydrocarbon group of R ¹ and R ² has 1 to 12 carbon atoms, especially 1 to 6 carbon atoms, specifically, an alkyl group such as methyl, ethyl, propyl and butyl, and cyclohexyl. And a cycloalkyl group such as a group and an aryl group such as a phenyl group. R ³ and R ⁴ are a hydrogen atom or a monovalent hydrocarbon group similar to R ¹ and R ² , or R ⁵
-C _p H _2p - at and at least one of R ^3, R ⁴ is R ⁵ -
C _p H _2p - and although, as the polycyclic fused aromatic group of the R ^5, naphthyl group, anthracenyl group, phenanthrenyl group, benzo phenanthrenyl group, a pyrenyl group, naphthacenyl group, a picenyl group , A perylenyl group,
The polycyclic fused aromatic group may be unsubstituted or substituted with a monovalent hydrocarbon group or the like.

In addition, n is an integer of 6 or more, preferably 10 to 10,000, more preferably 100 to 1
When it is used as a photoconductive material or a conductive material, the degree of polymerization is preferably high in order to sufficiently exhibit its properties. The weight average molecular weight is usually 5,000 to 5,000,000 in terms of polystyrene.
0, especially 10,000 to 2,000,000.

The polysilanes of the above formula (1) include a diorganohalogenosilane represented by the following general formula (2) and a polycyclic condensed aromatic group-containing dihalogenosilane represented by the following formula (3): The compound can be synthesized by reacting the polycyclic fused aromatic group-containing dihalogenosilane of 3) in an inert solvent in the presence of an alkali metal.

R ¹ R ² SiX ₂ ... (2) R ³ R ⁴ SiX ₂ ... (3) (wherein, R ^{1 to} R ⁴ have the same meaning as described above, and X is a halogen atom.)

The chlorosilane containing a polycyclic fused aromatic group may be either a monopendant type or a dipendant type, and the polycyclic fused aromatic group may be unsubstituted or substituted with an organic group. . In addition, a one-dimensional polymer or a cyclic body is formed by using dihalosilanes. However, by using trifunctional trihalosilanes, it is also possible to obtain network-like polysilanes. Furthermore, it is also possible to use halosilanes containing a carbon-carbon unsaturated bond in the main chain skeleton in advance.

The above-mentioned dihalogenosilane is prepared in an inert solvent,
The reaction is carried out in the presence of an alkali metal. As the inert solvent, one or more of xylene, toluene, dodecane, ethers, esters and the like are used, and as the alkali metal, Na and the like are used. In this case, the amount of the alkali metal used is preferably 2 to 3 times the mol of the dihalogenosilane.

The reaction temperature is from 50 to 200 ° C., especially from 100 to 200 ° C.
The temperature is preferably 150 ° C., and the reaction time is usually 1 to 1
0 hours.

After the reaction, the polysilane can be collected by adding methanol or the like to deactivate the alkali metal, collecting the organic layer, concentrating and precipitating the desired polysilane with acetone or the like.

The polycyclic fused aromatic group-pendant polysilane of the present invention thus obtained has a high electric conductivity when doped with an oxidizing dopant, and is therefore suitable as a photoconductive material or a conductive material. Used for

That is, oxidizing dopants for making the polysilane conductive include halogens such as chlorine, bromine and iodine, transition metal chlorides such as tin chloride and ferric chloride, antimony pentafluoride, and the like. Although a Lewis acid such as arsenic pentafluoride is effective, it is preferable to dope with iodine or ferric chloride which is safe and easy to handle. Doping methods include (1) so-called gas-phase (or dry) doping that is exposed to a vapor atmosphere of iodine or ferric chloride, and (2) a solution in which iodine or ferric chloride is dissolved in an inert solvent. Wet doping in which the polymer is immersed. (3) When the polymer is dissolved in a solution in which iodine, ferric chloride or the like is dissolved, the solution is formed into a film or coating by dry film formation and simultaneously doping. A method such as simultaneous doping is used.

In this case, the inert solvent used for the wet doping and the simultaneous doping in (2) and (3) is a solvent which does not react with iodine or ferric chloride to deactivate the ability as an electron accepting compound. Such as, hexane, octane, hydrocarbons such as cyclohexane, toluene, xylene, aromatics such as nitrobenzene, ethers, ethers such as tetrahydrofuran, esters such as ethyl acetate, methanol, Alcohols such as ethanol, dimethylformamide,
Examples include aprotic polar solvents such as dimethyl sulfoxide and hexamethylphosphoric triamide, nitromethane, and acetonitrile.

Among them, a solvent such as tetrahydrofuran dissolves the polymer very well and is particularly suitable for simultaneous doping. According to this simultaneous doping method, a polymer is dissolved in a solution containing a dopant, and the dissolved conductor is dried after casting, whereby a doped conductor can be obtained. The drying temperature is usually 0 to 1
It is preferably carried out at 50 ° C. at normal pressure or reduced pressure.

