JPH08245796A - Production of polysilane having pendant pyrrolyl group - Google Patents

Abstract

PURPOSE: To produce the subject polymer having high molecular weight and high electrical conductivity and useful for photoconductive material, electrically conductive material, etc., by reacting a dihalogenosilane containing pyrrolyl group and a diorganohalogenosilane with an alkali metal in an inert solvent. CONSTITUTION: This polysilane having pendant pyrrolyl group, expressed by formula IV (0<(k<=1; 0<=m<1; k+m=1; (n) is an integer of >=6) and useful for photoconductive material, electrically conductive material, etc., is produced by reacting a dihalogenosilane containing pyrrolyl group and expressed by formula I [R<1> is a univalent hydrocarbon residue having pyrrolyl group and expressed by formula II ((p) is an integer of 2-12; R<3> and R<4> are each H, an alkyl or an aryl); R<2> is a 4-12C long-chain alkyl; X is a halogen] or the above dihalogenosilane and a diorganohalogenosilane expressed by formula III (R<5> and R<6> are each a 4-12C long-chain alkyl) with an alkali metal (e.g. a sodium dispersion) in an inert solvent (e.g. toluene) at 110 deg.C for 2hr under agitation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to polysilanes having a pyrrolyl group as a substituent and useful as a photoconductive material or a conductive material, and a method for producing the same.

[0002]

2. Description of the Related Art Polysilane has hitherto been recognized as being useful as a resist material in the field of microelectronics and as a photoconductor in optoelectronics.

Initially, such polysilanes were mainly those having an alkyl group represented by a methyl group or a phenyl group as a substituent (R. West et al.,
J. Am. Chem. Soc. , 103, 7352 (1
981)).

Then, hydrogen as a substituent, polysilane having a substituent containing a reactive carbon-carbon double bond,
Since polysilanes having a halogenated alkyl group have been synthesized and it has become possible to crosslink polysilanes, expectations for their applications have increased (R. West et.
al. , J. et al. Organomet. Chem. , 30
0,327 (1986)).

In recent years, as other substituents, polysilane having a silyl group introduced (Japanese Patent Laid-Open No. 63-12636) and a phenolic substituent having been introduced have been reported to be applied to a resist material. Kaisho 63-113
No. 021).

Further, the present applicant has paid attention to the photoconductivity and conductivity of polysilane, and proposed a polysilane whose photodegradability is suppressed by introducing a substituent containing a carbazolyl group into polysilane (Japanese Patent Laid-Open No. Hei 10 (1999) -242242). No. 5-43702).

Further, the present applicant has previously proposed a pyrrolyl group pendant polysilane and a manufacturing method thereof (Japanese Patent Application No. 5-222162), but the molecular weight of the previously proposed pyrrolyl group pendant polysilane is sufficiently large. However, a method for surely obtaining pendant polysilanes of pyrrolyl group having higher molecular weight and higher electric conductivity is desired.

[0008]

Means for Solving the Problems The present inventor has conducted extensive studies in order to meet the above demand, and as a result, has a pyrrolyl group pendant polysilane having a long-chain alkyl group in the side chain represented by the following general formula (1). Or by reacting this with a diorganohalogenosilane having a long-chain alkyl group on the side chain represented by the following formula (3) in the presence of an alkali metal in an inert solvent, the following general formula (4) It was found that high molecular weight pyrrolyl group pendant polysilanes represented by are obtained, and further that the high molecular weight pyrrolyl group-containing polysilanes have further improved electric conductivity, and have completed the present invention. .

[0009]

Embedded image [Where R ¹ is the following formula (2)

[0010]

[Chemical 4] (Provided that p is an integer of 2 to 12, R ³ and R ⁴ represent a hydrogen atom, an alkyl group or an aryl group), and a pyrrolyl group-containing monovalent hydrocarbon group represented by R ² , R ⁵ and R ⁶ is a long-chain alkyl group having 4 to 12 carbon atoms, and X is a halogen atom. Also, k and m are 0 <k ≦ 1, 0 ≦ m <
It is a positive number of 1, k + m = 1, and n is an integer of 6 or more. ]

The present invention will be described in more detail below. The method for producing the pyrrolyl group-pendant polysilanes of the present invention is as follows: the pyrrolyl group-containing dihalogenosilane represented by the following general formula (1) alone or the pyrrolyl group-containing dihalogenosilane. A silane and a diorganosilane represented by the following general formula (3) are reacted with an alkali metal in an inert solvent.

R ¹ R ² SiX ₂ (1) R ⁵ R ⁶ SiX ₂ (3)

In the above formula, R ¹ is a monovalent hydrocarbon group containing a pyrrolyl group represented by the following formula (2).

