JP2721860B2 - Method for producing polysilane compound - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel method for producing a polysilane compound.

2. Description of the Related Art As a method for producing a polysilane compound, a method in which an alkali metal is allowed to act on dimethyldichlorosilane to carry out polymerization and the like have conventionally been employed. However,
In this method, for example, when the raw material is a silane compound having an unsaturated bond or the like, the reaction of the unsaturated bond portion proceeds preferentially due to the high reactivity of the unsaturated portion, and It is difficult to allow the polymerization reaction to proceed while leaving the bond. Therefore, it is not possible to produce a polysilane compound having an unsaturated bond by utilizing the above reaction.

In recent years, polysilane compounds having an unsaturated bond have attracted attention as a conductive material or a photosensitive resin, and development of a method for producing a polysilane compound having an unsaturated bond has been desired.

Under these circumstances, Chemistry Letters, 1149 (198
8) has 1,2-diethynyl-1,1,
1,2,2 silicon compound and carbon, such as tetramethyl disilane - Periodic Table a method of polymerizing by using a catalyst comprising a Group 6 atoms such as WCl ₆ compounds having carbon-carbon double bond is reported ing.

Here, X is a bond, an alkylene group, -0-, And so on.

However, the polysilane compound obtained by this method has a ring structure in which a silicon atom is incorporated, and the raw material component is a compound having a triple bond. Has no triple bond. Therefore, even if the above-mentioned reaction is used, the unsaturated bond cannot be completely introduced into the polysilane compound. Thus, when such a polysilane compound is to be used, for example, as a conductive material, there is a problem that the excellent properties of the polysilane compound and the polyacetylene compound are not sufficiently expressed in terms of conductivity.

Also, Journal of Organometallic Chemistry, 346 (1
988) reports a method of synthesizing a silane having an ethynyl group and a duplex of the silane using a palladium chain as a catalyst. However, according to this method, the obtained silane compound is a dimer, and for example, there is no mention of a compound expected to be useful as a conductive material.

That is, in the conventional technique for producing a polysilane compound, a triple bond is contained in the obtained polysilane compound by using a raw material having an unsaturated bond having a very high reactivity, such as a monomer having a triple bond. The method to introduce it has not been established.

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems associated with the prior art as described above, and it is an object of the present invention to produce a polysilane compound having a highly active unsaturated bond. It is intended to provide a new method that can be used.

More specifically, an object of the present invention is to provide a novel method capable of producing a polysilane compound having a triple bond in a molecular chain which is highly useful as, for example, a conductive material.

Means for Solving the Problems A method for producing a polysilane compound according to the present invention comprises the following formula (I) in the presence of a rhodium or iridium complex having an arylphosphine ligand. (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 m represents an integer in the range of 1 to 4.) By reacting, the following formula (II) (Wherein R ¹ , R ² and m are the same as described above, and n represents an integer of 2 or more).

According to the method of the present invention, since the rhodium or iridium complex having the arylphosphine ligand is used as a catalyst, the cyclic structure containing a silicon atom can be obtained by reacting the compound represented by the formula (I). The polysilane compound represented by the formula (II) having a silicon-silicon bond and an enyne structure alternately in the main chain can be obtained without forming

Hereinafter, the method for producing a polysilane compound according to the present invention will be described in detail.

The starting compound used in the method of the present invention has the following 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 m represents an integer in the range of 1 to 4.)

Here, the alkyl group usually has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Examples of such an alkyl group include a linear alkyl group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, a sec-
Butyl group, secondary alkyl group such as sec-amyl group, and ter
Examples thereof include tertiary alkyl groups such as t-butyl group and tert-amyl group.

The aryl group is a monovalent group having at least one aromatic ring, and the aromatic ring may have a substituent. Specific examples of such an aryl group include, for example, a phenyl group, a naphthyl group, a tolyl group and a xylyl group.

The aralkyl group is a monovalent group of an aliphatic hydrocarbon having at least one aromatic ring, and the aromatic ring contained therein may have a substituent. Specific examples of such an aralkyl group include, for example, a benzyl group, a phenethyl group, α-methylbenzyl, a tolyl group and the like.

In the above formula (I), m is an integer of 1 to 4, and is preferably 2.

Therefore, as the compound represented by the formula (I) which can be used as a raw material in the method of the present invention, for example, 1,2-diethynyl-1,1,2,2-tetramethyldisilane, 1,2-diethynyl -1,1,2,2-tetraethyldisilane, 1,2-diethynyl-1,1,2,2-tetra [isopropyl] disilane, 1,2-diethynyl-1,1,2,2-tetra (se
c-butyl] disilane, 1,2-diethynyl-1,1,2,2-tetra [3-methylbenzyl] disilane, 1,2-diethynyl-1,1,2,2-tetra [tert-butyl] Disilane, 1,2-
Diethynyl-1,1,2,2-tetra [2,2-dimethylbutyl]
Disilane, 1,2-diethynyl-1,1,2,2-tetraphenyldisilane, 1,2-diethynyl-1,1,2,2-tetranaphthyldisilane, 1,2-diethynyl-1,1,2 1,2-tetratolyldisilane, 1,2-diethynyl-1,1,2,2-tetrabenzyldisilane, 1,2-diethynyl-1,1,2,2-tetraphenethyldisilane, 1,2-diethynyl -1,1,2,2-tetra [α-methylbenzyl] disilane 1,2-diethynyl-1,2-diphenyl-1,2-dimethyldisilane, 1,2-diethynyl-1,2
-Diethyl-1,2-dimethyldisilane and the like.