However, in the wet method or the simultaneous doping method,
Often the polymer is degraded by the dopant, gelling or decomposing. On the other hand, the gas phase doping of (1) is particularly useful because a solvent is not used, drying is simple, and high conductivity is obtained.

In gas phase doping, the doping rate can be controlled by controlling the temperature and pressure of the dopant atmosphere. Here, in the case of iodine or antimony pentafluoride doping, the temperature is generally −30 ° C. to 2 ° C.
It is preferable to carry out in the range of 00 ° C. At lower temperatures, the doping rate is slower; at higher temperatures, polymer degradation may occur during doping. Also,
The pressure of the dopant atmosphere is 0.001 mmHg to 38 mmHg.
It is preferable to carry out in the range of 00 mmHg. At lower pressures, the doping rate is slower, and at higher pressures, it is difficult to expect an increase in doping rate even if the pressure is increased. In addition,
In the case of iodine and antimony pentafluoride, doping proceeds rapidly at normal temperature and normal pressure, but in the case of ferric chloride, the doping conditions are different from those of iodine and antimony pentafluoride due to the low vapor pressure. Ferric chloride doping is generally preferably performed at a temperature in the range of 50 ° C to 300 ° C. At lower temperatures, the doping rate is slower, and at higher temperatures, polymer degradation may occur during doping. The pressure is preferably set in the range of 0.001 mmHg to 760 mmHg. At lower pressures it is not economical because it takes a long time to reach that pressure, and at higher pressures the doping rate is very slow. More preferably, the doping of ferric chloride is performed at a pressure of 0.1 mmHg to 10 mmHg and a temperature range of 50C to 200C in order to effectively increase the conductivity of the polymer. According to this method, a conductive material can be manufactured by a very simple operation using ferric chloride having low toxicity without using a flammable solvent.

[0028]

The polycyclic fused aromatic group pendant polysilanes of the present invention exhibit high electrical conductivity by doping and are useful as photoconductive materials, conductive materials and the like. Further, according to the production method of the present invention, such polysilanes can be synthesized simply and reliably.

The conductive polysilane of the present invention has excellent shapeability and can be easily formed as a highly conductive film or coating film. , Can be widely used in electronic and communication fields.

[0030]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples.

[0031]

Embedded image

0.7 g of metallic sodium in a nitrogen atmosphere
(30 mmol) was added with 15 g of xylene, heated to 138 ° C., and vigorously stirred to prepare a sodium dispersion.

0.56 g (2 mm) of 3- (1-naphthyl) propylmethyldichlorosilane was added to the dispersion.
ol) and 1.91 g of methylphenyldichlorosilane (1
0 mmol) over 2 minutes and stirred at 138 ° C. for 4 hours. After the completion of the reaction, the mixture was cooled to room temperature, and about 5 ml of methanol was added dropwise to deactivate the remaining sodium, followed by washing with water. Next, the organic layer was taken out, dried over calcium chloride, and then the reaction mixture was concentrated. The obtained viscous substance was added to 100 ml of acetone to precipitate a polymer.
The precipitate was separated by filtration and dried under vacuum to obtain 0.15 g of a naphthyl-based pendant polysilane as a white precipitate.

According to GPC analysis, the weight average molecular weight distribution of this polymer was composed of two components, and was 51% in terms of polystyrene.
6,300 (10%) and 11,500 (90%). In addition, ultraviolet absorption derived from polysilane (λmax)
337 nm).

[0035]

Embedded image

Under a nitrogen atmosphere, 0.92 g of metallic sodium
(40 mmol) was added with 15 g of xylene, heated to 138 ° C., and vigorously stirred to prepare a sodium dispersion.

To this dispersion was added 1.42 g (5 mm) of 3- (1-naphthyl) propylmethyldichlorosilane.
ol) and 1.91 g of methylphenyldichlorosilane (1
0 mmol) over 1 minute and stirred at 138 ° C. for 5 hours. After the completion of the reaction, the mixture was cooled to room temperature, and about 5 ml of methanol was added dropwise to deactivate the remaining sodium, followed by washing with water. Next, the organic layer was taken out, dried over calcium chloride, and then the reaction mixture was concentrated. The obtained viscous substance was added to 100 ml of acetone to precipitate a polymer.
The precipitate was separated by filtration and dried under vacuum to obtain 0.34 g of a target naphthyl group-pendant polysilane as a white precipitate.

According to GPC analysis, the weight average molecular weight distribution of this polymer was composed of two components, and was 24 in terms of polystyrene.
3,700 (11%) and 11,500 (89%). In addition, ultraviolet absorption derived from polysilane (λmax)
336 nm).

[0039]

Embedded image

0.7 g of metallic sodium in a nitrogen atmosphere
(30 mmol) was added with 15 g of xylene, heated to 138 ° C., and vigorously stirred to prepare a sodium dispersion.