[0014]

Embedded image (However, in the formula, R ³ and R ⁴ are a hydrogen atom, an alkyl group or an aryl group, and p is an integer of 2 to 12.)

The alkyl group has 1 to 12 carbon atoms.
Among these, lower alkyl groups are particularly preferable, and aryl groups include those having 6 to 12 carbon atoms, and examples thereof include a phenyl group. R ³ and R ⁴ are preferably hydrogen atoms.

Also, R², R^Five, R⁶ Each has 4 carbons
~ 12 long chain alkyl groups, R², R^Five, R⁶This
By using a long chain alkyl group as described below,
With a weight average molecular weight of 50,000 or more, especially 100,000 or more
Group pendant polysilanes are sure to be obtained
It X is a halogen atom such as chlorine or bromine.

Here, as the starting material, the pyrrolyl group-containing dihalogenosilane represented by the general formula (1), for example, N-alkenylpyrrole and (organo) dihalogenohydrosilane are mixed at a molar ratio of 1 to 1.5. Then, it can be synthesized by an addition reaction. In this case, the addition reaction is preferably carried out in the presence of an addition-reactive catalyst such as chloroplatinic acid. The reaction conditions are not particularly limited, but are 0 to 1
It is desirable to set the temperature to 00 ° C. for 1 to 5 hours.

As the alkali metal used in the reaction of the halogenosilanes of the above formulas (1) and (3), for example, lithium, potassium, potassium sodium alloy, sodium or the like can be used, and sodium is preferably used among them. . The addition amount of this alkali metal is calculated by the formula (1)
It is preferable that the amount of the dihalogenosilanes of the formula (3) is 2 to 3 mol, particularly 2 to 2.1 mol per 1 mol of the total amount used. If the amount added is less than 2 mol, the reaction may not proceed sufficiently.

As the inert solvent, specifically, aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons such as decane, dodecane and tetralin are preferably used.
The amount used is preferably 1 to 10 times, particularly 2 to 5 times the total amount of the dihalogenosilanes of the formulas (1) and (3).

The reaction conditions of the dihalogenosilanes of the above formulas (1) and (3) and the alkali metal can be appropriately adjusted, but it is preferable to carry out the reaction under a temperature condition of 100 ° C. or higher for 1 to 6 hours.

In the production method of the present invention, an alkali metal is added to an inert solvent, heated and stirred, and then a mixture of dihalogenosilanes of the formulas (1) and (3) is added dropwise. The reaction proceeds exothermically and ends when the alkali metal is consumed.

In this case, by using the dihalogenosilanes of the formulas (1) and (3), a one-dimensional polymer or cyclic compound is produced. W. Weidman et al.
Am. Chem. Soc. , (1988). 110,2
As reported in 342, trifunctional trihalosilanes may be added, which may also give networked polysilanes. Further, it is also possible to use halosilanes containing a carbon-carbon unsaturated bond in the main chain skeleton in advance, and thereby a carbon-carbon unsaturated bond can be introduced into the polysilane skeleton.

After completion of the reaction, the excess alkali metal is deactivated with alcohol, and then the organic layer is taken out and precipitated from acetone or the like to obtain a polysilane represented by the following general formula (4).

[0024]

[Chemical 6]

Here, R ¹ , R ² , R ⁵ and R ⁶ have the same meanings as described above, k and m are positive numbers of 0 <k ≦ 1 and 0 ≦ m <1, and k + m = 1. However, preferably 0.5 ≦ k ≦
1, more preferably 0.65 ≦ k ≦ 1.

Further, n is an integer of 6 or more, but according to the present invention, n is 100 or more, particularly 100 to 10
To obtain high molecular weight polysilanes of
Weight average molecular weight is 50,000 in terms of polystyrene
5,000,000, especially 100,000-2,000
About 10,000 polysilanes can be reliably produced. The most preferable polysilanes in terms of electrical conductivity have a weight average molecular weight of 300,000 or more, particularly 500,000 or more.

The high molecular weight pyrrolyl group pendant polysilanes thus obtained have higher electric conductivity than ordinary methylphenyl polysilane and low molecular weight pyrrolyl group pendant polysilanes.

Therefore, the polysilanes of the formula (4) are
It can be suitably used as a photoconductive material or a conductive material.

[0029]

According to the present invention, the pyrrolyl group pendant polysilane having a high molecular weight and a high electric conductivity can be reliably produced.

[0030]

EXAMPLES The present invention will be described below in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, Pr is an N-pyrrolyl group, H
ex represents a hexyl group, Me represents a methyl group, and Ph represents a phenyl group.

[Example 1] As shown below, [(Py-C _{4
H 8 -) Si (n-} Hex)] was synthesized _n.