These compounds are usually used alone, but for example, two or more of them can be used in combination for adjusting the conductivity of the obtained polysilane compound.

According to the method of the present invention, the compound represented by the above formula (I) is polymerized in the presence of a rhodium or iridium complex having the aryl phosphine ligand.

In the present invention, specific examples of the complex particularly preferably used as the catalyst include, for example, tris (triphenylphosphine) rhodium chloride and chlorocarbonylbis (triphenylphosphine) iridium.

In the present invention, such a metal complex may be used alone or in combination of two or more.

In the method of the present invention, the metal complex as described above is used in an amount of usually 0.1 to 10 mol%, preferably 1 to 5 mol%, based on the compound represented by the formula (I) as a raw material. Can be

The polymerization of the compound represented by the formula (I) in the presence of such a metal complex can be carried out either in the absence or in the presence of a solvent.
Performed in the liquid phase. As described above, when the polymerization is performed in the liquid phase, the solvent is not particularly limited as long as it has no reactivity with the raw materials and the like. Specific examples of such solvents include, for example, aromatic hydrocarbon solvents, saturated hydrocarbon solvents, unsaturated hydrocarbon solvents, ether solvents, alcohol solvents, amide solvents, and the like. In particular, aromatic hydrocarbon solvents such as toluene, benzene, and xylene are preferably used. These solvents are used alone or as a mixture of two or more.

The polymerization reaction is usually carried out at a temperature in the range of -50 ° C to 100 ° C, preferably in the range of 0 to 50 ° C. Further, the polymerization reaction is carried out under reduced pressure or under increased pressure, and the reaction pressure is not limited, but may be from reduced pressure to 60 kg / cm ² . However, usually,
30kg / cm ^2, preferably in the range of 0~5kg / cm ^2. The reaction time is appropriately set in consideration of the reaction temperature, the pressure and the like, but is usually 5 minutes to 1 week, preferably
5 to 80 hours.

By such a reaction, the compound represented by the formula (I) forms a polysilane compound represented by the formula (II) according to the following reaction formula.

In the above, R ¹ , R ² , m and n are the same as described above, and in particular, n is preferably an integer of 10 or more.

Thus, the polysilane compound (II) obtained according to the present invention usually has a conductivity σ of 10 ⁻⁸ S / cm or less. By adding a dopant to such a polysilane compound, the conductivity σ is usually 0.01 to 1 S / cm.
Range. Therefore, such a polysilane compound can be used as a conductive material.

The dopant is not particularly limited, and a conventionally known dopant can be used.
Specific examples include, for example, I ₂ , SO ₃ , AsF _{5 and the} like. Further, SbF ₅ , SbCl ₅ or the like can also be used. These dopants can be used alone or in combination of two or more. In the present invention,
As the dopant, SbF ₅ is particularly preferable.

The polysilane compound obtained by the method of the present invention can be used as a photosensitive material or the like by utilizing, for example, photofunctionality having a silicon-silicon bond, in addition to the above-described conductive material. it can.

Effects of the Invention According to the present invention, a compound represented by the above formula (I) is polymerized using a rhodium or iridium complex having the above arylphosphine ligand as a catalyst, whereby a cyclic structure containing a silicon atom is obtained. The polysilane compound represented by the formula (II) having a silicon-silicon bond and an enyne structure in the main chain can be obtained without forming

Such a polysilane compound is particularly useful as a conductive material.

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

Example 1 Polymerization of 1,2-diethynyl-1,2-diphenyl-1,2-dimethyldisilane using rhodium complex 1.0 g of 1,2-diethynyl-1,2-diphenyl-1,2-dimethyldisilane and 10 ml of toluene Was dissolved. Tris (triphenylphosphine) rhodium chloride as a catalyst was added to this solution in an amount of 2 mol% with respect to the raw materials, and the mixture was stirred at room temperature under an argon atmosphere for 40 hours.

Next, toluene was distilled off under reduced pressure, and the residue was purified by reprecipitation using ethanol and isopropanol once each in this order, and the precipitate was collected by filtration. The resulting filtrate was a dark brown solid. The yield was 0.69 g. Yield 69%.

As a result of analyzing the obtained filtrate using GPC, the molecular weight (Mw) of this compound was about 18,000. The melting point of this compound was 136 ° C.