0.67 g of 3- (1-phenanthrenyl) propylmethyldichlorosilane was added to this dispersion.
(2 mmol) and 1.9 methylphenyldichlorosilane
1 g (10 mmol) was added over 2 minutes, and the mixture was stirred at 138 ° C for 4 hours. After the completion of the reaction, the mixture was cooled to room temperature, and about 5 ml of methanol was added dropwise to deactivate the remaining sodium, followed by washing with water. Next, the organic layer was taken out, dried over calcium chloride, and then the reaction mixture was concentrated. The obtained viscous substance was added to 100 ml of acetone to precipitate a polymer. The precipitate was separated by filtration and dried under vacuum to obtain 0.50 g of a phenanthrenyl group-pendant polysilane as a white precipitate, which was the target substance.

According to GPC analysis, the weight average molecular weight distribution of this polymer was composed of two components, and was 37% in terms of polystyrene.
6,400 (11%) and 7,900 (89%). In addition, ultraviolet absorption derived from polysilane (λmax)
336 nm).

[0043]

Embedded image

0.92 g of metallic sodium in a nitrogen atmosphere
(40 mmol) was added with 15 g of xylene, heated to 138 ° C., and vigorously stirred to prepare a sodium dispersion.

1.66 g of 3- (1-phenanthrenyl) propylmethyldichlorosilane was added to the dispersion.
(5 mmol) and 1.9 methylphenyldichlorosilane
1 g (10 mmol) was added over 1 minute, and the mixture was stirred at 138 ° C for 4 hours. After the completion of the reaction, the mixture was cooled to room temperature, and about 5 ml of methanol was added dropwise to deactivate the remaining sodium, followed by washing with water. Next, the organic layer was taken out, dried over calcium chloride, and then the reaction mixture was concentrated. The obtained viscous substance was added to 100 ml of acetone to precipitate a polymer. The precipitate was separated by filtration and dried under vacuum to obtain 1.40 g of a phenanthrenyl group-pendant polysilane as a white precipitate, which was the target substance.

According to GPC analysis, the weight average molecular weight distribution of this polymer was composed of two components, and was 93% in terms of polystyrene.
7,300 (15%) and 5,250 (85%). In addition, ultraviolet absorption derived from polysilane (λmax)
336 nm).

Examples 5 and 6, Comparative Examples 1 and 2 The polycyclic aromatic group pendant polysilanes obtained in Examples 2 and 4 were doped with iodine, and the electric conductivity was measured.
Table 1 also shows the results of (Bu ₂ Si) _n and (MePhSi) _n as comparative examples.

[0048]

[Table 1]

The method of measuring the conductivity is as follows. Four terminals are formed on a glass plate by platinum vapor deposition to form electrodes, and a polymer solution dissolved in a solvent is spin-coated thereon to form a thin film. The sample was used as a rate measurement sample, and the sample was brought into contact with iodine in a light-shielded and sealed state to track the change of the DC resistance with time, and the conductivity was determined from the resistance value at room temperature (25 ° C.). Also, when doped with ferric chloride by the same conductivity measurement method, it shows high electrical conductivity.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Shigeru Mori 3-2-1 Sakado, Takatsu-ku, Kawasaki-shi, Kanagawa Prefecture Shin-Etsu Chemical Co., Ltd. Corporate Research Center (56) References JP-A-6-256662 (JP) JP-A-5-255509 (JP, A) JP-A-5-313170 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 77/60 C08L 83/16 H01B 1/12 CA (STN) WPI (DIALOG)

Claims (3)

(57) [Claims] 1. A polycyclic fused aromatic group pendant polysilane represented by the following general formula (1). [(R ¹ R ² Si) _k (R ³ R ⁴ Si) _m ] _n (1) (wherein R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom or a monovalent hydrocarbon group) But at least one of R ³ and R ⁴
One is a monovalent hydrocarbon group containing a polycyclic fused aromatic group represented by the following formula. Also, k, m, and n are 0 ≦ k <1, 0
<M ≦ 1, k + m = 1, n ≧ 6. R ⁵ -C _p H _2p- (wherein, R ⁵ is a polycyclic fused aromatic group, and p is 1 ≦ p ≦
It is an integer of 12. ) 2. A diorganohalogenosilane represented by the following general formula (2) and a polycyclic condensed aromatic group-containing dihalogenosilane represented by the following general formula (3), or a polycyclic condensation of the formula (3) The method for producing polysilanes according to claim 1, wherein the aromatic group-containing dihalogenosilane is reacted in an inert solvent in the presence of an alkali metal. R ¹ R ² SiX ₂ (2) R ³ R ⁴ SiX ₂ (3) (wherein, R ^{1 to} R ⁴ have the same meanings as defined in claim 1, and X is a halogen atom) is there.) 3. A conductive polymer obtained by doping the polycyclic fused aromatic group pendant polysilane according to claim 1 with an oxidizing dopant.