1.1 g of metallic sodium under a nitrogen atmosphere
Toluene (15 g) was added to (50 mmol), the temperature was raised to 110 ° C., and the mixture was vigorously stirred to prepare a sodium dispersion.

Py-C ₄ H ₈ Si was added to this dispersion.
HexCl ₂ 4.6 g (15 mmol) was added over 1 minute, and the mixture was stirred at 110 ° C. for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, and MeO was added to deactivate the remaining sodium.
About 5 ml of H was added dropwise and further washed with water. Then, the organic layer was taken out and dried over calcium chloride, and then the reaction mixture was concentrated. The obtained viscous substance was added to 200 ml of ethanol to precipitate the polymer. The precipitate was filtered off and dried in vacuum to obtain 0.88 g of the desired pyrrolyl group pendant polysilane as a white solid. According to GPC analysis, the weight average molecular weight of this polymer was 784,100 in terms of polystyrene.

This polymer was dissolved in toluene and a film was formed on a glass substrate using a spin coater. After drying, the electric conductivity was measured while doping with iodine, and was 2 × 10 ⁻² S / cm.

Example 2 As shown below, {[(Py-C
_FourH₈-) Si (n-Hex) ]_0.67[N-Hex₂S
i]_0.33｝_nWas synthesized.

1.87 g of metallic sodium under a nitrogen atmosphere
20 g of toluene was added to (80 mmol), the temperature was raised to 110 ° C., and the mixture was vigorously stirred to prepare a sodium dispersion.

Py-C ₄ H ₈ -S was added to this dispersion.
iHexCl ₂ 6.1 g (20 mmol), Hex ₂ Si
2.7 g (10 mmol) of Cl ₂ was added over 2 minutes, and 11
The mixture was stirred at 0 ° C for 2 hours. After the reaction is complete, cool to room temperature,
Approximately 5 m of MeOH to deactivate the remaining sodium
l was added dropwise and further washed with water. Then, the organic layer was taken out and dried over calcium chloride, and then the reaction mixture was concentrated. The obtained viscous substance was added to 200 ml of ethanol to precipitate the polymer. The precipitate was filtered off and dried in vacuum to obtain 0.12 g of the desired pyrrolyl group pendant polysilane as a white solid. The weight average molecular weight of this polymer was 3 in terms of polystyrene by GPC analysis.
It was 49,500.

This polymer was dissolved in toluene and a film was formed on a glass substrate using a spin coater. After drying, the electric conductivity was measured while doping with iodine, and it was 4 × 10 ⁻³ S / cm.

[Embodiment 3] As shown below, {[Py-C _{4
H 8 -) Si (n-} Hex)] 0.5 [n-Hex 2 Si]
_0.5 } _n was synthesized.

1.87 g of sodium metal under nitrogen atmosphere
20 g of toluene was added to (80 mmol), the temperature was raised to 110 ° C., and the mixture was vigorously stirred to prepare a sodium dispersion.

Py-C ₄ H ₈ Si was added to this dispersion.
HexCl ₂ 4.6 g (15 mmol), Hex ₂ SiC
l ₂ 4.0 g (15 mmol) was added over 2 minutes, and 110
The mixture was stirred at ° C for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, and about 5 ml of MeOH was added to deactivate the remaining sodium.
Was added dropwise and washed with water. Then, the organic layer was taken out and dried over calcium chloride, and then the reaction mixture was concentrated. The obtained viscous substance was added to 200 ml of ethanol to precipitate the polymer. The precipitate was filtered off and dried in a vacuum to obtain 0.96 g of the desired pyrrolyl group pendant polysilane as a white solid. The weight average molecular weight of this polymer was 7 in terms of polystyrene by GPC analysis.
It was 37,900.

This polymer was dissolved in toluene and a film was formed on a glass substrate using a spin coater. After drying, the electric conductivity was measured while doping with iodine, and was 2 × 10 ⁻³ S / cm.

[Example 4] [(Py-C ₆
H ₁₂ −) Si (n-Hex)] _n was synthesized.

1.1 g of sodium metal under nitrogen atmosphere
Toluene (15 g) was added to (50 mmol), the temperature was raised to 110 ° C., and the mixture was vigorously stirred to prepare a sodium dispersion.

[0045] Py-C ₆ H ₁₂ in the dispersion -
6.6 g (20 mmol) of SiHexCl ₂ was added over 1 minute, and the mixture was stirred at 110 ° C. for 2 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and Me was added to deactivate the remaining sodium.
About 5 ml of OH was added dropwise, and the product was washed with water. Then, the organic layer was taken out and dried over calcium chloride, and then the reaction mixture was concentrated. The obtained viscous substance was added to 200 ml of ethanol to precipitate the polymer. The precipitate was filtered off and dried in a vacuum to obtain 0.20 g of a target pyrrolyl group pendant polysilane as a white solid. By GPC analysis, the weight average molecular weight of this polymer was 597,800 in terms of polystyrene.