The results of instrumental analysis of the obtained compound are as follows. ¹ H nuclear magnetic resonance spectrum (measured in CDCl ₃ solution, δ ppm) 0.47 (6H, brs, SiMe), 5.93 (1 H, d, J = 19 Hz), 6.66 (1
H, d, J = 19Hz), 6.87−7.91 (10H, m). ¹³ C nuclear magnetic resonance spectrum (measured in CDCl ₃ solution, δpp
m) −5.7, −5.4, −3.8, −3.7 (as MeSi); 91.5, 94.9
(As C≡C); 110.0 (olefinic carbon atom); 12
7.9,129.2,133.5,134.5,134.6 (carbon atom of aromatic ring);
134.6 (Olefin-based carbon atom). IR spectrum (measured by KBr method) νC≡C2 150 cm ⁻¹ As a result of the above instrumental analysis, the obtained dark brown solid was poly [(1,2-dimethyl-1,2-diphenyldisilanilene) butenoin]. In the formula (I), it was confirmed that n was about 60.

Example 2 Polymerization of 1,2-diethynyl-1,2-diethyl-1,2-dimethyldisilane using a rhodium complex 1.011 g of 1,2-diethynyl-1,2-diethyl-1,2-dimethyldisilane (6.08 × ^10-3 mol) and 0.1005 g of tris (triphenylphosphine) rhodium chloride as a catalyst (2
Mol%) in 10 ml of toluene, and under an argon stream,
Stirred at room temperature for 2 days.

After completion of the reaction, toluene was distilled off from the reaction mixture under reduced pressure, and poly [(1,2-diethyl-1,2
-Dimethyldisilanilen) butenyne] as a solid. This solid was purified by dissolving in chloroform, reprecipitating from ethanol, and then reprecipitating from isopropyl alcohol, yielding 0.4717 g.
(Yield 47%). Melting point 300 ° C or higher.

¹ H nuclear magnetic resonance spectrum (measured in CDCl ₃ solution, δ ppm) 0.37, 0.44, 0.51 (MeSi); 0.63-1.53 (EtSi); 5.77 −
6.74 (m, 9H, -C = C-). ¹³ C nuclear magnetic resonance spectrum (measured in CDCl ₃ solution, δpp
m) −6.59, −4.69 (MeSi); −5.38, 6.47, 8.04 (EtSi);
99.28,103.98 (-C @ C-), 124.29,124.57,143.74,14
3.96 (-C = C-). IR spectrum (measured by KBr method) νC≡C2146 cm ^-1 Example 3 Polymerization of 1,2 diethinyl-1,1,2,2-tetramethyldisilane using rhodium complex 1,2-diethynyl-1,1,2, 2-tetramethyldisilane 1.
In a two-necked flask in which 01 g (6.08 × 10 ^-3 mol) and 10 ml of the solvent toluene were replaced with argon, 0.100 g (2 mol%) of tris (triphenylphosphine) rhodium chloride as a catalyst was added at room temperature. Stirred for days.

During this period, the solvent was concentrated, and the obtained residue was reprecipitated twice with ethanol and once with isopropyl alcohol, and the obtained precipitate was filtered and dried. Yield 0.472 g (Yield 47
%). Melting point 30 ° C or higher. ¹ H nuclear magnetic resonance spectrum (measured in CDCl ₃ solution, δ ppm) 0.13, 0.20, 0.22, 0.29 (12H, 4 singlet, SiMe); 5.9
0,5.96,6.50,6.53 (2H, 4 double lines, J = 19Hz, hydrogen of olefin). ¹³ C nuclear magnetic resonance spectrum (measured in CDCl ₃ solution, δpp
m) −4.58, −4.47, −2.96, −2.85 (MeSi); 123.92, 124.1
3,144.72,145.04 (-C = C-); 92.80,93.04,107.99
(-C≡C-). IR spectrum (measured by KBr method) νC≡C2148 cm ^-1 Example 4 Polymerization of 1,2-diethynyl-1,2-diphenyl-1,2-dimethyldisilane using iridium complex 1,2-diethynyl-1,2- 0.5 g of diphenyl-1,2-dimethyldisilane was added in the presence of 27.5 mg (2 mol%) of chlorocarbonylbis (triphenylphosphine) iridium.
The mixture was heated under reflux in 5 ml of toluene for 10 hours.

During the cooling period, toluene was distilled off from the reaction mixture under reduced pressure and concentrated, and the obtained residue was reprecipitated once each with ethanol and isopropyl alcohol. The obtained solid was filtered and dried to obtain 0.15 g of a polysilane compound. Yield 30
%.

Claims (2)

(57) [Claims] (1) In the presence of a rhodium or iridium complex having an arylphosphine ligand, (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 m represents an integer in the range of 1 to 4.) The following formula (II) characterized by reacting (Wherein R ¹ , R ² and m are the same as described above, and n represents an integer of 2 or more). 2. The method for producing a polysilane compound according to claim 1, wherein the complex is tris (triphenylphosphine) rhodium chloride or chlorocarbonylbis (triphenylphosphine) iridium.