This polymer was dissolved in toluene and a film was formed on a glass substrate using a spin coater. After drying, the electric conductivity was measured while doping with iodine, and was 2 × 10 ⁻² S / cm.

[Embodiment 5] As shown below, {[(Py-C
₆ H ₁₂ −) Si (n-Hex)] _0.67 [n-Hex ₂ S
i] _0.33 ] _n was synthesized.

1.87 g of sodium metal under a nitrogen atmosphere
20 g of toluene was added to (80 mmol), the temperature was raised to 110 ° C., and the mixture was vigorously stirred to prepare a sodium dispersion.

[0049] Py-C ₆ H ₁₂ in the dispersion -
SiHexCl ₂ 6.6 g (20 mmol), Hex ₂ S
2.7 g (10 mmol) of iCl ₂ was added over 2 minutes, and 1
The mixture was stirred at 10 ° C for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, and about 5 ml of MeOH was added dropwise to deactivate the remaining sodium, followed by washing with water. Then, the organic layer was taken out and dried over calcium chloride, and then the reaction mixture was concentrated. The obtained viscous material was added to 200 ml of ethanol,
The polymer was precipitated. The precipitate was filtered off and dried in vacuum to obtain 0.76 g of the desired product, a pyrrolyl group pendant polysilane, as a white solid. By GPC analysis, the weight average molecular weight of this polymer was 780,900 in terms of polystyrene.

This polymer was dissolved in toluene and a film was formed on a glass substrate using a spin coater. After drying, the electric conductivity was measured while doping with iodine, and was 2 × 10 ⁻² S / cm.

[Embodiment 6] As shown below, {[(Py-C
₆ H ₁₂ −) Si (n-Hex)] _0.5 [n-Hex ₂ S
i] _0.5 ] _n was synthesized.

1.87 g of sodium metal under a nitrogen atmosphere
20 g of toluene was added to (80 mmol), the temperature was raised to 110 ° C., and the mixture was vigorously stirred to prepare a sodium dispersion.

[0053] Py-C ₆ H ₁₂ in the dispersion -
SiHexCl ₂ 5.0 g (15 mmol), Hex ₂ S
4.0 g (15 mmol) of iCl ₂ was added over 2 minutes, and 1
The mixture was stirred at 10 ° C for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, and about 5 ml of MeOH was added dropwise to deactivate the remaining sodium, followed by washing with water. Then, the organic layer was taken out and dried over calcium chloride, and then the reaction mixture was concentrated. The obtained viscous material was added to 200 ml of ethanol,
The polymer was precipitated. The precipitate was filtered off and dried in vacuum to obtain 0.40 g of the desired product, a pyrrolyl group pendant polysilane, as a white solid. By GPC analysis, the weight average molecular weight of this polymer was 251,800 in terms of polystyrene.

This polymer was dissolved in toluene and a film was formed on a glass substrate using a spin coater. After drying, the electric conductivity was measured while doping with iodine, and it was 4 × 10 ⁻³ S / cm.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Motoo Fukushima 3-2-1 Sakado, Takatsu-ku, Kawasaki-shi, Kanagawa Shin-Etsu Chemical Co., Ltd. Corporate Research Center

Claims (1)

[Claims] 1. The following general formula (1) R ¹ R ² SiX ₂ (1) [wherein R ¹ is the following formula (2): (However, p is an integer of 2 to 12, R ³ and R ⁴ are a hydrogen atom, an alkyl group or an aryl group.), And a pyrrolyl group-containing monovalent hydrocarbon group, and R ² has 4 to 4 carbon atoms. 12 are long-chain alkyl groups, and X is a halogen atom. ] The pyrrolyl group-containing dihalogenosilane represented by the following, or this pyrrolyl group-containing dihalogenosilane and the following general formula (3) R ⁵ R ⁶ SiX ₂ (3) [wherein, R ⁵ and R ⁶ are each a carbon atom] The long-chain alkyl group of several 4-12 is shown, and X is a halogen atom. ] The diorganohalogenosilane represented by the following general formula (4): is reacted with an alkali metal in an inert solvent. [Wherein R ¹ , R ² , R ⁵ and R ⁶ have the same meanings as described above, k and m are positive numbers 0 <k ≦ 1 and 0 ≦ m <1, and k + m
= 1 and n is an integer of 6 or more. ] The manufacturing method of the pyrrolyl group pendant polysilane shown by these.